WO2010067780A1 - 太陽電池裏面封止材用フィルム、太陽電池裏面封止材および太陽電池モジュール - Google Patents
太陽電池裏面封止材用フィルム、太陽電池裏面封止材および太陽電池モジュール Download PDFInfo
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- WO2010067780A1 WO2010067780A1 PCT/JP2009/070502 JP2009070502W WO2010067780A1 WO 2010067780 A1 WO2010067780 A1 WO 2010067780A1 JP 2009070502 W JP2009070502 W JP 2009070502W WO 2010067780 A1 WO2010067780 A1 WO 2010067780A1
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- film
- solar cell
- resin
- sealing material
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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Definitions
- the present invention has light resistance and moisture and heat resistance that can withstand use in harsh outdoor environments over a long period of time, and also has good design and adhesion to the terminal box adhesive silicone resin required for use in the outermost layer. It is related with the film for solar cell backside sealing materials which has the outstanding colored layer, the solar cell backside sealing material using the same, and a solar cell module.
- Solar cells used for photovoltaic power generation constitute the heart of a photovoltaic power generation system that directly converts sunlight energy into electrical energy, and are made of semiconductors such as silicon.
- solar cell elements are wired in series and in parallel, and various packaging is performed to protect the elements over a long period of about 20 years, and they are unitized.
- the unit incorporated in this package is called a solar cell module, and generally has a structure in which the surface exposed to sunlight is covered with glass, the gap is filled with a filler made of thermoplastic resin, and the back surface is protected with a sealing sheet. Yes.
- EVA resin ethylene-vinyl acetate copolymer resin
- the backside sealing material has mechanical strength, weather resistance, heat resistance, water resistance, chemical resistance, light reflectivity, water vapor barrier properties, thermal adhesiveness with fillers typified by EVA resin, and design properties. Not only are properties such as adhesion to the outermost terminal box mounting silicone resin required, but also exposure to ultraviolet light requires excellent light resistance.
- a white polyvinyl fluoride film (DuPont Co., Ltd., trade name: Tedlar (registered trademark)) can be exemplified, and a laminated structure in which a polyester film is sandwiched between the films.
- the back surface sealing material is widely used in such applications.
- surface or both surfaces of the polyester film is a light-resistant film (patent document 1), or a weather-resistant prescription agent (ultraviolet light).
- a specification incorporating an absorbent and a light stabilizer) has also been proposed and put into practical use.
- white pigments such as titanium oxide are kneaded into layers such as polyester films, and white films formed into practical use have also been put to practical use. (Patent Document 2).
- JP 2005-015557 A Japanese Patent Laid-Open No. 11-291432
- the polyvinyl fluoride film described above is a film having excellent weather resistance, but on the other hand, its mechanical strength is weak and it is softened by the heat of a hot press at 140 to 150 ° C. applied at the time of manufacturing a solar cell module.
- the protrusion of the element electrode portion may penetrate the filler layer.
- the dry coating film weight is about 5 g / m ⁇ 2 >. A relatively thick coating must be formed.
- the present invention employs the following configuration. That is, (1) The back surface of a solar cell in which a resin layer containing a resin obtained by copolymerizing an acrylic polyol resin with an ultraviolet absorber and a light stabilizer, a color pigment, and a plasticizer is laminated on at least one surface of a base film.
- Film for encapsulant (2) The film for solar cell backside sealing material according to (1), wherein the plasticizer is at least one selected from the group consisting of a polyester plasticizer, an epoxy plasticizer, and a phthalate plasticizer, (3) The film for solar cell backside sealing material according to (1) or (2), wherein the resin layer contains a polyisocyanate resin, (4) The solar cell back surface sealing material according to (3), wherein the polyisocyanate resin is at least one selected from the group consisting of an aliphatic isocyanate resin, an alicyclic isocyanate resin, and an araliphatic isocyanate resin.
- a white film and an inorganic oxide vapor deposition layer are formed on the surface of the film for solar cell backside sealing material according to any one of (1) to (5) opposite to the surface on which the resin layer is laminated.
- the present invention has light resistance and heat-and-moisture resistance that can withstand use in a harsh outdoor environment for a long period of time, and has good design and adhesion to a silicone resin for terminal box adhesion when used in the outermost layer. Moreover, the film for solar cell backside sealing materials which has the coloring layer excellent also in is obtained.
- the film for solar cell backside sealing material of the present invention is used, the adhesion to the silicon cell filler layer and the light reflectance are excellent, the performance of the solar cell module is improved, and the performance can be maintained for a long time.
- a solar cell back surface sealing material to be obtained is obtained.
- the film for solar cell backside sealing material of the present invention comprises, on at least one surface of a base film, a resin obtained by copolymerizing an acrylic polyol resin with an ultraviolet absorber and a light stabilizer, a color pigment, and a plasticizer.
- a resin obtained by copolymerizing an acrylic polyol resin with an ultraviolet absorber and a light stabilizer By including a laminated resin layer, it has light resistance and moisture and heat resistance superior to conventional ones, and also has good design and adhesion to the terminal box adhesive silicone resin required for use in the outermost layer. An excellent colored film can be obtained.
- Various resin films can be used as a base material for the film for solar cell backside sealing material of the present invention.
- Specific examples include polyester resin films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), resin films such as polycarbonate, polymethyl methacrylate, polyacrylate, polypropylene, and polyethylene, and resin films obtained by mixing these resins. It is done.
- a polyester resin film is preferable because it is excellent in strength, dimensional stability, and thermal stability, and a polyethylene terephthalate film such as PET or PEN is particularly preferable because it is inexpensive.
- the polyester resin may be a copolymer.
- copolymer component examples include diol components such as propylene glycol, diethylene glycol, neopentyl glycol, and cyclohexane dimethanol, isophthalic acid, adipic acid, azelaic acid, and sebacin.
- diol components such as propylene glycol, diethylene glycol, neopentyl glycol, and cyclohexane dimethanol, isophthalic acid, adipic acid, azelaic acid, and sebacin.
- the dicarboxylic acid component of an acid and its ester-forming derivative can be used.
- the film for solar cell backside sealing material of the present invention is excellent in light resistance, it is suitable for the outermost layer that is directly exposed to the outside air (humidity, temperature) and reflected ultraviolet light from the ground surface in the solar cell backside sealing material configuration. Can be used. From the viewpoint of using the outermost layer directly exposed to the outside air, it is preferable to use a resin film having excellent hydrolysis resistance as the base film. Normally, a polyester resin film is formed using a so-called polymer obtained by condensation polymerization of monomers as a raw material, and contains about 1.5 to 2% by mass of an oligomer positioned between the monomer and the polymer.
- a typical oligomer is a cyclic trimer, and a film with a high content of it causes a decrease in mechanical strength, cracks, breakage of materials, etc. due to the progress of hydrolysis due to rainwater, etc. in long-term exposure such as outdoors.
- a polyester resin film is formed from a polyester resin having a cyclic trimer content obtained by polymerization by a solid phase polymerization method of 1.0% by mass or less.
- the cyclic trimer content is measured by, for example, measuring the content (% by weight) relative to the resin weight by measuring by liquid chromatography using a solution in which 100 mg of a polymer is dissolved in 2 ml of orthochlorophenol. Is required.
- an antistatic agent for example, an ultraviolet absorber, a stabilizer, an antioxidant, a plasticizer, a lubricant, a filler, a coloring pigment, and the like are added to the resin film for the solar cell backside sealing material as necessary.
- the resin film etc. which added the agent within the range which does not impair the effect of this invention can also be used.
- polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN)
- resin films such as polycarbonate, polymethyl methacrylate, polyacrylate, polypropylene, and polyethylene, and a white pigment on a resin film obtained by mixing these resins
- the white film is used for the purpose of assisting energy conversion in the semiconductor element by reflecting the light incident on the back sheet, and is preferably arranged in a layer close to the cell.
- a white film preferably used as a base film is used for reflecting sunlight to improve power generation efficiency.
- a polyester resin film is preferable because it is excellent in strength, dimensional stability, and thermal stability, and a polyethylene terephthalate film such as PET or PEN is particularly preferable because it is inexpensive.
- the polyester resin constituting the polyester resin film is composed of polyethylene terephthalate in which 80 mol% or more of the structural unit is ethylene terephthalate, polyethylene naphthalate in which 80 mol% or more of the structural unit is ethylene naphthalate, Although represented by a polylactic acid film or the like in which 80 mol% or more of the unit is polylactic acid, it is not particularly limited.
- the polyester resin may be a copolymer.
- the copolymer component include diol components such as propylene glycol, diethylene glycol, neopentyl glycol, and cyclohexane dimethanol, isophthalic acid, adipic acid, azelaic acid, and sebacin.
- the dicarboxylic acid component of an acid and its ester-forming derivative can be used.
- titanium oxide or zinc oxide can be used as the white pigment.
- a white resin film having a whiteness of 80% or more and an opacity of 80% or more can be obtained.
- the white resin film may be added with additives such as an antistatic agent, an ultraviolet absorber, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a filler, as necessary, without impairing the effects of the present invention.
- additives such as an antistatic agent, an ultraviolet absorber, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a filler, as necessary, without impairing the effects of the present invention.
- a resin film or the like added within the range can also be used.
- the thickness of the resin film for the solar cell backside sealing material is not particularly limited, but it is preferably in the range of 25 to 250 ⁇ m in view of the withstand voltage characteristics and cost of the sealing sheet.
- the base film may be a water vapor barrier film in which at least one inorganic oxide layer is formed by vapor deposition for the purpose of imparting water vapor barrier properties.
- the “water vapor barrier film” in the present invention is a resin film having a water vapor transmission rate of 5 g / (m 2 ⁇ day) or less measured by the method B described in JIS K7129 (2000 version).
- As the water vapor barrier resin film at least one metal thin film layer or the like is formed on at least one surface of a polyester resin film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) or an olefin film such as polypropylene by vapor deposition or the like.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- an olefin film such as polypropylene by vapor deposition or the like.
- the thickness of the resin film is preferably in the range of 1 to 100 ⁇ m, more preferably in the range of 5 to 50 ⁇ m, particularly preferably for reasons such as stability and cost when forming the inorganic oxide layer. A thickness of about 10 to 30 ⁇ m is practical.
- Examples of the inorganic oxide constituting the inorganic oxide layer formed in the present invention include metal oxides and metal nitride oxides.
- the inorganic oxide layer can be formed by vapor deposition, sputtering, ion plating, plasma vapor deposition (CVD), or the like.
- the vacuum deposition method is the best at present.
- As the heating means of the vacuum deposition apparatus by the vacuum deposition method an electron beam heating method, a resistance heating method and an induction heating method are preferable.
- Examples of the metal oxide constituting the inorganic oxide layer include aluminum oxide, magnesium oxide, titanium oxide, tin oxide, indium oxide alloy, and silicon oxide.
- the metal nitride oxide includes silicon oxynitride. Etc. can be illustrated.
- inorganic oxides such as aluminum oxide, silicon oxide, silicon oxynitride, and mixtures thereof are preferably used from the viewpoint of water vapor barrier properties and production efficiency.
- the film thickness of the inorganic oxide layer is appropriately selected depending on the kind and configuration of the inorganic substance used, but generally it is preferably in the range of 2 to 300 nm, more preferably in the range of 3 to 100 nm, The range is preferably 5 to 50 nm.
- the film thickness exceeds 300 nm, especially in the case of a metal oxide layer, the flexibility (flexibility) decreases, and the thin film is cracked by an external force such as bending or pulling after film formation (in a post-processing step or the like). May cause pinholes and the like, and water vapor barrier properties may be significantly impaired.
- productivity since the formation speed of an inorganic layer falls, productivity may be reduced remarkably.
- the film thickness is less than 2 nm, it is difficult to obtain a uniform film, and the film thickness may not be sufficient, and the water vapor blocking function may not be sufficiently exhibited.
- a resin film if necessary, for example, a discharge treatment such as corona discharge or plasma discharge, or a surface treatment such as acid treatment may be performed.
- the resin layer laminated on the base film in the present invention includes (1) a resin obtained by copolymerizing an acrylic polyol resin, an ultraviolet absorber and a light stabilizer, (2) a color pigment, and (3) a plasticizer. It consists of In general, as a method for imparting ultraviolet light cutting performance to a resin layer and improving light resistance, an organic ultraviolet absorber or an inorganic ultraviolet absorber alone or a mixture of plural types is mixed with a binder resin, A light stabilizer (HALS) is used in combination for the purpose of increasing light stability by a mechanism for deactivating radicals excited by light.
- HALS light stabilizer
- the ultraviolet absorber or the light stabilizer is applied from the inside of the coating film in a high-temperature humidified environment or when receiving ultraviolet light. Bleeding out to the surface of the film not only changes wettability, adhesion of the coating surface, etc., but also tends to cause problems such as loss of the UV light cutting performance that was initially expressed.
- the copolymerization monomer for fixing the ultraviolet absorber and the light stabilizer vinyl monomers such as acrylic and styrene are highly versatile and economically preferable.
- the styrene vinyl monomer has an aromatic ring, and thus is easily yellowed, and from the viewpoint of light resistance, copolymerization with an acrylic vinyl monomer is most preferably used. Therefore, one polymerization monomer component constituting the acrylic resin is one or more unsaturated compounds in the group consisting of unsaturated carboxylic acid ester, unsaturated carboxylic acid, unsaturated hydrocarbon and vinyl ester.
- unsaturated carboxylic acid esters examples include methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, Examples thereof include isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate.
- unsaturated carboxylic acids examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, and fumaric acid.
- Suitable monomers that can be used include butadiene, ethylene, vinyl acetate and the like. Preference is given to unsaturated carboxylic acid esters. Among unsaturated carboxylic acid esters, methyl methacrylate and methyl acrylate are particularly preferable from the viewpoints of versatility, cost, and light stability.
- Polymerization monomer components used for the purpose of giving hydroxyl groups to acrylic resins include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl Examples thereof include monomers of unsaturated compounds such as methacrylate, 2-hydroxyvinyl ether, polyethylene glycol methacrylate, polypropylene glycol monoacrylate, and polypropylene glycol monomethacrylate. These unsaturated compounds having a hydroxyl group can be selected singly or in combination of two or more.
- the thickness of the resin layer is preferably 0.2 to 5 ⁇ m, more preferably 1 to 4 ⁇ m, and particularly preferably 2 to 4 ⁇ m.
- this resin layer is formed by a coating method, if the thickness of the resin layer is less than 0.2 ⁇ m, a phenomenon such as repellency or film breakage tends to occur during coating, and it is difficult to form a uniform coating film. In some cases, the adhesion to the film, and above all, the UV-cutting performance is not sufficiently exhibited. On the other hand, if the thickness of the resin layer exceeds 5 ⁇ m, the UV-cutting performance is sufficiently developed, but the coating method is restricted (specific process capable of thick film coating, device restrictions), and the production cost is increased. There are concerns that the coating film adheres to the film and the coating film peels easily.
- Examples of the solvent of the coating liquid for forming the resin layer in the present invention by the coating method include toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethylformamide, dimethylacetamide, methanol, Examples include ethanol and water, and the properties of the coating liquid may be either an emulsion type or a dissolution type.
- the method for forming the resin layer on the base film is not particularly limited, and a known coating method can be used.
- a coating method various methods can be applied.
- a roll coating method, a dip coating method, a bar coating method, a die coating method, a gravure roll coating method, or a combination of these methods can be used. It can.
- the gravure roll coating method is a preferable method for increasing the stability of the coating layer forming composition.
- UV absorber examples of the ultraviolet absorber copolymerized with the acrylic polyol resin include salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers.
- examples of the light stabilizer copolymerized with the acrylic polyol resin include hindered amine light stabilizers. Specifically, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6) decanedioate , 6-tetramethyl-1-octyloxy] -4-piperidinyl] ester and the like, modified products, polymers and derivatives thereof.
- hindered amine light stabilizers Specifically, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malon
- the coloring pigment used in the present invention is used for the purpose of causing the resin layer to develop color and maintaining the color tone (not fading).
- a white sheet is mainly used from the viewpoint of light reflectivity and design properties.
- the design property is excellent compared to the sheet in which the gaps between the power generation elements appear white. For this reason, the demand for black sheets is increasing.
- these pigments themselves also absorb and / or reflect light of a specific wavelength, the effect of protecting the resin base material from light can be obtained by coloring.
- coloring pigments various coloring pigments such as inorganic pigments and organic pigments can be used, but white or black currently in practical use is oxidized as a white pigment from the viewpoint of versatility, price, color development performance, and UV resistance. Titanium is preferred, and carbon black is preferred as the black pigment.
- the number average particle diameter is preferably 0.1 to 1.0 ⁇ m, and more preferably 0.2 to 0.5 ⁇ m from the viewpoint of dispersibility with respect to acrylic polyol resin and cost.
- the number average particle size of carbon black is preferably 0.01 to 0.5 ⁇ m, more preferably 0.02 to 0.1 ⁇ m from the viewpoint of dispersibility and cost.
- the blending amount of the above-described color pigment may be appropriately adjusted according to the design of the color tone to be developed. However, if the amount of pigment is too small, a color appearance with excellent design cannot be obtained. Conversely, if the amount is too large, the cost will be high, and the hardness of the resin layer will be greatly improved. Is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the resin obtained by copolymerizing an acrylic polyol resin with an ultraviolet absorber and a light stabilizer. .
- the plasticizer in the present invention contributes to improving the adhesion between the base film and the resin layer containing the acrylic polyol resin and the color pigment.
- acrylic polyol resin is not a resin material that has a particularly poor adhesion to various resin films, but when a colored pigment is compounded at a relatively high concentration for the purpose of coloring the resin layer, the hardness of the resin layer increases. Furthermore, since the concentration of the acrylic polyol resin in the resin layer is relatively lowered, the adhesion between the base film and the resin layer tends to be lowered.
- the hardness of a resin layer can be adjusted and the adhesive force with a base film can be improved by mix
- a polyester plasticizer, an epoxy plasticizer, a phthalate ester plasticizer, or a combination thereof is preferable from the viewpoint of heat resistance, weather resistance, cost, versatility, and the like.
- polyester plasticizer for example, an adipic acid plasticizer is preferably used.
- epoxy plasticizer for example, an epoxidized fatty acid ester is preferably used.
- epoxy plasticizer epoxidized vegetable oil can also be used, and examples thereof include epoxidized soybean oil and epoxidized linseed oil.
- phthalate ester plasticizer for example, dioctyl phthalate, diisononyl phthalate, disisodecyl phthalate, or dibutyl phthalate is preferably used.
- the blending amount of the plasticizer is preferably in the range of 4 to 40 parts by mass, more preferably 10 to 30 parts by mass, with respect to 100 parts by mass of the resin obtained by copolymerizing the acrylic polyol resin with the ultraviolet absorber and the light stabilizer. Part.
- the amount of the plasticizer is less than 4 parts by mass, the compounding effect is too small, and an improvement effect such as adhesion may not be sufficiently expected.
- the amount is more than 40 parts by mass, the relative amount of the acrylic polyol-based resin containing the ultraviolet absorber and the light stabilizer in the resin layer is greatly reduced, so that the ultraviolet resistance of the resin layer itself is lowered.
- the function of protecting the base film from ultraviolet rays (ultraviolet ray blocking performance) may be impaired.
- the coating liquid containing the acrylic polyol-based resin according to the present invention has a thermal stabilizer, an antioxidant, a reinforcing agent, a deterioration preventing agent, a weathering agent, a flame retardant, a mold release agent, as long as the characteristics are not impaired.
- a lubricant or the like may be added.
- heat stabilizers, antioxidants and deterioration inhibitors examples include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and mixtures thereof.
- reinforcing agents examples include clay, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, and oxidation.
- examples include zinc, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate whisker, boron nitride, graphite, glass fiber, and carbon fiber.
- Crosslinking agent As described above, a crosslinking agent having a functional group capable of reacting with the hydroxyl group of the acrylic polyol may be blended for the purpose of improving the properties of the resin layer.
- a crosslinking agent is used in combination, the effect of improving the adhesion between the base film and the resin layer or improving the heat resistance of the resin layer accompanying the introduction of a crosslinked structure can be obtained.
- the solar cell back surface sealing material is designed so that the resin layer in the present invention is located in the outermost layer, in the solar cell module manufacturing process, specifically in the glass laminating process (cell filling process), Since the resin layer is exposed to a heat treatment of 30 minutes or longer at a high temperature of about 150 ° C.
- diisocyanate used as a raw material for the aromatic polyisocyanate examples include m- or p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), 4,4'-, 2,4.
- NDI 1,5-naphthalene diisocyanate
- Examples include '-or 2,2'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), and 4,4'-diphenyl ether diisocyanate.
- diisocyanate used as a raw material for the araliphatic polyisocyanate examples include 1,3- or 1,4-xylylene diisocyanate (XDI) and 1,3- or 1,4-tetramethylxylylene diisocyanate (TMXDI). Etc. are exemplified.
- diisocyanate used as a raw material for the alicyclic polyisocyanate examples include 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI).
- diisocyanate used as a raw material for the aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-, 2,3- Examples include 1,3-butylene diisocyanate and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate.
- these diisocyanates may be used in combination, or may be used as a modified body such as a burette modified body (aliphatic) or a nurate modified body (alicyclic system).
- a resin containing an aromatic ring having a light absorption band in the ultraviolet region in the resin skeleton easily yellows upon irradiation with ultraviolet rays. Therefore, alicyclic polyisocyanate and aliphatic polyisocyanate. It is preferable to use a curing agent containing as a main component.
- ethanol is often used to wipe off the resin and dirt adhering to the outermost layer of the solar cell backside sealing material, and the outermost layer of the solar cell backside sealing material has ethanol resistance.
- Use of alicyclic polyisocyanate is required because curing of the resin layer proceeds from aliphatic polyisocyanate and ethanol resistance is improved by using a curing agent mainly composed of alicyclic polyisocyanate. Is preferred.
- the nurate modified body of hexamethylene diisocyanate is preferable from the viewpoint of easy progress of the crosslinking reaction with the acrylic polyol-based resin, the degree of crosslinking, heat resistance, and ultraviolet resistance.
- the thickness of the adhesive layer is preferably in the range of 1 to 5 ⁇ m. If it is less than 1 ⁇ m, it may be difficult to obtain sufficient adhesive strength. On the other hand, if it exceeds 5 ⁇ m, the coating speed of the adhesive does not increase, the aging performed for the purpose of developing the adhesive force (promoting the crosslinking reaction between the main agent and the curing agent), and further using the adhesive This is not preferable because the production cost increases due to an increase in the amount.
- the main resin used in combination with this isocyanate group-containing polymer examples include polyether resins, polyester resins, polyol resins, and other urethane resins and epoxy resins, depending on the detailed required characteristics and suitability for processing conditions. Can be appropriately selected and used. Further, depending on the configuration of the solar cell back surface sealing material, it is also conceivable that UV light reaches the above adhesive layer and induces photodegradation of the resin. From such a viewpoint, the resin used for forming the adhesive layer is preferably an aliphatic resin or an alicyclic resin that does not contain an aromatic ring or has a low content.
- the solar cell back surface sealing material is required to have various characteristics such as water vapor barrier property, light reflectivity, long-term moisture and light resistance, adhesion to cell filler, electrical insulation and the like.
- various company-specific sheet designs laminate designs are made in combination with various functional films, processing techniques such as vapor deposition and wet coating in accordance with the concept of functional division.
- one or more of a film having hydrolysis resistance, a white film, a film having inorganic oxide vapor deposition, and a film having thermal adhesiveness with EVA are added to the solar cell back surface sealing material film of the present invention.
- a protective sheet for solar cell back surface sealing that satisfies various required characteristics is obtained.
- a different type of film from the base film of the solar cell back surface sealing material film is laminated.
- the portion of the solar cell backside sealing material that becomes the outer side when incorporated in a solar cell module is a base film made of a hydrolysis-resistant film, and the resin layer in the present invention is formed on this base film.
- the design which arranges the hydrolysis-resistant and light-resistant coating film which did is preferable.
- a film having hydrolysis resistance layers (adhesive layer, film layer, etc.) located on the inner layer side from the film are protected from hydrolysis.
- the resin layer which has an ultraviolet cut performance is located in the outermost layer side, the layer inside this resin layer is protected from an ultraviolet-ray.
- a white film, a film having inorganic oxide vapor deposition, and a film having thermal adhesiveness with EVA are laminated. It is preferable.
- stacked on the film for solar cell backside sealing materials of this invention does not necessarily need to be 1 sheet, According to the characteristic to provide, combine each member film suitably and design a solar cell backside sealing material. It ’s fine.
- the characteristic evaluation method used in the present invention is as follows.
- Adhesive strength (coating strength of coating film) between base film and coating layer (resin layer) of the produced solar cell backside sealing material film ) was subjected to a cross-cut test based on the method described in JIS K 5400 (1990 edition), and the following characteristic classification was performed. ++: 100 square coating film remaining / 100 square medium +: 81-99 mass coating film remaining / 100 square film ⁇ : 80 mass or less remaining coating film / 100 square film.
- the ethanol resistance of the light-resistant coating layer was determined by immersing the sample in ethanol for 5 minutes and then rubbing it 50 times using Kimwipe (registered trademark). The classification was as follows. +: No change in coating film state before treatment-: Peeling of substrate and coating film is observed.
- the tested pseudo solar cell module sample is obtained by stacking an EVA sheet on the inner layer side (the surface opposite to the surface on which the coating layer of the base film is laminated) of the produced solar cell back surface sealing material. 3 mm semi-tempered glass was stacked, and after vacuuming using a commercially available glass laminator, press-treated for 15 minutes under a heating condition of 135 ° C. under a load of 29.4 N / cm 2 was used.
- As the EVA sheet a 500 ⁇ m thick sheet manufactured by Sanvik Co., Ltd. was used.
- the width of the test piece of the adhesive strength test was 10 mm, and each of the two test pieces was measured once, and the average value of the two measured values was taken as the value of the adhesive strength. It is judged that the adhesive strength is 100 N / 50 mm or more as a practically acceptable level.
- Hals hybrid polymer registered trademark
- BK1 solid content concentration
- acrylic resin 1 a coating agent manufactured by Nippon Shokubai Co., Ltd., characterized in that an ultraviolet absorber and a light stabilizer (HALS) are cross-linked to an acrylic polyol resin : 40% by mass, acrylic resin 1) was mixed together with the color pigments and the solvent shown in Table 1 and dispersed using a bead mill. Thereafter, plasticizers having the same composition as shown in Table 1 were added to obtain resin layer forming main coating materials 1 to 5 having a solid content concentration of 50% by mass.
- HALS light stabilizer
- Desmodur (registered trademark) N3300 solid content concentration: 100% by mass
- Sumika Bayer which is a nurate type (alicyclic) hexamethylene diisocyanate resin
- the solid content ratio with the acrylic resin 1 is 33/8.
- N-Propyl acetate was weighed and stirred for 15 minutes to obtain light-resistant coating layer forming coatings 1 to 5 having a solid content concentration of 20% by mass (resin solid content concentration).
- White pigment Titanium oxide particles JR-709 manufactured by Teika
- Black pigment Carbon black particles Special black 4A manufactured by Degussa
- Plasticizer 1 DIC Polyester Plasticizer Polysizer W-220EL Plasticizer 2: Epoxy plasticizer manufactured by DIC Eposizer W-121 Plasticizer 3: Epoxidized soybean oil plasticizer manufactured by DIC Corporation Eposizer W-100-EL Plasticizer 4: Phthalic acid ester plasticizer dioctyl phthalate manufactured by DIC.
- a light-resistant coating layer-forming coating material 8 was obtained in the same manner as the adjustment of the light-resistant coating layer-forming coating material 1 except that no color pigment was blended.
- a light-resistant coating layer-forming coating material 9 was obtained in the same manner as the preparation of the light-resistant coating layer-forming coating material 1 except that no plasticizer was added.
- Example 1 A hydrolysis-resistant polyethylene terephthalate film Lumirror (registered trademark) X10S (125 ⁇ m) having a cyclic trimer content of 1% by weight or less manufactured by Toray Industries, Inc. was prepared as a base film. On one surface of the base film, the light-resistant coating layer forming coating 1 is applied using a wire bar, dried at 150 ° C. for 30 seconds, and the coating amount after drying is 2.0 g / m 2. A light-resistant coating layer (resin layer) was provided. Thus, the film for solar cell back surface sealing material (henceforth, film for sealing materials) 1 was manufactured.
- Example 2 A sealing material film 2 was produced in the same manner as described in Example 1 except that a light-resistant coating layer (resin layer) was provided so that the coating amount after drying was 3.2 g / m 2 .
- a light-resistant coating layer resin layer
- Example 3 A sealing material film 3 was produced in the same manner as in Example 2 except that the light-resistant coating layer-forming coating material 2 was applied instead of the light-resistant coating layer-forming coating material 1.
- Example 4 A sealing material film 4 was produced in the same manner as in Example 2 except that the light-resistant coating layer-forming coating material 3 was applied instead of the light-resistant coating layer-forming coating material 1.
- Example 5 A sealing material film 5 was produced in the same manner as in Example 2 except that the light-resistant coating layer-forming coating material 4 was applied instead of the light-resistant coating layer-forming coating material 1.
- Example 6 A sealing material film 6 was produced in the same manner as in Example 2 except that the light-resistant coating layer-forming coating material 5 was applied instead of the light-resistant coating layer-forming coating material 1.
- Example 7 A sealing material film 7 was produced in the same manner as in Example 2 except that the light-resistant coating layer forming coating 6 was applied instead of the light-resistant coating layer forming coating 1.
- a sealing material film 8 was produced in the same manner as in Example 2 except that the light-resistant coating layer-forming coating material 7 was applied instead of the light-resistant coating layer-forming coating material 1.
- Example 2 A sealing material film 9 was produced in the same manner as in Example 2 except that the light-resistant coating layer forming coating 8 was applied instead of the light-resistant coating layer forming coating 1.
- Example 3 A sealing material film 10 was produced in the same manner as in Example 2 except that the light-resistant coating layer-forming paint 9 was applied instead of the light-resistant coating layer-forming paint 1.
- Comparative Example 4 A light-resistant coating layer is not formed, and Lumirror (registered trademark) X10S (manufactured by Toray Industries, Inc., 125 ⁇ m) is used as a sealing material film 11 as a comparative example.
- Lumirror registered trademark
- X10S manufactured by Toray Industries, Inc., 125 ⁇ m
- the light-resistant coating layer of the film 8 for encapsulating material obtained in Comparative Example 1 uses an acrylic resin to which an ultraviolet absorber and a light stabilizer (HALS) are added without crosslinking. Therefore, UV absorbers and light stabilizers bleed out from the coating surface to the coating surface in a high-temperature humidified environment or with UV light reception, and the UV cut performance is lost, increasing the ⁇ b value of the base film. And yellowing occurs.
- HALS light stabilizer
- the light-resistant coating layer of the sealing material film 10 obtained in Comparative Example 3 does not contain a plasticizer. Therefore, the adhesive force between the base film and the coat layer is slightly insufficient from the initial state, and the coating film (coat layer) after performing the moisture and heat resistance test and the ultraviolet irradiation test further has an adhesive force to the base film. It is getting worse. This is presumably because the coating film hardness after drying (formation) was increased as a result of adding a white pigment (titanium oxide) exceeding the amount of the acrylic polyol resin binder.
- the film 11 for sealing material obtained in Comparative Example 4 does not have an ultraviolet cut performance, and a colored pigment layer capable of adjusting the color tone of the film is also formed. Absent. Therefore, resin deterioration and yellowing occur with the irradiation of ultraviolet rays. Therefore, when used as the outermost layer of the solar cell backside sealing material, in extreme cases, the film has cracks, pinholes, etc., and there are functions required for the sealing sheet such as electrical insulation and water vapor barrier properties. In addition to being lost, there is a concern that affects the operation of the solar cell module.
- the light-resistant coating layer of the encapsulant film 6 obtained in Example 6 contains carbon black as a color pigment. Accordingly, the appearance of the film is black, and a black resin film that has been manufactured by a method of forming a film from a compound in which a black pigment typified by carbon black or the like is kneaded into the resin layer can be obtained by coating. . Furthermore, since the acrylic polyol resin has not only ultraviolet blocking performance but also excellent ultraviolet resistance of the resin itself, it also has a function of protecting the base film from ultraviolet rays.
- Example 8 The adhesive for dry laminating was applied with a wire bar to the film surface opposite to the light-resistant coating layer of the film for sealing material 2 obtained by the method described in Example 2, and dried at 80 ° C. for 45 seconds. A 3.5 ⁇ m adhesive layer 1 was formed. Next, a white polyethylene terephthalate film Lumirror (registered trademark) E20F (50 ⁇ m) manufactured by Toray Industries, Inc. was bonded to the adhesive layer 1 as a light reflective film using a hand roller. Further, a dry laminating adhesive was applied to the film surface of the laminated film opposite to the light-resistant coating layer with a wire bar and dried at 80 ° C. for 45 seconds to form a 3.5 ⁇ m adhesive layer 2. .
- Lumirror registered trademark
- E20F 50 ⁇ m
- an aluminum oxide vapor deposition polyethylene terephthalate film manufactured by Toray Film Processing Co., Ltd. having a water vapor barrier film is formed on the surface opposite to the aluminum oxide vapor deposition layer of Barrier Rocks (registered trademark) 1031HGTS (12 ⁇ m).
- a water vapor barrier film was prepared by coating a coating material and a heat-adhesive resin layer-forming coating material sequentially using a two-head tandem direct gravure coater under the following conditions. The aluminum oxide vapor deposition layer surface of the water vapor barrier film and the surface of the adhesive layer 2 of the laminate film were disposed so as to face each other, and were bonded together using a hand roller.
- seat which consists of 3 films produced was aged in the oven heated at 40 degreeC for 3 days, and the solar cell back surface sealing material 1 was obtained.
- -Adhesive layer coating conditions Aiming at dry film thickness of 0.2 ⁇ m, drying oven set temperature 120 ° -Thermal adhesive resin layer coating conditions: Aiming for dry film thickness of 1.0 ⁇ m, drying oven set temperature 100 ° C. ⁇ Coating speed: 100m / min Aging: After application and winding, aging at 40 ° C. for 2 days.
- Example 9 Solar cell backside sealing in the same manner as in Example 8 except that a polyethylene film (50 ⁇ m) manufactured by Toray Film Processing Co., Ltd., which has excellent adhesion to the EVA sheet, was used instead of the water vapor barrier film. Material 2 was obtained.
- Example 10 A solar cell back surface sealing material 3 was obtained in the same manner as in Example 8 except that the sealing material film 6 was used instead of the sealing material film 2.
- the solar cell backside sealing materials 1 to 3 obtained by the methods described in Examples 8 to 10 are all substrate films accompanying ultraviolet irradiation to the light-resistant coating layer side located on the outer layer side in the solar cell module configuration. There is no decrease in adhesion between the coating layer and the coating layer, and the yellowing of the coating layer and the substrate film is very small. Moreover, it is excellent also in the adhesive force with the filler (EVA) which is the characteristic requested
- EVA filler
- the solar cell back surface sealing material 4 obtained by the method described in Comparative Example 5 does not contain a color pigment in the outermost light-resistant coating layer, the effect of blinding the wiring pattern on the inner surface of the module cannot be obtained. Moreover, the color tone change (represented by ⁇ b value) of the appearance of the sealing material accompanying ultraviolet irradiation is observed. Therefore, when exposed to ultraviolet rays for a longer time, the ultraviolet rays reach the base film layer located in the inner layer of the light-resistant coating layer, and it is expected that the resin deterioration is gradually caused.
- the adhesion between the base film and the light-resistant coating layer decreases with the progress of the wet heat test or ultraviolet irradiation test, and when exposed to the outdoor environment, the adhesive strength with the silicone resin, that is, the terminal box also decreases. In extreme cases, the terminal box may be peeled off along with the coat layer.
- the solar cell back surface sealing material 6 obtained by the method described in Comparative Example 7 has no light-resistant coating layer formed on its outermost layer, that is, no ultraviolet-cutting coating layer is formed, and therefore its ultraviolet resistance. There is no sex. Therefore, it cannot be used as a back surface sealing material for a solar cell module intended for an installation form that may be exposed to reflected ultraviolet rays from the ground surface such as a field installation type.
- the method of the present invention has light resistance and heat and humidity resistance that can withstand use in a harsh outdoor environment for a long period of time, and yet has a design property.
- the film for solar cell back surface sealing materials which has a colored layer excellent also in the adhesive force with the silicone resin for terminal box adhesion required when using by outermost layer is obtained.
- the solar cell back surface sealing that has excellent adhesion to the silicon cell filler layer and light reflectivity, improves the performance of the solar cell module, and can maintain the performance over a long period of time. A material is obtained.
- the solar cell back surface sealing sheet of the present invention is not only excellent in light resistance and moisture and heat resistance, but also in design and adhesion to the terminal box adhesive silicone resin necessary for use in the outermost layer. Since it is suitably used in a module, the solar cell backside sealing sheet of the present invention and the solar cell module using the same are useful.
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Abstract
Description
(1) 基材フィルムの少なくとも片面に、アクリルポリオール系樹脂に紫外線吸収剤及び光安定化剤を共重合させた樹脂と、着色顔料と、可塑剤とを含む樹脂層が積層された太陽電池裏面封止材用フィルム、
(2) 前記可塑剤が、ポリエステル系可塑剤、エポキシ系可塑剤およびフタル酸エステル系可塑剤からなる群より選ばれた少なくとも1種である(1)の太陽電池裏面封止材用フィルム、
(3) 前記樹脂層が、ポリイソシアネート樹脂を含有する(1)又は(2)の太陽電池裏面封止材用フィルム、
(4) 前記ポリイソシアネート樹脂が、脂肪族系イソシアネート樹脂、脂環族系イソシアネート樹脂及び芳香脂肪族系イソシアネート樹脂からなる群より選ばれた少なくとも1種である(3)の太陽電池裏面封止材用フィルム、
(5) 前記着色顔料が酸化チタンである(1)~(4)のいずれかに記載の太陽電池裏面封止材用フィルム、
(6) (1)~(5)のいずれかに記載の太陽電池裏面封止材用フィルムの前記樹脂層が積層された面とは反対側の面に、白色フィルム、無機酸化物蒸着層を有するフィルム及びエチレン-酢酸ビニル共重合体との熱接着性を有するフィルムからなる群より選ばれた少なくとも1つのフィルムが積層された太陽電池用裏面封止材、
(7) (6)に記載の太陽電池裏面封止材の前記樹脂層が積層された側とは反対側の面と、太陽電池モジュールのシリコンセル充填材層面とを接着してなる太陽電池モジュール、
である。
本発明の太陽電池裏面封止材用フィルムは、基材フィルムの少なくとも片面に、アクリルポリオール系樹脂に紫外線吸収剤及び光安定化剤を共重合させた樹脂と、着色顔料と、可塑剤とを含む樹脂層を積層した構成とすることで、従来よりも優れた耐光性、耐湿熱性を有し、なおかつ意匠性、最外層で用いる場合に必要な端子ボックス接着用シリコーン樹脂との密着力にも優れた着色フィルムが得られるものである。
本発明の太陽電池裏面封止材用フィルムには種々の樹脂フィルムを基材として用いることができる。具体的には、ポリエチレンテレフタレート(PET)やポリエチレンナフタレート(PEN)などのポリエステル樹脂フィルムやポリカーボネート、ポリメチルメタクリレート、ポリアクリレート、ポリプロピレン、ポリエチレンなどの樹脂フィルム、これらの樹脂を混合した樹脂フィルムが挙げられる。中でも強度、寸法安定性、熱安定性に優れていることからポリエステル樹脂フィルムが好ましく、さらに安価であることからPETやPEN等のポリエチレンテレフタレートフィルムが特に好ましい。また、ポリエステル系樹脂は共重合体であっても良く、共重合成分としては、例えば、プロピレングリコール、ジエチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノール等のジオール成分、イソフタル酸、アジピン酸、アゼライン酸、セバシン酸およびそのエステル形成性誘導体のジカルボン酸成分などを使用することができる。
本発明における基材フィルムに積層する樹脂層は、(1)アクリルポリオール系樹脂と紫外線吸収剤及び光安定化剤とを共重合させた樹脂、(2)着色顔料、並びに(3)可塑剤とで構成されている。一般に、樹脂層に紫外線光カット性能を付与し、耐光性を向上させる手法としては、有機系紫外線吸収剤や無機系紫外線吸収剤を単独で、あるいは複数種を混合してバインダー樹脂に混ぜ、さらに光により励起されるラジカルを失活させるメカニズムによって光安定性を増す目的で光安定化剤(HALS)を併用する。しかし、バインダー樹脂に紫外線吸収剤や光安定化剤を後添加して形成した樹脂層では、高温加湿環境下、あるいは紫外線光受光に伴い、紫外線吸収剤や光安定化剤が塗膜中から塗膜表面にブリードアウトし、ぬれ性、塗膜表面の密着力などが変化するだけでなく、当初発現していた紫外線光カット性能が失われるといった不具合を生じやすい。
前記アクリルポリオール樹脂と共重合させる紫外線吸収剤としては、サリチル酸系、ベンゾフェノン系、ベンゾトリアゾール系、シアノアクリレート系等の紫外線吸収剤が例示できる。具体的には、例えば、サリチル酸系のp-t-ブチルフェニルサリシレート、p-オクチルフェニルサリシレート、ベンゾフェノン系の2,4-ジヒドロキシベンゾフェノン、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-5-スルホベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、ビス(2-メトキシ-4-ヒドロキシ-5-ベンゾイルフェニル)メタン、ベンゾトリアゾール系の2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2,2’-メチレンビス[4-(1,1,3,3-テトラメチルブチル)-6-(2Hベンゾトリアゾール-2-イル)フェノール]、シアノアクリレート系のエチル-2-シアノ-3,3’-ジフェニルアクリレート)、その他として、および2-(4,6-ジフェニル-1,3,5-トリアジン-2-イル)-5-[(ヘキシル)オキシ]-フェノールなどやこれらの変性物、重合物、誘導体などが例示できる。
また、同様に前記アクリルポリオール樹脂と共重合させる光安定化剤としては、ヒンダードアミン系等の光安定化剤が挙げられる。具体的には、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)〔[3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル]メチル〕ブチルマロネート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、メチル(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、デカン二酸ビス[2,2,6,6-テトラメチル-1-オクチルオキシ]-4-ピペリジニル]エステルなどやこれらの変性物、重合物、誘導体などが例示できる。
本発明において用いる着色顔料は、樹脂層に発色させるおよび色調の維持(退色しない)という目的で用いる。太陽電池用裏面封止シートとしては、光反射性及び意匠性の観点から白色のシートが主流であるが、近年、発電素子間の隙間が白色に見える前記シートと比較して意匠性に優れるという理由で黒色のシートの需要も拡大している。また、これらの顔料自体も特定の波長の光線を吸収および/または反射することから、着色することにより光線から樹脂基材を保護するという効果が得られる。
次に本発明の樹脂層に含有せしめる可塑剤について説明する。本発明における可塑剤は、基材フィルムと、アクリルポリオール系樹脂及び着色顔料を含む樹脂層との密着力向上に貢献する。元来、アクリルポリオール系樹脂は種々の樹脂フィルムに対する密着力が特段悪い樹脂材料ではないが、樹脂層の着色を目的に着色顔料を比較的高い濃度で配合した場合には樹脂層の硬度が高まり、さらに樹脂層中のアクリルポリオール系樹脂の濃度が相対的に低下するために、基材フィルムと樹脂層との間の密着力は低下する傾向にある。そこで、アクリルポリオール系樹脂と比較して樹脂軟化点が低い傾向にある可塑剤成分を配合することで樹脂層の硬度を調整し、基材フィルムとの密着力を向上させることができる。本発明で用いる可塑剤としては、ポリエステル系可塑剤、エポキシ系可塑剤、フタル酸エステル系可塑剤又はこれらの組み合わせが耐熱性、耐候性、コスト、汎用性などの観点から好ましい。
さらに、本発明にかかるアクリルポリオール系樹脂を含むコーティング液には、その特性を損なわない限りにおいて、熱安定剤、酸化防止剤、強化剤、劣化防止剤、耐候剤、難燃剤、離型剤、滑剤などを添加してもよい。
また、前記の通り、樹脂層の特性向上の目的でアクリルポリオールの水酸基と反応し得る官能基を有する架橋剤を配合しても良い。架橋剤を併用した場合には、基材フィルムと樹脂層との間の密着力の向上、あるいは架橋構造の導入に伴う樹脂層の耐熱性向上といった効果が得られる。特に、本発明における樹脂層が最外層に位置するように太陽電池裏面封止材の設計を施した場合には、太陽電池モジュール製造工程、具体的にはガラスラミネート工程(セル充填工程)において、樹脂層が最大150℃程度の高温下で、長い場合には30分以上の熱処理に曝されるため、特に耐熱性が要求される。本発明では、アクリルポリオール系樹脂と紫外線吸収剤及び光安定化剤とを共重合させた樹脂を用いることから、該樹脂が有する水酸基と反応し得る架橋剤の使用が可能であり、中でもポリイソシアネート系樹脂を硬化剤として使用し、ウレタン結合(架橋構造)の生成を促す処方が好ましい。架橋剤として用いるポリイソシアネート系樹脂としては、芳香族系ポリイソシアネート、芳香脂肪族系ポリイソシアネート、脂環族系ポリイソシアネートおよび脂肪族系ポリイソシアネート等が例示でき、各々以下に示すジイソシアネート化合物を原料とする樹脂である。
本発明によって得られる太陽電池裏面封止材用フィルムと他の樹脂フィルムを積層することで太陽電池裏面封止材が得られるが、フィルムを積層させてシート状に加工する手法としては、公知のドライラミネート法が利用できる。ドライラミネート法を用いた樹脂フィルムの貼り合わせには、ポリエーテルポリウレンタン系、ポリエステルポリウレタン系、ポリエステル系、ポリエポキシ系樹脂などを主剤とし、ポリイソシアネート系樹脂を硬化剤とする公知のドライラミネート用接着剤を用いることができる。ただし、これらの接着剤を用いて形成される接着剤層には、接着強度が長期間の屋外使用で劣化することに起因するデラミネーションなどを生じないこと、光線反射率の低下につながる黄変を生じないことなどが必要である。また、接着剤層の厚みとしては、好ましくは1~5μmの範囲である。1μm未満であると十分な接着強度が得られ難い場合がある。一方、5μmを越えると接着剤塗工のスピードが上がらない、接着力を発現させる(主剤及び硬化剤間の架橋反応を促進する)目的で行うエージングに長時間を要すること、さらには接着剤使用量が増加することなどを理由に生産コストが上がるため、好ましくない。
上記のようにして作成した太陽電池裏面封止材を太陽電池モジュールに使用するに際し、太陽電池裏面封止材の樹脂層が積層された側とは反対側の面を太陽電池モジュールのシリコンセル充填材層面とに接着させ、つまり太陽電池裏面封止材の樹脂層が積層された側を外側に向けて、太陽電池モジュールに組み込む。
本発明で用いた特性の評価方法は、下記のとおりである。
耐光性コート層(樹脂層)の塗布量は、コート層形成後に500cm2の面積に切り出し、その試験片の質量を質量(1)とした。次に、その試験片から樹脂層をメチルエチルケトンに溶解させ、剥がし取り、再び試験片の質量を測定し、質量(2)とした。続いて、下式に基づき、単位面積当たりの塗布量を算出した。この塗布量測定を3つの試験片について行い、その平均値を塗布量とした。
・塗布量[g/m2]={(質量(1))-(質量(2))}×20。
温度40℃、湿度90%RHの条件で、米国、モコン(MOCON)社製の水蒸気透過率透過率測定装置(機種名、パ-マトラン(登録商標)W3/31)を使用してJIS K7129(2000年版)に記載のB法(赤外センサー法)に基づいて測定した。また、2枚の試験片について各々測定を1回行い、2つの測定値の平均値を水蒸気透過率の値とした。水蒸気透過率の値が5g/(m2・day)以下であれば合格である。
太陽電池裏面封止材用フィルムの紫外線カット性能は、JIS K 7105(2006年度版)に基づいて、島津製作所社製紫外可視近赤外分光光度計UV-3150を使用し分光スペクトルの測定を実施した。UV光領域の光線カット性能について、特に360nmの波長の透過率を測定することで評価した。360nmの波長の透過率が5%以下であれば合格である。
作製した太陽電池裏面封止材用フィルムの基材フィルムとコーティング層(樹脂層)との間の密着力(塗膜密着力)について、JIS K 5400(1990年版)に記載の方法に基づいてクロスカット試験を実施し、下記の特性分類をした。
++:100マス塗膜残存/100マス中
+:81~99マス塗膜残存/100マス中
-:80マス以下の塗膜残存/100マス中。
岩崎電気社製アイスーパーUVテスターSUV-W151を用いて、60℃×50%RH雰囲気にて紫外線強度160mW/cm2で120時間、240時間紫外線照射後の表色系b値の測定を行った。また、太陽電池裏面封止用フィルムについては紫外線カット性能の評価、基材フィルム/コーティング樹脂層間の密着強度評価についても、それらの特性の耐紫外線性評価の目的で実施した。なお、実施例および比較例で作製した太陽電池裏面封止材の外層側耐紫外線性評価は、前記の照射条件で240時間紫外線照射を行った前後の表色系b値の変化を評価結果とした。
エスペック社製プレッシャクッカーTPS-211を用いて、120℃、100%RHの環境下で48時間、96時間の熱処理を太陽電池裏面封止材用フィルムに施した。その後、太陽電池裏面封止材用フィルムの紫外線カット性能の評価、基材フィルム/コーティング層間の密着強度評価について、それらの特性の耐湿熱性評価の目的で実施した。
耐光性コート層の耐エタノール性は、サンプルをエタノール中に5分間浸し、その後キムワイプ(登録商標)を使用して50回こすった後、塗膜の状態を観察し、下記分類とした。
+:処理前と塗膜状態変化なし
-:基材と塗膜の剥離がみられる。
JIS K 6854に基づいて、EVAシートとの接着力を測定した。試験した疑似太陽電池モジュールサンプルは作製した太陽電池裏面封止材の内層側(基材フィルムのコート層を積層した面とは反対面)面にEVAシートを重ね、さらにその上に厚さ0.3mmの半強化ガラスを重ね、市販のガラスラミネーターを用いて真空引き後に135℃加熱条件下、29.4N/cm2荷重で15分プレス処理をしたものを用いた。EVAシートは、サンビック(株)製の厚さ500μmのシートを用いた。接着強度試験の試験片の幅は10mmとし、2つの試験片について各々測定を1回行い、2つの測定値の平均値を接着強度の値とした。接着強度は100N/50mm以上あることが実用上問題ないレベルと判断する。
耐光性コート層と電気系統の端子ボックス(ジャンクションボックス)を接着させるために使用される専用のシリコーン樹脂との密着力を以下の方法で評価した。太陽電池裏面封止材用フィルムの耐光性コート層(樹脂層)上にダウコーニング社製Solar PV(登録商標)804を塗布し、もう1枚の太陽電池裏面封止材用フィルムを、耐光性コート層同士が向かい合うように重ね、接着した。この接着サンプルを室温下、1週間放置し、乾燥させて作製したサンプルを試験片とした。この試験片から幅15mmの短冊状に測定用試験片を3本切り出し、前述の充填材との接着強度の測定と同様の方法で剥離角度を90°の状態で接着強度測定を行った。測定は3本の短冊状試験片それぞれについて1回行い、得られた強度の平均値をシリコーン樹脂接着強度の値とした。なお、現在、東レ(株)製 ルミラー(登録商標) X10Sは太陽電池裏面封止材において最外層用フィルムとして使用されており、シリコーン樹脂接着性は十分実用上問題無い強度(8N/15mm)が得られていることから、その接着強度を実用上の要求特性レベルと判断する。
(株)日本触媒株式会社製の、紫外線吸収剤及び光安定化剤(HALS)がアクリルポリオール樹脂に架橋されたことを特徴とするコーティング剤であるハルスハイブリットポリマー(登録商標)BK1(固形分濃度:40質量%、アクリル樹脂1とする)に表1に示す配合の着色顔料および溶剤を一括混合し、ビーズミル機を用いて分散した。その後、同じく表1に示す配合の可塑剤を添加して、固形分濃度が50質量%である樹脂層形成用主剤塗料1~5を得た。
白色顔料:酸化チタン粒子 テイカ社製 JR-709
黒色顔料:カーボンブラック粒子 デグサ社製 スペシャルブラック4A
可塑剤1:DIC社製ポリエステル系可塑剤 ポリサイザーW-220EL
可塑剤2:DIC社製エポキシ系可塑剤 エポサイザーW-121
可塑剤3:DIC社製エポキシ化大豆油系可塑剤 エポサイザーW-100-EL
可塑剤4:DIC社製フタル酸エステル系可塑剤 ジオクチルフタレート。
硬化剤として、ヌレート型(脂環族系)ヘキサメチレンジイソシアネート樹脂である住化バイエル社製 デスモジュール(登録商標)N3300(固形分濃度:100質量%)を用いる換わりに、ビューレット型(脂肪族系)ヘキサメチレンジイソシアネート樹脂である住化バイエル社製 デスモジュール(登録商標)N3200(固形分濃度:100質量%)を用いる以外は耐光性コート層形成用塗料1の調整と同様の方法で耐光性コート層形成用塗料6を得た。
(耐光性コート層形成用塗料7の調整)
ハルスハイブリットポリマー(登録商標)BK1(固形分濃度:40質量%)を用いる換わりに、メチルメタクリル酸および2-ヒドロキシエチルメタクリレートを原料とするアクリル樹脂に、紫外線吸収剤及び光安定化剤(HALS)を架橋せずに後添加した樹脂(固形分濃度:40質量%、アクリル樹脂2とする)を用いる以外は耐光性コート層形成用塗料1の調整と同様の方法で耐光性コート層形成用塗料7を得た。
着色顔料を配合しない以外は耐光性コート層形成用塗料1の調整と同様の方法で耐光性コート層形成用塗料8を得た。
可塑剤を配合しない以外は耐光性コート層形成用塗料1の調整と同様の方法で耐光性コート層形成用塗料9を得た。
DIC(株)製ドライラミネート剤 ディックドライ(登録商標)LX-903を16質量部、硬化剤として大日本インキ化学工業(株)製KL-75を2質量部、および酢酸エチルを29.5質量部量りとり、15分間攪拌することにより固形分濃度20質量%のドライラミネート用接着剤を得た。
三井化学ポリウレタン(株)製ドライラミネート剤 タケラック(登録商標)A-310(ポリエステルポリウレタン樹脂)を12質量部、三井化学ポリウレタン(株)製の芳香族系ポリイソシアネート樹脂である タケネート(登録商標)A-3を1質量部、および酢酸エチルを212質量部量りとり、15分間攪拌することにより固形分濃度3質量%の接着層形成用塗料を得た。
中央理化工業(株)製のEVA系3元共重合樹脂含有水性エマルジョン塗料である アクアテックス(登録商標)MC-3800を20質量部、イソプロピルアルコールを10.8質量部、および水を22.6質量部量りとり、15分間攪拌することにより固形分濃度15質量%の熱接着性樹脂層形成用塗料を得た。
基材フィルムとして東レ(株)製の環状三量体の含有量が1重量%以下である耐加水分解性ポリエチレンテレフタレートフィルム ルミラー(登録商標)X10S(125μm)を準備した。この基材フィルムの一方の面に、ワイヤーバーを用いて耐光性コート層形成用塗料1を塗布し、150℃で30秒間乾燥し、乾燥後塗布量が2.0g/m2となるように耐光性コート層(樹脂層)を設けた。このようにして太陽電池裏面封止材用フィルム(以下、封止材用フィルム)1を製造した。
乾燥後塗布量が3.2g/m2となるように耐光性コート層(樹脂層)を設けた以外は実施例1に記載の方法と同様にして封止材用フィルム2を製造した。
耐光性コート層形成用塗料1の換わりに耐光性コート層形成用塗料2を塗布する以外は実施例2に記載の方法と同様にして封止材用フィルム3を製造した。
耐光性コート層形成用塗料1の換わりに耐光性コート層形成用塗料3を塗布する以外は実施例2に記載の方法と同様にして封止材用フィルム4を製造した。
耐光性コート層形成用塗料1の換わりに耐光性コート層形成用塗料4を塗布する以外は実施例2に記載の方法と同様にして封止材用フィルム5を製造した。
耐光性コート層形成用塗料1の換わりに耐光性コート層形成用塗料5を塗布する以外は実施例2に記載の方法と同様にして封止材用フィルム6を製造した。
耐光性コート層形成用塗料1の換わりに耐光性コート層形成用塗料6を塗布する以外は実施例2に記載の方法と同様にして封止材用フィルム7を製造した。
耐光性コート層形成用塗料1の換わりに耐光性コート層形成用塗料7を塗布する以外は実施例2に記載の方法と同様にして封止材用フィルム8を製造した。
耐光性コート層形成用塗料1の換わりに耐光性コート層形成用塗料8を塗布する以外は実施例2に記載の方法と同様にして封止材用フィルム9を製造した。
耐光性コート層形成用塗料1の換わりに耐光性コート層形成用塗料9を塗布する以外は実施例2に記載の方法と同様にして封止材用フィルム10を製造した。
耐光性コート層を形成しないで、ルミラー(登録商標)X10S(東レ(株)製、125μm)を封止材用フィルム11として、比較例とする。
比較例1で得られる封止材用フィルム8の耐光性コート層は、紫外線吸収剤及び光安定化剤(HALS)を架橋せずに後添加したアクリル樹脂を用いている。そのため、高温加湿環境下、あるいは紫外線受光に伴い、紫外線吸収剤や光安定化剤が塗膜中から塗膜表面にブリードアウトし、紫外線カット性能が失われるため、基材フィルムのΔb値が増加し、黄変が発生する。一方、実施例1~7で得られる封止材用フィルム1~7の場合、紫外線照射試験を長時間(240時間)にわたって続けても、L値、b値で代表するフィルム外観の色調にはほとんど変化が見られない。
比較例2で得られる封止材用フィルム9の耐光性コート層は、着色顔料を含まない。そのため、フィルム外観・色調を変化させることはできないが、紫外線カット性能は紫外線吸収剤および光安定化剤が共重合されたアクリル樹脂の性能により高い性能を示している。ただし、さらに紫外線照射を継続した長期屋外使用を想定した場合には、表色系b値の変化が実施例1~7で得られる封止材用フィルムと比較して大きくなる。このことから、着色顔料を配合することで、フィルム外観の色調コントロールが行えるだけでなく、顔料による光線の吸収あるいは反射の効果に起因して、フィルムの耐紫外線性がより向上していることがわかる。
比較例3で得られる封止材用フィルム10の耐光性コート層は、可塑剤を含まない。そのため、基材フィルムとコート層間の密着力が初期の状態からやや不足しており、耐湿熱試験および紫外線照射試験を行った後の塗膜(コート層)は、基材フィルムに対する密着力がさらに悪化している。これは、アクリルポリオール樹脂バインダーの量を超える程の白色顔料(酸化チタン)を配合した結果、乾燥(形成)後の塗膜硬度が大きくなったためと考えられる。湿熱試験あるいは紫外線照射試験の際には、さらに熱、光のエネルギーにより塗膜状態が変化し、基材フィルムとの密着力も顕著に悪化する傾向がある。実用上は本発明のコート層がモジュール最外面に位置するような設計を想定していることから、高温高湿下、紫外線受光環境に長時間曝した場合には、ジャンクションボックスが、コート層と一体化した状態で裏面封止シートから脱落する事態も想定される。
比較例4で得られる封止材用フィルム11(コート層が形成されていないルミラー(登録商標)X10Sフィルムそのもの)は、紫外線カット性能が無く、フィルムの色調を整え得る着色顔料層も形成されていない。そのため、紫外線の照射に伴い、樹脂劣化、黄変が発生する。従って、太陽電池裏面封止材の最外層に用いた場合には、極端なケースではフィルムに割れ、ピンホールなどが生じ、電気絶縁性、水蒸気遮断性など、封止シートに要求される機能が失われるだけでなく、太陽電池モジュールの動作にも影響する懸念がある。
実施例6で得られる封止材用フィルム6の耐光性コート層は、着色顔料としてカーボンブラックを含有する。従って、フィルム外観は黒色となり、従来樹脂層にカーボンブラックなどに代表される黒色顔料を練りこんだコンパウンドを原料として、製膜する方法で製造していた黒色樹脂フィルムをコート加工で得ることができる。さらに、アクリルポリオール樹脂が紫外線遮断性能を有するばかりでなく、樹脂自体の耐紫外線性にも優れるため、基材フィルムを紫外線から保護する機能も兼ね備える。また、実施例1~5,7で得られる封止材用フィルム1~5,7と同様に、紫外線遮断性能の耐湿熱性及び耐紫外線性も十分に兼ね備えている。
(実施例1~6と、実施例7との比較)
実施例7で得られる封止材用フィルム7の耐光性コート層は、硬化剤としてビューレット型(脂肪族系)ヘキサメチレンジイソシアネート樹脂を用いている。そのため、ヌレート型(脂環族系)ヘキサメチレンジイソシアネート樹脂と比べて塗膜の硬化が進みにくく、封止材用フィルムの最外層に必要な特性である耐エタノール性が低下する傾向が実施例1~6に対してある。
実施例2に記載の方法で得た封止材用フィルム2の耐光性コート層とは反対側のフィルム表面に、ドライラミネート用接着剤をワイヤーバーで塗布し、80℃で45秒間乾燥して3.5μmの接着剤層1を形成した。次に、接着剤層1に、光反射性フィルムとして東レ(株)製白色ポリエチレンテレフタレートフィルム ルミラー(登録商標)E20F(50μm)をハンドローラーを用いて貼り合わせた。さらに、このラミネートフィルムの耐光性コート層とは反対側のフィルム表面に、ドライラミネート用接着剤をワイヤーバーで塗布し、80℃で45秒間乾燥して3.5μmの接着剤層2を形成した。これとは別に、水蒸気バリア性フィルムを有する東レフィルム加工(株)製 酸化アルミ蒸着ポリエチレンテレフタレートフィルム バリアロックス(登録商標)1031HGTS(12μm)の酸化アルミ蒸着層とは反対側の面に、接着層形成用塗料及び熱接着性樹脂層形成用塗料を下記条件で2ヘッドのタンデム型ダイレクトグラビアコーターを用いて順次、塗工した水蒸気バリア性フィルムを用意した。この水蒸気バリア性フィルムの酸化アルミ蒸着層面と、先ほどのラミネートフィルムの接着剤層2の面とが面するように配し、ハンドローラーを用いて貼り合わせた。このようにして作製したフィルム3枚からなるシートを40℃に加熱したオーブン内で3日間エージングして太陽電池裏面封止材1を得た。
・接着層塗工条件:乾燥膜厚0.2μm狙い、乾燥オーブン設定温度120℃
・熱接着性樹脂層塗工条件:乾燥膜厚1.0μm狙い、乾燥オーブン設定温度100℃
・塗工スピード:100m/min
・エージング:塗布・巻取り後、40℃下で2日間エージング。
水蒸気バリア性フィルムの換わりに、EVAシートとの密着力に優れる東レフィルム加工(株)製ポリエチレンフィルム(50μm)を用いた以外は、実施例8に記載の方法と同様にして太陽電池裏面封止材2を得た。
封止材用フィルム2の換わりに封止材用フィルム6を用いた以外は、実施例8に記載の方法と同様にして太陽電池裏面封止材3を得た。
封止材用フィルム1の換わりに封止材用フィルム9を用いた以外は、実施例8に記載の方法と同様にして太陽電池裏面封止材4を得た。
封止材用フィルム1の換わりに封止材用フィルム10を用いた以外は、実施例8に記載の方法と同様にして太陽電池裏面封止材5を得た。
封止材用フィルム1の換わりに封止材用フィルム11を用いた以外は、実施例8に記載の方法と同様にして太陽電池裏面封止材6を得た。
実施例8~10に記載の方法で得られる太陽電池裏面封止材1~3は、いずれも太陽電池モジュール構成において外層側に位置する耐光性コート層側への紫外線照射に伴う、基材フィルムとコーティング層間の密着力の低下は見られず、さらに、コーティング層および基材フィルムの黄変は非常に小さい。また、太陽電池裏面封止材に要求される特性である充填材(EVA)との密着力にも優れ、ガスバリア性フィルムを構成中に含む封止材1および3は水蒸気遮断性にも優れる。一方、比較例5に記載の方法で得られる太陽電池裏面封止材4は最外層の耐光性コート層に着色顔料を含まないため、モジュール内面の配線パターンなどを目隠しする効果は得られず、また紫外線照射に伴う封止材外観の色調変化(Δb値で代表して示す)が見られる。従って、さらに長時間紫外線に曝されれば、耐光性コート層の内層に位置する基材フィルム層にまで紫外線が到達し、少しずつ樹脂劣化を引き起こすことが予想される。
比較例6に記載の方法で得られる太陽電池裏面封止材5は最外層の耐光性コート層に可塑剤を含まないため、封止材の最外層に位置する耐光性コート層と基材フィルムとの間の密着力が初期の時点でやや不十分であり、湿熱試験あるいは紫外線照射試験を行った後には密着強度不良に至る。このようなコート層特性であるために、シリコーン樹脂接着性に関しても、実用上問題の無いルミラーX10Sフィルムを、コート層を形成することなく封止材最外層に使用している封止材6と比較して大幅に弱い強度となっている。基材フィルムと耐光性コート層間の密着力が湿熱試験あるいは紫外線照射試験の進行に伴い低下する挙動から、屋外環境に曝された場合に、シリコーン樹脂、つまりは端子ボックスとの接着力も低下していき、極端なケースでは端子ボックスがコート層ごと剥離するという事態も懸念される。
比較例7に記載の方法で得られる太陽電池裏面封止材6は、その最外層に耐光性コート層が形成されておらず、すなわち紫外線カット性コート層が形成されていないため、その耐紫外線性は全く無い。従って、フィールド設置型など地表面などからの照り返しの紫外線に曝される可能性がある設置形態を想定した太陽電池モジュールの用途には、裏面封止材として使用することはできない。
Claims (7)
- 基材フィルムの少なくとも片面に、アクリルポリオール系樹脂に紫外線吸収剤及び光安定化剤を共重合させた樹脂と、着色顔料と、可塑剤とを含む樹脂層が積層された太陽電池裏面封止材用フィルム。
- 前記可塑剤が、ポリエステル系可塑剤、エポキシ系可塑剤およびフタル酸エステル系可塑剤からなる群より選ばれた少なくとも1種である請求項1の太陽電池裏面封止材用フィルム。
- 前記樹脂層が、ポリイソシアネート樹脂を含有する請求項1又は2の太陽電池裏面封止材用フィルム。
- 前記ポリイソシアネート樹脂が、脂肪族系イソシアネート樹脂、脂環族系イソシアネート樹脂及び芳香脂肪族系イソシアネート樹脂からなる群より選ばれた少なくとも1種である請求項3の太陽電池裏面封止材用フィルム。
- 前記着色顔料が酸化チタンである請求項1に記載の太陽電池裏面封止材用フィルム。
- 請求項1に記載の太陽電池裏面封止材用フィルムの前記樹脂層が積層された面とは反対側の面に、白色フィルム、無機酸化物蒸着層を有するフィルム及びエチレン-酢酸ビニル共重合体との熱接着性を有するフィルムからなる群より選ばれた少なくとも1つのフィルムが積層された太陽電池用裏面封止材。
- 請求項6に記載の太陽電池裏面封止材の前記樹脂層が積層された側とは反対側の面と、太陽電池モジュールのシリコンセル充填材層面とを接着してなる太陽電池モジュール。
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EP2509112A4 (en) * | 2009-12-03 | 2013-08-21 | Toray Industries | FILM FOR A REAR SIDED FOIL FOR SOLAR CELLS |
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JP2012142349A (ja) * | 2010-12-28 | 2012-07-26 | Henkel Japan Ltd | 太陽電池バックシート用接着剤 |
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JP2015185687A (ja) * | 2014-03-24 | 2015-10-22 | 富士フイルム株式会社 | 太陽電池用バックシート部材及びその製造方法、太陽電池用バックシート並びに太陽電池モジュール |
WO2016157587A1 (ja) * | 2015-03-31 | 2016-10-06 | 太陽インキ製造株式会社 | 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板 |
JPWO2016157587A1 (ja) * | 2015-03-31 | 2018-01-25 | 太陽インキ製造株式会社 | 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板 |
Also Published As
Publication number | Publication date |
---|---|
CN102246318A (zh) | 2011-11-16 |
JPWO2010067780A1 (ja) | 2012-05-17 |
EP2369637A1 (en) | 2011-09-28 |
KR101624928B1 (ko) | 2016-05-27 |
CN102246318B (zh) | 2015-06-17 |
US20110259390A1 (en) | 2011-10-27 |
TWI499066B (zh) | 2015-09-01 |
EP2369637B1 (en) | 2014-02-26 |
EP2369637A4 (en) | 2012-06-27 |
TW201034219A (en) | 2010-09-16 |
JP5609115B2 (ja) | 2014-10-22 |
KR20110097786A (ko) | 2011-08-31 |
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