WO2011068067A1 - 太陽電池裏面封止シート用フィルム - Google Patents
太陽電池裏面封止シート用フィルム Download PDFInfo
- Publication number
- WO2011068067A1 WO2011068067A1 PCT/JP2010/070960 JP2010070960W WO2011068067A1 WO 2011068067 A1 WO2011068067 A1 WO 2011068067A1 JP 2010070960 W JP2010070960 W JP 2010070960W WO 2011068067 A1 WO2011068067 A1 WO 2011068067A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solar cell
- film
- resin layer
- sealing sheet
- resin
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- 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
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Definitions
- the present invention relates to a film for solar cell backside sealing sheet having light resistance and electrical insulating properties that can withstand use in a harsh outdoor environment for a long period of time. Moreover, this invention relates to the solar cell backside sealing sheet and solar cell module using the film for solar cell backside sealing sheets of this invention.
- Solar cells used for photovoltaic power generation constitute the heart of a photovoltaic power generation system that converts sunlight energy directly into electrical energy.
- Solar cells are made of semiconductors such as silicon.
- the solar cells are unitized by wiring various solar cell elements in series and in parallel and applying various packaging to protect the elements over a long period of about 20 years.
- the unit incorporated in this package is called a solar cell module.
- the solar cell module has a configuration in which a surface that is exposed to sunlight is covered with glass, a gap is filled with a filler made of a thermoplastic resin, and a back surface is protected with a sealing sheet.
- ethylene-vinyl acetate copolymer resin hereinafter referred to as EVA resin
- EVA resin ethylene-vinyl acetate copolymer resin
- the backside sealing sheet has mechanical strength, weather resistance, heat resistance, water resistance, light resistance, chemical resistance, light reflectivity, water vapor barrier properties, and thermal bonding with fillers typified by EVA resin. Characteristics such as sex are required.
- the back surface sealing sheet is required to be excellent in light resistance because it is exposed to ultraviolet light, and to be excellent in electrical insulation from the viewpoint of preventing occurrence of a short circuit in the solar cell system.
- a white polyvinyl fluoride film (DuPont Co., Ltd., trade name: Tedlar (registered trademark)) can be exemplified.
- a backside sealing sheet having a laminated structure in which a polyester film is sandwiched with a polyvinyl fluoride film is widely used in solar cell applications.
- stacked the polyester-type film excellent in the weather resistance and gas barrier property is also proposed as a back surface sealing sheet (patent document 1).
- the back surface sealing sheet of the solar cell is required to have a partial discharge voltage of 700 V or 1000 V depending on the power generation capacity of the cell in order to protect the solar cell module from damage due to voltage application. For this reason, proposals have been made to improve the partial discharge voltage.
- the polyvinyl fluoride film described above is a film having excellent weather resistance, but on the other hand, its mechanical strength is weak. Therefore, it may be softened by the heat of 140 to 150 ° C. hot press applied at the time of manufacturing the solar cell module, and the protrusion of the solar cell element electrode part may penetrate the filler layer. Furthermore, since it is expensive, it also becomes an obstacle in terms of reducing the cost of the solar cell module. In terms of electrical insulation, the partial discharge voltage of the resin film depends on the thickness of the film, so that the thickness of the film increases. Therefore, the cost is inevitably increased as workability deteriorates during cutting.
- the adhesion strength between the films to be bonded is weakened.
- solar cell modules are often installed obliquely on the ground surface mainly in Europe. In such a manner of installation, the solar cell is exposed to ultraviolet light reflected from the ground surface for a long period of time, so that the outer layer surface of the backside sealing sheet turns yellow, and the beauty of the film appearance is impaired. In addition, in extreme cases, cracks and the like occur in the back surface sealing sheet, and there is a concern that characteristics such as electrical insulation and water vapor barrier properties may be impaired.
- the present invention employs the following configuration. That is, the film for solar cell backside sealing sheet of the present invention is a resin, a conductive material and a color pigment in which an acrylic polyol resin and an ultraviolet absorber and / or a light stabilizer are copolymerized on at least one surface of a base film. And the conductive material content is 5 to 20 mass% with respect to the entire resin layer, and the surface resistance of the resin layer is 1.0 ⁇ 10 9 to 1.0 ⁇ 10 6. 15 ⁇ / ⁇ .
- the solar cell back surface sealing sheet of the present invention includes the film for solar cell back surface sealing sheet of the present invention.
- the solar cell module of the present invention includes the solar cell back surface sealing sheet and the cell filler layer of the present invention, and the solar cell back surface sealing sheet and the cell filler layer are bonded.
- a film for solar cell backside sealing sheet excellent in partial discharge voltage which is one index of light resistance and electrical insulation, can be obtained.
- the film for solar cell backside sealing sheet of the present invention includes a resin obtained by copolymerizing an acrylic polyol-based resin, an ultraviolet absorber and / or a light stabilizer, a conductive material, and a color pigment on at least one surface of a base film.
- the resin layer is laminated, the content of the conductive material is 5 to 20% by mass with respect to the entire resin layer, and the surface resistance of the resin layer is 1.0 ⁇ 10 9 to 1.0 ⁇ 10 15 ⁇ / ⁇ . is there.
- Various films can be used as a base material for the film for solar cell backside sealing sheet.
- 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 polyester resin 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.
- polyphenylene sulfide (PPS) having high hydrolysis resistance, heat resistance and flame retardancy can also be used.
- the film for solar cell backside sealing sheet is excellent in light resistance, it should be suitably used for the outermost layer that is directly exposed to the outside air (humidity, temperature) or reflected from the ground surface in the solar cell backside sealing sheet configuration. Can do.
- the base film is preferably a resin film having excellent hydrolysis resistance.
- 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 from a polyester resin having a cyclic trimer content of 1.0% by mass or less obtained by polymerization by a solid phase polymerization method as a raw material, under high temperature and high humidity It is possible to suppress the hydrolysis of the film, and a film having excellent heat resistance and weather resistance can be obtained.
- the cyclic trimer content is measured by, for example, measuring the content (% by mass) relative to the resin mass by measuring by liquid chromatography using a solution obtained by dissolving 100 mg of a polymer in 2 ml of orthochlorophenol. Is required.
- additives such as an antistatic agent, an ultraviolet absorber, a stabilizer, an antioxidant, a plasticizer, a lubricant, a filler, and a coloring pigment are added in a range that does not impair the effects of the present invention. Can be added within.
- the thickness of the base film is not particularly limited, but is preferably in the range of 1 to 250 ⁇ m in view of the voltage resistance characteristics, cost, etc. of the sealing sheet.
- the lower limit of the thickness is more preferably 25 ⁇ m or more.
- a water vapor barrier film in which at least one inorganic oxide layer is formed by vapor deposition or the like may be used 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).
- 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.
- the base film is preferably stretched in the biaxial direction so that the thermal dimensional stability is good. Moreover, you may perform surface treatments, such as discharge treatments, such as corona discharge and plasma discharge, or acid treatment, to a base film as needed.
- the resin layer laminated on the base film in the present invention is composed of (1) a resin obtained by copolymerizing an acrylic polyol resin and an ultraviolet absorber and / or a light stabilizer, (2) a conductive material, and (3) a color pigment. Including.
- a resin obtained by copolymerizing an acrylic polyol resin and an ultraviolet absorber and / or a light stabilizer a resin obtained by copolymerizing an acrylic polyol resin and an ultraviolet absorber and / or a light stabilizer
- a conductive material e.g., titanium dioxide, titanium dioxide, titanium silicates, titanium silicates, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium silicate, titanium
- an acrylic polyol resin is especially used among the acrylic resins so that an appropriate crosslinked structure can be introduced into the resin layer. It is preferable to use it. Since the solar cell backside sealing sheet using the solar cell backside sealing sheet film is exposed to high temperature treatment in the solar cell module manufacturing process, the resin layer is required to have heat resistance.
- 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 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, isobutyl methacrylate , T-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and the like.
- unsaturated carboxylic acids examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, and fumaric acid.
- Other monomers include butadiene, ethylene, vinyl acetate and the like.
- 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.
- the lower limit of the thickness of the resin layer is more preferably 1 ⁇ m or more, and particularly preferably 3 ⁇ m or more.
- the upper limit of the thickness of the resin layer is more preferably 4 ⁇ m or less.
- the thickness of the resin layer exceeds 5 ⁇ m, the UV-cutting performance is sufficiently exhibited, but the coating method is restricted, the production cost is increased, the coating film adheres to the transport roll, and the coating film peels off accompanying it. There is a concern that it is easy to generate.
- Examples of the solvent of the coating liquid for forming the resin layer by the coating method include toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethylformamide, dimethylacetamide, methanol, ethanol and water. Etc. can be illustrated.
- 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. Various methods can be applied as the coating method, and a roll coating method, a dip coating method, a bar coating method, a die coating method, a gravure roll coating method, and the like, or a combination of these methods can be used. Among these, the gravure roll coating method is a preferable method because the stability of the resin layer is increased.
- 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 to be 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
- a method for producing a copolymer resin of a light stabilizer, an ultraviolet absorber and an acrylic polyol is disclosed in detail in JP-A-2002-90515 [0019] to [0039].
- HALS HYBRID registered trademark
- an acrylic monomer and UV absorber copolymer as an active ingredient
- the electrically conductive material in this invention is mix
- the required characteristics of the solar cell back surface sealing sheet have a withstand voltage characteristic, and one of product specifications is a partial discharge voltage. Selection and use of members according to the system voltage is determined for the solar cell module, and the solar cell back surface sealing sheet showing a higher partial discharge voltage can be widely used in the solar cell module.
- the partial discharge voltage of the film for solar cell backside sealing sheet is improved.
- the surface resistance value of the resin layer surface is 1.0 ⁇ 10 9 to 1.0 ⁇ 10 15 ⁇ / ⁇ .
- the lower limit of the surface resistance value is preferably 1.0 ⁇ 10 11 ⁇ / ⁇ or more.
- the upper limit of the surface resistance value is preferably 1.0 ⁇ 10 14 ⁇ / ⁇ or less.
- the surface resistance value is less than 1.0 ⁇ 10 9 ⁇ / ⁇
- the conductive material is exposed on the surface of the coating film due to deterioration or disappearance of the resin layer when exposed outdoors for a long time, and the surface resistance value is 1. It may be less than 0 ⁇ 10 7 ⁇ / ⁇ . In this case, since a conductive phenomenon may occur on the film surface, wet insulation, which is a characteristic necessary for the solar cell back surface sealing sheet, may not be ensured.
- the surface resistance value is larger than 1.0 ⁇ 10 15 ⁇ / ⁇ , the effect of improving the partial discharge voltage may not be obtained. This is presumed to be because a partial discharge voltage is generated without the potential of the film surface being leveled.
- the resin layer has a surface resistance of 1.0 ⁇ 10 7 to 1.0 ⁇ 10 15 ⁇ after being irradiated with ultraviolet rays at 60 ° C. ⁇ 50% RH in an ultraviolet irradiation cumulative amount of 384 kWh / m 2. / ⁇ is preferred.
- the resin layer deteriorates and disappears due to ultraviolet irradiation, and the conductive material is exposed on the surface of the coating film, so that the surface resistance value is 1.0 ⁇ 10 7 ⁇ / ⁇ .
- the surface resistance before irradiation is set to the range of 1.0 ⁇ 10 9 to 1.0 ⁇ 10 15 . It is preferable to do.
- the lower limit of the surface resistance is more preferably 1.0 ⁇ 10 11 or more.
- Antistatic agents can be used as the conductive material.
- Antistatic agents include nonionic antistatic agents such as ethylene glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, pentael slit, sorbitol and other polyhydric alcohols and / or fatty acid esters thereof, polyethylene glycol and Examples thereof include fatty acid esters thereof, higher alcohols, polyhydric alcohols, polyethylene glycol adducts or polypropylene glycol adducts of alkylphenols.
- glycerin fatty acid ester, polyethylene glycol and / or fatty acid ester thereof are preferably used as an antistatic agent.
- the polyhydric alcohol can be used as it is, but it is more preferable to convert it into a fatty acid ester by an esterification reaction with a fatty acid.
- Fatty acids are not particularly limited, but are saturated fatty acids such as lauric acid (C12), valtic acid (C16), stearic acid (C18), behenic acid (C22), palmitoleic acid, oleic acid, erucic acid, linoleic acid, etc.
- Unsaturated fatty acids and the like are advantageously used in terms of cost.
- coconut oil fatty acid, soybean oil fatty acid, beef tallow fatty acid, sardine oil fatty acid and the like, and mixed fatty acids derived from natural products can also be used.
- the polyhydric alcohol is esterified with these fatty acids, it is preferable that at least one hydroxyl group remains per molecular structural unit of the polyhydric alcohol.
- the polyethylene glycol When polyethylene glycol and / or a fatty acid ester thereof is used as an antistatic agent, the polyethylene glycol preferably has an ethylene oxide repeating unit of 4 to 10,000, more preferably 100 to 8000, and particularly preferably 1000 to 6000. Is particularly preferably used.
- Polyethylene glycol can be used as it is as an antistatic agent.
- the terminal hydroxyl group may or may not remain.
- the higher alcohol is not particularly limited as long as it has 6 or more carbon atoms, but is representatively easily available industrially.
- the first alcohol include nonyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and oleyl alcohol. Mixtures such as sperm alcohol and jojoba alcohol, and reduced alcohols such as beef tallow alcohol and coconut alcohol can also be used.
- alkylphenol polyethylene glycol adduct or polypropylene glycol adduct examples of the alkylphenol include nonylphenol, dodecylphenol, octylphenol, octylcresol and the like.
- examples of the ionic antistatic agent include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and alkyl diphenyl sulfonates.
- Anionic antistatic agents such as phosphorus-containing antistatic agents such as alkyl phosphonates, alkyl phosphate esters, alkyl phosphites, alkyl phosphonates, alkyl phosphonates, and quaternary ammonium Examples thereof include cationic antistatic agents such as chloride, quaternary ammonium sulfate, and quaternary ammonium nitrate, and nonionic antistatic agents. Any ionic antistatic agent can be used. Examples of the anionic antistatic agent include Prisurf (registered trademark) M208F manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. and Persoft (registered trademark) EDO manufactured by NOF Corporation.
- Examples include Persoft (registered trademark) EL.
- Examples of the cationic antistatic agent include Nopcostat (registered trademark) SN A-2 manufactured by San Nopco, Cathiogen (registered trademark) ES-L manufactured by Daiichi Kogyo Seiyaku, and Elegan (registered trademark) 264WAX manufactured by NOF Corporation.
- Examples include Footogen (registered trademark) 310 manufactured by Neos, and Elicon (registered trademark) PQ-50B manufactured by Soken Chemical Co., Ltd.
- Examples of the nonionic antistatic agent include Neugen (registered trademark) TDS-30 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. and Neugen (registered trademark) ET-189.
- a conductive polymer compound as a conductive component, it is possible to impart antistatic properties to the resin layer.
- the conductive polymer include a polyacetylene polymer, a polypyrrole polymer, a polythiophene polymer, and a polyaniline polymer.
- an inorganic solid conductive material such as a conductive particle such as a carbon-based material or a metal-based material, or a filler can be used in order to maintain a satisfactory partial discharge voltage and surface resistance even after ultraviolet irradiation.
- Such materials include carbon-based materials such as carbon black, graphite, fullerene, and carbon nanotubes, indium oxide, zinc oxide, tin oxide, potassium titanate, titanium oxide, tin-antimony oxide, and indium-tin oxide. And antimony-tin oxides.
- at least one inorganic material selected from the group consisting of zinc oxide, titanium oxide, and potassium titanate is preferable. Further, it is particularly preferable to use a titanium oxide coated with tin oxide.
- conductive fibers As the inorganic solid conductive material.
- the specific size of the conductive fibers is such that the number average fiber diameter is 0.1 to 1.0 ⁇ m and the number average fiber length is about 2 to 30 ⁇ m.
- needle crystal fibers having a number average fiber length of 5 to 15 ⁇ m are preferable.
- the shape may be a rod-like shape, a needle-like shape with both ends or one end pointed, or a bent thread-like shape.
- the fiber itself may have conductivity, or the fiber surface may be coated with a conductive material.
- a spherical conductive material Compared with a spherical, three-dimensional, or plate-like conductive material (hereinafter referred to as a spherical conductive material), the conductive fibers are likely to come into contact with each other when the same amount is blended. Therefore, if the content is the same, a higher partial discharge voltage can be obtained than when a spherical conductive material is used. Alternatively, since a sufficient conductive network can be formed even with a small amount of content, a partial discharge voltage equal to or higher than that when using a conductive material such as a spherical shape can be obtained.
- the content of the conductive material in the resin layer can be reduced, and a resin obtained by copolymerizing an acrylic polyol resin and an ultraviolet absorber and / or a light stabilizer. It can occupy most of the resin layer. Therefore, sufficient light resistance can be obtained, and both partial discharge voltage and light resistance can be achieved.
- the conductive material a material in which the surface of an inorganic fiber is coated with a conductive material is preferable. This is because, as described above, the inorganic solid conductive material can maintain the initial partial discharge voltage even after ultraviolet irradiation. Particularly preferred is a needle-like conductive material in which titanium oxide is coated with tin oxide and the number average fiber length is 5 to 15 ⁇ m.
- a needle-like conductive material in which titanium oxide is coated with tin oxide and the number average fiber length is 5 to 15 ⁇ m.
- An example of such an inorganic fiber whose surface is coated with a conductive material is Dento (registered trademark) “WK500”, a conductive ceramic material manufactured by Otsuka Chemical Co., Ltd.
- the content of organic antistatic agents such as organic compound antistatic agents, ionic antistatic agents or conductive polymer compounds, and inorganic solid conductive materials may be used alone or in combination of two or more.
- the total content is 5 to 20% by mass with respect to the entire resin layer.
- the lower limit of the content is preferably 10% by mass or more.
- the antistatic agent cannot sufficiently form a conductive network, and the conductivity is difficult to develop and may be insufficient.
- the surface resistance value is less than 1.0 ⁇ 10 7 ⁇ / ⁇ , and the wet insulation that is a characteristic necessary for the solar cell back surface sealing sheet may not be ensured. is there.
- the organic antistatic agent itself turns yellow when irradiated with ultraviolet rays, when the content exceeds 20% by mass, there is a concern that the appearance of the film is deteriorated and the partial discharge voltage is lowered.
- cationic antistatic agents such as quaternary ammonium chloride, quaternary ammonium sulfate, and quaternary ammonium nitrate and inorganic solid conductive materials are used from the viewpoint of heat resistance and heat and humidity resistance.
- quaternary ammonium chloride quaternary ammonium sulfate
- quaternary ammonium nitrate quaternary ammonium nitrate
- inorganic solid conductive materials are used from the viewpoint of heat resistance and heat and humidity resistance.
- an inorganic solid conductive material is particularly preferably used.
- Coloring pigments For the purposes of (1) coloring the resin layer, (2) maintaining the color tone (not fading), (3) cutting ultraviolet rays and / or visible light, and (4) preventing the decrease in surface resistance.
- a white sheet is mainly used from the viewpoint of light reflectivity and design, but in recent years, the design is superior to the sheet in which the gap between the power generation elements looks white. For this reason, the demand for black sheets is increasing. Further, since these pigments themselves also absorb and / or reflect light having a specific wavelength, the effect of protecting the substrate film from ultraviolet rays and / or visible light can be obtained by coloring.
- the resin layer by protecting the resin layer from ultraviolet rays, it is possible to reduce deterioration and disappearance of the resin layer even when exposed outdoors for a long period of time, and to prevent a decrease in surface resistance due to the conductive material being exposed to the coating surface.
- the wet insulation which is a characteristic required for a solar cell backside sealing sheet can be ensured.
- the solar cell backside sealing sheet is brought into contact with water (electrolytic solution) in the wet insulation test, an effect that the resistance value does not decrease even when water comes into contact with the surface resistance value is set high.
- the color pigment various color pigments such as inorganic pigments and organic pigments can be used.
- white or black currently in practical use, titanium oxide is preferred as the white pigment and carbon black is preferred as the black pigment from the viewpoints of versatility, price, color development performance, and UV resistance.
- titanium oxide preferably has a number average particle size of 0.1 to 1.0 ⁇ m. From the viewpoint of dispersibility with respect to the acrylic polyol resin and cost, it is more preferably 0.2 to 0.5 ⁇ m. Similarly, the number average particle diameter of carbon black is preferably 0.01 to 0.5 ⁇ m. From the viewpoint of dispersibility and cost, it is more preferably 0.02 to 0.1 ⁇ m.
- the content of the color pigment is preferably 40 to 70% by mass with respect to the entire resin layer. As for the minimum of content, 45 mass% or more is more preferable. The upper limit of the content is more preferably 55% by mass or less.
- the content of the color pigment is less than 40% by mass, the ultraviolet ray and / or visible light cutting performance is poor, and the base film may be deteriorated or yellowed when exposed to the outdoors for a long time.
- the conductive material may be exposed on the surface of the coating film due to deterioration / disappearance of the resin layer, which may reduce the surface resistance value.
- the content of the color pigment exceeds 70% by mass, the filler amount is too large, and thus chalking may occur on the surface of the resin layer.
- the hardness of a resin layer will become high significantly and there exists a possibility that the adhesive force with a base material may be insufficient.
- cost will become high.
- 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.
- the effect of improving the adhesion between the base film and the resin layer or improving the solvent resistance and heat resistance of the resin layer accompanying the introduction of the crosslinked structure can be obtained.
- the solar cell back surface sealing sheet is designed so that the resin layer in the present invention is located in the outermost layer
- the glass laminating process cell filling process
- heat resistance is particularly required.
- solvent cleaning is required because there is a wiping operation with ethanol or other organic solvent as a cleaning operation after the module is assembled.
- a crosslinking agent is added to the surface of the coating film and the partial discharge voltage is improved. Therefore, it is necessary to consider whether or not a cross-linking agent is blended in consideration of the balance between the improvement in partial discharge voltage and the improvement in adhesion, solvent resistance, and heat resistance.
- a conductive material such as a sphere is used as the conductive material, it is preferable not to add a crosslinking agent in order to achieve the partial discharge voltage required for the film for solar cell backside sealing sheet.
- a resin obtained by copolymerizing an acrylic polyol resin and an ultraviolet absorber and / or a light stabilizer is used, it is possible to use a crosslinking agent capable of reacting with the hydroxyl group of the resin.
- a prescription that uses a polyisocyanate resin as a curing agent and promotes the formation of urethane bonds (crosslinked structure) is preferred.
- the polyisocyanate resin used as the cross-linking agent include aromatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Each of the following diisocyanate compounds is used as a raw material. Resin. These may be used alone or in combination of two or more.
- 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
- MDI 2,2'-diphenylmethane diisocyanate
- TDI 2,4- or 2,6-tolylene diisocyanate
- 4,4'-diphenyl ether diisocyanate and the like are exemplified.
- diisocyanate used as a raw material for the araliphatic polyisocyanate examples include 1,3- or 1,4-xylylene diisocyanate (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate (TMXDI), and the like. Is 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), 4,4'-, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate (hydrogenated MDI), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, and 1,3-or Examples include 1,4-bis (isocyanatomethyl) cyclohexane (hydrogenated XDI).
- 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- or Examples include 1,3-butylene diisocyanate and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate.
- a polyisocyanate raw material a combination of a plurality of these diisocyanates may be used, and a modified product such as a burette modified product or a nurate modified product may be used.
- a resin containing an aromatic ring having a light absorption band in the ultraviolet region in the resin skeleton is liable to yellow with ultraviolet irradiation, and therefore, an alicyclic polyisocyanate and / or an aliphatic group.
- a curing agent mainly composed of polyisocyanate.
- an alicyclic polyisocyanate in which the resin layer is further cured from the viewpoint of solvent resistance.
- a nurate-modified product of hexamethylene diisocyanate is preferable from the viewpoints of easy progress of a crosslinking reaction with an acrylic polyol resin, the degree of crosslinking, heat resistance, ultraviolet resistance, and the like.
- a solar cell back surface sealing sheet is obtained by laminating a film for solar cell back surface sealing sheet and another resin film.
- a known dry laminating method can be used as a method of laminating films and processing into a sheet.
- polyether polyurethanes, polyester polyurethanes, polyesters, polyepoxy resins, etc. are the main ingredients, and known for dry laminates using polyisocyanate resins as curing agents.
- An adhesive can be used. However, the adhesive layer formed using these adhesives does not cause delamination due to deterioration of the adhesive strength after long-term outdoor use, and yellowing that leads to a decrease in light reflectance. It is necessary not to produce such.
- the thickness of the adhesive layer is preferably in the range of 1 to 5 ⁇ m. If the thickness is less than 1 ⁇ m, sufficient adhesive strength may not be obtained. 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 strength (promoting the crosslinking reaction between the main agent and the curing agent), and the use of the adhesive Production costs may increase due to increased volume.
- a known dry laminating adhesive can be used as a material used for forming the adhesive layer.
- adhesives for dry laminating are prepared by diluting two resins, a main agent and a cross-linking agent, with a diluting solvent.
- the cross-linking agent is highly reactive with active hydroxyl groups, its reaction rate and initial adhesion.
- the prescription using an isocyanate group-containing polymer with a fast onset is preferred.
- 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 sheet, it is also conceivable that ultraviolet rays reach the above adhesive layer and induce 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 sheet using the film for solar cell back surface sealing sheet is demonstrated.
- the solar cell back surface sealing sheet is required to have various characteristics represented by water vapor barrier properties, light reflectivity, long-term moisture and light resistance, adhesion to cell fillers, 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.
- the film for solar cell backside sealing sheet of the present invention is different from the substrate film among the film having hydrolysis resistance, the white film, the film having inorganic oxide deposition, and the film having thermal adhesiveness with EVA.
- a solar cell back surface sealing sheet satisfying various required characteristics can be obtained.
- the portion of the solar cell backside sealing sheet that becomes the outer side when incorporated in the solar cell module is a hydrolysis-resistant film as a base film, and this base film is used for a solar cell backside sealing sheet.
- stacks a film is preferable.
- a resin layer having ultraviolet and / or visible light cutting performance is located on the outermost layer side, the layer inside the resin layer is protected from ultraviolet and / or visible light.
- one or more of a white film, a film having an inorganic oxide vapor deposition, and a film having thermal adhesiveness with EVA are laminated on the surface opposite to the surface on which the resin layer of the base film is laminated. Is preferred.
- a white film is laminated, light reflectivity is imparted, when a film having an inorganic oxide vapor deposition layer is laminated, water vapor barrier property is imparted, and when a film having thermal adhesiveness with EVA is laminated Is provided with adhesion to the cell filler layer.
- stacked on the film for solar cell backside sealing sheets of this invention does not necessarily need to be one sheet, According to the characteristic to give, combine each member film suitably and design a solar cell backside sealing sheet. It ’s fine.
- a vapor deposition layer, a sputter layer, a wet coating layer, etc. for the purpose of imparting functionality are formed on any layer as long as it is a portion other than the resin layer in the present invention. May be.
- the following method is mentioned as an example of the manufacturing method of the film for solar cell backside sealing sheets.
- a base film for example, a hydrolysis resistant polyethylene terephthalate film Lumirror (registered trademark) X10S manufactured by Toray Industries, Inc. is prepared.
- the coating agent which mixed the main ingredient which disperse
- the film for solar cell backside sealing sheets can be obtained by coating this coating material on a base film using a gravure roll coating method.
- the solar cell backside sealing sheet includes a white film, a film having an inorganic oxide vapor-deposited layer, and ethylene-vinyl acetate on the side opposite to the side on which the resin layer of the solar cell backside sealing sheet is laminated. It can be obtained by laminating at least one film selected from the group consisting of films having thermal adhesiveness with a copolymer using a dry laminating method.
- the characteristic evaluation method used in the present invention is as follows.
- Water vapor transmission rate was measured based on the method B (infrared sensor method) described in JIS K7129 (2000 version) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH.
- a water vapor transmission rate measuring device Permatran (registered trademark) W3 / 31 manufactured by MOCON (USA) was used as a measuring device.
- Permatran registered trademark
- W3 / 31 manufactured by MOCON (USA) was used.
- Each of the two test pieces was measured once, and the average value of the two measured values was used as the water vapor transmission rate.
- UV-cut performance (spectral spectrum measurement) Based on JIS K 7105 (2006 edition), the spectrum was measured.
- an ultraviolet-visible near-infrared spectrophotometer UV-3150 manufactured by Shimadzu Corporation was used as a measuring apparatus.
- the ultraviolet cut performance of the film for solar cell backside sealing sheet was evaluated by measuring the light transmittance at a wavelength of 360 nm.
- the surface resistance value of the resin layer was measured in an environment of 23 ° C. and 65% RH. About the sample in which the resin layer is not formed, the probe electrode part was applied to the base film surface, and it measured. The measurement was performed on three test pieces. The average value of the measured values was defined as the surface resistance value.
- a surface resistivity meter MCP-HT450 manufactured by Mitsubishi Chemical was used as a measuring device.
- the partial discharge voltage was measured in the environment of 23 degreeC and 65% RH.
- the measuring device used was a partial discharge tester KPD2050 manufactured by Kikusui Electronics Corporation. About the sample in which the resin layer is formed, voltage was applied and measured from the resin layer surface. About the sample without a resin layer, it applied and measured from the base film surface. Ten test pieces were each measured once, and a total of 10 data were collected. The average of the measured values was defined as the partial discharge voltage.
- Ultraviolet resistance evaluation Ultraviolet irradiation (ultraviolet irradiation cumulative amount 384 kWh / m 2 ) was performed for 240 hours at an ultraviolet intensity of 160 mW / cm 2 in a 60 ° C. ⁇ 50% RH atmosphere.
- an Isuper UV tester SUV-W151 manufactured by Iwasaki Electric Co., Ltd. was used as a test apparatus. The color system b value before and after that was measured.
- UV irradiation is performed in the same manner for the purpose of evaluating the UV resistance of those characteristics, and the evaluation before and after that is performed. It was.
- the EVA sheet is laminated on the inner layer side (the surface opposite to the surface on which the resin layer of the base film is laminated) of the solar cell back surface sealing sheet, and a 0.3 mm thick semi-strengthened layer is further formed thereon. Stacked glass. Next, a vacuum was drawn using a commercially available glass laminator, and press treatment was performed for 15 minutes under a heating condition of 135 ° C. under a load of 3 kgf / cm 2 to produce a pseudo solar cell module sample. As the EVA sheet, a 500 ⁇ m thick sheet manufactured by Sanvik Co., Ltd. was used.
- the light reflectance was measured on the inner layer side of the back surface sealing sheet (the surface opposite to the surface on which the resin layer of the base film was laminated).
- the reflectance at a wavelength of 600 nm was used as a representative.
- a spectrophotometer MPC-3100 manufactured by Shimadzu Corporation was used as a measuring apparatus.
- a pseudo solar cell module sample was prepared in the same manner as in the above (10). Using this pseudo solar cell module, the wet insulation resistance was measured based on the method described in IEC61215 10.15. The module was immersed in the electrolytic solution, and the terminal of the testing machine was brought into contact with the module output terminal and the electrolytic solution, and a leakage current was measured by applying a voltage of 500V. The insulation resistance is required to be 400 M ⁇ or more at a solar cell module area of 0.1 m 2 or less, and 40 M ⁇ or more at 0.1 m 2 or more.
- Hals hybrid polymer (registered trademark) BK1 solid content concentration: 40% by mass, acrylic resin) manufactured by Nippon Shokubai Co., Ltd., in which an ultraviolet absorber and a light stabilizer (HALS) are crosslinked with an acrylic polyol resin 1) was prepared.
- Acrylic resin 1 conductive material, color pigment and solvent were mixed together in the blending amounts shown in Table 1 and dispersed using a bead mill machine to obtain a main component paint having a solid content concentration of 50% by mass.
- the following products were used as conductive materials and colored pigments.
- Conductive material An inorganic solid conductive material which is a needle-like crystal in which titanium oxide is coated with tin oxide. The number average fiber length is distributed in the range of 5 to 15 ⁇ m.
- White pigment Titanium oxide particles JR-709 manufactured by Teika Black pigment: Carbon black particles Special black 4A manufactured by Degussa.
- Desmodur (registered trademark) N3300 solid content concentration: 100% by mass
- Desmodur (registered trademark) N3300 solid content concentration: 100% by mass
- the main agent paint / nurate type hexamethylene diisocyanate resin 100/4. It mix
- a diluent: n-propyl acetate was added so as to obtain a paint having a solid content concentration of 20% by mass (resin solid content concentration), and the mixture was stirred for 15 minutes.
- a resin layer forming coating material 1 having a solid content concentration of 20% by mass (resin solid content concentration) was obtained.
- Resin layer forming coating material 2 was obtained in the same manner as the adjustment of resin layer forming coating material 1 except that the blending amount shown in Table 1 was set so that the content of the conductive material relative to the resin solid content was 19% by mass. .
- Resin layer forming paint 3 was obtained in the same manner as the adjustment of resin layer forming paint 1 except that the blending amount shown in Table 1 was set so that the content of the conductive material relative to the resin solid content was 6% by mass. .
- Resin layer-forming coating material 5 was obtained in the same manner as in the preparation of resin layer-forming coating material 1 except that the blending amount shown in Table 1 was adjusted so that the content of the color pigment relative to the resin solid content was 40% by mass. .
- Resin layer-forming coating material 6 was obtained in the same manner as the adjustment of resin layer-forming coating material 1 except that the blending amount shown in Table 1 was set so that the content of the color pigment relative to the resin solid content was 70% by mass. .
- Resin layer forming coating material 7 was obtained in the same manner as the adjustment of resin layer forming coating material 1 except that the blending amount shown in Table 1 was adjusted so that the content of the color pigment relative to the resin solid content was 35% by mass. .
- Resin layer-forming coating material 8 was obtained in the same manner as in the preparation of resin layer-forming coating material 1 except that the blending amount shown in Table 1 was adjusted so that the content of the color pigment relative to the resin solid content was 75% by mass. .
- Resin layer-forming coating material except for using DeSmodur (registered trademark) N3200 (solid content concentration: 100% by mass) manufactured by Sumika Bayer, which is a burette type hexamethylene diisocyanate resin, instead of the nurate type hexamethylene diisocyanate resin.
- a resin layer-forming coating material 9 was obtained in the same manner as in the adjustment of No. 1.
- Resin layer forming coating material 10 was obtained in the same manner as the adjustment of resin layer forming coating material 1 except that the blending amount shown in Table 2 was set so that the content of the conductive material relative to the resin solid content was 4% by mass. .
- Resin layer forming coating material 11 was obtained in the same manner as the adjustment of resin layer forming coating material 1 except that the blending amount shown in Table 2 was set so that the content of the conductive material relative to the resin solid content was 25% by mass. .
- a resin layer-forming coating material 12 was obtained in the same manner as the adjustment of the resin layer-forming coating material 1 except that the conductive material was not blended and the amount shown in Table 2 was used.
- Resin layer-forming coating material 13 was obtained in the same manner as the adjustment of resin layer-forming coating material 1 except that the coloring pigments were not blended and the amounts shown in Table 2 were used.
- Example 1 A hydrolysis-resistant polyethylene terephthalate film Lumirror (registered trademark) X10S (125 ⁇ m) having a cyclic trimer content of 1% by mass or less was prepared as a base film. On one surface of the base film, the resin layer forming paint 1 was applied using a wire bar, dried at 120 ° C. for 30 seconds, and a resin layer having a coating amount of 4.0 g / m 2 was provided after drying. . Thus, the film 1 for solar cell backside sealing sheets was manufactured.
- Lumirror registered trademark
- X10S 125 ⁇ m
- Example 2 A solar cell backside sealing sheet film 2 was produced in the same manner as in Example 1 except that the resin layer forming paint 2 was applied instead of the resin layer forming paint 1.
- Example 3 A solar cell backside sealing sheet film 3 was produced in the same manner as described in Example 1 except that the resin layer forming paint 3 was applied instead of the resin layer forming paint 1.
- Example 4 A solar cell backside sealing sheet film 4 was produced in the same manner as in Example 1 except that the resin layer forming paint 4 was applied instead of the resin layer forming paint 1.
- Example 5 A solar cell backside sealing sheet film 5 was produced in the same manner as described in Example 1, except that the resin layer forming paint 5 was applied instead of the resin layer forming paint 1.
- Example 6 A solar cell backside sealing sheet film 6 was produced in the same manner as described in Example 1, except that the resin layer forming paint 6 was applied instead of the resin layer forming paint 1.
- Example 7 A solar cell backside sealing sheet film 7 was produced in the same manner as in Example 1 except that the resin layer forming paint 7 was applied instead of the resin layer forming paint 1.
- Example 8 A solar cell backside sealing sheet film 8 was produced in the same manner as described in Example 1, except that the resin layer forming paint 8 was applied instead of the resin layer forming paint 1.
- Example 9 A solar cell backside sealing sheet film 9 was produced in the same manner as in Example 1 except that the resin layer forming paint 9 was applied instead of the resin layer forming paint 1.
- Example 1 A solar cell backside sealing sheet film 10 was produced in the same manner as in Example 1 except that the resin layer forming paint 10 was applied instead of the resin layer forming paint 1.
- Example 2 A solar cell backside sealing sheet film 11 was produced in the same manner as in Example 1 except that the resin layer forming paint 11 was applied instead of the resin layer forming paint 1.
- Example 5 A solar cell backside sealing sheet film 14 was produced in the same manner as in Example 1 except that the resin layer forming paint 14 was applied instead of the resin layer forming paint 1.
- Films 1 to 3 for solar cell backside sealing sheets of Examples 1 to 3 have an excellent partial discharge voltage characteristic in which the content of the conductive material in the resin layer is in the range of 5 to 20% by mass. It was. The surface resistance value decreased as the content approached 20% by mass, and the partial discharge voltage tended to decrease as the content approached 5% by mass.
- the film 4 for solar cell backside sealing sheet of Example 4 uses a cationic antistatic agent as a conductive material and has poor UV resistance, so the partial discharge voltage decreases after UV irradiation and the ⁇ b value increases. It was observed.
- the content of the color pigment in the resin layer is changed within the range of 35 to 75% by mass.
- Example 7 When the content was less than 40% by mass, the UV-cut performance was not sufficient, and thus an increase in ⁇ b value after UV irradiation was observed (Example 7). On the other hand, when the content exceeded 70% by mass, the amount of filler was too large, and thus choking was observed on the surface of the resin layer.
- the film 9 for solar cell backside sealing sheet of Example 9 has changed the hexamethylene diisocyanate resin, which is a curing agent, from a nurate type to a burette type, and has insufficient solvent resistance due to insufficient curing of the coating film. The coating film was peeled off.
- seat of the comparative example 4 does not contain a color pigment in a resin layer. Therefore, the resin layer could not be protected from ultraviolet rays, and the resin layer was deteriorated / disappeared by ultraviolet irradiation, and the surface resistance value was reduced to 1.0 ⁇ 10 5 ⁇ / ⁇ or less. Moreover, since the ultraviolet light cutting performance was poor, the ⁇ b value of the base film increased to 12.2 with the irradiation of ultraviolet rays, and yellowing occurred.
- the film 14 for solar cell backside sealing sheet of the comparative example 5 uses the acrylic resin which added the ultraviolet absorber and the light stabilizer (HALS) after the addition as an acrylic resin which comprises a resin layer, without bridge
- HALS ultraviolet absorber and the light stabilizer
- the solar cell backside sealing sheet film 15 of Comparative Example 6 (Lumirror (registered trademark) X10S film itself in which no resin layer is formed) does not have ultraviolet light cutting performance and includes a conductive material that improves the partial discharge voltage. A resin layer is not formed. Therefore, the partial discharge voltage was as low as 650 V, and resin degradation and yellowing occurred with the irradiation of ultraviolet light.
- the film when used in the outermost layer of the solar cell backside sealing sheet, in extreme cases, the film is cracked, pinholes, etc., and the 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 the operation of the solar cell module may be adversely affected.
- Example 10 A white polyethylene terephthalate film Lumirror (registered trademark) E20F (50 ⁇ m) manufactured by Toray Industries, Inc. was prepared as a light reflective film.
- a water vapor barrier film an aluminum oxide vapor-deposited polyethylene terephthalate film manufactured by Toray Film Processing Co., Ltd. Barrier Rocks (registered trademark) 1031HGTS (12 ⁇ m) on the surface opposite to the aluminum oxide vapor-deposited layer, a coating for forming an adhesive layer and heat bonding
- a film was prepared by sequentially coating the coating material for forming the conductive resin layer using a two-head tandem direct gravure coater under the following conditions.
- Adhesive layer coating conditions Aiming at dry film thickness of 0.2 ⁇ m, drying oven set temperature 120 ° C -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.
- the adhesive for dry lamination was applied with a wire bar on the surface of the base film opposite to the resin layer of the film for solar cell backside sealing sheet 1 of Example 1, and dried at 80 ° C. for 45 seconds to 3.5 ⁇ m.
- the adhesive layer was formed.
- a light reflective film was bonded to the adhesive layer using a hand roller.
- an adhesive for dry lamination was applied with a wire bar on the light reflective film surface opposite to the resin layer of the laminate film, and dried at 80 ° C. for 45 seconds to form a 3.5 ⁇ m adhesive layer. .
- steam barrier film was bonded together to this adhesive bond layer using the hand roller.
- seat which consists of three films produced was aged in the oven heated at 40 degreeC for 3 days, and the solar cell back surface sealing sheet 1 was obtained.
- Example 11 A solar cell was produced in the same manner as in Example 10 except that a white polyethylene film (100 ⁇ m) manufactured by Toray Film Processing Co., Ltd., which has excellent adhesion to the EVA sheet, was used instead of E20F and the water vapor barrier film. The back surface sealing sheet 2 was obtained.
- the solar cell backside sealing sheet 3 is the same as the method described in Example 10 except that the solar cell backside sealing sheet film 11 of Comparative Example 2 is used instead of the solar cell backside sealing sheet film 1.
- the solar cell backside sealing sheet 4 is the same as the method described in Example 10 except that the solar cell backside sealing sheet film 12 of Comparative Example 3 is used instead of the solar cell backside sealing sheet film 1.
- the solar cell backside sealing sheet 5 is the same as the method described in Example 10 except that the solar cell backside sealing sheet film 15 of Comparative Example 6 is used instead of the solar cell backside sealing sheet film 1.
- the solar cell backside sealing sheets 1 and 2 of Examples 10 and 11 both show a high partial discharge voltage of 1000 V or higher, and can be suitably used as a backside sealing sheet for solar cell modules having a high system voltage. . Moreover, the fall of the adhesive force between a base film and a resin layer accompanying ultraviolet irradiation to the resin layer side located in the outer layer side in the solar cell module structure was not seen. Furthermore, the yellowing of the resin layer and the substrate film was very small.
- This solar cell backside sealing sheet 5 is a solar cell that assumes a solar cell module application that requires a high system voltage and an installation configuration that may be exposed to reflected ultraviolet rays from the ground surface such as a field installation type. It cannot be used for module purposes.
- the solar cell module using the solar cell back surface sealing sheet of the present invention is a solar cell module excellent in durability.
- the film for solar cell backside sealing sheet of the present invention is excellent in partial discharge voltage, which is one index of light resistance and electrical insulation, and can be suitably used for a solar cell backside sealing sheet. Furthermore, this solar cell back surface sealing sheet can be used suitably for a solar cell module.
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Abstract
Description
太陽電池裏面封止シート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等のポリエステル樹脂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。更に高い耐加水分解性、耐熱性、難燃性を持つポリフェニレンサルファイド(PPS)を使用することもできる。また、従来から裏面封止用シート用フィルムとして用いられているポリフッ化ビニルに代表されるフッ素系フィルムを使用することも可能である。
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および/または光安定化剤とを共重合させた樹脂、(2)導電材料および(3)着色顔料とを含んでいる。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することがある。そのため、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。これに対して、本発明では、ポリエステル樹脂、オレフィン系樹脂などと比較して、比較的耐光性に優れるアクリル系樹脂に紫外線吸収剤および/または光安定化剤を共重合させた樹脂をバインダー樹脂として用いることで、上記の課題の解決を図っている。また、基材フィルムと樹脂層との密着力向上、あるいは樹脂層の耐熱性向上のために、樹脂層に適切な架橋構造を導入できるように、アクリル系樹脂の中でも、特にアクリルポリオール系樹脂を用いるのが好ましい。太陽電池裏面封止シート用フィルムを用いた太陽電池裏面封止シートは、太陽電池モジュール製造工程において、高温処理に曝されるので、樹脂層には耐熱性が要求される。
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。
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。
本発明における導電材料は、太陽電池裏面封止シート用フィルムの部分放電電圧を向上させる目的で配合される。前記の通り、太陽電池裏面封止シートの要求特性に耐電圧特性があり、製品規格の1つに部分放電電圧がある。太陽電池モジュールにはシステム電圧に応じた部材の選定・使用が定められており、より高い部分放電電圧を示す太陽電池裏面封止シートの方が、広く太陽電池モジュールでの使用が可能となる。樹脂層に導電材料を配合すると、太陽電池裏面封止シート用フィルムの部分放電電圧が向上する。部分放電電圧向上のメカニズムは、現時点で明らかではないが、導電性の付与によりフィルム表面の電位が平準化されていることが寄与しているものと推測される。部分放電電圧の向上効果を得るために、樹脂層表面の表面抵抗値は1.0×109~1.0×1015Ω/□である。表面抵抗値の下限は1.0×1011Ω/□以上が好ましい。表面抵抗値の上限は1.0×1014Ω/□以下が好ましい。
マッコウアルコールやホホバアルコール等の混合物や、牛脂アルコール、およびヤシアルコール等の還元アルコールを用いることもできる。
さらに、帯電防止剤としてイオン系の帯電防止剤を使用する場合、イオン系の帯電防止剤としては、例えば、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタリンスルホン酸塩、アルキルジフェニルスルホン酸塩等のスルホン酸塩系帯電防止剤、アルキルリン酸エステル、アルキル亜リン酸塩、アルキルホスホン酸塩、アルキルホスホン酸エステル等の含リン系帯電防止剤などのアニオン系帯電防止剤や、第4級アンモニウムクロライド、第4級アンモニウムサルフェート、第4級アンモニウムナイトレートなどのカチオン系帯電防止剤、さらにはノニオン系の帯電防止剤が挙げられる。いずれのイオン性帯電防止剤も使用可能であり、アニオン系帯電防止剤としては、例えば、第一工業製薬社製プライサーフ(登録商標)M208Fや日油社製パーソフト(登録商標)EDO、同じくパーソフト(登録商標)ELなどが例示できる。また、カチオン性帯電防止剤としては、例えば、サンノプコ社製ノプコスタット(登録商標)SN A-2、第一工業製薬社製カチオーゲン(登録商標)ES-L、日油社製エレガン(登録商標)264WAX、ネオス社製フタージェント(登録商標)310、綜研化学社製エレコンド(登録商標)PQ-50Bなどが例示できる。また、ノニオン性帯電防止剤としては、例えば、第一工業製薬社製ノイゲン(登録商標)TDS-30、同じくノイゲン(登録商標)ET-189などが例示できる。
本発明に用いる着色顔料は、(1)樹脂層を着色する、(2)色調の維持(退色しない)、(3)紫外線および/または可視光カット、(4)表面抵抗の低下防止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、光反射性およ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紫外線および/または可視光から基材フィルムを保護するという効果が得られる。
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。
太陽電池裏面封止シート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シートが得られる。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ないことがある。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(主剤およ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ことがある。
太陽電池裏面封止シート用フィルムを用いた太陽電池裏面封止シートについて説明する。太陽電池裏面封止シートには水蒸気遮断性、光反射性、長期耐湿熱・耐光耐久性、対セル充填剤密着力、電気絶縁性などに代表される種々の特性が要求される。現在、これらの要求特性を満たすべく、機能分割の考え方に則って、種々の機能性フィルム、蒸着、ウェットコーティングなどの加工技術を組み合わせた各社各様のシート設計(積層設計)がなされている。
本発明で用いた特性の評価方法は、下記の通りである。
樹脂層形成後に太陽電池裏面封止シート用フィルムを500cm2の面積に切り出し、その試験片の質量を質量(1)[g]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)[g]とした。続いて、下式に基づき単位面積当たりの樹脂層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。
サンプルをエタノール中に5分間浸し、その後キムワイプを使用して50回こすった。その後、下記(7)項と同様にして部分放電電圧を測定した。また塗膜の状態を観察し、下記のように分類した。
A:処理前と塗膜状態変化なし。
B:基材と塗膜の剥離がみられる。
温度40℃、湿度90%RHの条件で、JIS K7129(2000年版)に記載のB法(赤外センサー法)に基づいて水蒸気透過率を測定した。測定装置は、米国モコン(MOCON)社製の水蒸気透過率測定装置パ-マトラン(登録商標)W3/31を使用した。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。
JIS K 7105(2006年度版)に基づいて、分光スペクトルの測定を実施した。測定装置は、島津製作所社製紫外可視近赤外分光光度計UV-3150を使用した。太陽電池裏面封止シート用フィルムの紫外線カット性能は、360nmの波長の光線透過率を測定することで評価した。
作製した太陽電池裏面封止シート用フィルムの基材フィルムと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た。結果を下記のように分類した。
AA:100マス塗膜残存/100マス中
A:81~99マス塗膜残存/100マス中
B:80マス以下の塗膜残存/100マス中。
23℃、65%RHの環境下で樹脂層の表面抵抗値の測定を行った。樹脂層が形成されていないサンプルについては、基材フィルム面にプローブ電極部を当てて測定した。測定は3枚の試験片について行った。測定値の平均値を表面抵抗値とした。測定装置は、三菱化学製表面抵抗率計MCP-HT450を使用した。
23℃、65%RHの環境下で部分放電電圧の測定を行った。測定装置は、菊水電子工業社製部分放電試験機KPD2050を使用した。樹脂層が形成されているサンプルについては、樹脂層面から電圧をかけ測定した。樹脂層が無いサンプルについては、基材フィルム面から電圧をかけ測定した。10枚の試験片について各1回ずつ測定を行い、合計10個のデータを採取した。測定値の平均を部分放電電圧とした。
60℃×50%RH雰囲気にて紫外線強度160mW/cm2で240時間紫外線照射(紫外線照射積算量384kWh/m2)を行った。試験装置は、岩崎電気社製アイスーパーUVテスターSUV-W151を使用した。その前後の表色系b値の測定を行った。また、紫外線カット性能の評価、基材フィルム/樹脂層間の密着強度評価、表面抵抗の評価についても、それらの特性の耐紫外線性評価の目的で同様に紫外線照射を実施しその前後の評価を行った。
120℃、100%RHの環境下で48Hrの熱処理を太陽電池裏面封止シート用フィルムに施した。試験装置は、エスペック社製プレッシャクッカーTPS-211を使用した。その後、太陽電池裏面封止シート用フィルムの紫外線カット性能の評価、基材フィルム/樹脂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。
太陽電池裏面封止シートの内層側(基材フィルムの樹脂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た。次いで、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、3kgf/cm2荷重で15分プレス処理をして、疑似太陽電池モジュールサンプルを作成した。EVAシートは、サンビック(株)製の500μm厚シートを用いた。
この疑似太陽電池モジュールサンプルのガラス側から光を入射し、裏面封止シートの内層側(基材フィルムの樹脂層を積層した面とは反対面)について、光線反射率を測定した。反射率の測定値としては、600nmの波長における反射率を代表して用いた。測定装置は、島津製作所(株)製分光光度計MPC-3100を使用した。
前記(10)項と同様にして疑似太陽電池モジュールサンプルを作成した。この疑似太陽電池モジュールを使用して、JISK 6854-2(1999年版)に基づいて、EVAシートとの接着力を測定した。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回行った。2つの測定値の平均値を接着強度の値とした。接着強度が100N/50mm以上あることが実用上問題ないレベルであると判断する。
前記(10)項と同様にして疑似太陽電池モジュールサンプルを作成した。この疑似太陽電池モジュールを使用して、IEC61215 10.15に記載の方法に基づいてWet絶縁抵抗の測定を行った。モジュールを電解液に浸し、試験機の端子をモジュール出力端子と電解液に接触させ、500Vの電圧を印加して漏れ電流を測定した。絶縁抵抗は太陽電池モジュール面積0.1m2以下にて400MΩ以上、0.1m2以上にて40MΩ以上必要である。
樹脂層を形成したフィルムを40℃の環境下で3日間エージングを行った。エージング後の樹脂層表面を観察して、下記のように分類とした。
A:塗膜にチョーキングが発生していない
B:塗膜にチョーキングが発生している。
アクリル樹脂として、(株)日本触媒製の、紫外線吸収剤および光安定化剤(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)を用意した。アクリル樹脂1、導電材料、着色顔料および溶剤を表1に示す配合量で一括混合し、ビーズミル機を用いて分散し、固形分濃度が50質量%である主剤塗料を得た。導電材料、着色顔料としては下記の製品を使用した。
導電材料:酸化チタンに酸化スズを被覆した針状結晶である無機固体導電材料。数平均繊維長は5~15μmの範囲で分布している。
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。
樹脂固形分に対する導電材料の含有量が19質量%となるように表1に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料2を得た。
樹脂固形分に対する導電材料の含有量が6質量%となるように表1に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料3を得た。
無機固形導電材料の代わりにカチオン性帯電防止剤である綜研化学社製エレコンド(登録商標)PQ-50Bを配合する以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料4を得た。
樹脂固形分に対する着色顔料の含有量が40質量%となるように表1に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料5を得た。
樹脂固形分に対する着色顔料の含有量が70質量%となるように表1に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料6を得た。
樹脂固形分に対する着色顔料の含有量が35質量%となるように表1に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料7を得た。
樹脂固形分に対する着色顔料の含有量が75質量%となるように表1に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料8を得た。
ヌレート型ヘキサメチレンジイソシアネート樹脂の代わりに、ビューレット型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、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料9を得た。
樹脂固形分に対する導電材料の含有量が4質量%となるように表2に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料10を得た。
樹脂固形分に対する導電材料の含有量が25質量%となるように表2に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料11を得た。
導電材料を配合せず表2に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料12を得た。
着色顔料を配合せず表2に示す配合量とする以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料13を得た。
アクリル樹脂として、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、紫外線吸収剤および光安定化剤(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)を用意した。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%)を用いる代わりに、このアクリル樹脂2を用いる以外は、樹脂層形成用塗料1の調整と同様の方法で樹脂層形成用塗料14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分間攪拌した。こうして固形分濃度20%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分間攪拌した。こうして固形分濃度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分間攪拌した。こうして固形分濃度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質量%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樹脂層形成用塗料1を塗布し、120℃で30秒間乾燥し、乾燥後塗布量が4.0g/m2の樹脂層を設けた。このようにして太陽電池裏面封止シート用フィルム1を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料2を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム2を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料3を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム3を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料4を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム4を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料5を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム5を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料6を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム6を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料7を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム7を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料8を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム8を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料9を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム9を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料10を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム10を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料11を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム11を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料12を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム12を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料13を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム13を製造した。
樹脂層形成用塗料1の代わりに樹脂層形成用塗料14を塗布する以外は、実施例1に記載の方法と同様にして太陽電池裏面封止シート用フィルム14を製造した。
樹脂層を形成しないで、ルミラー(登録商標)X10S(東レ(株)製、125μm)を太陽電池裏面封止シート用フィルム15とした。
実施例1~3の太陽電池裏面封止シート用フィルム1~3は、樹脂層中の導電材料の含有量が5~20質量%の範囲内であり、優れた部分放電電圧の特性を有していた。含有量が20質量%に近づくほど表面抵抗値が低下し、5質量%に近づくほど部分放電電圧が低下する傾向が見られた。実施例4の太陽電池裏面封止シート用フィルム4は、導電材料としてカチオン性帯電防止剤を使用しており、耐紫外線性に乏しいため、紫外線照射後の部分放電電圧の低下およびΔb値の増加が見られた。実施例5~8の太陽電池裏面封止シート用フィルム5~8は、樹脂層中の着色顔料の含有量を35~75質量%の範囲内で変更している。含有量が40質量%未満になると紫外線カット性能が十分ではないため、紫外線照射後のΔb値の増加が見られた(実施例7)。一方、含有量が70質量%を超えるとフィラー量が多すぎるため樹脂層表面にチョーキングが見られ、樹脂成分が少ないため塗膜密着力も低下した(実施例8)。実施例9の太陽電池裏面封止シート用フィルム9は、硬化剤であるヘキサメチレンジイソシアネート樹脂をヌレート型からビューレット型へ変更しており、塗膜の硬化が不十分なため耐溶剤性に乏しく塗膜剥がれが見られた。
比較例1の太陽電池裏面封止シート用フィルム10は樹脂層中に導電材料を4質量%含むが、樹脂層の導電性、表面抵抗値を変化させるには不十分な配合量であるために、部分放電電圧は向上するに至らなかった。一方、比較例2の太陽電池裏面封止シート用フィルム11は樹脂層中に導電材料を25質量%含むが、樹脂層の導電性が高くなりすぎるために表面抵抗値は105Ω/□以下となった。また比較例3は、樹脂層中に導電材料を含まない。そのため、比較例1と同様に樹脂層の導電性は不十分であり、部分放電電圧は向上するに至らなかった。
比較例4の太陽電池裏面封止シート用フィルム13は、樹脂層中に着色顔料を含まない。そのため、紫外線から樹脂層を保護することができず、紫外線照射により樹脂層の劣化・消失を引き起こし、表面抵抗値が1.0×105Ω/□以下まで低下した。また紫外線光カット性能が乏しいため、紫外線照射に伴い基材フィルムのΔb値が12.2まで増加し、黄変が発生した。
比較例5の太陽電池裏面封止シート用フィルム14は、樹脂層を構成するアクリル樹脂として紫外線吸収剤および光安定化剤(HALS)を架橋せずに後添加したアクリル樹脂が使用されている。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樹脂層表面にブリードアウトし、紫外線光カット性能が失われたため、基材フィルムのΔb値が増加し、黄変が発生した。
比較例6の太陽電池裏面封止シート用フィルム15(樹脂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、紫外線光カット性能が無く、また部分放電電圧を向上せしめる導電材料を含む樹脂層も形成されていない。そのため、その部分放電電圧は650Vと低く、紫外線光の照射に伴い、樹脂劣化、黄変が発生した。従って、太陽電池裏面封止シートの最外層に用いた場合には、極端な場合にはフィルムに割れ、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悪影響を及ぼす懸念がある。
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)を用意した。水蒸気バリア性フィルムとして、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、接着層形成用塗料およ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、塗工したフィルムを用意した。
・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。
E20Fおよび水蒸気バリア性フィルムの代わりに、EVAシートとの密着力に優れる東レフィルム加工(株)製白色ポリエチレンフィルム(100μm)を用いた以外は、実施例10に記載の方法と同様にして太陽電池裏面封止シート2を得た。
太陽電池裏面封止シート用フィルム1の代わりに、比較例2の太陽電池裏面封止シート用フィルム11を用いた以外は、実施例10に記載の方法と同様にして太陽電池裏面封止シート3を得た。
太陽電池裏面封止シート用フィルム1の代わりに、比較例3の太陽電池裏面封止シート用フィルム12を用いた以外は、実施例10に記載の方法と同様にして太陽電池裏面封止シート4を得た。
太陽電池裏面封止シート用フィルム1の代わりに、比較例6の太陽電池裏面封止シート用フィルム15を用いた以外は、実施例10に記載の方法と同様にして太陽電池裏面封止シート5を得た。
実施例10,11の太陽電池裏面封止シート1,2は、いずれも1000V以上の高い部分放電電圧を示し、高いシステム電圧の太陽電池モジュール用裏面封止シートとしても、好適に用いることができる。また、太陽電池モジュール構成において外層側に位置する樹脂層側への紫外線照射に伴う、基材フィルムと樹脂層間の密着力の低下は見られなかった。さらに、樹脂層および基材フィルムの黄変は非常に小さかった。
比較例7の太陽電池裏面封止シート3は最外層の樹脂層中に導電材料を25質量%を含むため、樹脂層の導電性が高くなりすぎ、表面抵抗値は105Ω/□以下となり、Wet絶縁性が400MΩ未満となった。そのため、太陽電池裏面封止シートに必要な特性である電気絶縁性が確保できなかった。
比較例8の太陽電池裏面封止シート4は導電材料を含まないため、850Vと部分放電電圧は低い値を示した。この太陽電池裏面封止シート4は、高いシステム電圧の要求される太陽電池モジュール用途での使用は困難である。
比較例9の太陽電池裏面封止シート5は、その最外層に樹脂層が形成されていない。すなわち紫外線光をカットしあるいは導電材料を含む樹脂層が形成されていないため、部分放電電圧および耐紫外線性はいずれも低かった。この太陽電池裏面封止シート5は、高いシステム電圧が要求される太陽電池モジュール用途、および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使用できない。
Claims (9)
- 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と紫外線吸収剤および/または光安定化剤とが共重合した樹脂、導電材料ならびに着色顔料を含む樹脂層が積層され、該導電材料の含有量が、該樹脂層全体に対して5~20質量%であり、該樹脂層の表面抵抗が1.0×109~1.0×1015Ω/□である、太陽電池裏面封止シート用フィルム。
- 前記導電材料がカチオン性帯電防止剤および/または無機固体導電材料である、請求項1の太陽電池裏面封止シート用フィルム。
- 前記無機固体導電材料が繊維状の構造である、請求項2の太陽電池裏面封止シート用フィルム。
- 前記無機固体導電材料が、酸化スズが被覆された酸化チタンであり、かつ数平均繊維長が5~15μmの針状結晶である、請求項3の太陽電池裏面封止シート用フィルム。
- 前記着色顔料の含有量が、前記樹脂層全体に対して40~70質量%である、請求項1~4のいずれかの太陽電池裏面封止シート用フィルム。
- 60℃×50%RH雰囲気下、紫外線照射積算量384kWh/m2の条件で紫外線を照射した後の前記樹脂層の表面抵抗が、1.0×107~1.0×1015Ω/□である、請求項1~5のいずれかの太陽電池裏面封止シート用フィルム。
- 前記樹脂層が、脂肪族系ポリイソシアネート樹脂、脂環族系ポリイソシアネート樹脂、芳香族系ポリイソシアネートおよび芳香脂肪族系ポリ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種のポリイソシアネート樹脂を含む請求項1~6のいずれかの太陽電池裏面封止シート用フィルム。
- 請求項1~7のいずれかの太陽電池裏面封止シート用フィルムを含む、太陽電池裏面封止シート。
- 請求項8の太陽電池裏面封止シートとセル充填剤層を含み、該太陽電池裏面封止シートと該セル充填剤層とが接着された、太陽電池モジュール。
Priority Applications (4)
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JP2011523230A JPWO2011068067A1 (ja) | 2009-12-03 | 2010-11-25 | 太陽電池裏面封止シート用フィルム |
EP10762853.9A EP2509112A4 (en) | 2009-12-03 | 2010-11-25 | FILM FOR A REAR SIDED FOIL FOR SOLAR CELLS |
US13/512,427 US20120227795A1 (en) | 2009-12-03 | 2010-11-25 | Film for backside sealing sheet of solar cell |
CN2010800499838A CN102668116A (zh) | 2009-12-03 | 2010-11-25 | 太阳能电池背面密封片材用膜 |
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JP2009-275264 | 2009-12-03 |
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WO2011068067A1 true WO2011068067A1 (ja) | 2011-06-09 |
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PCT/JP2010/070960 WO2011068067A1 (ja) | 2009-12-03 | 2010-11-25 | 太陽電池裏面封止シート用フィルム |
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US (1) | US20120227795A1 (ja) |
EP (1) | EP2509112A4 (ja) |
JP (1) | JPWO2011068067A1 (ja) |
KR (1) | KR20120115214A (ja) |
CN (1) | CN102668116A (ja) |
TW (1) | TW201131792A (ja) |
WO (1) | WO2011068067A1 (ja) |
Cited By (1)
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JP2014114350A (ja) * | 2012-12-07 | 2014-06-26 | Dic Corp | 硬化性コーティング組成物、積層ポリエステル樹脂フィルム及び太陽電池バックシート |
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KR20110098901A (ko) * | 2008-11-28 | 2011-09-02 | 도레이 카부시키가이샤 | 태양전지용 이면 밀봉시트용 필름 |
WO2013051661A1 (ja) * | 2011-10-07 | 2013-04-11 | 東洋紡株式会社 | 太陽電池用白色ポリエステルフィルム、これを用いた太陽電池裏面封止シートおよび太陽電池モジュール |
EP2824717B1 (en) * | 2013-07-09 | 2016-12-28 | Agfa-Gevaert | A backsheet for photovoltaic modules |
JP6122726B2 (ja) * | 2013-07-29 | 2017-04-26 | 日東シンコー株式会社 | シール材 |
CN113334887A (zh) * | 2014-03-07 | 2021-09-03 | 3M创新有限公司 | 耐久性挤出型染色聚酯膜 |
CN110218438A (zh) * | 2019-06-27 | 2019-09-10 | 深圳市上古光电有限公司 | 一种太阳电池板复合树脂薄膜材料及其制备方法 |
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US20120227795A1 (en) | 2012-09-13 |
EP2509112A4 (en) | 2013-08-21 |
JPWO2011068067A1 (ja) | 2013-04-18 |
KR20120115214A (ko) | 2012-10-17 |
TW201131792A (en) | 2011-09-16 |
EP2509112A1 (en) | 2012-10-10 |
CN102668116A (zh) | 2012-09-12 |
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