CN102628158A - Preparing method of film and evaporation material, film, film sheet and lamination sheet used for evaporation - Google Patents
Preparing method of film and evaporation material, film, film sheet and lamination sheet used for evaporation Download PDFInfo
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- CN102628158A CN102628158A CN2012100085091A CN201210008509A CN102628158A CN 102628158 A CN102628158 A CN 102628158A CN 2012100085091 A CN2012100085091 A CN 2012100085091A CN 201210008509 A CN201210008509 A CN 201210008509A CN 102628158 A CN102628158 A CN 102628158A
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Abstract
The invention provides a manufacturing method of a film having good transparency and gas blocking performance, evaporation material used for evaporation for obtaining the film, the film obtained through the method, film sheet and laminating sheet having the film. The manufacturing method of the film in the invention is characterized in that sublimable evaporation material composed of a first oxide and fusing evaporation material composed of a second oxide are used. By using a vacuum film forming method and an evaporation method at the same time, the oxide film composed of the first oxide and the second oxide is formed on the substrate.
Description
Technical field
The present invention relates to sull, the diaphragm that possesses this film and lamination sheets that the method for manufacture of the excellent film of various characteristicses such as a kind of transparency, gas barrier property, the common vapor deposition that is fit to form this film obtain with the vapor deposition material, through this method.More detailed; It is excellent to relate to these various characteristicses, especially is suitable as sull, the diaphragm that possesses this film and lamination sheets that the method for manufacture of the film of gas barrier property materials such as liquid-crystal display, OLED display, plasma display or solar module, the common vapor deposition that is fit to form this film obtain with the vapor deposition material, through this method.
Background technology
Equipment such as liquid-crystal display, OLED display or solar cell are unable to undergo moisture usually; Make its characteristic because of moisture absorption deterioration promptly, so must be equipped with the assembly that has highly moistureproof, promptly prevents infiltrations such as oxygen or water vapour or submerged gas barrier property.
For example, in the example of solar cell, be provided with backboard at the back side with the opposite side of the sensitive surface of solar module.This backboard is representational to have the backboard that on base material, comprises gas barrier property material with highly moistureproof and their parts of protection etc.
Backboard as this formation solar module; For example disclose through high-strength heat-resistant property, weathering resistance resin sandwich moisture resistance tinsel, the back-protective that the solar module that vitreous vapor deposition epithelium forms is set in one of which side in addition is with sheet material (for example the referenced patent document 1).In this sheet material, use tinsels such as aluminium foil, zinc-plated iron foil, zinc-plated iron foil as gas barrier property material.
In addition, disclose range upon range of high moisture barrier films and high Weather-proof film and make its integrated solar cell cover plate materials that forms use the solar cell (for example the referenced patent document 2) in the side guard block overleaf.Use following film in the high moisture barrier films in this solar cell cover plate materials; Promptly on base material films such as PET film, form moisture barrier films as gas barrier property material by CVD (cvd), PVD (evaporation reaction) method etc., said moisture barrier films is made up of filming of inorganic oxides such as silicon-dioxide, aluminum oxide.
And, disclosing and have base material film and blocking layer, the blocking layer is the transparent blocking film (for example the referenced patent document 3) through film forming inorganic nitride film of hollow cathode type ion plating or inorganic nitrogenize sull.And, disclose the solar module (for example the referenced patent document 4) that the permeable barrier more than a kind that stops water vapour, oxygen, resolvent or additive is set on the surface of solar cell device.Use the composite package more than 2 kinds of filming or comprising those through the compsn that constitutes by polycondensate as the blocking layer in this solar module based on the hydrolysis of the vapor-deposited film of resin molding, barrier property resin molding, inorganic oxide, silicon compound.
And, disclose the photovoltaic module (for example the referenced patent document 5) that possesses the blocking layer that constitutes by plastic film that is inorganic oxide layer or plastic composite.In this inorganic oxide layer, aluminum oxide or silicon oxide use as its coated material.And; Disclose the used for solar batteries backside protective sheet that constitutes by duplexer, said duplexer other duplexers (for example the referenced patent document 6) heat-resisting, the weathered plastics film on heat-resisting, weathered plastics film, the inorganic oxide film layer being set and constituting by same resin in this film aspect laminated.In this used for solar batteries backside protective sheet, use by any thin film layer that forms in silicon oxide or the aluminum oxide as the inorganic oxide film layer.
And, disclose the duplexer (for example the referenced patent document 7) that the metal oxide layer of the zinc oxide film with ultraviolet screener characteristic that forms at the metal or the semi-conductor that stack gradually on the base material film with transparency more than 3 valencys that mix and gas barrier property excellence forms.As the metal oxide layer of this duplexer, use silicon oxide, aluminum oxide or Natural manganese dioxide.
And, disclose gas blocking layer that the single face at least at the polymeric membrane base material is made up of metal or MOX through the vapour deposition process film forming and the transparent gas that on this gas blocking layer, forms the resin layer that contains ultrafine particle and interdict composite film material (for example the referenced patent document 8) with anti-uv.As the gas blocking layer of this transparency gas blocking composite film material, use the single layer structure that constitutes by aluminium or multilayer mechanism or by aluminum oxide, silicon oxide and magnesian at least a kind of single layer structure that constitutes or multilayered structure.
Patent documentation 1: the flat 2-44995 communique of Japanese Utility Model bulletin (the 41st～44 row on requirement of utility model logon right and 5 hurdles)
Patent documentation 2: the open 2000-174296 communique of Japanese Patent (claim 1, claim 7 and [0019] section)
Patent documentation 3: the open 2000-15737 communique (claim 1) of Japanese Patent
Patent documentation 4: the open 2001-217441 communique (claim 1,3) of Japanese Patent
Patent documentation 5: the public table of Japanese Patent 2002-520820 communique (claim 1 and [0019] section)
Patent documentation 6: the open 2002-134771 communique (claim 1,2) of Japanese Patent
Patent documentation 7: the openly flat 7-256813 communique of Japanese Patent (claim 1,3 reaches [0015]～[0016] section)
Patent documentation 8: the open 2000-6305 communique of Japanese Patent (claim 1,7,8 reaches [0020] section)
Yet as gas barrier property material, therefore if this sheet material is applied on the backboard of solar module, there is the anxiety of proof voltage decline, electric current leakage in the back-protective shown in the above-mentioned patent documentation 1 with tinsels such as sheet material use aluminium foils.
And, if the thickness of tinsel becomes below the 20 μ m in the sheet material of use tinsel, then being increased in the pin hole that produces between thermotolerance, weathering resistance resin and the tinsel, the gas barrier property descends significantly.On the other hand, if the thickness of thickening tinsel then can produce the problem of manufacturing cost rising and so on; And; Need classify as waste,, and can not use sensitive surface at solar cell perhaps because of light tight; And produce the tinsel burr at power supply terminal with around the jack, the danger of short circuit is arranged.
In addition, inorganic oxides such as the silicon-dioxide that in above-mentioned patent documentation 2～8, uses, aluminum oxide if obtain higher gas barrier property, then must be guaranteed the thickness of film for more than the 100nm, can not say that even so the gas barrier property is abundant.
Summary of the invention
The object of the present invention is to provide and a kind ofly can form the film-forming method of the excellent film of the transparency and gas barrier property and common vapor deposition that film forms usefulness is used the vapor deposition material.
Another object of the present invention is to provide a kind of transparency and excellent film, the diaphragm that possesses this film and the lamination sheets of gas barrier property.
The 1st viewpoint of the present invention, be the method for manufacture of film; Wherein, Sublimability vapor deposition material that use is made up of the 1st oxide compound and the meltbility vapor deposition material that constitutes by the 2nd oxide compound; Utilize common vapour deposition method, on base material, form the sull that constitutes by the 1st oxide compound and the 2nd oxide compound through vacuum film formation method while vapor deposition.
The 2nd viewpoint of the present invention, promptly according to the invention of the 1st viewpoint, further, be that mode more than 0.03 makes up sublimability vapor deposition material that is made up of the 1st oxide compound and the meltbility vapor deposition material that is made up of the 2nd oxide compound with the basicity of the film that forms.
The 3rd viewpoint of the present invention, promptly according to the invention of the 1st or the 2nd viewpoint; Further, be that 5～85: 95～15 mode makes up sublimability vapor deposition material that is made up of the 1st oxide compound and the meltbility vapor deposition material that is made up of the 2nd oxide compound with the molar ratio of the 1st oxide compound of the film that forms and the 2nd oxide compound.
The 4th viewpoint of the present invention, promptly according to the invention of the 1st to the 3rd viewpoint, further, the 1st oxide compound of sublimability vapor deposition material is for being selected from ZnO, CaO, MgO, SnO
2And CeO
2In at least a kind, the 2nd oxide compound of meltbility vapor deposition material is for being selected from SiO
2, Al
2O
3And TiO
2In at least a kind.
The 5th viewpoint of the present invention, promptly according to the invention of the 1st to the 4th viewpoint, further, the vacuum film formation method is any one in electron beam evaporation plating method, ion plating method, reactive plasma vapour deposition method, electrical resistance heating or the induction heating.
The 6th viewpoint of the present invention, promptly according to the invention of the 1st to the 5th viewpoint, further, the median size of the 2nd oxide particle of the median size of the 1st oxide particle of sublimability vapor deposition material and meltbility vapor deposition material is respectively 0.1～10 μ m.
The 7th viewpoint of the present invention, promptly altogether vapor deposition use the vapor deposition material, wherein, is used for the method for manufacture according to the 1st to the 6th viewpoint, comprises the sublimability vapor deposition material that is made up of the 1st oxide compound and the combination of the meltbility vapor deposition material that is made up of the 2nd oxide compound.
The 8th viewpoint of the present invention, promptly according to the invention of the 7th viewpoint, further, the 1st oxide compound of sublimability vapor deposition material is for being selected from ZnO, CaO, MgO, SnO
2And CeO
2In at least a kind, the 2nd oxide compound of meltbility vapor deposition material is for being selected from SiO
2, Al
2O
3And TiO
2In at least a kind.
The 9th viewpoint of the present invention, be a kind of invention according to the 7th or the 8th viewpoint, further, the median size of the 2nd oxide particle of the median size of the 1st oxide particle of sublimability vapor deposition material and meltbility vapor deposition material is respectively 0.1～10 μ m.
The 10th viewpoint of the present invention, be sull; Method of manufacture through according to the 1st to the 6th viewpoint obtains; Sublimability vapor deposition material that use is made up of the 1st oxide compound and the meltbility vapor deposition material that constitutes by the 2nd oxide compound; Utilize common vapour deposition method film forming, and constitute by the 1st oxide compound and the 2nd oxide compound through vacuum film formation method while vapor deposition.
The 11st viewpoint of the present invention, be a kind of diaphragm 10; Wherein, As shown in Figure 1, through method of manufacture, on the 1st base material film 11, form sull 12 and form according to the 1st to the 6th viewpoint; The vacuum film formation method of said sull utilization through the meltbility vapor deposition material that uses the sublimability vapor deposition material that is made up of the 1st oxide compound and be made up of the 2nd oxide compound be the common vapour deposition method film forming of vapor deposition simultaneously, and is made up of the 1st oxide compound and the 2nd oxide compound.
The 12nd viewpoint of the present invention, promptly according to the invention of the 11st viewpoint, further, the vacuum film formation method is any one in electron beam evaporation plating method, ion plating method, reactive plasma vapour deposition method, electrical resistance heating or the induction heating.
The 13rd viewpoint of the present invention, promptly according to the invention of the 11st or the 12nd viewpoint, further, be 0.3g/m at the vapor permeability S of condition held in the time of 1 hour of 20 ℃ of temperature, relative humidity 50%RH
2Below it.
The 14th viewpoint of the present invention, be lamination sheets 20, wherein as shown in Figure 1, form sides at film 12 according to the diaphragm 10 of the 11st to the 13rd viewpoint, form through adhesive coating 13 range upon range of the 2nd base material films 14.
In the film-forming method of the present invention; Film forming when utilization is controlled through the common vapour deposition method of vacuum film formation method while vapor deposition; Therefore can also be utilized in and fail to make the combination of materials of forming uniform film in the method in the past; So the material range of choice broadens, can make the film of diversified composition equably.And the barrier property of the individual layer of the film that obtains is excellent, and therefore available less range upon range of number obtains than high barrier property, therefore can boost productivity, and can also reduce cost.And through being made as the blocking film of individual layer or less range upon range of number, the thickness attenuation of total can alleviate breaking when making the blocking film, warpage etc.When but the blocking film that this thickness is thin is used for the solar cell of bending, improves resistance to bend(ing) and improve the weather resistance of solar cell.In addition, because the transparency of the film that obtains is excellent, therefore can in the long wavelength zone, keep high permeability.Therefore, solar module is made as resin system but not during glass, also effective as the blocking material of sensitive surface, help to improve the rate of permeation of solar cell.And, through making up sublimability vapor deposition material that constitutes by the 1st oxide compound and the meltbility vapor deposition material that constitutes by the 2nd oxide compound so that the basicity of the film that forms is mode 0.03 or more, therefore can form the transparency with excellence and the film of gas barrier property.And; The median size of the 2nd oxide particle of the median size of the 1st oxide particle of sublimability vapor deposition material and meltbility vapor deposition material is respectively 0.1～10 μ m; Can form the good and thick vapor-deposited film of vapor deposition efficient thus, so can keep higher gas barrier property and make its stabilization.
Altogether vapor deposition of the present invention owing to comprise the sublimability vapor deposition material that is made up of the 1st oxide compound and the combination of the meltbility vapor deposition material that is made up of the 2nd oxide compound, therefore can form the transparency with excellence and the film of gas barrier property with the vapor deposition material.And the median size of the 2nd oxide particle of the median size of the 1st oxide particle of sublimability vapor deposition material and meltbility vapor deposition material is respectively 0.1～10 μ m; Can form the good and thick vapor-deposited film of vapor deposition efficient thus, so can keep higher gas barrier property and make its stabilization.
The sull of film of the present invention for being made up of the 1st oxide compound and the 2nd oxide compound utilizes the common vapour deposition method film forming through vacuum film formation method while vapor deposition, therefore has the excellent transparency and gas barrier property.
Diaphragm of the present invention possesses by utilizing through vacuum film formation method film forming the 1st oxide compound of common vapour deposition method of vapor deposition and the sull that the 2nd oxide compound constitutes simultaneously, thereby has the excellent transparency and gas barrier property.And the vapor permeability S of condition held in the time of 1 hour that has at 20 ℃ of temperature, relative humidity 50%RH is 0.3g/m
2Very high below it and so on and the deterioration less gas barrier property that causes because of the passage of time.
In addition, lamination sheets of the present invention adopts the 2nd base material film further to be layered in the structure of the film formation side of above-mentioned diaphragm through adhesive coating.Thus, the 2nd base material film can protective film, therefore can keep higher gas barrier property and make its stabilization.
Description of drawings
Fig. 1 is the sectional view of stepped construction of schematically representing diaphragm and the lamination sheets of embodiment of the present invention.
Fig. 2 is the figure that schematically representes the cross section structure of diaphragm in the past.
Fig. 3 is the figure of cross section structure that schematically representes the diaphragm of embodiment of the present invention.
Nomenclature
The 10-diaphragm, 11-the 1st base material film, 12-film, 13-adhesive coating, 14-the 2nd base material film, 20-lamination sheets.
Embodiment
Then, according to accompanying drawing the mode that is used for embodiment of the present invention is described.
The method of manufacture of film of the present invention; It is characterized in that; Sublimability vapor deposition material that use is made up of the 1st oxide compound and the meltbility vapor deposition material that constitutes by the 2nd oxide compound; Utilize common vapour deposition method, on base material, form the sull that constitutes by the 1st oxide compound and the 2nd oxide compound through vacuum film formation method while vapor deposition.
When for example using the one-piece type vapor deposition material that contains 2 kinds of oxide compounds to carry out film forming; If be prone to the combination of oxide compound (sublimability oxide compound) with the easy fused oxide compound (meltbility oxide compound) of distillation; Even then the temperature for the distillation of sublimability oxide compound also is difficult to the meltbility oxide compound that distils, so there is the problem that is difficult to make uniform film of composition and so in its result.
In the method for manufacture of the present invention; Film forming when utilization is controlled through the common vapour deposition method of vacuum film formation method while vapor deposition; Therefore can also be utilized in and fail to make the combination of materials of forming uniform film in the method in the past; So the material range of choice broadens, and can make the film of diversified composition equably.
The sublimability vapor deposition material that uses among the present invention is meant vapor deposition not fusion of material when heating vapor deposition material and the vapor deposition material that element distils takes place that meltbility vapor deposition material is meant that the vapor deposition material of elements vaporization also takes place through liquid phase in the fusion that the vapor deposition material takes place when heating vapor deposition material.
The 1st oxide powder of sublimability vapor deposition material is for being selected from ZnO, CaO, MgO, SnO
2And CeO
2In at least a kind, the 1st oxide compound purity of the 1st oxide powder is more than 98%, to be preferably more than 99.5%.The 2nd oxide powder of meltbility vapor deposition material is for being selected from SiO
2, Al
2O
3And TiO
2In at least a kind, the 2nd oxide compound purity of the 2nd oxide powder is more than 98%, to be preferably more than 98.4%.Wherein, with the 1st oxide compound purity in the 1st oxide powder be limited to more than 98% be because, if less than 98%, then the compactness of film worsens because of impurity, the result is interdicted characteristic and is descended.And, with the 2nd oxide compound purity of the 2nd oxide powder be limited to more than 98% be because, if less than 98%, then the compactness of film worsens because of impurity, the result is interdicted characteristic and is descended.In addition, the purity of the powder in this specification sheets is meant according to spectrum analysis method (inductively coupled plasma emmission spectrometric analysis device: the purity of Japanese Jarrell Ash manufactured ICAP-88) measuring.
And the median size of the 2nd oxide particle of the median size of the 1st oxide particle of this sublimability vapor deposition material and meltbility vapor deposition material is respectively 0.1～10 μ m.And the 1st oxide compound in the formed film and the molar ratio of the 2nd oxide compound are controlled to be 5～85: 95～15.And, be that mode more than 0.03 makes up sublimability vapor deposition material that is made up of the 1st oxide compound and the meltbility vapor deposition material that is made up of the 2nd oxide compound with the basicity of formed film.Use the 1st oxide particle and the 2nd oxide particle of miniaturization like this, utilize common vapour deposition method, can make the film that is controlled to predetermined proportion and forms manifest higher gas barrier property through vacuum film formation method while vapor deposition.
Its technological reason can be estimated as as follows: generally when for (1) only by the 1st oxide particle or only by the single film of forming of the 2nd oxide particle, (2) though comprise the 1st oxide particle and any side of the 2nd oxide particle both sides contain proportional less film the time; As shown in Figure 2, the sull 32 that on the 1st base material film 11, forms becomes the structure that the crystallization phases of column crystal is gathered for the infiltration direction of gas abreast.Because gas molecules such as water vapour advance along the interface of the crystal boundary of gathering abreast, so the barrier property in the film 32 of the crystalline structure of gathering above-mentioned column crystal abreast is lower.On the other hand; When the 1st oxide particle that contains miniaturization with the mode that becomes predetermined proportion or the 2nd oxide particle; As shown in Figure 3, the part that the sull 12 that on the 1st base material film 11, forms becomes the column crystal of the film that forms single composition is burst apart and near the microtexture of the densification of non-crystalline state.Because in microtexture near the densification of non-crystalline state, gas molecules such as water vapour need grow distance move in labyrinth-like inner, so in film 12, improve barrier property near the microtexture of the densification of above-mentioned non-crystalline state.Like this, crystalline texture is not column crystal, and film forming is for being fit to prevent infiltration or submerged structure such as moisture, thereby improves the gas barrier property.
And; Also may be thought of as as follows: if make the 1st oxide particle that contained and both sides' miniaturization of the 2nd oxide particle; Then when making film growth through vapour deposition method; Enough a spot of electron beams of ability or plasma body carry out film forming, so can form fine and close film, improve the gas barrier property thus.Wherein, With the 1st oxide particle and the 2nd oxide particle both sides' median size be limited in the above-mentioned scope be because; If each median size is less than lower value, then in the manufacturing process of vapor deposition material, the cohesion of powder becomes obviously and hinders mixing; If each median size surpasses higher limit, then can not fully obtain being formed with the virtual effect of holding body admittedly that helps improve the gas barrier property.In addition, in this specification sheets, median size is meant; According to laser diffraction/scattering method (Microtrack method); Utilize a day machine dress manufactured (FRA type), use sodium hexametaphosphate as dispersion agent, 1 minute is made as the particle diameter of the value equalization that made 3 mensuration in 30 seconds.
And; It is because if the molar ratio of the 1st oxide compound is less than 5, then proportionally too diminish containing of the 1st oxide particle that the molar ratio of the 1st oxide compound and the 2nd oxide compound is limited in the above-mentioned scope; Near single composition, thereby can't form film with fine and close microtexture.And; If the molar ratio of the 2nd oxide compound is less than 15; Then proportionally too diminish containing of the 2nd oxide particle, near single composition, thus the structure that the crystallization phases that adopts column crystal easily of becoming is gathered for the infiltration direction of gas abreast; So the gas that becomes is prone to pass through the reduction of gas blocking characteristic.
In addition, with the basicity of formed film be defined in more than 0.03 be because, if less than the become microtexture of the densification that is difficult to adopt the non-crystalline state that bursts apart near the part of column crystal of 0.03 o'clock film.Should " basicity " be to propose, for example in his works " K.Morinaga, H.Yoshida And H.Takebe:J.Am Cerm.Soc., 77,3113 (1994) ", utilize the basicity of formula regulation glass powder as follows by gloomy strong forever inferior people.This extracts is as follows.
" oxide M
iThe M of O
iBonding strength between the-O is as the gravitation A between positively charged ion-oxonium ion
i, can obtain through following formula.
A
i＝Z
i·Z
02-/(r
i+r
02-)
2＝Z
i·2/(r
i+1.40)
2
Z
i: cationic valence mumber, oxonium ion are 2
R
i: cationic ionic radius
Oxonium ion does
This A
iB reciprocal
i(1/A
i) be made as the single component oxide M
iThe oxygen delivery capacity of O.
B
i≡1/A
i
If with this B
iBe normalized to B
CaO=1, B
SiO2=0, then can obtain the B of each single component oxide compound
i-index.If through cation fraction B to this each composition of multicomponent system expansion
i-index then can be calculated the B-index (=basicity) of melt of the glass oxide compound of any composition.
B＝∑n
i·B
i
n
i: cation fraction
The basicity of regulation be like above-mentioned expression oxygen delivery capacity like this, and value is supplied with oxygen more greatly more easily, causes more easily and the giving and accepting of the oxygen of other MOXs.”
Among the present invention; The index of the basicity of relevant glass powder; Be glass to be replaced as oxide compound make an explanation, thus with the basicity of oxide mixture as becoming in the film index of putting in order near the index of the easness of the microtexture of the densification of non-crystalline state.The situation of glass is meant the notion of fusion and so on, but serves as basic with the phenomenon that produces the mechanism that forms glass when the film forming among the present invention.Become ionic condition from the element of vapor deposition material distillation, on substrate, pile up element with nonequilibrium state.If the basicity of the film that at this moment obtains through above-mentioned formula is more than 0.03, then film is grown up with glassy (noncrystalline), and arranges element systematically with very fine and close state.
Through the film that method of manufacture of the present invention obtains, the barrier property of individual layer is excellent, therefore can obtain higher barrier property by less range upon range of number, so can boost productivity, can also reduce cost.And be made as the blocking film of individual layer or less range upon range of number, the thickness attenuation that amounts to thus can alleviate breaking when making the blocking sheet, warpage etc.When but the blocking film that this thickness is thin is used on the solar cell of bending, improves resistance to bend(ing) and improve the weather resistance of solar cell.And; Owing to have higher gas barrier property; Therefore except the purposes of the gas barrier property materials such as moisture barrier films of the backboard that constitutes solar cell, can also be suitable as liquid-crystal display, OLED display or illumination with gas barrier property material uses such as OLED displays.And this film can obtain the transparency that rate of permeation is the excellence more than 85%, therefore can in the long wavelength zone, keep high permeability.Therefore also be suitable as gas barrier property of having relatively high expectations and the parts that require printing opacity and so on, the gas barrier property material that for example in the sensitive surface side of solar cell or the image vision side of indicating meter etc., uses etc.
Then, diaphragm of the present invention and lamination sheets are together explained this method of manufacture.As shown in Figure 1; Diaphragm 10 of the present invention has the 1st base material film 11 and film of the present invention 12; Said film uses sublimability vapor deposition material that is made up of above-mentioned the 1st oxide compound and the meltbility vapor deposition material that is made up of the 2nd oxide compound, utilizes the common vapour deposition method film forming through vacuum film formation method while vapor deposition.And the diaphragm 10 that lamination sheets 20 of the present invention has the invention described above reaches the 2nd base material film 14 that adheres to the film formation side of this diaphragm 10 through adhesive coating 13.
The 1st base material film 11 and the 2nd base material film 14 preferably have the physical strength of withstanding long hot and humid degree environmental testing or weathering resistance etc.For example, can enumerate resin moldings such as polyethylene terephthalate (PET), polycarbonate, polymethylmethacrylate, polyacrylic ester, PEN (PEN), polyarylester, polyethersulfone, cellulosetri-acetate (TAC), cyclic olefin (being total to) polymers.These resin moldings also can be combined with fire retardant, inhibitor, UV light absorber and static inhibitor etc. as required.The thickness of the 1st base material film 11 and the 2nd base material film 14 is preferably 5～300 μ m, further is preferably 10～150 μ m.
Sublimability vapor deposition material that use is made up of above-mentioned the 1st oxide compound and the meltbility vapor deposition material that constitutes by the 2nd oxide compound, utilize through the vacuum film formation method simultaneously common vapour deposition method vapor deposition on the 1st base material film 11 of vapor deposition form film 12 as gas barrier property material.The thickness of film 12 is preferably in 10～200nm scope.If less than lower value, then be difficult to obtain sufficient gas barrier property, and the weather resistance of film is prone to reduce as gas barrier property material.On the other hand, if surpass higher limit, then can waste material, and become according to thickness effect and to be easy to generate the be full of cracks that causes because of external force such as complications.Wherein, the thickness of film 12 is especially preferably in 20～100nm scope.Formation method as film 12; Be preferably electron beam evaporation plating method (Electron Beam Evaporation Method; Below be called the EB method), ion plating method, reactive plasma vapour deposition method (Reactive Plasma Deposition Method below is called the RPD method), electrical resistance heating or induction heating equal vacuum become embrane method.
In addition; Though do not illustrate among Fig. 1; But, the prime coat that comprises acrylic polyol, isocyanic ester, silane coupling agent also can be set as required perhaps before the vapor deposition operation, utilize enforcement surface treatments such as plasma body for the adhesion strength of raising on the 1st base material film 11 with film 12.
On the other hand, under the state that exposes on film 12 surfaces that form,, scratch or the abrasion film surface, then the gas barrier property is brought considerable influence if during installation sheet.Therefore, the gas barrier property tunicle etc. on not shown protective film 12 surface preferably is set on film 12.This gas barrier property tunicle can be after film 12 surface coated be for example mixed silicon compound, titanium compound, zirconia compound, tin compound or its hydrolyzate with alkoxyl group and are had the solution of water-soluble polymer hydroxy, heat drying and forming.This gas barrier property tunicle not only plays a role as the resist of film 12, also has the effect that improves the gas barrier property.
For example after the condition held of 20 ℃ of temperature, relative humidity 50%RH 1 hour, the vapor permeability S that under the condition of 40 ℃ of temperature, relative humidity 90%RH, measures is shown as 0.3g/m to the diaphragm of the present invention 10 that forms like this
2Below it.
In addition; In lamination sheets 20 of the present invention; Film at the diaphragm 10 of the invention described above forms side, be on the film 12 or above-mentioned gas barrier property tunicle on form adhesive coating 13, the 1st base material film 11 that this adhesive coating 13 is formed with film 12 as being used to fit and the tackiness agent of the 2nd base material film 14 play a role.Therefore, need adhesion strength not can through long-time and deterioration, do not produce delamination etc. and can flavescence etc. condition, for example can enumerate polyurethanes, polyester, polyester-polyurethane class, polycarbonate-based, gather epoxy-amine class, hot melt class tackiness agent etc.The laminating method of adhesive coating 13 can be range upon range of with well-known methods such as dry laminate methods.
Through adhesion the 2nd base material film 14 and fit complete layer lamination 20 on this adhesive coating 13.In addition; As shown in Figure 1; Film 12 may not be defined in the lamination sheets of 1 layer of 1 layer of laminated separately with adhesive coating 13, also can be made as alternately laminated film 12 and adhesive coating 13, or 2～10 layers multilayer of miscellaneous part such as laminate film 12, above-mentioned gas barrier property tunicle and adhesive coating 13 alternately or brokenly.Thus, can further improve gas barrier property or weathering resistance.
Backboard, liquid-crystal display or OLED display or illumination that this lamination sheets 20 can be suitable as solar module utilize with purposes such as OLED displays.
[embodiment]
Then, embodiments of the invention and comparative example together are elaborated.
< embodiment 1 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:20 mole %, SiO
2: 80 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and SiO contained in the vapor deposition material
2Contained ZnO, SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 2 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:50 mole %, SiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and SiO contained in the vapor deposition material
2Contained ZnO, SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 3 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:80 mole %, SiO
2: 20 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and SiO contained in the vapor deposition material
2Contained ZnO, SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 4 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:20 mole %, Al
2O
3: 80 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and Al contained in the vapor deposition material
2O
3Contained ZnO, Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 5 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:50 mole %, Al
2O
3: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and Al contained in the vapor deposition material
2O
3Contained ZnO, Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 6 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:80 mole %, Al
2O
3: 20 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and Al contained in the vapor deposition material
2O
3Contained ZnO, Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 7 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:20 mole %, TiO
2: 80 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and TiO contained in the vapor deposition material
2Contained ZnO, TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 8 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:50 mole %, TiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and TiO contained in the vapor deposition material
2Contained ZnO, TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 9 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:80 mole %, TiO
2: 20 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and TiO contained in the vapor deposition material
2Contained ZnO, TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 10 >
Prepare median size respectively and be 0.6 μ m, purity and be 99.8% high-purity C aO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes CaO:50 mole %, SiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With CaO particle and SiO contained in the vapor deposition material
2Contained CaO, SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 11 >
Prepare median size respectively and be 0.6 μ m, purity and be 99.8% high-purity C aO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes CaO:50 mole %, Al
2O
3: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With CaO particle and Al contained in the vapor deposition material
2O
3Contained CaO, Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 12 >
Prepare median size respectively and be 0.6 μ m, purity and be 99.8% high-purity C aO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes CaO:50 mole %, TiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With CaO particle and TiO contained in the vapor deposition material
2Contained CaO, TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 13 >
Prepare median size respectively and be 0.9 μ m, purity and be 99.7% MgO of high purity powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes MgO:50 mole %, SiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With MgO particle and SiO contained in the vapor deposition material
2Contained MgO, SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 14 >
Prepare median size respectively and be 0.9 μ m, purity and be 99.7% MgO of high purity powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes MgO:50 mole %, Al
2O
3: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With MgO particle and Al contained in the vapor deposition material
2O
3Contained MgO, Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 15 >
Prepare median size respectively and be 0.9 μ m, purity and be 99.7% MgO of high purity powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes MgO:50 mole %, TiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With MgO particle and TiO contained in the vapor deposition material
2Contained MgO, TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 16 >
Preparing median size respectively is that 0.7 μ m, purity are 99.8% high purity SnO
2Powder is as the 1st oxide powder of sublimability vapor deposition material, and preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes SnO
2: 50 moles of %, SiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With SnO contained in the vapor deposition material
2Particle and SiO
2Contained SnO in particulate median size, the film
2, SiO
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 17 >
Preparing median size respectively is that 0.7 μ m, purity are 99.8% high purity SnO
2Powder is as the 1st oxide powder of sublimability vapor deposition material, and preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes SnO
2: 50 moles of %, Al
2O
3: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With SnO contained in the vapor deposition material
2Particle and Al
2O
3Contained SnO in particulate median size, the film
2, Al
2O
3Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 18 >
Preparing median size respectively is that 0.7 μ m, purity are 99.8% high purity SnO
2Powder is as the 1st oxide powder of sublimability vapor deposition material, and preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes SnO
2: 50 moles of %, TiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With SnO contained in the vapor deposition material
2Particle and TiO
2Contained SnO in particulate median size, the film
2, TiO
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 19 >
Preparing median size respectively is that 0.7 μ m, purity are 99.5% high-purity C eO
2Powder is as the 1st oxide powder of sublimability vapor deposition material, and preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes CeO
2: 50 moles of %, SiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With CeO contained in the vapor deposition material
2Particle and SiO
2Contained CeO in particulate median size, the film
2, SiO
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 20 >
Preparing median size respectively is that 0.7 μ m, purity are 99.5% high-purity C eO
2Powder is as the 1st oxide powder of sublimability vapor deposition material, and preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes CeO
2: 50 moles of %, Al
2O
3: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With CeO contained in the vapor deposition material
2Particle and Al
2O
3Contained CeO in particulate median size, the film
2, Al
2O
3Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 21 >
Preparing median size respectively is that 0.7 μ m, purity are 99.5% high-purity C eO
2Powder is as the 1st oxide powder of sublimability vapor deposition material, and preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through reactive plasma vapour deposition method (RPD method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes CeO
2: 50 moles of %, TiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With CeO contained in the vapor deposition material
2Particle and TiO
2Contained CeO in particulate median size, the film
2, TiO
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 22 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through electron beam evaporation plating method (EB method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:50 mole %, SiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and SiO contained in the vapor deposition material
2Contained ZnO, SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 1.
< embodiment 23 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through electron beam evaporation plating method (EB method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:50 mole %, Al
2O
3: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and Al contained in the vapor deposition material
2O
3Contained ZnO, Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 2.
< embodiment 24 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through electron beam evaporation plating method (EB method) while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:50 mole %, TiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and TiO contained in the vapor deposition material
2Contained ZnO, TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< embodiment 25 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through electrical resistance heating while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:50 mole %, SiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and SiO contained in the vapor deposition material
2Contained ZnO, SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< embodiment 26 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through electrical resistance heating while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:50 mole %, Al
2O
3: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and Al contained in the vapor deposition material
2O
3Contained ZnO, Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 2.
< embodiment 27 >
Prepare median size respectively and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material, preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned 2 kinds of vapor deposition materials, is on the PET film of 75 μ m at thickness, utilizes the common vapor deposition through electrical resistance heating while vapor deposition, and the containing ratio in the controlling diaphragm becomes ZnO:50 mole %, TiO
2: 50 moles of %, film forming thickness are the film of 100nm, and form diaphragm.With ZnO particle and TiO contained in the vapor deposition material
2Contained ZnO, TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 1 >
Prepare median size and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through reactive plasma vapour deposition method (RPD method) film forming thickness, and forms diaphragm.The containing ratio of ZnO contained in ZnO particulate median size contained in the vapor deposition material, the film and the basicity of film are shown in the following table 2.
< comparative example 2 >
Preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through reactive plasma vapour deposition method (RPD method) film forming thickness, and forms diaphragm.With SiO contained in the vapor deposition material
2Contained SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 3 >
Preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through reactive plasma vapour deposition method (RPD method) film forming thickness, and forms diaphragm.With Al contained in the vapor deposition material
2O
3Contained Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 4 >
Preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through reactive plasma vapour deposition method (RPD method) film forming thickness, and forms diaphragm.With TiO contained in the vapor deposition material
2Contained TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 5 >
Prepare median size and be 0.6 μ m, purity and be 99.8% high-purity C aO powder the 1st oxide powder as sublimability vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through reactive plasma vapour deposition method (RPD method) film forming thickness, and forms diaphragm.The containing ratio of CaO contained in CaO particulate median size contained in the vapor deposition material, the film and the basicity of film are shown in the following table 2.
< comparative example 6 >
Prepare median size and be 0.9 μ m, purity and be 99.7% MgO of high purity powder the 1st oxide powder as sublimability vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through reactive plasma vapour deposition method (RPD method) film forming thickness, and forms diaphragm.The containing ratio of MgO contained in MgO particulate median size contained in the vapor deposition material, the film and the basicity of film are shown in the following table 2.
< comparative example 7 >
Preparing median size is that 0.7 μ m, purity are 99.8% high purity SnO
2Powder is as the 1st oxide powder of sublimability vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through reactive plasma vapour deposition method (RPD method) film forming thickness, and forms diaphragm.With SnO contained in the vapor deposition material
2Contained SnO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 8 >
Preparing median size is that 0.7 μ m, purity are 99.5% high-purity C eO
2Powder is as the 1st oxide powder of sublimability vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through reactive plasma vapour deposition method (RPD method) film forming thickness, and forms diaphragm.With CeO contained in the vapor deposition material
2Contained CeO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 9 >
Prepare median size and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through electron beam evaporation plating method (EB method) film forming thickness, and forms diaphragm.The containing ratio of ZnO contained in ZnO particulate median size contained in the vapor deposition material, the film and the basicity of film are shown in the following table 2.
< comparative example 10 >
Preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through electron beam evaporation plating method (EB method) film forming thickness, and forms diaphragm.With SiO contained in the vapor deposition material
2Contained SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 11 >
Preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through electron beam evaporation plating method (EB method) film forming thickness, and forms diaphragm.With Al contained in the vapor deposition material
2O
3Contained Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 12 >
Preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through electron beam evaporation plating method (EB method) film forming thickness, and forms diaphragm.With TiO contained in the vapor deposition material
2Contained TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 13 >
Prepare median size and be 0.8 μ m, purity and be 99.8% high purity ZnO powder the 1st oxide powder as sublimability vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through electrical resistance heating film forming thickness, and forms diaphragm.The containing ratio of ZnO contained in ZnO particulate median size contained in the vapor deposition material, the film and the basicity of film are shown in the following table 2.
< comparative example 14 >
Preparing median size is that 0.7 μ m, purity are 99.8% high purity SiO
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through electrical resistance heating film forming thickness, and forms diaphragm.With SiO contained in the vapor deposition material
2Contained SiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 15 >
Preparing median size is that 0.6 μ m, purity are 99.8% high purity Al
2O
3Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through electrical resistance heating film forming thickness, and forms diaphragm.With Al contained in the vapor deposition material
2O
3Contained Al in particulate median size, the film
2O
3Containing ratio and the basicity of film be shown in the following table 2.
< comparative example 16 >
Preparing median size is that 0.4 μ m, purity are 99.8% high purity Ti O
2Powder is as the 2nd oxide powder of meltbility vapor deposition material.Using above-mentioned single vapor deposition material, is on the PET film of 75 μ m at thickness, is the film of 100nm through electrical resistance heating film forming thickness, and forms diaphragm.With TiO contained in the vapor deposition material
2Contained TiO in particulate median size, the film
2Containing ratio and the basicity of film be shown in the following table 2.
< comparison test and estimate 1 >
Obtain the 1st contained in the film that is shown in following table 1～table 2 oxide compound and the 2nd oxide compound containing ratio (mol%) in film through following calculation formula.
Thickness is measured as follows, promptly on the top of the vapor deposition source of the 1st oxide compound and the 2nd oxide compound the film thickness tester is set respectively, measures the thickness from the vapor-deposited film of each vapor deposition source.
Be total to the thickness t=t of the blocking film of vapor deposition
1+ t
2
Wherein, t
1Be the thickness of the 1st oxide compound, t
2It is the thickness of the 2nd oxide compound.
The heavy w of film on 10cm * 10cm angular substrate
The heavy w of the film of the 1st oxide compound
1=t
1* 10
-7* 10 * 10 * d
1
The heavy w of the film of the 2nd oxide compound
2=t
2* 10
-7* 10 * 10 * d
2
Wherein, d
1Be the theoretical density of the 1st oxide compound, d
2It is the theoretical density of the 2nd oxide compound.
The molecular weight Mol of the 1st oxide compound in the film
1=w
1/ M
1
The molecular weight Mol of the 2nd oxide compound in the film
2=w
2/ M
2
Wherein, M
1Be the molecular weight of the 1st oxide compound, M
2It is the molecular weight of the 2nd oxide compound.
Containing ratio (the mol%)=Mol of the 1st oxide compound in film
1/ (Mol
1+ Mol
2) * 100
Containing ratio (the mol%)=Mol of the 2nd oxide compound in film
2/ (Mol
1+ Mol
2) * 100
Then, the diaphragm that in embodiment 1～27 and comparative example 1～16, obtains is measured vapor permeability, and estimate the gas barrier property.In addition, these diaphragms are carried out determination of light transmittance, and estimate the transparency.These results are shown in the following table 1～table 2.
(1) gas barrier property: after diaphragm placed 1 hour in the clean room that is set at 20 ℃ of temperature, relative humidity 50%RH; Utilize the vapor permeability determinator (model name is a PERMATRAN-W type 3/33) of MOCON manufactured, under the condition of 40 ℃ of temperature, relative humidity 90%RH, measure vapor permeability.
(2) transmittance: utilize the spectrophotometer (model name is U-4000) of Hitachi Co., Ltd's manufactured, diaphragm is measured the transmittance in 380～780nm wavelength.
[table 1]
[table 2]
Obvious from table 1 and table 2, use in the diaphragm of the film forming comparative example 1～16 of single vapor deposition material, as a result of the transmittance aspect obtains 85～99% high transmission rate, but vapor permeability S is bigger, and the gas barrier property is relatively poor.
On the other hand, use in 2 kinds of vapor deposition materials and the diaphragm through the embodiment 1～27 of evaporation film-forming altogether, the transmittance aspect obtains 85～91% high transmission rate, and vapor permeability S is 0.18g/m
2Below it, wherein, in embodiment 1～3, embodiment 5, embodiment 7, embodiment 8, embodiment 10～20, embodiment 22～25, be 0.1g/m
2Below it.
In addition; If respectively to utilize the vapor deposition material obtain under the same conditions and with different methods carry out film forming embodiment 2,22,25 or embodiment 5,23,26, embodiment 8,24,27, comparative example 1～4, comparative example 9～12 respectively, comparative example 13～16 compares; Then can find to be worse than slightly tendency, possess the sufficient gas barrier property and the transparency but also be judged as through the film forming embodiment of EB method 22,23,24, film through the film forming embodiment 25,26,27 of electrical resistance heating through the film forming film of RPD method according to assessment item.
Can confirm from these results, utilize the film of evaporation film-forming altogether of the present invention to have very excellent the gas barrier property and the transparency.
Utilizability on the industry
Various characteristicses such as the transparency of film of the present invention, gas barrier property are excellent, therefore especially can be suitable as the gas barrier property material use of liquid-crystal display, OLED display, plasma display or solar module etc.
Claims (14)
1. the method for manufacture of a film is characterized in that,
Sublimability vapor deposition material that use is made up of the 1st oxide compound and the meltbility vapor deposition material that constitutes by the 2nd oxide compound; Utilize common vapour deposition method, on base material, form the sull that constitutes by said the 1st oxide compound and said the 2nd oxide compound through vacuum film formation method while vapor deposition.
2. the method for manufacture of film as claimed in claim 1, wherein,
The mode that becomes more than 0.03 with the basicity of the film of said formation makes up sublimability vapor deposition material that is made up of said the 1st oxide compound and the meltbility vapor deposition material that is made up of said the 2nd oxide compound.
3. according to claim 1 or claim 2 the method for manufacture of film, wherein,
Become 5～85 with the 1st oxide compound of the film of said formation and the molar ratio of the 2nd oxide compound: 95～15 mode makes up sublimability vapor deposition material that is made up of said the 1st oxide compound and the meltbility vapor deposition material that is made up of said the 2nd oxide compound.
4. the method for manufacture of film as claimed in claim 1, wherein,
The 1st oxide compound of said sublimability vapor deposition material is for being selected from ZnO, CaO, MgO, SnO
2And CeO
2In at least a kind, the 2nd oxide compound of said meltbility vapor deposition material is for being selected from SiO
2, Al
2O
3And TiO
2In at least a kind.
5. the method for manufacture of film as claimed in claim 1, wherein,
Said vacuum film formation method is any one in electron beam evaporation plating method, ion plating method, reactive plasma vapour deposition method, electrical resistance heating or the induction heating.
6. the method for manufacture of film as claimed in claim 1, wherein,
The median size of the 2nd oxide particle of the median size of the 1st oxide particle of said sublimability vapor deposition material and said meltbility vapor deposition material is respectively 0.1～10 μ m.
7. a common vapor deposition is used the vapor deposition material, it is characterized in that,
Be used for each described method of manufacture of claim 1 to 6,
Comprise the combination of sublimability vapor deposition material that constitutes by said the 1st oxide compound and the meltbility vapor deposition material that constitutes by said the 2nd oxide compound.
8. vapor deposition altogether as claimed in claim 7 is used the vapor deposition material, wherein,
The 1st oxide compound of said sublimability vapor deposition material is for being selected from ZnO, CaO, MgO, SnO
2And CeO
2In at least a kind, the 2nd oxide compound of said meltbility vapor deposition material is for being selected from SiO
2, Al
2O
3And TiO
2In at least a kind.
9. use the vapor deposition material like claim 7 or 8 described vapor depositions altogether, wherein,
The median size of the 2nd oxide particle of the median size of the 1st oxide particle of said sublimability vapor deposition material and said meltbility vapor deposition material is respectively 0.1～10 μ m.
10. sull, wherein,
Obtain through each described method of manufacture in the claim 1 to 6,
Sublimability vapor deposition material that use is made up of said the 1st oxide compound and the meltbility vapor deposition material that is made up of said the 2nd oxide compound utilize through the vacuum film formation method common vapour deposition method film forming of vapor deposition simultaneously, and are made up of said the 1st oxide compound and said the 2nd oxide compound.
11. a diaphragm, wherein,
Through each described method of manufacture in the claim 1 to 6; On the 1st base material film, forming sull forms; Said sull uses sublimability vapor deposition material that is made up of said the 1st oxide compound and the meltbility vapor deposition material that is made up of said the 2nd oxide compound; Utilize common vapour deposition method film forming, and constitute by said the 1st oxide compound and said the 2nd oxide compound through vacuum film formation method while vapor deposition.
12. diaphragm as claimed in claim 11, wherein,
Said vacuum film formation method is any one in electron beam evaporation plating method, ion plating method, reactive plasma vapour deposition method, electrical resistance heating or the induction heating.
13. like claim 11 or 12 described diaphragms, wherein,
The vapor permeability S of condition held in the time of 1 hour at 20 ℃ of temperature, relative humidity 50%RH is 0.3g/m
2Below it.
14. a lamination sheets, the film of this lamination sheets each described diaphragm in claim 11 to 13 forms side, forms through range upon range of the 2nd base material film of adhesive coating.
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| JP2011-020713 | 2011-02-02 | ||
| JP2011020713A JP2012158820A (en) | 2011-02-02 | 2011-02-02 | Method for producing thin film and vapor deposition material for co-vapor deposition for forming thin film, thin film obtained by the method, thin film sheet having the thin film, and laminated sheet |
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Cited By (3)
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| CN104733578A (en) * | 2013-12-19 | 2015-06-24 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Preparation method for thin film used for DBR |
| CN105008123A (en) * | 2013-02-20 | 2015-10-28 | 东洋纺株式会社 | Gas barrier film |
| CN113260463A (en) * | 2018-12-26 | 2021-08-13 | Ａｇｃ株式会社 | Substrate with water-and oil-repellent layer, vapor deposition material, and method for producing substrate with water-and oil-repellent layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014073598A (en) * | 2012-10-03 | 2014-04-24 | Toray Ind Inc | Gas barrier film |
| CN113227441A (en) * | 2018-12-26 | 2021-08-06 | Ａｇｃ株式会社 | Vapor deposition material, method for producing substrate with base layer, and method for producing substrate with water-and oil-repellent layer |
| WO2020137993A1 (en) * | 2018-12-26 | 2020-07-02 | Ａｇｃ株式会社 | Vapor deposition material, method for producing substrate with base layer, and method for producing substrate with water and oil-repellent layer |
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| CN113260463B (en) * | 2018-12-26 | 2023-09-22 | Ａｇｃ株式会社 | Substrate with water-repellent oil-repellent layer, vapor deposition material, and method for producing substrate with water-repellent oil-repellent layer |
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Application publication date: 20120808 |