CN103173717A - Evaporation material used for formation of steam barrier film, film forming method, and steam barrier film - Google Patents
Evaporation material used for formation of steam barrier film, film forming method, and steam barrier film Download PDFInfo
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- CN103173717A CN103173717A CN2012103594182A CN201210359418A CN103173717A CN 103173717 A CN103173717 A CN 103173717A CN 2012103594182 A CN2012103594182 A CN 2012103594182A CN 201210359418 A CN201210359418 A CN 201210359418A CN 103173717 A CN103173717 A CN 103173717A
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Abstract
The present invention provides an evaporation material used for formation of a steam barrier film simultaneously having colourless transparency and higher steam barrier capacity, a film forming method, and a steam barrier film formed by the method. The evaporation material used for formation of the steam barrier film consists of a first oxide having the purity higher than 98% and less than 100% and a second oxide having the purity higher than 98% and less than 100%, and is characterized in that: the first oxide is WO3, the second oxide is at least one of ZnO or SiO, when molar weights of the first oxide and the second oxide are respectively set as X mole and Y mole, composition ratio is 0.05 <= X mole / (X mole + Y mole) <= 0.95.
Description
Technical field
The present invention relates to be used to form in a kind of wrapping material at electronicss such as liquid-crystal display, OLED display or solar cell or food, medicine etc. etc. the evaporation material of the water vapour barrier film that possesses simultaneously water white transparency and higher water-vapor barrier and film thereof and the water vapour barrier film by the method film forming.
Background technology
The equipment such as liquid-crystal display, OLED display or solar cell are unable to undergo moisture usually, make its characteristic promptly deteriorated because of moisture absorption, have highly moistureproof, namely prevent the assembly with gas barrier that oxygen or water vapour etc. see through or enter so must be equipped with.
For example, in the example of solar cell, be provided with backboard at the back side of the opposite side of the sensitive surface of solar module.The representative example of this backboard is, by the backboard that utilizes the water vapour barrier film with highly moistureproof of film forming on base material such as evaporation material and their parts of protection etc. to consist of.And, except the equipment such as above-mentioned solar cell, the water-vapor barrier of also having relatively high expectations in wrapping material of food and medicine etc. etc., what generally be widely known by the people is wrapping material of water vapour barrier film etc., and this water vapour barrier film comes film forming by possessing in surperficial evaporation silicon oxide, aluminum oxide or the aluminum metallic foil etc. of plastics.
And the water vapour barrier film also requires the transparency except the water vapour block.This be because, such as in food and pharmaceutical packing material etc., also possess the transparency except the water vapour block, do not break a seal thus and can have an X-rayed contents yet and confirm.And, if possess the transparency, when for example being used in the sensitive surface side of the light-emitting area of OLED display and solar cell, can not cause the sense of vision disadvantage that indicating meter shows yet, and, do not hinder the light that is subjected to of sunlight, also can provide wet fastness.Therefore, wish also to possess the transparency in the field of these electronicss.
As relating to this technology that possesses the water vapour barrier film of water-vapor barrier and the transparency, disclose and use SiO evaporation material and pass through electron beam evaporation plating method (Electron Beam Evaporation Method, hereinafter referred to as the EB method) the gas barrier film (for example, referring to Patent Document 1) of formation SiOx film on base material film.In the gas barrier film shown in this patent documentation 1, as the water vapour barrier film, possess the SiOx film that forms by the EB method, can access thus the transparency and the water vapor transmission rate (WVTR) 5g/m of visible light transmissivity more than 85%
2The very high gas barrier that it is following.
And, as barrier layer for gases, disclose the gas barrier laminated film (for example, referring to Patent Document 2) that possesses the water vapour barrier film that is formed by aluminum oxide.In gas barrier laminated film shown in this patent documentation 2, the stacked barrier layer for gases that is formed by aluminum oxide on transparent substrate, and with the stacked predetermined coating layer of pre-determined thickness, possess thus the transparency, even and can access implement as the common processing of wrapping material and gas barrier can be not deteriorated yet higher gas barrier.
Patent documentation 1: Japanese Patent Publication 2008-266760 communique (claim 1～3)
Patent documentation 2: Japanese Patent Publication 2010-052222 communique (claim 1, [0006] section)
Yet, except the above-mentioned transparency and water-vapor barrier, wish that not only the water vapour barrier film is transparent, and water white transparency.When being gas barrier film shown in above-mentioned patent documentation 1 grade in the past, possesses sufficient water-vapor barrier, and, also realized the visible light transmissivity more than 85% about the transparency, has sufficient transparency, but can see that the SiOx film that possesses as the water vapour barrier film becomes light yellow transparent tendency, is difficult for becoming colourless transparent film.Especially, when using wrapping material for food, abstain from yellow, but when considering from the aspects such as impact of the colour developing when being used in the display surface side of indicating meter or tone, the also less transparent film of preferred hue in the fields such as electronics.
And, to consider from production or cost aspect, hope can be with lower energy film forming, and film forming speed is very fast.On the other hand, in the laminate film shown in above-mentioned patent documentation 2 in the past, although possess higher water-vapor barrier, but because aluminum oxide is the low-vapor pressure material, so film deposition system is limited, and, need high-energy during the film forming vapor-deposited film, therefore leaving problem aspect production or cost.Like this, when making high-quality water vapour barrier film, the output reduction during for film forming or the high speed of film forming speed not only rely on the improvement of device aspect, also require the improvement of material aspect etc.
Summary of the invention
The object of the present invention is to provide a kind of evaporation material that is used to form the water vapour barrier film that possesses simultaneously water white transparency and higher water-vapor barrier and film thereof and the water vapour barrier film by the method film forming.
Another object of the present invention is to provide a kind of can form with evaporation material and film thereof with the water vapour barrier film that low-yield and high speed film forming possess the water vapour barrier film of water white transparency and higher water-vapor barrier simultaneously.
The 1st viewpoint of the present invention is a kind ofly to be more than 98% and to be to form more than 98% and less than the water vapour barrier film that 100% the 2nd oxide compound consists of to use the evaporation material less than 100% the 1st oxide compound and purity by purity, and wherein, above-mentioned the 1st oxide compound is WO
3, above-mentioned the 2nd oxide compound is at least one party in ZnO or SiO, during with the containing molar weight and be made as respectively X mole, Y mole of above-mentioned the 1st oxide compound and the 2nd oxide compound, ratio of components is 0.05≤X mole/(X mole+Y mole)≤0.95.
The 2nd viewpoint of the present invention is the invention according to the 1st viewpoint, and wherein, the evaporation material further is made of the granule of the median size 1～10mm that processes through granulation.
The 3rd viewpoint of the present invention is the invention according to the 1st viewpoint, and wherein, the evaporation material further is made of the pellet through stamping forming diameter 5～30mm, thickness 1～20mm.
The 4th viewpoint of the present invention is a kind of film of water vapour barrier film, and this film utilizes the evaporation material of the 1st to the 3rd viewpoint, carries out film forming by electrical resistance heating, electron beam evaporation plating method or reactive plasma vapour deposition method.
The 5th viewpoint of the present invention is a kind of water vapour barrier film, and this water vapour barrier film utilizes the evaporation material of the 1st to the 3rd viewpoint and forms by the vacuum film formation method, and b
*The absolute value of value is less than 3, and water vapor transmission rate (WVTR) is 0.1g/m
2More than it and less than 1.0g/m
2My god.
The evaporation material of the 1st viewpoint of the present invention is a kind ofly to be more than 98% and to be to form more than 98% and less than the water vapour barrier film that 100% the 2nd oxide compound consists of to use the evaporation material less than 100% the 1st oxide compound and purity by purity, and wherein, above-mentioned the 1st oxide compound is WO
3, above-mentioned the 2nd oxide compound is at least one party in ZnO or SiO.And during with the containing molar weight and be made as respectively X mole, Y mole of above-mentioned the 1st oxide compound and the 2nd oxide compound, ratio of components is 0.05≤X mole/(X mole+Y mole)≤0.95.Thus, can form the water vapour barrier film that possesses simultaneously water white transparency and higher water-vapor barrier.And 1st oxide compound and 2nd oxide compound contained due to the evaporation material are high vapor pressure material, therefore can be with the low-yield and above-mentioned high-quality water vapour barrier film of high speed film forming.
The 4th viewpoint of the present invention is a kind of film of water vapour barrier film, and this film utilizes evaporation material of the present invention, carries out film forming by electrical resistance heating, electron beam evaporation plating method or reactive plasma vapour deposition method.Therefore in film of the present invention, carry out the film forming of water vapour barrier film due to the evaporation material that utilizes the invention described above, can possess simultaneously with low-yield and high speed film forming the water vapour barrier film of water white transparency and higher water-vapor barrier.Therefore, be not defined as membrane method, also can the high-quality water vapour barrier film of film forming by above-mentioned any means.
The 5th viewpoint of the present invention is a kind of water vapour barrier film, and this water vapour barrier film utilizes evaporation material of the present invention and forms by the vacuum film formation method, and b
*The absolute value of value is less than 3, and water vapor transmission rate (WVTR) is 0.1g/m
2More than it and less than 1.0g/m
2My god.Water vapour barrier film of the present invention is owing to being to utilize the evaporation material film forming of the invention described above and possess simultaneously water white transparency and the high-quality water vapour barrier film of higher water-vapor barrier, therefore also can preferably use in the light-emitting area side (the display surface sides of image etc.) such as OLED display etc.
Embodiment
Then, describe being used for implementing mode of the present invention.
It is a kind ofly to be more than 98% and to be to form more than 98% and less than the water vapour barrier film that 100% the 2nd oxide compound consists of to use the evaporation material less than 100% the 1st oxide compound and purity by purity that water vapour barrier film of the present invention forms with the evaporation material, wherein, above-mentioned the 1st oxide compound is WO
3, above-mentioned the 2nd oxide compound is at least one party in ZnO or SiO.And during with the containing molar weight and be made as respectively X mole, Y mole of above-mentioned the 1st oxide compound and the 2nd oxide compound, ratio of components is 0.05≤X mole/(X mole+Y mole)≤0.95.
The 1st oxide compound is made as WO
3, and the reason that the 2nd oxide compound is made as at least one party in ZnO or SiO is, the first, be for can form water-vapor barrier higher and tone is less transparent be water white film.Can see following tendency: WO
3Easily form film azury, ZnO or SiO easily form lurid film on the other hand.Therefore, with WO
3Be that the 1st oxide compound is made as necessary constituent material, any one party of ZnO or SiO or both are that the 2nd oxide compound is made as other constituent materials, can form transparent and colourless film thus.
And, the second, be because WO
3, ZnO and SiO be high vapor pressure material.High vapor pressure material is the material that demonstrates very high vapour pressure when being made as a certain steady temperature.Therefore, all use high vapor pressure material as the oxide compound of the material that is used for the evaporation material, thus by vacuum film formation method etc. on base material during film forming water vapour barrier film, can be to compare more low-yield with the evaporation material that uses the low-vapor pressure material and to carry out at a high speed.In addition, in this manual, high vapor pressure material refers to show 1 * 10 under 1200 ℃
-1The material of the vapour pressure that Pa is above, low-vapor pressure material refer to show less than 1 * 10 under 1200 ℃
-1The material of the vapour pressure of Pa.
And, in the present invention, the purity of the 1st oxide compound, the 2nd oxide compound is made as respectively more than 98% and less than 100% reason be because, when purity less than 98% the time, crystallinity worsens because of impurity, barrier properties descends as a result, on the other hand, be because with purity be made as 100% be actually impossible.Wherein, preferred more than 99.5% and less than 100%.In addition, the purity of the 1st oxide compound, the 2nd oxide compound is used in respectively the value representation that the evaporation material forms front powder chronometry.And, the purity of the purity of powder for measuring by spectrum analysis method (inductively coupled plasma emmission spectrometric analysis device: Nippon Jarrell-Ash Co., the ICAP-88 that Ltd. makes).
And, during with the containing molar weight and be made as respectively X mole, Y mole of above-mentioned the 1st oxide compound and the 2nd oxide compound, the reason that ratio of components is made as 0.05≤X mole/(X mole+Y mole)≤0.95 is because less than lower value or when surpassing higher limit, cause b when ratio of components
*The absolute value of value surpasses 3, can't obtain colorless film.Wherein, preferred ratio of components is made as 0.01≤X mole/(X mole+Y mole)≤0.70.
And the evaporation material can be the granule of processing through granulation, can be also through stamping forming pellet.Compare with the evaporation material of partical, the evaporation material that is made of granule is because need not impact briquetting, and is therefore comparatively excellent aspect the simplification of manufacturing process or cost degradation.On the other hand, compare with the evaporation material of granule shape, the evaporation material that is made of pellet is comparatively excellent aspect more difficult generation splash.
When the evaporation material was made as the granule of processing through granulation, the median size of preferred particulates body was 1～10mm.This be because, during less than lower value, splash occurs frequently sometimes when the median size of granule, on the other hand, if surpass higher limit, specific surface area diminishes, and therefore sometimes causes yield polymer films to reduce.Wherein, especially preferred median size is 2～5mm.
And when being made as the evaporation material through stamping forming pellet, the diameter of preferred pellet is 5～30mm, and thickness is 1～20mm.When the diameter of pellet or thickness during less than lower value, the shape-retentivity of formed body a little less than, therefore sometimes produce breach or crackle.Be on the other hand because, if the diameter of pellet or thickness surpass higher limit, because the friction from the punch die wall causes stamping pressure different according to the position of formed body inside, so the strain sometimes of the shape after sintering or the internal structure heterogeneity that becomes.Wherein, the diameter of especially preferred pellet is 10～25mm, and thickness is 1～20mm.
And, all the median size of contained above-mentioned the 1st oxide particle of preferred evaporation material is in the scope of 0.1～20 μ m for any situation of the evaporation material that is made of granule and the evaporation material that is made of pellet, and the median size of the 2nd oxide particle is in the scope of 0.1～20 μ m.The median size that why is the 1st contained oxide particle of granule or pellet and the 2nd oxide particle with the evaporation material is limited in above-mentioned scope, because when the median size of each oxide compound during less than lower value, in the manufacturing process of evaporation material, the cohesion of powder becomes significantly, hinders equably and mixes.And be because if use median size less than the powder of lower value, can see the tendency of the film that is difficult to obtain excellent in te pins of durability.Can infer this be because, if the powder that median size is very little is as raw material, although can access denser membrane structure, the specific surface area of grain circle increases but then, and becomes larger because of the impact that diffuses to the damage that the interior water vapour of film produces.Because if the median size of each oxide particle surpasses higher limit, can see the tendency of the effect that can't obtain fully being formed with the virtual sosoloid that helps to improve water-vapor barrier on the other hand.Wherein, the median size of especially preferred the 1st oxide particle is in the scope of 0.5～10 μ m, and the median size of the 2nd oxide particle is in the scope of 0.5～10 μ m.In addition, in this specification sheets, so-called median size refers to, according to laser diffraction, scattering method (Microtrack method), utilize day machine dress company's system (FRA type), use sodium hexametaphosphate as dispersion agent, 1 minute is made as 30 seconds and measures 3 times, makes the particle diameter of its measured value equalization.And, the 2nd oxide compound be ZnO and SiO both the time, the median size of preferred two kind of the 2nd oxide particle is respectively in above-mentioned scope.
According to more than, water vapour barrier film of the present invention forms with in the evaporation material, can form the water vapour barrier film that possesses simultaneously water white transparency and higher water-vapor barrier.Particularly, possessing water vapor transmission rate (WVTR) (Water Vapor Transmission Rate:WVTR) is 0.1g/m
2More than it and less than 1.0g/m
2It very high water-vapor barrier.In addition, be difficult at present make water vapor transmission rate (WVTR) less than 0.1g/m
2It water vapour barrier film.And the transmittance with visible region is the transparency more than 75%.Therefore, except the purposes as the gas barrier materials such as wrapping material of the moisture barrier films of the backboard that consists of solar cell or food, medicine etc., water vapour barrier film of the present invention can also be preferably used as the sensitive surface side of solar cell or liquid-crystal display, OLED display or illumination with the gas barrier material of the display surface side of OLED display etc.And, be not only transparently, and be to demonstrate b
*Therefore the absolute value of value especially can not abstained from when being used for the wrapping material of food less than 3 water white transparency yet, and, namely be used in the display surface side of indicating meter, also can not affect colour developing or tone and damp proof effect etc. is provided.In addition, in the present invention, so-called b
*Value refers to, based on the impartial color space L of International Commission on Illumination (CIE) in recommendation in 1976
*, a
*, b
*Value.Wherein, L
*Be lightness index, expression brightness, a
*And b
*Be chromaticity index, the expression chroma.Work as a
*And b
*For on the occasion of the time, the expression redness is tied to yellow system, when be negative value, represents blue series.Also stipulate this color notation in JIS Z 8729.The b that uses in the present invention
*Value becomes the benchmark of the yellow hue of evaluated for film in most thin film fabrication business.
And, as above-mentioned evaporation material of the present invention owing to all using high vapor pressure material as the oxide compound that uses in material, so on base material during film forming water vapour barrier film, film deposition system is not defined, can be with low-yield and carry out at a high speed.Therefore, all can the high-quality water vapour barrier film of film forming by any vacuum film formation method, particularly, can enumerate EB method, electrical resistance heating or reactive plasma vapour deposition method (Reactive Plasma Deposition Method is hereinafter referred to as the RPD method) etc.
Then, describe take the situation of making by sintering process as the manufacture method of representative to evaporation material of the present invention.At first the manufacture method of the evaporation material that is made of pellet described.At first, mix purity as the 1st oxide powder and be preferably high purity powdered form 98% or more, be preferably high purity powdered form, tackiness agent and organic solvent more than 98% as the purity of the 2nd oxide powder, preparing concentration is the slurry of 30～75 quality %.The slurry of preferred preparation 40～65 quality %.In addition, the 1st oxide powder and the 2nd oxide powder are adjusted and mix with the mode that the ratio of components of the 2nd oxide compound satisfies above-mentioned scope with the 1st oxide compound in the evaporation material after making.With the concentration limits of slurry fix on 30～75 quality % be because, if surpass 75 quality %, because above-mentioned slurry is non-water system, therefore there is the problem points that is difficult to carry out stable mixing granulation, if less than 30 quality %, can't obtain having the sintered compact of the densification of uniform tissue.And, the median size of relevant the 1st oxide powder that uses, the median size of the 2nd oxide powder, because the median size of the median size of the 1st oxide powder contained in the evaporation material after making, the 2nd oxide powder is adjusted into reason in above-mentioned scope, preferably the median size with the 1st oxide powder is located in the scope of 0.1～20 μ m, and the median size of the 2nd oxide powder is located in the scope of 0.1～20 μ m.
Preferably utilize polyoxyethylene glycol or polyvinyl butyral acetal etc. as tackiness agent, and preferably utilize ethanol or propyl alcohol etc. as organic solvent.Tackiness agent preferably adds 0.2～5.0 quality %.
And, the wet mixing of high purity powdered form, tackiness agent and organic solvent, especially high purity powdered form with as the wet mixing of the organic solvent of dispersion medium by wet ball-milling or stir mill and carry out.In wet ball-milling, when utilizing ZrO
2During ball processed, utilizing diameter is a large amount of ZrO of 5～10mm
2Ball wet mixing processed 8～24 hours is preferably 20～24 hours.With ZrO
2It is because if less than 5mm, mixing will become insufficient, if surpass 10mm, has the unfavorable condition that increases impurity that the diameter of ball processed is limited to 5～10mm.And it is because even long-time continuous is mixed, also seldom produce impurity that mixing time reaches 24 hours most.
In stirring mill, utilizing diameter is the ZrO of 1～3mm
2Ball processed, wet mixing 0.5～1 hour.With ZrO
2It is because if less than 1mm, mixing will become insufficient, if surpass 3mm, has the unfavorable condition that increases impurity that the diameter of ball processed is limited to 1～3mm.And, mixing time be short to the longest 1 hour and be because, if surpass 1 hour, be not only the mixing of raw material, and ball itself can wear and tear also, therefore become the reason that produces impurity, and as long as just can mix fully in 1 hour.
Then, implement that above-mentioned slurry is carried out spray-dired granulation and process to make the mixing granulation powder with desirable median size.Above-mentioned spraying drying preferably utilizes spray-dryer to carry out.
When obtaining the evaporation material that is consisted of by pellet, follow above-mentioned granulation and process, put into predetermined mold, carry out impact briquetting with predetermined pressure.Predetermined mold is utilized uniaxial pressing device or isostatic cool pressing (CIP; Cold Isostatic Press) shaped device.In the uniaxial pressing device, with 750～2000kg/cm
2(73.55～196.1MPa), preferably with 1000～1500kg/cm
2(98.1～147.1MPa) pressure carries out the single shaft extrusion forming to prilling powder, in the CIP shaped device, with 1000～3000kg/cm
2(98.1～294.2MPa), preferably with 1500～2000kg/cm
2(147.1～196.1MPa) pressure carries out the CIP moulding to prilling powder.It is in order to improve the density of formed body that pressure is limited in above-mentioned scope, and prevents the distortion after sintering, and need not to carry out post-treatment.
In addition, with the preset temperature sintered moulded body.Sintering in atmosphere, rare gas element, vacuum or reducing gas atmosphere with more than 1000 ℃, the temperature of preferred 1200～1400 ℃, carried out 1～10 hour, preferred 2～5 hours.Although above-mentioned sintering under atmospheric pressure carries out, as hot pressing (HP) sintering or hip moulding (HIP; Hot Isostatic Press) when sintering carries out pressure sintering, preferably carried out 1～5 hour with the temperature more than 1000 ℃ in rare gas element, vacuum or reducing gas atmosphere.According to more than, can access the evaporation material by consisting of through stamping forming pellet of the present invention.
Then, the manufacture method of the evaporation material that is made of granule described.Particularly, at first, with the manufacture method of the above-mentioned evaporation material that is consisted of by pellet in the same manner, prepare the 1st oxide powder and the 2nd oxide powder.Prepare the butyral such as polyvinyl butyral resin and be the cellulose-based resins such as resin or ethyl cellulose as adhesive resin, and prepare the general solvent such as acetone as solvent, adhesive resin is dissolved in prepares binder solution in solvent.Binder solution is preferably butyral: acetone: the solution that ethanol mixes in the ratio of weight ratio 2.5:12.5:85.With as the acetone solution of the general solvent butyral as tackiness agent, and add ethanol, adjust thus the liquid measure of binder solution.
In above-mentioned illustration, although ethanol is used for liquid measure adjustment and granular size adjustment, if but define solvent as used herein by surface tension and vapour pressure, the vapour pressure material 25～250mmHg scope in of preferred surface tension force in 15～50mN/m scope, under 25 ℃.It is because if less than 15mN/m, raw material powder does not condense, and is difficult to form particle that the surface tension of solvent is located in above-mentioned scope.And be because if surpass 50mN/m, because cohesive force is stronger, therefore be difficult to control granular size.If the surface tension of each material of illustration, water is 72mN/m, and benzene is 28.9mN/m, and acetone is 23.3mN/m, and methyl alcohol is 22.6mN/m, and ethanol is 22.55mN/m.And, with the vapour pressure of solvent be located in above-mentioned scope be because, if less than 25mmHg, cause needing the plenty of time in the drying process after granulation, if surpass 250mmHg, can cause evaporating in the granulation operation, therefore be difficult to form particle.If the vapour pressure of each material of illustration, water is 23.8mmHg, and acetone is 231.06mmHg, and ethanol is 59.0mmHg.
Then, raw material powder and binder solution are dropped in the small-sized tablets press of orbiting vane, stir certain hour with desirable rotating speed, thus with the particle diameter granulation of particle to desirable size.When the input amount of raw material powder is made as 100 quality %, preferred 5～50 quality % of the input amount of binder solution, especially preferred 20 quality %.If the input amount of binder solution is less than lower value, produce the absolute magnitude of tackiness agent very few and disperse inhomogeneously and raw material powder can't form granular unfavorable condition, if the input amount of binder solution surpasses higher limit, the viscosity that produces mixing raw material is too high and be difficult to control the unfavorable condition of particle diameter.At this, preferably drop into several times for the Uniform Dispersion of binder solution.Preferred 500～the 1500rpm of rotating speed, especially preferred 750rpm.And 1 time is stirred the hold-time is about 30 seconds.If this moment, the particle diameter of particle was desirable size, directly tap into into firing process.If the particle diameter of particle is less than desirable size, the rotating speed by reducing blade and stir to make particle to grow up when adding ethanol bit by bit.And the particle diameter of particle is greater than desirable when size, and the rotating speed by improving blade also stirs and dwindled particle in 2～5 seconds.
In firing process, at first, carry out heating up in 1 hour in ℃ scope of room temperature～70, keep removing after 1 hour the organic solvent in binder solution under 70 ℃.Then, be warming up to 600 ℃ with 50 ℃/hr, keep removing after 2 hours the tackiness agent in binder solution under 600 ℃.At last, be warming up to sintering temperature (1000～1500 ℃) with 100 ℃/hr, keep carrying out sintering after 5 hours.Afterwards, make its naturally cooling in stove after being cooled to 500 ℃ with 100 ℃/hr.
By above step, can access the evaporation material that is consisted of by granule.In this manufacture method, when the stirring raw material powder comes granulation, only drop into binder solution, and the particle of the desirable particle diameter of granulation.Therefore, easily adjust granular size.And, even just in case too add oarse-grained particle diameter, also can be by carrying out drying and pulverizing and only come like a cork granulation again with the ethanol adjustment.Especially the evaporation material that is consisted of by granule, different from the pellet through high-pressure molding, do not exert pressure before burning till and moulding is made.
[embodiment]
Then, together embodiments of the invention are elaborated with comparative example.
＜embodiment 1 〉
At first, preparing median size is that 1.2 μ m, purity are 99.7% high purity WO
3Powder is as the 1st oxide powder, prepare median size and be 0.9 μ m, purity and be 99.7% SiO powder as the 2nd oxide powder, prepare polyvinyl butyral acetal as tackiness agent, prepare ethanol as organic solvent, by the wet mixing based on ball mill, these raw materials are mixed, and preparation concentration is the slurry of 50 quality %.
At this moment, the ratio of mixture of the 1st oxide powder and the 2nd oxide powder is adjusted, so that with the 1st oxide compound (WO
3) be made as X mole, the ratio of components when the 2nd oxide compound (SiO) is made as Y mole: X/(X+Y) become 0.05.
Then, utilize spray-dryer to carry out spraying drying to the slurry of above-mentioned preparation, after obtaining median size and be the mixing granulation powder of 0.9 μ m, this prilling powder is put into predetermined mold, by the impact briquetting of uniaxial pressing device.Make resulting formed body in air atmosphere with the temperature sintering of 1300 ℃ 5 hours, obtain the evaporation material that the pellet by diameter 20mm, thickness 10mm consists of.
Then, using evaporation material obtained above, is the water vapour barrier film of 100nm by EB method film forming thickness on glass substrate.In following table 1, the ratio of components of evaporation material obtained above is shown: X/(X+Y).
＜embodiment 2～7, comparative example 1～3 〉
With the 1st oxide compound (WO
3) be made as X mole, the ratio of components when the 2nd oxide compound (SiO) is made as Y mole: X/(X+Y) be adjusted into the value shown in following table 1, be identically formed the evaporation material with embodiment 1 in addition, film forming water vapour barrier film.
＜embodiment 8～14, comparative example 4～6 〉
Using median size is that 1.0 μ m, purity are that 99.7% ZnO powder is as the 2nd oxide powder, with the 1st oxide compound (WO
3) be made as X mole, the ratio of components when the 2nd oxide compound (ZnO) is made as Y mole: X/(X+Y) be adjusted into the value shown in following table 2, be identically formed the evaporation material with embodiment 1 in addition, film forming water vapour barrier film.
＜embodiment 15～21, comparative example 7～9 〉
As shown in the following Table 3, the ZnO powder that uses in the SiO powder that uses in use embodiment 1 and embodiment 8 is as the 2nd oxide powder, with the 1st oxide compound (WO
3) be made as X mole, the 2nd oxide compound (SiO) and be made as Y1 mole, the ratio of components when the 2nd oxide compound (ZnO) is made as Y2 mole: X/(X+Y1+Y2) be adjusted into the value shown in following table 3, be identically formed the evaporation material with embodiment 1 in addition, film forming water vapour barrier film.
＜embodiment 22～31, comparative example 10～13 〉
The thickness of water vapour barrier film is made as the thickness shown in following table 4, is identically formed the evaporation material with embodiment 3 in addition, film forming water vapour barrier film.
＜embodiment 32,34 〉
As shown in the following Table 5, carry out respectively the film forming of water vapour barrier film by electrical resistance heating, RPD method, be identically formed the evaporation material with embodiment 23 in addition, film forming water vapour barrier film.In addition, for relatively, in table 5 and above-described embodiment 23 is shown.
＜embodiment 33,35 〉
As shown in the following Table 5, carry out respectively the film forming of water vapour barrier film by electrical resistance heating, RPD method, be identically formed the evaporation material with embodiment 3 in addition, film forming water vapour barrier film.In addition, for relatively, in table 5 and above-described embodiment 3 is shown.
＜comparison test and evaluation 〉
About the water vapour barrier film of film forming in embodiment 1～35 and comparative example 1～13, thickness, water vapor transmission rate (WVTR), b have been measured
*Value and transmittance.The results are shown in following table 1～table 5.
(1) thickness of water vapour barrier film: utilize the contact pin type surface shape measurer to be determined at the thickness of the water vapour barrier film of film forming on substrate.
(2) water vapor transmission rate (WVTR): utilize MOCON company water vapor transmission rate (WVTR) determinator processed (model name is PERMATRAN-W type 3/33), in being set as the above-mentioned water vapor transmission rate (WVTR) determinator of 40 ℃ of temperature, relative humidity 90%RH, barrier film was kept 1 hour, then measure water vapor transmission rate (WVTR) under the condition of 40 ℃ of temperature, relative humidity 90%RH.
(3) b
*Value: be the b of aberration to the Lab that utilizes color computer (Suga Test Instruments Co., Ltd. make) to obtain
*Value is measured.
(4) transmittance: the spectrophotometer (model name is U-4000) that utilizes Hitachi Co., Ltd to make, the transmittance of water vapour barrier film in 380～780nm wavelength measured.
[table 1]
Apparent from table 1, if embodiment 1～7 and comparative example 1～3 are compared, at the WO that does not comprise as the 1st oxide compound
3And the comparative example 1 that only is made of SiO and ratio of components though water vapor transmission rate (WVTR) and transmittance demonstrate sufficient value, become b less than in 0.05 comparative example 2
*The absolute value of value is the flaxen transparent film more than 3, fails to obtain colourless transparent film.On the other hand, surpass in 0.95 comparative example 3, though water vapor transmission rate (WVTR) and transmittance illustrate sufficient value, b at ratio of components
*The absolute value of value becomes more than 3, becomes transparent film azury a little.
On the other hand, in embodiment 1～7, water vapor transmission rate (WVTR) and transmittance demonstrate sufficient value, and b
*The absolute value of value becomes less than 3, can access colourless transparent film.
[table 2]
Apparent from table 2, if embodiment 8～14 and comparative example 4～6 are compared, at the WO that does not comprise as the 1st oxide compound
3And the comparative example 4 that only is made of ZnO and ratio of components though water vapor transmission rate (WVTR) and transmittance illustrate sufficient value, become b less than in 0.05 comparative example 5
*The absolute value of value is the flaxen transparent film more than 3, fails to obtain colourless transparent film.On the other hand, surpass in 0.95 comparative example 6, though water vapor transmission rate (WVTR) and transmittance illustrate sufficient value, b at ratio of components
*The absolute value of value becomes more than 3, becomes transparent film azury a little.
On the other hand, in embodiment 8～14, water vapor transmission rate (WVTR) and transmittance demonstrate sufficient value, and b
*The absolute value of value becomes less than 3, can access colourless transparent film.
[table 3]
Apparent from table 3, if embodiment 15～21 and comparative example 7～9 are compared, at the WO that does not comprise as the 1st oxide compound
3And the comparative example 7 that only is made of SiO and ZnO and ratio of components though water vapor transmission rate (WVTR) and transmittance illustrate sufficient value, become b less than in 0.05 comparative example 8
*The absolute value of value is the flaxen transparent film more than 3, fails to obtain colourless transparent film.On the other hand, surpass in 0.95 comparative example 9, though water vapor transmission rate (WVTR) and transmittance illustrate sufficient value, b at ratio of components
*The absolute value of value becomes more than 3, becomes transparent film azury a little.
On the other hand, in embodiment 15～21, water vapor transmission rate (WVTR) and transmittance demonstrate sufficient value, and b
*The absolute value of value becomes less than 3, can access colourless transparent film.
[table 4]
Apparent from table 4, in thickness being made as comparative example 10 less than 30nm, comparative example 11, b
*The absolute value of value becomes less than 3, can access colorless film, and though show good transmittance, water vapor transmission rate (WVTR) surpasses 1.0g/m
2My god, fail to obtain higher water-vapor barrier.And, in the comparative example 12 that thickness is made as 520nm, b
*The absolute value of value becomes less than 3, can access colorless film, and, though show good transmittance, causing producing a plurality of be full of cracks, water vapor transmission rate (WVTR) surpasses 1.0g/m
2My god, fail to obtain higher water-vapor barrier.On the other hand, in the comparative example 13 that thickness is made as 530nm, b
*The absolute value of value becomes more than 3, and water vapor transmission rate (WVTR) surpasses 1.0g/m
2My god.
On the other hand, in the embodiment 3 that thickness is made as 30～500nm and embodiment 22～31, water vapor transmission rate (WVTR) and transmittance demonstrate sufficient value, and, b
*The absolute value of value becomes less than 3, can access colourless transparent film.Can determine thus, ratio of components is made as at 0.30 o'clock, thickness is located in the scope of 30～500nm as effectively.
[table 5]
Apparent from table 5, at the embodiment 32 that carries out film forming by electrical resistance heating, embodiment 33 and carry out embodiment 34, the embodiment 35 of film forming by the RPD method in, also with the embodiment 23, the embodiment 3 that carry out film forming by the EB method in the same manner, can access the higher colourless transparent film of water-vapor barrier.
Claims (5)
1. a water vapour barrier film forms and uses the evaporation material, and be more than 98% and be to consist of more than 98% and less than 100% the 2nd oxide compound less than 100% the 1st oxide compound and purity by purity, wherein,
Described the 1st oxide compound is WO
3, described the 2nd oxide compound is at least one party in ZnO or SiO,
During with the containing molar weight and be made as respectively X mole, Y mole of described the 1st oxide compound and described the 2nd oxide compound, ratio of components is 0.05≤X mole/(X mole+Y mole)≤0.95.
2. water vapour barrier film as claimed in claim 1 forms and uses the evaporation material, wherein,
The granule that described evaporation material is 1～10mm by the median size of processing through granulation consists of.
3. water vapour barrier film as claimed in claim 1 forms and uses the evaporation material, wherein,
Described evaporation material is made of the pellet through stamping forming diameter 5～30mm, thickness 1～20mm.
4. the film of a water vapour barrier film, right to use requires the described evaporation material of any one in 1～3, carries out film forming by electrical resistance heating, electron beam evaporation plating method or reactive plasma vapour deposition method.
5. water vapour barrier film, right to use require in 1～3 the described evaporation material of any one and form by the vacuum film formation method, and b
*The absolute value of value is less than 3, and water vapor transmission rate (WVTR) is 0.1g/m
2More than it and less than 1.0g/m
2My god.
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| JP2011281563A JP2013129893A (en) | 2011-12-22 | 2011-12-22 | Vapor deposition material for depositing water vapor barrier film, method for depositing water vapor barrier film, and water vapor barrier film deposited by the method |
| JP2011-281563 | 2011-12-22 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136159A (en) * | 1992-10-27 | 1994-05-17 | Kanegafuchi Chem Ind Co Ltd | Transparent conductive film and its production |
| JP2007226994A (en) * | 2006-02-21 | 2007-09-06 | Univ Of Tokushima | Method of manufacturing transparent conductive film |
| CN102191455A (en) * | 2010-03-15 | 2011-09-21 | 三菱综合材料株式会社 | Vapour deposition material for forming film, film sheet and laminated sheet having the same |
| CN102191461A (en) * | 2010-03-04 | 2011-09-21 | 三菱综合材料株式会社 | Vapor phase deposition material for forming film, film sheet with the film, and laminated sheet |
-
2011
- 2011-12-22 JP JP2011281563A patent/JP2013129893A/en active Pending
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2012
- 2012-09-24 CN CN2012103594182A patent/CN103173717A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136159A (en) * | 1992-10-27 | 1994-05-17 | Kanegafuchi Chem Ind Co Ltd | Transparent conductive film and its production |
| JP2007226994A (en) * | 2006-02-21 | 2007-09-06 | Univ Of Tokushima | Method of manufacturing transparent conductive film |
| CN102191461A (en) * | 2010-03-04 | 2011-09-21 | 三菱综合材料株式会社 | Vapor phase deposition material for forming film, film sheet with the film, and laminated sheet |
| CN102191455A (en) * | 2010-03-15 | 2011-09-21 | 三菱综合材料株式会社 | Vapour deposition material for forming film, film sheet and laminated sheet having the same |
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