WO2012124742A1 - 積層防湿フィルム - Google Patents
積層防湿フィルム Download PDFInfo
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- WO2012124742A1 WO2012124742A1 PCT/JP2012/056596 JP2012056596W WO2012124742A1 WO 2012124742 A1 WO2012124742 A1 WO 2012124742A1 JP 2012056596 W JP2012056596 W JP 2012056596W WO 2012124742 A1 WO2012124742 A1 WO 2012124742A1
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- moisture
- proof film
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- laminated
- proof
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- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
Definitions
- the present invention relates to a laminated moisture-proof film, and more particularly to a laminated moisture-proof film that can be suitably used for a surface protective material for a solar cell module.
- a moisture-proof film in which an inorganic layer such as silicon oxide is formed on the surface of a resin film substrate is laminated with other resin films and used for various packaging applications.
- liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, organic electroluminescence (EL) elements, organic TFTs, organic semiconductor sensors, organic light emitting devices and other organic devices, electronic paper, film capacitors, inorganic EL elements, color filters It is also used for new applications such as base film and vacuum heat insulating material used in the industry. In these applications, more demanding performance has been demanded of laminated moisture-proof films, and development of excellent laminated moisture-proof films with little deterioration of moisture resistance under long-term use and high-temperature conditions has been made.
- Patent Document 1 proposes a back surface protection material for a solar cell module using a moisture-proof film in which an inorganic oxide is deposited on a resin sheet instead of a metal foil. And a laminated body composed of a weather-resistant base material layer and a cyclic polyolefin-based resin layer, and further, an inorganic oxide vapor deposition film is provided on one surface of the laminated body.
- a protective sheet for solar cell modules is disclosed.
- Patent Documents 2 and 3 propose a laminated sheet having a plurality of moisture-proof films in which an inorganic oxide is vapor-deposited on a resin sheet. In Patent Document 2, a metal oxide vapor-deposited film is formed on one surface.
- a back protective sheet for a solar cell module in which a first vapor deposition resin layer, an intermediate resin layer, and a second vapor deposition resin layer having a metal oxide vapor deposition film on one surface are laminated by dry lamination The back surface protection sheet for solar cell modules by which the vapor deposition film of the said 1st vapor deposition resin layer and the said 2nd vapor deposition resin layer is arrange
- positioned at the said intermediate resin layer side is disclosed.
- at least three layers of a vapor-deposited resin layer having a metal oxide vapor-deposited film on one surface are sequentially laminated by dry laminating, and the vapor-deposited resin layer is water vapor at 40 ° C. and 90% RH, respectively.
- Patent Document 4 contains two or more composite films in which a vapor-deposited film of inorganic oxide or metal is formed on at least one surface of the non-hygroscopic resin layer, and the vapor-deposited film surface of the composite film has an adhesive layer.
- a moisture-proof multilayer film containing a layer structure laminated with the vapor deposition film surface of another composite film within the range of 1 to 4 is disclosed.
- the dry laminating process is a laminating method using a reactive adhesive for adhesion between layers to be laminated, and a strong adhesive between layers can be obtained, while a reactive adhesive reacts.
- Accompanying bubbles may be mainly composed of carbon dioxide. The bubbles generated between the layers are normally transmitted through the inside of the layer made of the resin sheet and released to the outside. Therefore, by providing an appropriate aging period after the lamination, the bubbles generated between the layers naturally disappear. .
- examples of solar cell elements include group III-V such as single crystal silicon type, polycrystalline silicon type, amorphous silicon type, gallium-arsenide, copper-indium-selenium, and cadmium-tellurium.
- Crystal silicon type using a moisture-proof film having a conventional water vapor transmission rate of up to about 0.1 [g / m 2 ⁇ day].
- High moisture resistance with water vapor transmission rate of 0.01 [g / m 2 ⁇ day] or less for solar cell elements such as semiconductor type, dye sensitized type, organic thin film type, etc.
- Surface protection material is required, and it is a problem to obtain a highly moisture-proof laminated film while preventing foaming between layers.
- the present invention has been made in view of the above situation, and by combining a high moisture-proof moisture-proof film and a relatively low moisture-proof moisture-proof film, the residual solvent between the moisture-proof film layers and the generation of bubbles are suppressed.
- the present invention (1) Moisture-proof film A having a water vapor transmission rate (WTR (A)) at 40 ° C. and 90% RH of 1.0 [g / m 2 ⁇ day] or less, and an inorganic layer on one side of the substrate, A moisture barrier film B having a moisture vapor transmission rate (WTR (B)) at 40 ° C. and 90% RH of 10% or less of the moisture barrier film A (WTR (A)) was laminated via an adhesive layer.
- the water vapor transmission rate (WTR (B)) at 40 ° C. and 90% RH is 0.001 [g / m 2 ⁇ day] or more and 0.1 [g / m 2 ⁇ day], a moisture-proof film B having a structure laminated via an adhesive layer, (3) Water vapor permeability (WVTR (L)) of laminated moisture-proof film at 40 ° C. and 90% RH is lower than [WTR (A) ⁇ WTR (B)] / [WTR (A) + WTR (B)]
- the laminated moisture-proof film according to any one of (1) and (2) above,
- the water vapor permeability (WVTR (L)) of the laminated moisture-proof film at 40 ° C. and 90% RH is 80% of [WTR (A) ⁇ WTR (B)] / [WTR (A) + WTR (B)].
- the moisture permeation rate (WTR (A)) at 40 ° C. and 90% RH of the moisture-proof film A is 0.1 [g / m 2 ⁇ day] or more, (1), (3 ) Or (4) laminated moistureproof film, (6)
- the moisture-proof film A has a water vapor transmission rate (WTR (A)) at 40 ° C.
- Laminated moisture-proof film according to any one of (7) The moisture-proof film A has a water vapor transmission rate (WTR (A)) at 40 ° C. and 90% RH of 0.4 [g / m 2 ⁇ day] or more, (1) to (6) ) Laminated moisture-proof film according to any one of (8) The moisture-proof film A has a water vapor transmission rate (WTR (A)) at 40 ° C. and 90% RH of 0.6 [g / m 2 ⁇ day] or more, (1) to (7 ) Laminated moisture-proof film according to any one of
- the moisture permeability of the moisture-proof film B at 40 ° C. and 90% RH (WTR (B)) is 0.001 [g / m 2 ⁇ day] or more and 0.1 [g / m 2 ⁇ day] or less.
- the moisture vapor transmission film B has a water vapor transmission rate (WTR (B)) at 40 ° C. and 90% RH of 0.001 [g / m 2 ⁇ day] or more and 0.05 [g / m 2 ⁇ day] or less.
- the laminated moisture-proof film according to any one of the above (1) to (9), (11) The laminated moisture-proof film according to any one of the above (1) to (10), wherein the moisture-proof film A is a film having at least one layer made of a resin composition containing a cyclic olefin polymer.
- (12) The laminated moisture-proof film according to any one of the above (1) to (10), wherein the moisture-proof film A is a film having an inorganic layer on one side of the substrate, (13)
- the weatherproof film, the moistureproof film B and the moistureproof film A are provided in this order from the exposed side, and the moistureproof film B is provided on the inorganic layer side of the moistureproof film A.
- the laminated moisture-proof film according to (12) above which has a weather-resistant film, a moisture-proof film A, and a moisture-proof film B in this order from the exposed side, and has a substrate of the moisture-proof film A on the inorganic layer side of the moisture-proof film B ,
- the adhesive layer comprises an adhesive, and the adhesive contains at least one of polycarbonate polyol, polyether polyol, acrylic polyol, polyurethane polyol and polyester polyol as a main agent.
- a laminated moisture-proof film that is excellent in transparency, extremely moisture-proof, and can reduce the amount of bubbles generated between moisture-proof films, particularly
- the laminated moisture-proof film which can be used for the surface protection material for solar cell modules, and the surface protection member for solar cells using this laminated moisture-proof film are provided.
- FIG. 1 Schematic sectional view showing a laminated moisture-proof film according to an embodiment of the present invention.
- Typical sectional drawing which shows the laminated moisture-proof film which concerns on the form different from the laminated moisture-proof film of FIG.
- Typical sectional drawing which shows the laminated moisture-proof film which concerns on the form different from the laminated moisture-proof film of FIG.
- a laminated moisture-proof film is produced by dry lamination or the like.
- dry laminating a moisture-proof film having an inorganic layer and a resin film an adhesive diluted with a solvent is applied to the resin film to a predetermined thickness, and the solvent is evaporated by drying, for example, in the range of 100 ° C to 140 ° C.
- An adhesive layer is formed on the resin film.
- the laminated moisture-proof film is manufactured through pasting at a predetermined temperature by laminating the inorganic layer surface of the moisture-proof film toward the adhesive side.
- Curing is performed, for example, in the range of 30 ° C. to 80 ° C. for 1 day to 1 week.
- the solvent contained in the adhesive coating liquid during dry lamination is diffused from the inside to the outside in the laminated film because of the high moisture-proof property of the high moisture-proof film. Further, volatilization from the surface is difficult, it remains between the laminated films, and foaming becomes remarkable by heating.
- the inventors have a relatively low moisture-proof film, an inorganic layer on one side, and a water vapor transmission rate of 40 ° C. and 90% RH is 10% or less of the value of the relatively low moisture-proof film. It was found that a laminated moisture-proof film that does not cause foaming by heating and is excellent in transparency and moisture resistance can be obtained by laminating a highly moisture-proof film that is a dry laminate process through an adhesive layer. . A relatively low moisture-proof moisture-proof film having a water vapor transmission rate at 40 ° C.
- the moisture-proof moisture-proof film In the laminated moisture-proof film, in the moisture-proof measurement environment of 40 ° C. and 90% RH, when the highly moisture-proof moisture-proof film is an outer layer, the moisture-proof moisture-proof film prevents water vapor from entering the laminated moisture-proof film.
- a low-humidity state In the inorganic thin film surface of the relatively low moisture-proof moisture-proof film on the inner surface side, a low-humidity state is formed as compared with the measurement environment for water vapor permeability. This low-humidity state significantly reduces moisture adsorption on the relatively low moisture-proof moisture-proof film, and as a result, the moisture permeation of the relatively low moisture-proof moisture-proof film decreases and the moisture-proof property of the moisture-proof film increases.
- the relatively low moisture-proof moisture-proof film also suppresses the entry of water vapor to the laminated moisture-proof film to some extent, and the highly moisture-proof film on the inner surface side.
- a low humidity state is formed as compared with the measurement environment of water vapor transmission rate. This low humidity state significantly reduces moisture adsorption on the inorganic layer surface of the highly moisture-proof moisture-proof film, and as a result, the moisture penetration of the moisture-proof film is further reduced, and the moisture-proof property of the moisture-proof film is increased. As a result, a laminated moisture-proof film having excellent moisture resistance can be obtained.
- the laminated moisture-proof film of the present invention has a moisture-proof film A having a water vapor transmission rate (WTR (A)) at 40 ° C. and 90% RH of 1.0 [g / m 2 ⁇ day] or less, and inorganic on one side of the substrate.
- the moisture-proof film B has the structure laminated
- the laminated moisture-proof film according to another invention of the present application has a water vapor transmission rate (WTR (A)) at 40 ° C. and 90% RH of 0.1 [g / m 2 ⁇ day] or more, 1.0 [ g / m 2 ⁇ day] or less, a moisture-proof film A and an inorganic layer on one side of the substrate, and a water vapor transmission rate (WTR (B)) at 40 ° C. and 90% RH is 0.001 [g / m 2 ⁇ day] or more and less than 0.1 [g / m 2 ⁇ day], the moisture-proof film B has a structure in which it is laminated via an adhesive layer.
- WTR (A) water vapor transmission rate
- WTR (B) water vapor transmission rate
- the moisture-proof film A in the laminated moisture-proof film of the present invention has a water vapor transmission rate (WTR (A)) at 40 ° C. and 90% RH of 1.0 [g / m 2 ⁇ day] or less.
- WTR (A) water vapor transmission rate
- the moisture permeability of the moisture-proof film A (WTR (A)) is 40 ° C., 90% RH.
- WTR (A) water vapor transmission rate
- the moisture permeability of the moisture-proof film A (WTR (A)) is in the above range, even if the moisture-proof property of the laminated moisture-proof film is high, it is easy for the solvent to pass through the moisture-proof film A and due to heating. Foaming is difficult to occur.
- Examples of such a moisture-proof film A include a moisture-proof resin film and a film having an inorganic layer on one side of a substrate.
- Examples of the moisture-proof resin film include a film having at least one layer composed of a resin composition containing a cyclic olefin polymer (hereinafter, sometimes referred to as “cyclic olefin polymer moisture-proof film”).
- the content of the cyclic olefin polymer in the layer is preferably 50 to 100% by mass.
- the cyclic olefin polymer Since the main skeleton is composed of carbon, the cyclic olefin polymer is excellent in water repellency, coating properties and environmental safety, and is suitably used for the moisture-proof film A of the present invention.
- the cyclic olefin-based polymer there are mainly three configurations according to the following (A) to (C).
- the cyclic olefin component bicyclohept-2-ene (2-norbornene) and its derivatives such as norbornene, 6-methylnorbornene, 6-ethylnorbornene, 6-n-butylnorbornene
- Examples include 5-propylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,6-dimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, and the like.
- the cyclic olefin-based random copolymer having the configuration (A) is a copolymer of a linear olefin component and the above cyclic olefin component, and the present invention is in terms of fluidity, transparency, and water vapor barrier properties. Is preferably used.
- the linear olefin component to be copolymerized with the cyclic olefin component ⁇ -olefin having 2 to 20 carbon atoms is preferably used.
- ethylene propylene, 1-butene, 1-pentene, 1-hexene, 1 -Heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-butene-1, 4-methyl-pentene-1, and the like.
- ethylene is preferably used as the linear olefin component
- norbornene or tetracyclododecene is preferable as the cyclic olefin component from the viewpoints of industrial availability, various characteristics, and economical efficiency.
- the cyclic olefin component and the linear olefin component to be copolymerized may be used alone or in combination of two or more.
- the content (mol%) of the cyclic olefin component in the cyclic olefin-based random copolymer is not particularly limited, but when the ethylene-norbornene random copolymer is taken as an example, the norbornene component is preferably 1 mol. % Or more, more preferably 10 mol% or more, further preferably 15 mol% or more, and preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less. If it exists in this range, since it is excellent in melt viscosity at the time of using for the surface protection member for solar cells, a mechanical characteristic, economical efficiency, etc., it is preferable.
- cyclic olefin polymer for example, commercially available products such as Arton (trade name) manufactured by JSR Corporation, ZEONEX (trade name) manufactured by Nippon Zeon Co., Ltd. can be used. Cyclic olefin polymers generally have heat resistance, high transparency, and a film made of a resin composition containing a cyclic olefin polymer has a low water vapor transmission rate per unit area and excellent water vapor barrier properties. Yes.
- cyclic olefin polymer moisture-proof film for example, one or more of the above cyclic olefin polymers are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method are used.
- a cyclic olefin polymer moisture-proof film is produced by a method of forming a film after mixing before film formation, If necessary, for example, a cyclic olefin polymer moisture-proof film obtained by stretching in a uniaxial or biaxial direction using a tenter method or a tuber method can be obtained.
- the thickness of the moisture-proof resin film is preferably 12 to 700 ⁇ m, more preferably 25 to 500 ⁇ m, from the viewpoint of achieving both moisture resistance and flexibility.
- the visible light transmittance is 85% or more, preferably 90% or more, more preferably 92% or more, and the incident sun. It is desirable to have a property of transmitting light because an improvement in power generation efficiency can be achieved.
- Various resin compounding agents and additives can be added for the purpose of improving and modifying flame retardancy, antifungal properties, electrical properties, puncture resistance, etc. From a very small amount to several tens of percent, it can be arbitrarily added depending on the purpose.
- general additives for example, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizer fillers, antistatic agents, flame retardants, flame retardants, pigments, etc. are used.
- a modifying resin or the like can also be used.
- the surface of the cyclic olefin moisture-proof film is subjected to, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, chemicals, etc.
- Oxidation treatment and other pretreatment can be optionally applied, and a primer coat agent layer, an undercoat agent layer, or a deposition anchor coat is previously formed on the surface of the cyclic olefin moisture-proof film.
- An agent layer or the like can be arbitrarily formed.
- a resin composition containing a polyester resin, a polyurethane resin or the like as a main component of the vehicle can be used.
- the coating agent layer is formed by using, for example, a solvent type, aqueous type, or emulsion type coating agent, a roll coating method, a gravure roll coating, etc.
- the coating can be performed by using a coating method such as a method, a kiss coating method, or the like.
- the coating timing is after the formation of the cyclic polyolefin moisture-proof film or after the biaxial stretching treatment. As a process or at the time of film formation, it can be carried out by an inline process of a biaxial stretching process or the like.
- the moisture-proof film A of the present invention include a film having an inorganic layer on one side of the substrate as described above. By this inorganic layer, the inner surface side of the solar cell can be protected from moisture permeation. Moreover, when an inorganic layer has high transparency, when it uses as a surface protection material, improvement in power generation efficiency can be achieved.
- a resin film is preferable, and any material can be used as long as it is a resin that can be used for a normal solar cell material.
- polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene, amorphous polyolefins such as cyclic polyolefins, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), nylon 6 , Nylon 66, nylon 12, polyamide such as copolymer nylon, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, polyvinyl Examples include butyral, polyarylate, fluororesin, acrylic resin, and biodegradable resin.
- thermoplastic resin is preferable and polyester, polyamide, and polyolefin are more preferable from points, such as a film physical property and cost.
- polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are particularly preferable from the viewpoint of film properties.
- the base material is a known additive, for example, an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer such as a weathering stabilizer, a lubricant, a crosslinking agent, an antiblocking agent, An antioxidant etc. can be contained.
- an ultraviolet absorber various commercially available products can be applied, and examples thereof include various types such as benzophenone, benzotriazole, triazine, and salicylic acid ester.
- benzophenone ultraviolet absorbers examples include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-n. -Dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2 , 4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4, 4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, etc. But Kill.
- benzotriazole ultraviolet absorber examples include hydroxyphenyl-substituted benzotriazole compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-butylphenyl).
- Benzotriazole 2- (2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3-methyl-5-t- Butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2- (hydroxy-3,5-di-t-butylphenyl) benzotriazole, etc.
- triazine ultraviolet absorbers examples include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- ( Examples include 4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) phenol.
- salicylic acid esters include phenyl salicylate and p-octylphenyl salicylate.
- the addition amount of the ultraviolet absorber is usually about 0.01 to 2.0% by mass, preferably 0.05 to 0.5% by mass in the substrate.
- a hindered amine light stabilizer is suitably used as a weather stabilizer that imparts weather resistance in addition to the above ultraviolet absorber.
- a hindered amine light stabilizer does not absorb ultraviolet rays like an ultraviolet absorber, but exhibits a remarkable synergistic effect when used together with an ultraviolet absorber.
- hindered amine light stabilizers include dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1 , 3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ 2, 2,6,6-tetramethyl-4-piperidyl ⁇ imino ⁇ ], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) separate, 2- (3 , 5-Di-tert-4 Hydroxybenzyl) -2-n-n
- the resin film as the substrate is formed by using the above raw materials, but when used as the substrate, it may be unstretched or stretched. Also, one or more kinds of resin films may be laminated.
- a substrate can be produced by a conventionally known method. For example, a raw material resin is melted by an extruder, extruded by an annular die or a T die, and rapidly cooled to be substantially amorphous and not oriented. An unstretched film can be manufactured. Further, by using a multilayer die, it is possible to produce a single layer film made of one kind of resin, a multilayer film made of one kind of resin, a multilayer film made of various kinds of resins, and the like.
- the unstretched film is subjected to a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like.
- a film stretched in a uniaxial direction or a biaxial direction can be produced by stretching in a direction (horizontal axis) perpendicular thereto.
- the thermal shrinkage at 150 ° C. is preferably 0.01 to 5%, and more preferably 0.01 to 2%.
- a biaxially stretched polyethylene naphthalate film a biaxially stretched polyethylene terephthalate film, a coextruded biaxially stretched film of polyethylene terephthalate and polyethylene naphthalate, or a copolymer of polyethylene terephthalate and / or polyethylene naphthalate and other resins Extruded biaxially stretched films are preferred.
- the thickness of the substrate is generally about 5 to 100 ⁇ m, preferably 8 to 50 ⁇ m, more preferably 12 to 25 ⁇ m from the viewpoint of productivity and ease of handling.
- anchor coating agent examples include solvent-based or aqueous polyester resins, isocyanate resins, urethane resins, acrylic resins, modified vinyl resins, vinyl alcohol resins, and other alcoholic hydroxyl group-containing resins, vinyl butyral resins, nitrocellulose resins, and oxazoline group-containing resins.
- anchor coating agents include solvent-based or aqueous polyester resins, isocyanate resins, urethane resins, acrylic resins, modified vinyl resins, vinyl alcohol resins, and other alcoholic hydroxyl group-containing resins, vinyl butyral resins, nitrocellulose resins, and oxazoline group-containing resins.
- Carbodiimide group-containing resins methylene group-containing resins, epoxy group-containing resins, modified styrene resins, modified silicone resins, and the like. These can be used alone or in combination of two or more.
- the anchor coat layer may contain a silane coupling agent, a titanium coupling agent, a UV absorber, a stabilizer such as a weathering stabilizer, a lubricant, an anti-blocking agent, an antioxidant, etc., if necessary. it can.
- a silane coupling agent such as a titanium coupling agent, a UV absorber, a stabilizer such as a weathering stabilizer, a lubricant, an anti-blocking agent, an antioxidant, etc.
- a stabilizer such as a weathering stabilizer, a lubricant, an anti-blocking agent, an antioxidant, etc.
- the ultraviolet absorber and the weather resistance stabilizer those mentioned in the description of the base material can be used. It is also possible to use a polymer type in which the ultraviolet absorber and / or weathering stabilizer is copolymerized with the above-described resin.
- a known coating method is appropriately adopted.
- any method such as a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, and a coating method using a spray can be used.
- the substrate may be immersed in a resin solution.
- the solvent can be evaporated using a known drying method such as hot air drying or hot roll drying at a temperature of about 80 to 200 ° C. or infrared drying.
- the crosslinking process by electron beam irradiation can also be performed.
- the formation of the anchor coat layer may be a method performed in the middle of the substrate production line (inline) or a method performed after the substrate is manufactured (offline).
- the thickness of the anchor coat layer is preferably 10 to 200 nm, more preferably 10 to 100 nm, from the viewpoint of adhesion to the inorganic layer.
- any method such as a vapor deposition method and a coating method can be used, but a vapor deposition method is preferred in that a uniform thin film having a high gas barrier property can be obtained.
- This vapor deposition method includes methods such as physical vapor deposition (PVD) and chemical vapor deposition (CVD). Examples of physical vapor deposition include vacuum deposition, ion plating, and sputtering. Examples of chemical vapor deposition include plasma CVD using plasma and a catalyst that thermally decomposes a material gas using a heated catalyst. Examples include chemical vapor deposition (Cat-CVD).
- Examples of the inorganic substance constituting the inorganic layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, hydrogenated carbon, and the like, or oxides, carbides, nitrides, or mixtures thereof.
- the diamond-like carbon mainly composed of inorganic oxides such as silicon oxide, silicon oxynitride and aluminum oxide, nitrides such as silicon nitride, and hydrogenated carbon is used because of no risk of leakage of current when used in preferable.
- silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide are preferable in that high gas barrier properties can be stably maintained.
- the thickness of the inorganic layer is preferably 10 to 1000 nm, more preferably 40 to 1000 nm, still more preferably 40 to 800 nm, and particularly preferably 50 to 600 nm from the viewpoint of stable moistureproof performance.
- the inorganic layer may be a single layer or multiple layers.
- the thickness of the moisture-proof film having an inorganic layer on one side of the substrate is generally about 5 to 100 ⁇ m, preferably 8 to 50 ⁇ m, more preferably 12 to 25 ⁇ m from the viewpoint of productivity and ease of handling.
- the adjustment of the water vapor transmission rate (WTR (A)) of the moisture-proof film A is the composition of the resin composition constituting the film, the type of resin and the film.
- the thickness can be adjusted.
- the moisture-proof film A is a film having an inorganic layer on one side of the substrate, the selection of the material constituting the substrate and the inorganic layer, the thickness of the inorganic layer, and the material constituting the inorganic layer are inorganic oxides. In this case, the oxidation number of the oxide and the thickness of the entire moisture-proof film A can be adjusted.
- the moisture-proof property of the moisture-proof film A is determined by the amount of moisture diffusion in the moisture-proof film A and the moisture concentration difference between both sides of the moisture-proof film A.
- the moisture-proof film B having high moisture-proof property is disposed on the exposed side, moisture transmitted through the inner surface side is suppressed, and the moisture-proof difference of the moisture-proof film A is reduced by reducing the moisture concentration difference between the front and back of the moisture-proof film A. Can be improved.
- positioning the moisture-proof film A to the exposure side the moisture which permeate
- the moisture-proof film B has an inorganic layer on one side of the substrate, and has a water vapor transmission rate (WTR (B)) at 40 ° C. and 90% RH of 10% or less of the value of the moisture-proof film A. It is preferably 5% or less, more preferably 3% or less.
- WTR water vapor transmission rate
- the obtained laminated moisture-proof film has high moisture-proof properties, while the solvent in the adhesive coating liquid relatively easily permeates the moisture-proof film A and the solvent remains. Without volatilization from the surface to the outside of the laminated moisture-proof film, foaming due to heating can also be prevented.
- the moisture permeability of the moisture-proof film B is preferably 0.1 [g / m 2 ⁇ day] or less at 40 ° C. and 90% RH, more preferably 0.05 [g / m 2 ⁇ day] or less. More preferably, it is 0.03 [g / m 2 ⁇ day] or less, and particularly preferably 0.005 [g / m 2 ⁇ day] or less.
- the moisture-proof film B has a water vapor transmission rate (WTR (B)) of 0.001 [g / m 2 ⁇ day] or more and 0.1 [g / m 2 Less than day, preferably 0.001 [g / m 2 ⁇ day] or more, 0.05 [g / m 2 ⁇ day] or less, more preferably 0.001 [g / m 2 ⁇ day] or more, 0 0.02 [g / m 2 ⁇ day] or less.
- WTR (B) water vapor transmission rate
- an inorganic layer has high transparency, when it uses as a surface protection material, improvement in power generation efficiency can be achieved.
- the base material and the inorganic layer constituting the moisture-proof film B those mentioned in the description of the moisture-proof film A can be used.
- the anchor coat layer mentioned in the description of the moisture-proof film A can be preferably provided.
- the thickness of the inorganic layer is preferably 10 to 1000 nm, more preferably 40 to 1000 nm, still more preferably 40 to 800 nm, and particularly preferably 50 to 600 nm, from the viewpoint of high moisture-proof performance and transparency.
- the inorganic layer may be a single layer or multiple layers.
- the thickness of the substrate is generally about 5 to 100 ⁇ m, preferably 8 to 50 ⁇ m, more preferably 12 to 25 ⁇ m from the viewpoint of productivity and ease of handling.
- the thickness of the moisture-proof film B is generally about 5 to 100 ⁇ m, preferably 8 to 50 ⁇ m, more preferably 12 to 25 ⁇ m from the viewpoint of productivity and ease of handling.
- Adjustment of the water vapor transmission rate (WTR (B)) of the moisture-proof film B can be made by selecting the base material, selecting the material constituting the inorganic layer, the thickness of the inorganic layer, and the material constituting the inorganic layer being an inorganic oxide. This can be done by adjusting the oxidation number of the oxide, the thickness of the entire moisture-proof film B, and the like.
- the laminated moisture-proof film of the present invention has the moisture-proof film A and the moisture-proof film B, and has a water vapor transmission rate (WVTR (L)) at 40 ° C. and 90% RH of [WTR (A) ⁇ WTR. (B)] / [WTR (A) + WTR (B)] is preferable.
- WVTR (L) water vapor transmission rate
- the moisture-proof properties such as reinforcing defects on the surface of the inorganic layer, which is a factor that reduces the moisture-proof properties of the moisture-proof film in the adhesive used, are improved.
- the moisture-proof property of a laminated body is derived
- W water vapor transmission rate
- the laminated moisture-proof film can have a lower value and is extremely excellent in moisture-proof property. This means that the laminated moisture-proof film by the combination of the high moisture-proof film and the low moisture-proof film of the present invention has a significant moisture-proof improvement effect.
- the water vapor transmission rate (WVTR (L)) of the laminated moisture-proof film is preferably 80% or less of the value of W, more preferably 75% or less, and even more preferably 72% or less.
- the laminated moisture-proof film is preferable because of its excellent transparency.
- the moisture-proof film A and the moisture-proof film B are laminated.
- the moisture-proof film A is a film having an inorganic layer on one side of the substrate
- the viewpoint of maintaining long-term moisture-proof performance. Therefore, the inorganic layer side of one moisture-proof film and the base material surface of the other moisture-proof film are preferably laminated together.
- an adhesive layer is provided between the moisture-proof film A and the moisture-proof film B.
- a polyurethane-based adhesive is preferably used, and specific examples of the main agent of the adhesive include a polycarbonate polyol, a polyether polyol, an acrylic polyol, a polyurethane polyol, or a composition containing a polyester polyol. From the viewpoints of stability, humidity stability, etc., those containing at least one of polycarbonate polyol, polyether polyol, and polyurethane polyol are more preferable.
- the main agent of the adhesive preferably contains 20 to 70% by mass, more preferably 30 to 50% by mass of at least one selected from polycarbonate polyol, polyether polyol and polyurethane polyol.
- the said content means the total amount, when using together 2 or more types chosen from polycarbonate polyol, polyether polyol, and polyurethane polyol.
- the polycarbonate polyol can be obtained using, for example, diphenyl carbonate and diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol (NPG), and cyclohexanediol as raw materials.
- the polyether polyol can be obtained, for example, by performing ring-opening polymerization of alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran using an alkali catalyst or an acid catalyst as a catalyst.
- alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran
- an alkali catalyst or an acid catalyst as a catalyst.
- active hydrogen-containing compound serving as a starting material for the ring-opening polymerization
- polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol can be used.
- the polyacrylic polyol can be obtained by copolymerizing a (meth) acrylic acid ester having a hydroxyl group and another monomer.
- (meth) acrylic acid esters include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, methyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate having an alicyclic structure. Can be mentioned.
- Preferable examples include polyacryl polyols obtained by polymerizing monomers such as methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate having an alicyclic structure, and polyacryl polyols obtained by copolymerizing these monomers.
- the polyurethane polyol can be obtained by urethanizing diol and diisocyanate at a ratio of hydroxyl group to isocyanate group of 1 or more.
- a diol component or a diisocyanate component can be arbitrarily selected.
- the diol component and the diisocyanate component can be selected in consideration of the fluidity of the polyurethane polyol and the solubility in a solvent.
- the diol component is preferably a diol having a primary hydroxyl group such as propylene glycol, tetramethylene glycol, or neopentyl glycol.
- the isocyanate component include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic isocyanates.
- Polyester polyols include, for example, dicarboxylic acid compounds such as succinic acid, glutaric acid, adipic acid, isophthalic acid (IPA), terephthalic acid (TPA), and diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and cyclohexanediol. Or those composed of polytetramethylene glycol or the like.
- dicarboxylic acid compounds such as succinic acid, glutaric acid, adipic acid, isophthalic acid (IPA), terephthalic acid (TPA), and diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and cyclohexanediol. Or those composed of polytetramethylene glycol or the like.
- polyester polyol As a raw material is preferable in terms of high adhesion to a base material, but from the viewpoint of suppressing thermal deterioration due to hydrolysis of ester bonds, a polyester polyol having a small number of ester bond groups that can serve as hydrolysis points is used. It is desirable to choose. For example, it is desirable to have a glycol having a long alkyl chain such as neopentyl glycol (NPG) or a glycol having an alicyclic structure such as 1,4-cyclohexanedimethanol. Furthermore, it is desirable to select a hydrolysis-resistant polyester polyol having a polyether structure in the main chain structure such as polytetramethylene glycol (PTMG). In such a polyester polyol, the molecular weight per ester group is preferably 100 to 5,000, more preferably 120 to 3,000.
- NPG neopentyl glycol
- PTMG polytetramethylene glycol
- Diisocyanate is preferable as the curing agent used for the adhesive, for example, aliphatic type such as hexamethylene diisocyanate (HDI), aromatic type such as xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Examples include alicyclic systems such as dicyclohexylmethane diisocyanate (H12MDI).
- XDI which is an aromatic diisocyanate
- IPDI which is an alicyclic diisocyanate
- IPDI which is an alicyclic diisocyanate is more preferable.
- the main component contains polycarbonate polyol, it is excellent in terms of high heat resistance and high moisture resistance, but it is desirable to combine it as an HDI-based curing agent from the viewpoint that yellowing hardly occurs.
- a material containing an epoxy compound as a main component may be used.
- the moisture-proof film A and the moisture-proof film B are further combined with a weather-resistant film having excellent hydrolysis resistance and weather resistance, and a sealing material. It is preferable to provide a back film or the like that ensures adhesion and withstand voltage. Specifically, from the viewpoint of obtaining higher moisture resistance as a laminate, it is preferable to provide a weather-resistant film on the moisture-proof film B side, a back film or the like on the moisture-proof film A side, and weather resistance from the exposed side. It is preferable to laminate
- the present invention from the viewpoint of permeating the residual solvent from the laminate, it is preferable to provide a weather resistant film on the moisture-proof film A side and a back film on the moisture-proof film B side. It is also a preferable aspect to laminate the weather resistant film, the moisture-proof film A, the moisture-proof film B, and the back film in this order. Furthermore, in the present invention, from the viewpoint of ensuring the interlayer strength of the laminated moisture-proof film, the weather-resistant film and moisture-proof film A or B, and the moisture-proof film A or B and back film are each laminated via an adhesive layer. Preferably there is.
- the laminated moisture-proof film of the present invention depends on its use, it is preferably transparent when used in a solar cell or the like, but it can be used in combination with other non-transparent members.
- the weather-resistant film is not particularly limited as long as it has weather resistance.
- polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoro Fluorine resin films such as propylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF), or
- a resin composition obtained by mixing an ultraviolet absorber with a resin such as acrylic, polycarbonate, polyethylene terephthalate (PET), or polyethylene naphthalate (PEN) is preferably used.
- tetrafluoroethylene / ethylene copolymer (ETFE) and tetrafluoroethylene / hexafluoropropylene copolymer (FEP) are more preferably used as the resin.
- a low-shrinkage weathering substrate such as polyethylene naphthalate is preferred because the change in characteristics is preferably small even in temperature / humidity changes during vacuum lamination and high temperature and high humidity.
- a polyethylene terephthalate film or a fluorine-based film having a large shrinkage rate it is preferable to use a film that has been subjected to low shrinkage or the like by prior heat treatment.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- a film in which a layer containing an ultraviolet absorber is provided on a film obtained by forming a resin composition such as a polyester resin is preferably used.
- a film in which a layer containing an ultraviolet absorber is provided on a hydrolysis-resistant polyester film or a hydrolysis-resistant polyester film is preferably used.
- the ultraviolet absorber to be used those mentioned in the above description of the substrate can be used.
- the addition amount of the ultraviolet absorber is usually about 0.01 to 2.0% by mass, preferably 0.05 to 0.5% by mass in the weather resistant film.
- a hindered amine light stabilizer is suitably used as a weather stabilizer that imparts weather resistance in addition to the above ultraviolet absorber.
- the hindered amine light stabilizer those mentioned in the description of the base material can be used.
- the amount of the hindered amine light stabilizer added is usually about 0.01 to 0.5% by mass in the weather resistant film, and 0.05 to 0.3% by mass is preferably added.
- the thickness of the weather-resistant film is generally about 20 to 200 ⁇ m, preferably 20 to 100 ⁇ m, more preferably 20 to 50 ⁇ m from the viewpoint of film handling and cost.
- the back film is highly flexible and excellent in UV durability and humidification durability, and is mainly one of polypropylene, polylactic acid, and polyvinylidene fluoride.
- One containing at least two is preferable, and it is preferable that these resins are contained in total of 50% by mass or more.
- the thickness of the back film is generally about 25 to 300 ⁇ m, and is preferably 50 to 300 ⁇ m, more preferably 50 to 250 ⁇ m from the viewpoint of film handling and cost.
- the laminated moisture-proof film of the present invention can be used as a surface protection member for solar cells as it is or by being bonded to a glass plate or the like.
- the surface protective material of the present invention it may be produced by a known method.
- a solar cell module can be manufactured by using the surface protective material of the present invention for the layer structure of a surface protective member such as a solar cell upper protective material and a lower protective material, and fixing the solar cell element together with a sealing material.
- a surface protective member such as a solar cell upper protective material and a lower protective material
- fixing the solar cell element together with a sealing material e.g., a sealing material.
- Examples of such solar cell modules include various types.
- a solar cell element for example, a structure in which a sealing material and a lower protective material are formed on an amorphous solar cell element formed on a fluororesin protective material by sputtering or the like can be used.
- the above-mentioned sealing material may not be used.
- Examples of solar cell elements include single crystal silicon type, polycrystalline silicon type, amorphous silicon type power generation elements, III-V group and II-VI group compounds such as gallium-arsenide, copper-indium-selenium, and cadmium-tellurium.
- Examples thereof include a compound type power generation element such as a semiconductor type, a flexible type power generation element such as a dye sensitizing type and an organic thin film type.
- the members constituting the solar cell module produced using the surface protective material of the present invention are not particularly limited, but examples of the sealing material include an ethylene-vinyl acetate copolymer. Can do.
- the upper protective member and the lower protective member other than the surface protective member of the present invention are single layer or multilayer sheets such as inorganic materials such as metals and various thermoplastic resin films, for example, metals such as tin, aluminum, and stainless steel. Examples thereof include inorganic materials such as glass, polyester, inorganic vapor-deposited polyester, fluorine-containing resins, and single-layer or multilayer protective materials such as polyolefin.
- the surface of the upper and / or lower protective material can be subjected to a known surface treatment such as a primer treatment or a corona treatment in order to improve the adhesion to the sealing material or other members.
- an upper protective material surface protective material of the present invention
- sealing material sealing material / solar cell element / sealing material / lower protective material described above for a solar cell module produced using the surface protective material of the present invention
- the surface protective material, sealing resin layer, solar cell element, sealing resin layer, and lower protective material of the present invention are laminated in order from the sunlight receiving side, and a junction box (solar cell) is further formed on the lower surface of the lower protective material.
- a terminal box for connecting wiring for taking out electricity generated from the element to the outside is bonded.
- the solar cell elements are connected by wiring in order to conduct the generated current to the outside. The wiring is taken out through a through hole provided in the backsheet and connected to the junction box.
- the solar cell module As a manufacturing method of the solar cell module, a known manufacturing method can be applied, and it is not particularly limited, but in general, an upper protective material, a sealing material, a solar cell element, a sealing material, a lower protective material. And a step of vacuum-sucking them and heat-pressing them. Also, batch type manufacturing equipment, roll-to-roll type manufacturing equipment, and the like can be applied.
- the upper protective material, the sealing material, the solar cell element, the sealing material, and the lower protective material are preferably 130 to 180 ° C., more preferably 130 to 150 ° C. with a vacuum laminator according to a conventional method. It can be easily produced by heat and pressure bonding with a time of 2 to 15 minutes, a pressing pressure of 0.5 to 1 atm, and a pressing time of preferably 8 to 45 minutes, more preferably 10 to 40 minutes.
- the solar cell module produced using the surface protective material of the present invention is a small solar cell represented by a mobile device, a large solar cell installed on a roof or a roof, etc., depending on the type and module shape of the applied solar cell. It can be applied to various uses, both indoors and outdoors.
- Moisture-proof property of moisture-proof film and laminated moisture-proof film ⁇ Measurement of water vapor transmission rate: calculation from change in bag weight>
- the moisture-proof films a-1 to 5 and 7 the moisture-proof films D-1, D-2, D-4, D-5, D-
- JIS Z 0222 “Moisture permeability test method for moisture-proof packaging containers”
- JIS Z 0208 “Moisture permeability test method for moisture-proof packaging materials (cup method)” ”
- the following method was used for evaluation.
- Moisture-proof films a-1 to 5, 7 or laminated moisture-proof films D-1, D-2, D-4, D-5, D-7 to D-10 and D Using two sheets each of -13 to D-15, a bag was prepared in which about 20 g of anhydrous calcium chloride was added as a hygroscopic agent and the four sides were sealed so that the inorganic vapor-deposited surface was outside for all samples. Place it in a constant temperature and humidity device with a humidity of 90%, measure the mass until about 200 days at intervals of 72 hours or more, and determine the water vapor transmission rate (g / m from the slope of the regression line between the elapsed time after the fourth day and the bag weight. 2 ⁇ day) was calculated.
- differential pressure method water vapor transmission rate measurement was performed for films with water vapor transmission rate less than [0.01 g / m 2 ⁇ day] as measured from the change in bag weight. did.
- water vapor transmission rate was measured using a DELTAPERRM machine manufactured by Technolox.
- the apparatus sandwiches a laminate between an upper chamber and a lower chamber, detects water vapor transmission from the upper chamber of the humidity condition to the lower chamber of the vacuum condition by pressure change, and water vapor transmission rate [g / m 2 ⁇ day] Get.
- the calculation of water vapor transmission rate is based on the measured values at 40 RH and 90 RH% for the upper chamber and 40 RH for the lower chamber, and the measured values at 0 RH% for both the upper and lower chambers after 2 weeks from the start of measurement. Calculated by subtracting.
- PVDF polyvinylidene fluoride
- Moisture-proof film a-1 A moisture barrier film a-1 was obtained using a Mitsubishi Tech Tech Barrier P2 in which silica was deposited on a 12 ⁇ m polyethylene terephthalate resin film. Further, the moisture resistance measured by the above method was 0.610 [g / m 2 ⁇ day].
- Moisture-proof film a-2 A moisture barrier film a-2 was obtained using a Mitsubishi resin tech barrier TX in which silica was deposited on a 12 ⁇ m polyethylene terephthalate resin film. The moisture resistance measured by the above method was 0.400 [g / m 2 ⁇ day].
- Moisture-proof film a-3 A moisture barrier film a-3 was obtained using a Mitsubishi resin tech barrier LX in which silica was deposited on a 12 ⁇ m polyethylene terephthalate resin film. Moreover, the moisture resistance measured by the above-mentioned method was 0.200 [g / m 2 ⁇ day].
- Moisture-proof film a-6 Using a biaxially stretched polyethylene naphthalate film (made by Teijin DuPont, “Q51C12”) having a thickness of 12 ⁇ m as a substrate, using a vacuum evaporation apparatus, the SiO was evaporated under vacuum to form a 50 nm thick SiOx vacuum. A vapor deposition film (PVD inorganic layer) was formed. Next, a plasma chemical vapor deposition film (CVD inorganic layer) having a thickness of 3 nm was formed on the surface of the inorganic layer using HMDSN (hexamethyldisilazane) under a plasma in which argon gas was introduced.
- HMDSN hexamethyldisilazane
- SiO was evaporated on the plasma CVD inorganic layer under vacuum to form a 50-nm-thick SiOx PVD inorganic layer to obtain a moisture-proof film a-6.
- the moisture-proof performance of the moisture-proof film a-6 thus prepared was 0.0030 [g / m 2 ⁇ day].
- Moisture-proof film a-7 A 32-mm single-screw extruder equipped with a T-die containing an ethylene-norbornene random copolymer (manufactured by Polyplastics Co., Ltd., trade name: TOPAS 9506X1, norbornene content: 22 mol%) as a cyclic olefin polymer. It was melt-kneaded at a set temperature of 260 ° C. and rapidly cooled with a 20 ° C. cast roll to obtain a cyclic olefin moisture-proof film (COC) having a thickness of 0.5 mm. Moreover, the moisture-proof performance measured by the above-mentioned method was 0.500 [g / m 2 ⁇ day].
- COC cyclic olefin moisture-proof film
- Coating solution “GOHSENOL” manufactured by Nippon Gosei Co., Ltd. (degree of saponification: 97.0 to 98.8 mol%, degree of polymerization: 2400) was added to 2810 g of ion-exchanged water and added to an aqueous solution obtained by heating and dissolving. While stirring at 0 ° C., 645 g of 35% hydrochloric acid was added. Subsequently, 3.6 g of butyraldehyde was added with stirring at 10 ° C., and after 5 minutes, 143 g of acetaldehyde was added dropwise with stirring to precipitate resin fine particles.
- H62 manufactured by Rock Paint Co., Ltd. is used as a curing agent containing an aliphatic hexamethylene diisocyanate component, resulting in a mass ratio of 10: 1.
- this adhesive coating solution After applying this adhesive coating solution to a 50 ⁇ m PET film, it is bonded to the moisture-proof films a-1 to a-7, cured and measured for water vapor transmission rate, and the moisture-proof property to the moisture-proof films a-1 to a-7 is used as the adhesive. It was confirmed that there was no improvement effect.
- Example 1 The weather-resistant film 1 is coated and dried with an adhesive coating solution so that the solid content is 6 g / m 2 , the moisture-proof film a-4 is used as the moisture-proof film B, and the inorganic layer of the moisture-proof film a-4 is directed to the adhesive surface. And then laminated by dry lamination. Thereafter, the adhesive coating liquid is applied and dried on the substrate side of the moisture-proof film a-4 of the laminated film so as to have a solid content of 6 g / m 2, and the moisture-proof film a-1 is used as the moisture-proof film A.
- the surface of 1 inorganic layer was bonded and cured at 40 ° C. for 5 days to prepare a laminated moisture-proof film D-1 having a thickness of 66 ⁇ m, and the moisture resistance, foamability and haze change were measured and evaluated. The results are shown in Table 2.
- Example 2 A laminated moisture-proof film D-2 having a thickness of 66 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-2 was used as the moisture-proof film A, and the moisture resistance, foamability, and haze change were measured and evaluated. The results are shown in Table 2.
- Example 3 A laminated moisture-proof film D-3 having a thickness of 66 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-3 was used as the moisture-proof film A, and the moisture resistance, foamability, and haze change were measured and evaluated. The results are shown in Table 2.
- Example 4 In Example 3, the moisture-proof film on the weather resistant film side was replaced. That is, the adhesive coating liquid is applied to the weather resistant film 1 and dried so as to have a solid content of 6 g / m 2 , the moisture-proof film a-3 is used as the moisture-proof film A, and the inorganic layer of the moisture-proof film a-3 is used as the adhesive surface. It stuck together by the dry laminate. Thereafter, the adhesive coating liquid is applied and dried on the substrate side of the moisture-proof film a-3 of the laminated film so as to have a solid content of 6 g / m 2, and the moisture-proof film a-4 is used as the moisture-proof film B. Then, the inorganic layer surface of No.
- Example 5 A laminated moisture-proof film D-5 having a thickness of 66 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-2 was used as the moisture-proof film A and the moisture-proof film a-5 was used as the moisture-proof film B. And the degree of change in haze were measured and evaluated. The results are shown in Table 2.
- Example 6 A laminated moisture-proof film D-6 having a thickness of 66 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-3 was used as the moisture-proof film A and the moisture-proof film a-6 was used as the moisture-proof film B. And the degree of change in haze were measured and evaluated. The results are shown in Table 2.
- Example 7 A laminated moisture-proof film D-7 having a thickness of 554 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-7 was used as the moisture-proof film A, and the moisture resistance, foamability and haze change were measured and evaluated. The results are shown in Table 2.
- Example 8 In Example 7, the moisture-proof film on the weather resistant film side was replaced. That is, the adhesive coating solution is applied to the weather resistant film 1 and dried so as to have a solid content of 6 g / m 2 , the moisture-proof film a-7 is used as the moisture-proof film A, and the inorganic layer of the moisture-proof film a-7 is used as the adhesive surface. It stuck together by the dry laminate. Thereafter, the adhesive coating liquid is applied and dried on the base material side of the moisture-proof film a-7 of the laminated film so as to have a solid content of 6 g / m 2, and the moisture-proof film a-4 is used as the moisture-proof film B. 4 were laminated and cured at 40 ° C. for 5 days to prepare a laminated moisture-proof film D-8 having a thickness of 554 ⁇ m, and the moisture resistance, foamability and haze change were measured and evaluated. The results are shown in Table 2.
- Comparative Example 1 A laminated moisture-proof film D-9 having a thickness of 66 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-3 was used for both the moisture-proof film A and the moisture-proof film B. Were measured and evaluated. The results are shown in Table 2.
- Comparative Example 2 A laminated moisture-proof film D-10 having a thickness of 66 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-3 was used as the moisture-proof film B and the moisture-proof film a-2 was used as the moisture-proof film A. And the degree of change in haze were measured and evaluated. The results are shown in Table 2.
- Comparative Example 3 A laminated moisture-proof film D-11 having a thickness of 66 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-4 was used for both the moisture-proof film A and the moisture-proof film B. Were measured and evaluated. The results are shown in Table 2.
- Comparative Example 4 A laminated moisture-proof film D-12 having a thickness of 66 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-6 was used as the moisture-proof film B and the moisture-proof film a-4 was used as the moisture-proof film A. And the degree of change in haze were measured and evaluated. The results are shown in Table 2.
- Comparative Example 5 A laminated moisture-proof film D-13 having a thickness of 554 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-3 was used as the moisture-proof film B and the moisture-proof film a-7 was used as the moisture-proof film A. And the degree of change in haze were measured and evaluated. The results are shown in Table 2.
- Comparative Example 6 A laminated moisture-proof film D-14 having a thickness of 554 ⁇ m was prepared in the same manner as in Example 1 except that the moisture-proof film a-2 was used as the moisture-proof film B and the moisture-proof film a-7 was used as the moisture-proof film A. And the degree of change in haze were measured and evaluated. The results are shown in Table 2.
- Comparative Example 7 In Comparative Example 5, the moisture-proof film on the weather resistant film side was replaced. That is, the adhesive coating solution is applied to the weather resistant film 1 and dried so as to have a solid content of 6 g / m 2 , the moisture-proof film a-7 is used as the moisture-proof film A, and the inorganic layer of the moisture-proof film a-7 is used as the adhesive surface. It stuck together by the dry laminate. Thereafter, the adhesive coating liquid is applied and dried on the base material side of the moisture-proof film a-7 of the laminated film so as to have a solid content of 6 g / m 2, and the moisture-proof film a-3 is used as the moisture-proof film B. 3 inorganic layers were bonded and cured at 40 ° C. for 5 days to produce a laminated moisture-proof film D-15 having a thickness of 554 ⁇ m, and the moisture resistance, foamability and haze change were measured and evaluated. The results are shown in Table 2.
- Examples 1 to 8 relating to the laminated moisture-proof films D-1 to D-8 in which the water vapor transmission rates of the moisture-proof film A and the moisture-proof film B are within the specified range of the present invention are all excellent in moisture resistance and prevention of bubble generation.
- the haze did not deteriorate and was excellent in transparency.
- Comparative Examples 1, 2, and 5 to 7 in which the water vapor transmission rate of the moisture proof film corresponding to the moisture proof film B is outside the range defined in the present invention, generation of bubbles was suppressed, but the laminated moisture proof film was 40 ° C.,
- the water vapor transmission rate (WTR (L)) at 90% RH showed the same degree of moisture resistance as the theoretically derived value W.
- Comparative Example 3 in which the moisture-proof film corresponding to each of the moisture-proof film A and the moisture-proof film B has the same low water vapor transmission rate
- Comparative Example 4 in which each water-proof film has a low water vapor transmission rate are the laminated moisture-proof films obtained. Although the moisture resistance of the film was good, bubbles remained.
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Abstract
Description
これらの用途において、積層防湿フィルムには、より厳しい性能が求められるようになり、長期使用や高温条件下における防湿性の劣化が少ない優れた積層防湿フィルムの開発がなされてきた。
また、特許文献2、3には、無機酸化物が樹脂のシートに蒸着された防湿フィルムを複数有する積層シートが提案されており、特許文献2では、一方の表面に金属酸化物の蒸着膜を有する第1蒸着樹脂層と、中間樹脂層と、一方の表面に金属酸化物の蒸着膜を有する第2蒸着樹脂層とがドライラミネート加工により積層された太陽電池モジュール用裏面保護シートであって、前記第1蒸着樹脂層及び前記第2蒸着樹脂層の蒸着膜が前記中間樹脂層側に配置される太陽電池モジュール用裏面保護シートが開示されている。更に、特許文献3では、一方の表面に金属酸化物の蒸着膜を有する蒸着樹脂層の少なくとも3層を順次ドライラミネート加工により積層し、前記蒸着樹脂層は、それぞれ40℃、90%RHにおける水蒸気透過度が0.03~0.5[g/m2・日]である太陽電池モジュール用裏面保護シートの製造方法が開示されている。
また、特許文献4は、非吸湿性樹脂層の少なくとも片面に無機酸化物若しくは金属の蒸着膜が形成された複合フィルムを2枚以上含有し、該複合フィルムの蒸着膜面が、接着剤層を介して、他の複合フィルムの蒸着膜面と積層された層構成を1~4の範囲内で含有する防湿性多層フィルムが開示されている。
(1)40℃、90%RHにおける水蒸気透過率(WTR(A))が1.0[g/m2・日]以下である防湿フィルムA、及び基材の片面に無機層を有し、40℃、90%RHにおける水蒸気透過率(WTR(B))が前記防湿フィルムAの水蒸気透過率(WTR(A))の10%以下である防湿フィルムBが接着剤層を介して積層された構成を有することを特徴とする積層防湿フィルム、
(2)40℃、90%RHにおける水蒸気透過率(WTR(A))が0.1[g/m2・日]以上、1.0[g/m2・日]以下である防湿フィルムA、及び基材の片面に無機層を有し、40℃、90%RHにおける水蒸気透過率(WTR(B))が0.001[g/m2・日]以上、0.1[g/m2・日]未満である防湿フィルムBが、接着剤層を介して積層された構成を有することを特徴とする積層防湿フィルム、
(3)40℃、90%RHにおける積層防湿フィルムの水蒸気透過率(WVTR(L))が、[WTR(A)×WTR(B)]/[WTR(A)+WTR(B)]より低い値であることを特徴とする上記(1)または(2)のいずれかに記載の積層防湿フィルム、
(5)防湿フィルムAの40℃、90%RHにおける水蒸気透過率(WTR(A))が0.1 [g/m2・日]以上であることを特徴とする上記(1)、(3)または(4)のいずれかに記載の積層防湿フィルム、
(6)防湿フィルムAの40℃、90%RHにおける水蒸気透過率(WTR(A))が0.2 [g/m2・日]以上であることを特徴とする上記(1)~(5)のいずれかに記載の積層防湿フィルム、
(7)防湿フィルムAの40℃、90%RHにおける水蒸気透過率(WTR(A))が0.4[g/m2・日]以上であることを特徴とする上記(1)~(6)のいずれかに記載の積層防湿フィルム、
(8)防湿フィルムAの40℃、90%RHにおける水蒸気透過率(WTR(A))が0.6[g/m2・日]以上であることを特徴とする上記(1)~(7)のいずれかに記載の積層防湿フィルム、
(10)防湿フィルムBの40℃、90%RHにおける水蒸気透過率(WTR(B))が0.001[g/m2・日]以上、0.05[g/m2・日]以下であることを特徴とする上記(1)~(9)のいずれかに記載の積層防湿フィルム、
(11)防湿フィルムAが環状オレフィン系重合体を含む樹脂組成物からなる層を少なくとも一層有するフィルムであることを特徴とする上記(1)~(10)のいずれかに記載の積層防湿フィルム、
(12)防湿フィルムAが基材の片面に無機層を有するフィルムであることを特徴とする上記(1)~(10)のいずれかに記載の積層防湿フィルム、
(13)耐候性フィルム、防湿フィルムB及び防湿フィルムAを曝露側からこの順に有し、かつ防湿フィルムAの無機層側に防湿フィルムBの基材を有することを特徴とする上記(12)に記載の積層防湿フィルム、
(15)接着剤層が接着剤からなり、かつ該接着剤が主剤としてポリカーボネートポリオール、ポリエーテルポリオール、アクリルポリオール、ポリウレタンポリオール及びポリエステルポリオールのうち少なくとも1種を含むことを特徴とする上記(1)~(14)のいずれかに記載の積層防湿フィルム、
(16)太陽電池用表面保護部材に用いられる上記(1)~(15)のいずれかに記載の積層防湿フィルム、
(17)化合物系発電素子太陽電池モジュール又はフレキシブル太陽電池モジュールの表面保護部材に用いられる上記(1)~(16)のいずれかに記載の積層防湿フィルム、
(18)上記(1)~(17)のいずれかに記載の積層防湿フィルムを有することを特徴とする太陽電池用表面保護部材、
(20)上記(18)または(19)に記載の太陽電池用表面保護材を用いて作製された太陽電池モジュール、
に関する。
一般に、積層防湿フィルムはドライラミネート加工等により作成される。無機層を有する防湿フィルムと樹脂フィルムとのドライラミネート加工では、樹脂フィルムに溶剤を用いて希釈した接着剤を所定の厚みに塗布し、例えば100℃から140℃の範囲での乾燥により溶剤を蒸発させ樹脂フィルム上に接着剤層を形成する。その後、防湿フィルムの無機層面を接着剤側に向けて貼合し、所定の温度での養生を経て積層防湿フィルムが製造される。養生は、例えば30℃から80℃の範囲で1日から1週間行なわれる。
通常、高防湿フィルム同士をドライラミネート加工する場合、ドライラミネート加工時に接着剤塗液に含まれている溶剤は、高防湿フィルムの高防湿性の故に、積層フィルム内において内側から外側への拡散、及び表面からの揮発が困難であり、積層フィルム間に残留し、また、加熱により発泡が顕著となる。
これは、上記の構成とすることにより、接着剤塗液中の溶剤が比較的容易に低防湿性のフィルムを透過し、積層防湿フィルムの外へ揮発し、溶剤が残留しないためと考えられる。
一方、比較的低防湿性の防湿フィルムを外層とする場合も同様に該比較的低防湿性の防湿フィルムにより積層防湿フィルムへの水蒸気の進入がある程度抑制され、内面側の高防湿性の防湿フィルムの無機層面においては水蒸気透過率の測定環境と比べ低湿度状態が形成される。この低湿度状態は高防湿性の防湿フィルムの無機層面への水分吸着を著しく減少させ、その結果,高防湿性の防湿フィルムの水分の透過がより減少し、該防湿フィルムの防湿性が上昇することとなり、防湿性に優れた積層防湿フィルムが得られる。
本発明の積層防湿フィルムは、40℃、90%RHにおける水蒸気透過率(WTR(A))が1.0[g/m2・日]以下である防湿フィルムA、及び基材の片面に無機層を有し、40℃、90%RHにおける水蒸気透過率(WTR(B))が前記防湿フィルムAの値の10%以下である防湿フィルムBを有する積層防湿フィルムであって、前記防湿フィルムA及び防湿フィルムBが、接着剤層を介して積層した構成を有することを特徴とする。
また、本出願のもう一つの発明である積層防湿フィルムは、40℃、90%RHにおける水蒸気透過率(WTR(A))が0.1[g/m2・日]以上、1.0[g/m2・日]以下である防湿フィルムA、及び基材の片面に無機層を有し、40℃、90%RHにおける水蒸気透過率(WTR(B))が0.001[g/m2・日]以上、0.1 [g/m2・日]未満である防湿フィルムBが、接着剤層を介して積層された構成を有することを特徴とする。
以下、各構成層について説明する。
本発明の積層防湿フィルムにおける防湿フィルムAは、40℃、90%RHにおける水蒸気透過率(WTR(A))が1.0[g/m2・日]以下である。本発明における、防湿フィルムA及び防湿フィルムBの組み合わせにおいて、接着剤塗液中の溶剤が残留しないためには、防湿フィルムAの水蒸気透過率(WTR(A))は、40℃、90%RHで好ましくは0.1[g/m2・日]以上であり、より好ましくは0.2[g/m2・日]以上であり、更に好ましくは0.4[g/m2・日]以上であり、特に好ましくは0.6[g/m2・日]以上である。防湿フィルムAの水蒸気透過率(WTR(A))が上記の範囲であれば、積層防湿フィルムの防湿性が高い場合であっても、溶剤が防湿フィルムAを透過することが容易であり加熱による発泡がおき難い。
このような防湿フィルムAとしては、防湿性の樹脂フィルムや、基材の片面に無機層を有するフィルムが挙げられる。
防湿性の樹脂フィルムとしては、環状オレフィン系重合体を含む樹脂組成物からなる層を少なくとも1層有するフィルムが挙げられる(以下、「環状オレフィン系重合体防湿フィルム」ということがある。)。該層中の環状オレフィン系重合体の含有量は50~100質量%であるのが好ましい。
(A):直鎖状オレフィン成分と環状オレフィン成分とからなる環状オレフィン系ランダム共重合体
(B):環状オレフィン成分からなる開環重合体もしくはその水素化物
(C):(A)と(B)との混合物
ここで、環状オレフィン成分の例としては、ビシクロヘプト-2-エン(2-ノルボルネン)及びその誘導体、例えば、ノルボルネン、6-メチルノルボルネン、6-エチルノルボルネン、6-n-ブチルノルボルネン、5-プロピルノルボルネン、1-メチルノルボルネン、7-メチルノルボルネン、5,6-ジメチルノルボルネン、5-フェニルノルボルネン、5-ベンジルノルボルネン等を挙げることができる。
環状オレフィン系重合体としては、例えばJSR株式会社製アートン(商品名)、日本ゼオン株式会社製ゼオネックス(商品名)等の市販品を使用することもできる。
環状オレフィン系重合体は一般的に耐熱性があり、透明性が高く、また環状オレフィン系重合体を含む樹脂組成物からなるフィルムは単位面積あたりの水蒸気透過率が低く、水蒸気バリア性に優れている。
使用する紫外線吸収剤としては、種々の市販品が適用でき、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系、サリチル酸エステル系など各種タイプのものを挙げることができる。ベンゾフェノン系紫外線吸収剤としては、例えば、2-ヒドロキシ-4-メトキシベンゾフェノン、2-ヒドロキシ-4-メトキシ-2'-カルボキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノン、2-ヒドロキシ-4-n-ドデシルオキシベンゾフェノン、2-ヒドロキシ-4-n-オクタデシルオキシベンゾフェノン、2-ヒドロキシ-4-ベンジルオキシベンゾフェノン、2-ヒドロキシ-4-メトキシ-5-スルホベンゾフェノン、2-ヒドロキシ-5- クロロベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2,2'-ジヒドロキシ-4-メトキシベンゾフェノン、2,2'-ジヒドロキシ-4、4'-ジメトキシベンゾフェノン、2,2'、4,4'-テトラヒドロキシベンゾフェノンなどを挙げることができる。
上記の紫外線吸収剤以外に耐候性を付与する耐候安定剤としては、ヒンダードアミン系光安定化剤が好適に用いられる。ヒンダードアミン系光安定化剤は、紫外線吸収剤のようには紫外線を吸収しないが、紫外線吸収剤と併用することによって著しい相乗効果を示す。
また、1種以上の樹脂フィルムが積層されたものであってもよい。
かかる基材は、従来公知の方法により製造することができ、例えば、原料樹脂を押出機により溶融し、環状ダイやTダイにより押出して、急冷することにより実質的に無定型で配向していない未延伸フィルムを製造することができる。また、多層ダイを用いることにより、1種の樹脂からなる単層フィルム、1種の樹脂からなる多層フィルム、多種の樹脂からなる多層フィルム等を製造することができる。
上記基材の厚さは、一般に5~100μm程度であり、生産性や取り扱いやすさの点から8~50μmが好ましく、12~25μmが更に好ましい。
紫外線吸収剤及び耐候安定剤としては、前述の基材の説明において挙げたものが使用できる。該紫外線吸収剤及び/または耐候安定剤が前記した樹脂と共重合したポリマータイプのものも使用することもできる。
アンカーコート層の厚みは無機層との密着性の観点から、10~200nmであることが好ましく、10~100nmであることがより好ましい。
上記基材の片面に無機層を有する防湿フィルムの厚さは、一般に5~100μm程度であり、生産性や取り扱いやすさの点から8~50μmが好ましく、12~25μmが更に好ましい。
防湿フィルムAの防湿性は防湿フィルムA内の水分拡散の大小と防湿フィルムA表裏両側の水分濃度差により決定される。本発明では高い防湿性をもった防湿フィルムBを曝露側に配置する場合、内面側へ透過する水分を抑制し、防湿フィルムA表裏間での水分濃度差を低減することにより防湿フィルムAの防湿性を向上させることができる。また、防湿フィルムAを曝露側に配置する場合、内面側へ透過する水分を抑制し、防湿フィルムBの表裏間での水分濃度差を低減することにより防湿フィルムBの防湿性をより向上させることができる。
本発明において、防湿フィルムBは、基材の片面に無機層を有し、40℃、90%RHにおける水蒸気透過率(WTR(B))が前記防湿フィルムAの値の10%以下であるものであり、好ましくは5%以下であり、より好ましく3%以下である。上記比率を10%以下とすることで、得られる積層防湿フィルムは、高い防湿性を有し、一方で接着剤塗液中の溶剤は比較的容易に防湿フィルムAを透過し、溶剤が残留せず表面から積層防湿フィルム外へ揮発し、加熱による発泡も防止できる。
更に防湿フィルムBの水蒸気透過率は、40℃、90%RHで0.1[g/m2・日]以下であるのが好ましく、より好ましくは0.05[g/m2・日]以下、更に好ましくは0.03[g/m2・日]以下、特に好ましくは0.005[g/m2・日]以下である。
前記無機層により、湿気の透過による太陽電池の内面側を保護することができる。また、無機層が高い透明性を有する場合は、表面保護材として用いた際、発電効率の向上を達成できる。
防湿フィルムBを構成する基材、無機層としては、前記防湿フィルムAの説明において挙げたものが使用できる。更には、好ましくは前記防湿フィルムAの説明において挙げたアンカーコート層を設けることができる。
また、上記基材の厚さは、一般に5~100μm程度であり、生産性や取り扱いやすさの点から8~50μmが好ましく、12~25μmが更に好ましい。従って、上記防湿フィルムBの厚さは、一般に5~100μm程度であり、生産性や取り扱いやすさの点から8~50μmが好ましく、12~25μmが更に好ましい。
本発明の積層防湿フィルムは、前記防湿フィルムA及び前記防湿フィルムBを有するものであるが、その40℃、90%RHにおける水蒸気透過率(WVTR(L))が、[WTR(A)×WTR(B)]/[WTR(A)+WTR(B)]より低い値であることが好ましい。
接着剤を用いて複数の防湿フィルムを積層した積層防湿フィルムにおいて、使用する接着剤に防湿フィルムの防湿性を低下させている要因である無機層表面内の欠陥を補強するなどの防湿性を向上させる効果がない場合、積層体の防湿性は各々の防湿フィルムの防湿性への寄与から直列的に導き出されると考えられる。すなわち、得られる積層防湿フィルムの40℃、90%RHにおける水蒸気透過率(W)は、1/W=1/WTR(A)+1/WTR(B) と表され、W=[WTR(A)×WTR(B)]/[WTR(A)+WTR(B)]として理論的に求めることができる。
上記観点から、積層防湿フィルムの水蒸気透過率(WVTR(L))は、上記Wの値の80%以下が好ましく、より好ましくは75%以下、さらに好ましくは72%以下である
更に、実施例記載の方法により求めた積層防湿フィルムの初期ヘイズ値が30以下であり、かつヘイズの変化度が1~2であると、積層防湿フィルムが透明性に優れるため好ましい。
また、本発明の積層防湿フィルムにおいては、上記防湿フィルムAと防湿フィルムBの間に接着剤層を有する。
ポリカーボネートポリオールは、例えば、ジフェニルカーボネートと、エチレングリコール、プロピレングリコール、ブタンジオール、ネオペンチルグリコール(NPG)、シクロヘキサンジオール等のジオールとを原料として得ることができる。
ジオール成分、ジイソシアネート成分は、ポリウレタンポリオールの流動性や溶剤への溶解性等を考慮して選択することができる。ジオール成分として好ましくは、プロピレングリコール、テトラメチレングリコール、ネオペンチルグリコール等の1級水酸基を有するジオールが挙げられる。また、イソシアネート成分としては、脂肪族ジイソシアネート、脂環系ジイソシアネート、芳香族イソシアネートが挙げられる。
更に、例えばポリテトラメチレングリコール(PTMG)のように主鎖構造にポリエーテル構造を含む、耐加水分解ポリエステルポリオールを選択することが望ましい。このようなポリエステルポリオールとしては、エステル基1個当たりの分子量が、好ましくは100~5,000、より好ましくは120~3,000である。
硬化後に高い耐熱性をもたせる硬化剤として、例えば芳香族系ジイソシアネートであるXDI、及び脂環系ジイソシアネートであるIPDI等が好ましい。更に、接着剤の黄変を防ぐためには脂環系ジイソシアネートであるIPDI等がより好ましい。
また、より熱的に安定な接着剤層を得るために、主剤にエポキシ系化合物を含んだものを用いてもよい。
本発明における接着剤の主剤と硬化剤の好ましい配合比は、接着剤中に残留する反応性官能基を減らす観点から、質量比で、主剤/硬化剤=5~25、また官能基のモル比で、NCO/OH=0.8~9である。
本発明の積層防湿フィルムは、その用途にもよるが、太陽電池などに使用する場合は透明であることが好ましいが、他の非透明部材との併用も任意である。
前記耐候性フィルムは、耐候性を有するものであれば特に限定されないが、例えば、ポリテトラフルオロエチレン(PTFE)、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体(PFA)、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体(FEP)、テトラフルオロエチレン・エチレン共重合体(ETFE)、ポリクロロトリフルオロエチレン(PCTFE)、ポリビニリデンフルオライド(PVDF)及びポリビニルフルオライド(PVF)等のフッ素樹脂フィルム、或いは、アクリル、ポリカーボネート、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)等の樹脂に紫外線吸収剤を混合した樹脂組成物を製膜したものが好ましく用いられる。
真空ラミネーション時や高温高湿時の温度・湿度変化においてもその特性変化が小さいことが好ましいことから、ポリエチレンナフタレートなどの低収縮性耐候基材が好ましい。また、収縮率が大きいポリエチレンテレフタレートフィルムやフッ素系フィルムの場合は、事前の熱処理による低収縮化等が行われたフィルムを使用することが好ましい。
また、太陽電池保護材への使用を考えると可撓性に富み、耐熱性、防湿性、紫外線耐久性に優れる性能を有する耐候性フィルムであることが望ましく、フッ素系フィルムや紫外線吸収剤を含有する耐加水分解性ポリエステルフィルムや耐加水分解性ポリエステルフィルムに紫外線吸収剤を含有する層を設けたフィルムが好ましく用いられる。
該紫外線吸収剤の添加量は、耐候性フィルム中、通常、0.01~2.0質量%程度であり、0.05~0.5質量%添加することが好ましい。
上記の紫外線吸収剤以外に耐候性を付与する耐候安定剤としては、ヒンダードアミン系光安定化剤が好適に用いられる。ヒンダードアミン系光安定化剤としては、前述の基材の説明において挙げたものが使用できる。該ヒンダードアミン系光安定化剤の添加量は、耐候性フィルム中、通常、0.01~0.5質量%程度であり、0.05~0.3質量%添加することが好ましい。
太陽電池は発電時の発熱や太陽光の輻射熱などで、その使用温度が85~90℃程度まで昇温する為、該背面フィルムの融点が使用温度以下であると背面フィルムは軟化し動作中に本来の太陽電池素子を保護する機能が失われる。従って背面フィルムとしては、ポリプロピレン(PP)、ポリ乳酸(PLA)、ポリフッ化ビニル(PVF)、ポリフッ化ビニリデン(PVDF)、酪酢酸セルロース(CAB)などの樹脂に紫外線吸収剤や着色剤を練り込んだ樹脂組成物を成膜したものが好ましく用いられるが、これらに限定されるものではない。
背面フィルムの厚さは、一般に25~300μm程度であり、フィルムの取り扱いやすさとコストの点から好ましくは50~300μm、より好ましくは50~250μmである。
本発明の積層防湿フィルムは、そのまま、あるいはガラス板等と貼り合わせて太陽電池用表面保護部材として用いることができる。本発明の表面保護材を用いて本発明の太陽電池モジュール及び/又は太陽電池を製造するには、公知の方法により、作成すれば良い。
(1)防湿フィルム及び積層防湿フィルムの防湿性
<水蒸気透過率測定:袋重量変化からの算出>
防湿フィルムa-1~5、7については、防湿フィルム作成後、一週間40℃保管後の時点で、また、積層防湿フィルムD-1、D-2、D-4、D-5、D-7~D-10及びD-13~D-15については、ドライラミネート養生後にJIS Z 0222「防湿包装容器の透湿度試験方法」、JIS Z 0208「防湿包装材料の透湿度試験方法(カップ法)」の諸条件を参照し、次の手法で評価した。
透湿面積10.0cm×10.0cm角の防湿フィルムa-1~5、7又は積層防湿フィルムD-1、D-2、D-4、D-5、D-7~D-10及びD-13~D-15をそれぞれ2枚用い、全てのサンプルに関して無機蒸着面を外側となるよう吸湿剤として無水塩化カルシウム約20gを入れ四辺を封じた袋を作製し、その袋を温度40℃相対湿度90%の恒温恒湿装置に入れ、72時間以上の間隔でおよそ200日目まで質量測定し、4日目以降の経過時間と袋重量との回帰直線の傾きから水蒸気透過率(g/m2・日)を算出した。
太陽電池モジュールに供したガスバリアフィルムのうち、袋重量変化からの算出による水蒸気透過率測定で水蒸気透過率が[0.01g/m2・日]未満のフィルムについて、差圧法水蒸気透過率測定を実施した。
防湿フィルムa-6については、防湿フィルム作成後、一週間40℃保管後の時点で、また、積層防湿フィルムD-3、D-6、D-11、D-12については、ドライラミネート養生後にTechnolox社製DELTAPERM機を用いて水蒸気透過率を測定した。該装置は、上室と下室の間に積層体を挟み、湿度条件の上室から真空条件の下室への水蒸気透過を圧力変化で検出し、水蒸気透過率[g/m2・日]を得る。水蒸気透過率の算出は、測定開始から2週間経過以後において、上室40℃90RH%及び下室40℃0RH%での測定値から、上室及び下室とも40℃0RH%での測定値を差し引いて求めた。
積層防湿フィルムD-1~D-15を10.0cm×10.0cm角切り出し150℃オーブンに30分保持し耐候性フィルム側と反対の面より目視にて発泡の有無を確認した
◎:10.0cm×10.0cm角サンプル全面に発泡が認められないもの
○:10.0cm×10.0cm角サンプルの一部に発泡が認められるもの
×:10.0cm×10.0cm角サンプルの全面に発泡が認められるもの
積層防湿フィルムD-1~D-15を15.0cm×15.0cm角切り出し、150℃、30分の熱処理後に、JIS-K7136に準じ、積層防湿フィルムのヘイズ値を測定した(初期ヘイズ値)。なお、ヘイズ値測定は日本電色工業社製ヘイズメーターNDH2000を用いた。
さらに、切り出した上記熱処理後の積層防湿フィルムD-1~D-15をJIS C 60068-2-66に準じ、加速試験であるプレッシャークッカー試験(120℃、湿度100%で32時間(PC32))を行ない、その後ヘイズ値を測定した。なお、プレッシャークッカー試験はトミー精工社製プレッシャークッカー試験LSK-500を用いた。
ヘイズの変化度は、[プレッシャークッカー試験(PC32)後のヘイズ値/初期ヘイズ値]により算出した。なお、プレッシャークッカー試験(PC32)前後で気泡が発生しない場合は、ヘイズの変化がないためヘイズの変化度は1となる。
<耐候性フィルム1>
アルケマ社製ポリフッ化ビニリデン(PVDF)系フィルムKynar 302-PGM-TR(厚み:30μm)を使用した。
防湿フィルムa-1
12μmポリエチレンテレフタレート樹脂フィルムにシリカを蒸着した三菱樹脂製テックバリアP2を使用して防湿フィルムa-1とした。また上述の方法で測定した防湿性は0.610[g/m2・日]であった。
12μmポリエチレンテレフタレート樹脂フィルムにシリカを蒸着した三菱樹脂製テックバリアTXを使用して防湿フィルムa-2とした。また上述の方法で測定した防湿性は0.400[g/m2・日]であった。
12μmポリエチレンテレフタレート樹脂フィルムにシリカを蒸着した三菱樹脂製テックバリアLXを使用して防湿フィルムa-3とした。また上述の方法で測定した防湿性は0.200[g/m2・日]であった。
基材として、厚さ12μmの二軸延伸ポリエチレンナフタレートフィルム(帝人デュポン製、「Q51C12」)を用い、そのコロナ処理面に、下記のコート液を塗布乾燥して厚さ0.1μmのコート層を形成した。
次いで、真空蒸着装置を使用して1.33×10-3Pa(1×10-5Torr)の真空下でSiOを加熱蒸発させ、コート層上に厚さ40nmのSiOx(x=1.5)無機層を有する防湿フィルムa-4を得た。作成した防湿フィルムa-4の防湿性能は0.015[g/m2・日]であった。
基材として、厚さ12μmの二軸延伸ポリエチレンナフタレートフィルム(帝人デュポン製、「Q51C12」)を用い、そのコロナ処理面に、下記のコート液を塗布乾燥して厚さ0.1μmのコート層を形成した。
次いで、真空蒸着装置を使用して1.33×10-3Pa(1×10-5Torr)の真空下でSiOを加熱蒸発させ、コート層上に厚さ15nmのSiOx(x=1.5)無機層を有する防湿フィルムa-5を得た。作成した防湿フィルムa-5の防湿性能は0.040[g/m2・日]であった。
基材として、厚さ12μmの二軸延伸ポリエチレンナフタレートフィルム(帝人デュポン製、「Q51C12」)を用い、真空蒸着装置を使用して、真空下でSiOを蒸発させ、厚さ50nmのSiOxの真空蒸着膜(PVD無機層)を形成した。次いで、アルゴンガスを導入したプラズマ下で、HMDSN(ヘキサメチルジシラザン)を用い、無機層面上に厚さ3nmのプラズマ化学蒸着膜(CVD無機層)を形成した。次いで、プラズマCVD無機層上に、真空下でSiOを蒸発させ、厚さ50nmのSiOxのPVD無機層を形成し防湿フィルムa-6とした。
作成した防湿フィルムa-6の防湿性能は0.0030[g/m2・日]であった。
環状オレフィン系重合体として、エチレン-ノルボルネンランダム共重合体(ポリプラスチックス(株)社製、商品名:TOPAS 9506X1、ノルボルネン含有量:22モル%)をTダイを備えた32mm単軸押出機を用いて設定温度260℃で溶融混練し、20℃のキャストロールで急冷製膜することにより厚みが0.5mmの環状オレフィン防湿フィルム(COC)を得た。また上述の方法で測定した防湿性能は0.500[g/m2・日]であった。
日本合成(株)製「ゴーセノール」(ケン化度:97.0~98.8mol%、重合度:2400)のポリビニルアルコール樹脂220gをイオン交換水2810gに加え加温溶解した水溶液に、20℃で攪拌しながら35%塩酸645gを加えた。次いで、10℃でブチルアルデヒド3.6gを攪拌しながら添加し、5分後に、アセトアルデヒド143gを攪拌しながら滴下し、樹脂微粒子を析出させた。次いで、60℃で2時間保持した後、液を冷却し、炭酸水素ナトリウムで中和し、水洗、乾燥し、ポリビニルアセトアセタール樹脂粉末(アセタール化度75mol%)を得た。
また、架橋剤としてイソシアネート樹脂(住友バイエルウレタン(株)製「スミジュールN-3200」)を用い、水酸基に対するイソシアネート基の当量比が1:2になるように混合した。
ポリウレタンポリオール成分を含む主剤としてロックペイント株式会社製HD1013を使用し、脂肪族系のヘキサメチレンジイソシアナート成分を含む硬化剤としてロックペイント株式会社製H62を使用し、質量比で10:1となるように混合し、固形分濃度が30%となるように酢酸エチルで希釈して接着剤塗液を調製した。また本接着剤塗液を50μmPETフィルムに塗布後、防湿フィルムa-1~a-7と貼合、養生し水蒸気透過率を測定し、接着剤に防湿フィルムa-1~a-7に対する防湿性向上効果がないことを確認した。
耐候性フィルム1に接着剤塗液を固形分6g/m2となるよう塗布乾燥し、防湿フィルムBとして防湿フィルムa-4を用い、該防湿フィルムa-4の無機層を接着剤面に向けてドライラミネートによって貼合した。
その後、積層フィルムの防湿フィルムa-4の基材側に接着剤塗液を固形分6g/m2となるよう塗布乾燥し、防湿フィルムAとして防湿フィルムa-1を用い、該防湿フィルムa-1の無機層面を貼合し、40℃×5日間養生し、厚み66μmの積層防湿フィルムD-1を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムAとして防湿フィルムa-2を用いたこと以外は実施例1と同様にして厚み66μmの積層防湿フィルムD-2を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムAとして防湿フィルムa-3を用いたこと以外は実施例1と同様にして厚み66μmの積層防湿フィルムD-3を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
実施例3において、耐候性フィルム側になる防湿フィルムを入れ替えた。
すなわち、耐候性フィルム1に接着剤塗液を固形分6g/m2となるよう塗布乾燥し、防湿フィルムAとして防湿フィルムa-3を用い、該防湿フィルムa-3の無機層を接着剤面に向けてドライラミネートによって貼合した。
その後、積層フィルムの防湿フィルムa-3の基材側に接着剤塗液を固形分6g/m2となるよう塗布乾燥し、防湿フィルムBとして防湿フィルムa-4を用い、該防湿フィルムa-4の無機層面を貼合し、40℃×5日間養生し、厚み66μmの積層防湿フィルムD-4を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムAとして防湿フィルムa-2を用い、防湿フィルムBとして防湿フィルムa-5を用いたこと以外は実施例1と同様にして厚み66μmの積層防湿フィルムD-5を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムAとして防湿フィルムa-3を用い、防湿フィルムBとして防湿フィルムa-6を用いたこと以外は実施例1と同様にして厚み66μmの積層防湿フィルムD-6を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムAとして防湿フィルムa-7を用いたこと以外は実施例1と同様にして厚み554μmの積層防湿フィルムD-7を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
実施例7において、耐候性フィルム側になる防湿フィルムを入れ替えた。
すなわち、耐候性フィルム1に接着剤塗液を固形分6g/m2となるよう塗布乾燥し、防湿フィルムAとして防湿フィルムa-7を用い、該防湿フィルムa-7の無機層を接着剤面に向けてドライラミネートによって貼合した。
その後、積層フィルムの防湿フィルムa-7の基材側に接着剤塗液を固形分6g/m2となるよう塗布乾燥し、防湿フィルムBとして防湿フィルムa-4を用い、該防湿フィルムa-4の無機層面を貼合し、40℃×5日間養生し、厚み554μmの積層防湿フィルムD-8を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムA、防湿フィルムBのいずれにも防湿フィルムa-3を用いたこと以外は実施例1と同様にして厚み66μmの積層防湿フィルムD-9を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムBとして防湿フィルムa-3を用い、防湿フィルムAとして防湿フィルムa-2を用いたこと以外は実施例1と同様にして厚み66μmの積層防湿フィルムD-10を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムA、防湿フィルムBのいずれにも防湿フィルムa-4を用いたこと以外は実施例1と同様にして厚み66μmの積層防湿フィルムD-11を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムBとして防湿フィルムa-6を用い、防湿フィルムAとして防湿フィルムa-4を用いたこと以外は実施例1と同様にして厚み66μmの積層防湿フィルムD-12を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムBとして防湿フィルムa-3を用い、防湿フィルムAとして防湿フィルムa-7を用いたこと以外は実施例1と同様にして厚み554μmの積層防湿フィルムD-13を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
防湿フィルムBとして防湿フィルムa-2を用い、防湿フィルムAとして防湿フィルムa-7を用いたこと以外は実施例1と同様にして厚み554μmの積層防湿フィルムD-14を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
比較例5において、耐候性フィルム側になる防湿フィルムを入れ替えた。
すなわち、耐候性フィルム1に接着剤塗液を固形分6g/m2となるよう塗布乾燥し、防湿フィルムAとして防湿フィルムa-7を用い、該防湿フィルムa-7の無機層を接着剤面に向けてドライラミネートによって貼合した。
その後、積層フィルムの防湿フィルムa-7の基材側に接着剤塗液を固形分6g/m2となるよう塗布乾燥し、防湿フィルムBとして防湿フィルムa-3を用い、該防湿フィルムa-3の無機層面を貼合し、40℃×5日間養生し、厚み554μmの積層防湿フィルムD-15を作成し防湿性、発泡性及びヘイズ変化度を測定及び評価した。結果を表2に示す。
2 防湿フィルムA
3 防湿フィルムB
4 基材
5 無機層
6 耐候性フィルム
7 接着剤層
8 背面フィルム
Claims (20)
- 40℃、90%RHにおける水蒸気透過率(WTR(A))が1.0[g/m2・日]以下である防湿フィルムA、及び基材の片面に無機層を有し、40℃、90%RHにおける水蒸気透過率(WTR(B))が前記防湿フィルムAの水蒸気透過率(WTR(A))の10%以下である防湿フィルムBが接着剤層を介して積層された構成を有することを特徴とする積層防湿フィルム。
- 40℃、90%RHにおける水蒸気透過率(WTR(A))が0.1[g/m2・日]以上、1.0[g/m2・日]以下である防湿フィルムA、及び基材の片面に無機層を有し、40℃、90%RHにおける水蒸気透過率(WTR(B))が0.001[g/m2・日]以上、0.1[g/m2・日]未満である防湿フィルムBが、接着剤層を介して積層された構成を有することを特徴とする積層防湿フィルム。
- 40℃、90%RHにおける積層防湿フィルムの水蒸気透過率(WVTR(L))が、[WTR(A)×WTR(B)]/[WTR(A)+WTR(B)]より低い値であることを特徴とする請求項1または2に記載の積層防湿フィルム。
- 40℃、90%RHにおける積層防湿フィルムの水蒸気透過率(WVTR(L))が、[WTR(A)×WTR(B)]/[WTR(A)+WTR(B)]の80%以下である請求項1~3のいずれかに記載の積層防湿フィルム。
- 防湿フィルムAの40℃、90%RHにおける水蒸気透過率(WTR(A))が0.1 [g/m2・日]以上であることを特徴とする請求項1、3および4のいずれかに記載の積層防湿フィルム。
- 防湿フィルムAの40℃、90%RHにおける水蒸気透過率(WTR(A))が0.2 [g/m2・日]以上であることを特徴とする請求項1~5のいずれかに記載の積層防湿フィルム。
- 防湿フィルムAの40℃、90%RHにおける水蒸気透過率(WTR(A))が0.4[g/m2・日]以上であることを特徴とする請求項1~6のいずれかに記載の積層防湿フィルム。
- 防湿フィルムAの40℃、90%RHにおける水蒸気透過率(WTR(A))が0.6[g/m2・日]以上であることを特徴とする請求項1~7のいずれかに記載の積層防湿フィルム。
- 防湿フィルムBの40℃、90%RHにおける水蒸気透過率(WTR(B))が0.001[g/m2・日]以上、0.1[g/m2・日]以下であることを特徴とする請求項1及び3~8のいずれかに記載の積層防湿フィルム。
- 防湿フィルムBの40℃、90%RHにおける水蒸気透過率(WTR(B))が0.001[g/m2・日]以上、0.05[g/m2・日]以下であることを特徴とする請求項1~9のいずれかに記載の積層防湿フィルム。
- 防湿フィルムAが環状オレフィン系重合体を含む樹脂組成物からなる層を少なくとも一層有するフィルムであることを特徴とする請求項1~10のいずれかに記載の積層防湿フィルム。
- 防湿フィルムAが基材の片面に無機層を有するフィルムであることを特徴とする請求項1~10のいずれかに記載の積層防湿フィルム。
- 耐候性フィルム、防湿フィルムB及び防湿フィルムAを曝露側からこの順に有し、かつ防湿フィルムAの無機層側に防湿フィルムBの基材を有することを特徴とする請求項12に記載の積層防湿フィルム。
- 耐候性フィルム、防湿フィルムA及び防湿フィルムBを曝露側からこの順に有し、かつ防湿フィルムBの無機層側に防湿フィルムAの基材を有する請求項12に記載の積層防湿フィルム。
- 接着剤層が接着剤からなり、かつ該接着剤が主剤としてポリカーボネートポリオール、ポリエーテルポリオール、アクリルポリオール、ポリウレタンポリオール及びポリエステルポリオールのうち少なくとも1種を含むことを特徴とする請求項1~14のいずれかに記載の積層防湿フィルム。
- 太陽電池用表面保護部材に用いられる請求項1~15のいずれかに記載の積層防湿フィルム。
- 化合物系発電素子太陽電池モジュール又はフレキシブル太陽電池モジュールの表面保護部材に用いられる請求項1~16のいずれかに記載の積層防湿フィルム。
- 請求項1~17のいずれかに記載の積層防湿フィルムを有することを特徴とする太陽電池用表面保護部材。
- 防湿フィルムA及び防湿フィルムBが各々の無機層を曝露面側に有する請求項18に記載の太陽電池用表面保護部材。
- 請求項18または19に記載の太陽電池用表面保護材を用いて作製された太陽電池モジュール。
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EP12758160.1A EP2687363B1 (en) | 2011-03-15 | 2012-03-14 | Laminated moisture proof film |
US14/004,958 US20140000699A1 (en) | 2011-03-15 | 2012-03-14 | Laminated moisture proof film |
CN201280012784.9A CN103415392B (zh) | 2011-03-15 | 2012-03-14 | 叠层防湿膜 |
KR1020137023203A KR20140046400A (ko) | 2011-03-15 | 2012-03-14 | 적층 방습 필름 |
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US (1) | US20140000699A1 (ja) |
EP (1) | EP2687363B1 (ja) |
KR (1) | KR20140046400A (ja) |
CN (1) | CN103415392B (ja) |
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EP2660047A1 (en) * | 2010-12-28 | 2013-11-06 | Mitsubishi Plastics, Inc. | Laminated moisture-proof film |
JP5536697B2 (ja) * | 2011-03-15 | 2014-07-02 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
US10305058B2 (en) * | 2014-11-11 | 2019-05-28 | Sharp Kabushiki Kaisha | Electroluminescent device and method for producing same |
CN105990459A (zh) * | 2015-02-28 | 2016-10-05 | 汉能新材料科技有限公司 | 一种柔性封装复合膜及其制造方法 |
KR20170048787A (ko) * | 2015-10-27 | 2017-05-10 | 세메스 주식회사 | 기판 처리 장치 및 기판 처리 방법 |
WO2017099016A1 (ja) * | 2015-12-08 | 2017-06-15 | 東レ株式会社 | 積層フィルム |
JP6123927B1 (ja) * | 2016-02-24 | 2017-05-10 | 大日本印刷株式会社 | 真空断熱材用外包材、真空断熱材、および真空断熱材付き機器 |
CN107403724A (zh) * | 2016-05-20 | 2017-11-28 | 稳懋半导体股份有限公司 | 化合物半导体集成电路的抗湿气结构 |
JP2018116543A (ja) * | 2017-01-19 | 2018-07-26 | 日東電工株式会社 | タッチパネル用フィルム積層体 |
CN110603148A (zh) * | 2017-05-19 | 2019-12-20 | 富士胶片株式会社 | 阻气膜及阻气膜的制造方法 |
CN108630775B (zh) * | 2018-05-29 | 2021-03-16 | 浙江巨化技术中心有限公司 | 一种涂料封装的薄膜太阳能电池及其成型方法 |
CN112747392B (zh) * | 2019-10-31 | 2022-07-05 | 青岛海尔智能技术研发有限公司 | 无水加湿模块、用于控制无水加湿模块的方法及装置、直流电空调 |
CN118103564A (zh) * | 2021-10-12 | 2024-05-28 | 维实洛克Mwv有限责任公司 | 高阻隔纤维素结构和纤维素容器 |
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TW201244116A (en) | 2012-11-01 |
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US20140000699A1 (en) | 2014-01-02 |
EP2687363A1 (en) | 2014-01-22 |
KR20140046400A (ko) | 2014-04-18 |
CN103415392A (zh) | 2013-11-27 |
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