TW201133895A - Film for solar cells backside sealing sheet - Google Patents

Abstract

A film for solar cells backside sealing sheet of the present invention is formed by laminating a resin layer comprising a fluorine-based resin, a coloring pigment and melamine cyanurate on at least one surface of the side of a base film. The present invention provides the film for solar cells backside sealing sheet having excellent light resistance and humidity resistance.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for backing a sheet for solar cell backing, which has light resistance and moist heat resistance which can withstand the use in a harsh environment outside the long-term outdoor environment. . Further, the present invention relates to a solar cell backside sealing sheet and a solar cell module using the film for sealing a sheet on the back side of a solar cell of the present invention. [Prior Art] In recent years, there has been concern about the depletion of petroleum and coal-based fossil fuels, and it is urgent to ensure the development of alternative energy obtained through such fossil fuels. Therefore, various methods such as nuclear power generation, hydropower generation, wind power generation, and solar power generation have been studied and have actually been utilized. The solar power generation system that directly converts solar energy into electrical energy has been put into practical use as a semi-permanent and pollution-free new energy source. Surprisingly, solar power generation has increased the price-performance ratio above actual utilization and is highly expected as a clean energy source. The solar cell used in solar power generation constitutes the heart of a solar power generation system that directly converts the energy of sunlight into electrical energy. The solar cell is made up of semiconductors such as 矽. In the solar cell, the solar cell elements are connected in series and in parallel, and are packaged in various packages for protecting the components over a period of about 20 years. The unit assembled into this package is called a solar cell module. The solar cell module has a structure in which a surface covered with sunlight is covered with glass, a crucible made of a thermoplastic resin is used, and a back surface is buried, and the back surface is protected by a sealing sheet. S: 201133895 The ethylene-vinyl acetate copolymer resin (hereinafter referred to as EVA resin) is often used for the ruthenium material because of its excellent transparency and moisture resistance. On the other hand, the back sealing sheet requires mechanical strength, weather resistance, heat resistance, water resistance, chemical resistance, light reflectivity, electrical insulating properties, water vapor barrier properties, and enamel fillers represented by EVA resins. Thermal adhesion, conceivability, and adhesion to the outermost terminal box assembly with a siloxane-based resin. In addition to this, it is required to have excellent light resistance to the back sealing sheet due to exposure to ultraviolet rays. The film for the back sealing sheet used in the prior art may, for example, be a white polyvinyl fluoride film (DuPont, trade name: Tedlar (registered trademark)). A back-sealed sheet having a laminate structure in which a polyester film is sandwiched by a polyvinyl fluoride film is widely used for solar cell applications. In addition, it has been proposed to form a light-resistant film of an acrylic resin coating film containing a UV absorber "light stabilizer" on one side or both sides of a polyester film, and has been put into practical use (Patent Document 1). In addition, a specification in which an ultraviolet absorber or a light stabilizer is uniformly mixed into a polyester film has been proposed and put into practical use (Patent Document 2). Further, a white film obtained by uniformly mixing a white pigment such as titanium oxide into a layer of a polyester film or the like has also been put into practical use (Patent Document 3). The white film is light-resistant in view of the small change in the appearance of the film as the ultraviolet light is exposed. [Prior Art Document] [Patent Document] Patent Document 1: JP-A-2005-015557, No. JP-A-2011-188105 Patent Document 2: JP-A-2009-188105, Patent Document 3: Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei 1 1 -29 1 432 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] However, the polyvinyl fluoride film is a film having excellent weather resistance. On the other hand, the mechanical strength is weak, and the 140 is added by the solar cell module. The heat of 150 ° C is softened by heat, and the protrusion of the electrode portion of the solar cell element will penetrate through the ruthenium layer. Also, due to the high price, it has become an obstacle in terms of the low price of solar battery modules. Further, in order to create a colored film represented by white or the like, and to improve the concept of the back-sealing sheet, it is necessary to combine it with a higher-priced colored film. Further, in the polyester film of Patent Document 1 or Patent Document 2, the ultraviolet absorber or the light stabilizer is discharged on the surface of the coating film or the film in accordance with a high temperature humidification environment or ultraviolet light. Therefore, not only the wettability, the adhesion of the surface, and the like are changed, but the original light resistance which is found to be lost is likely to be lost. Further, the white film of Patent Document 3 is based on the fact that the change in the appearance of the film which is exposed to ultraviolet light is small in accordance with the light absorbing ability of the pigment component, although it has a certain degree of ultraviolet resistance, the resin of the main material is not The film properties represented by the photosensitivity, such as the breaking strength elongation, are gradually lowered by the ultraviolet irradiation. In addition, in recent years, the development of the long life of the solar cell module itself has been in progress. The situation in which the European-centered solar cell module is placed obliquely on the ground will increase. Under such circumstances, experience long-term exposure

S .201133895 UV rays from the ground. Therefore, in the case where the outer layer of the back sealing sheet is not formed with the light resistance which undergoes long-term stability, the sealing sheet will turn yellow' not only the aesthetic appearance of the film will be impaired, but in extreme cases, the sealing sheet will occur. Cracks and the like are also concerned that various properties such as electrical insulation or water vapor barrier properties required in the sheet are impaired. [Means for Solving the Problem] The present invention has the following structure in order to solve such a problem. In other words, the film for solar cell backside sealing sheet of the present invention has a resin layer containing a fluorine-based resin, a coloring pigment, and melamine melamine in at least a single layer of the substrate film. Further, the solar cell backside sealing sheet of the present invention contains the film for a solar cell backside sealing sheet of the present invention. Further, the solar cell module of the present invention comprises the solar cell backside sealing sheet and the unit ruthenium layer of the present invention, and is followed by a solar cell backside sealing sheet and a unit ruthenium layer. [Effect of the Invention] According to the present invention, a film for a solar cell backside sealing sheet having excellent light resistance and moist heat resistance can be obtained, and a solar cell backside sealing sheet using the same can be obtained. Further, according to the comparative aspect of the present invention, it is possible to further obtain a film for a solar cell backside sealing sheet which is excellent in flame retardancy and has little caking property or powdering property, and a solar cell back sealing sheet which uses the same. . Further, when the solar cell backside sealing sheet of the present invention is used, a solar cell module having excellent durability can be obtained. [Embodiment]

S 201133895 [Formation for Carrying Out the Invention] The film for a solar cell backside sealing sheet of the present invention can be obtained by a resin layer containing at least a single layer of a fluorine film, a coloring pigment, and a melamine cyanate film. It is better known as excellent sex and heat and humidity resistance. [Substrate film] Various resin films can be used as the base film for the film for sealing the sheet on the back side of the solar cell. Specifically, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (pen) or polycarbonate, polymethyl methacrylate, polyacrylate propylene, or the like can be exemplified. Resin film of polyethylene or the like 'Thin resin mixed with these resins' is preferably a polyester film from the viewpoint of excellent strength, dimensional stability, and thermal stability. Further, from the viewpoint of inexpensiveness, it is particularly preferred as PET or the like. Polyester resin film. Further, the polyester resin may be a copolymerization component, for example, a diol component such as propylene glycol, diethylene glycol or neopentylcyclohexane dimethanol; isophthalic acid, adipic acid, acid or hydrazine; A dicarboxylic acid component or the like of a diacid and an ester-forming derivative thereof. Polyphenylene (PPS) having higher hydrolysis resistance, heat resistance, and flame retardancy is also used. Further, it is also possible to use a fluorine-based film which is conventionally used as a film for a backside sealing sheet and which is made of polyvinyl fluoride. Since the film for sealing the sheet on the back side of the solar cell has excellent optical properties, it can be applied to the solar cell back-sealing sheet structure, and can be applied to the exposed gas (humidity, humidity) or from the ground. Electron dimethyl tree, poly film. Point, PEN, alcohol, bismuth The outermost layer of thioether resistant to direct UV 201133895 light. From the viewpoint of the outermost layer for direct exposure to the outside air, the base film is preferably a resin film having excellent hydrolysis resistance. The "polyester resin film" is a film formed by a so-called polymer raw material which is obtained by polycondensing a monomer, and contains an oligomer of about 1.5 to 2% by mass between the monomer and the polymer. The representative of the oligomer is a cyclic triad, and the film is contained in a large amount, and the film is subjected to long-term exposure such as indoors, and cracks or breakage occur due to a decrease in mechanical strength or hydrolysis due to rain or the like. In this case, the polyester resin film of the content of the cyclic triad obtained by the solid phase polymerization method of 1.0% by mass or less is used as a raw material to form a film of the polyester resin film, and high temperature can be suppressed. Further, it is possible to obtain a film excellent in heat resistance and weather resistance by hydrolysis under humidity. The measurement of the content of the above-mentioned cyclic triad is carried out, for example, by using a liquid chromatograph in which 100 mg of the polymer is dissolved in a solution of 2 ml of o-chlorophenol, and the content (% by mass) of the resin mass is measured. The method can be obtained. In the base film, an additive such as an antistatic agent, an ultraviolet absorbing agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, a chelating agent, a coloring pigment, or the like can be added as long as it does not impair the effects of the present invention. . Although the thickness of the base film is not particularly limited, it is preferably in the range of 1 to 250 μτη when considering the withstand voltage characteristics, cost, and the like of the sealing sheet. The lower limit of the thickness is more preferably 25 μπι or more. For the purpose of imparting water vapor barrier properties to the base film, a water vapor barrier film in which at least one inorganic oxide layer is formed by a vapor deposition method or the like may be used. The "water vapor barrier film" in the present invention is advantageous.

S 201133895 A resin film having a water vapor permeability of 5 g/(m2 · day ) or less as measured by Method B described in JIS Κ7 1 29 (2000 edition). The thickness of the above-mentioned resin film is preferably in the range of 1 to ΙΟΟμηη, more preferably in the range of 5 to 5 〇μπι., particularly preferably in the range of 10 to 30 μm, for reasons of stability or cost at the time of forming the inorganic oxide layer. The scope. The base film is preferably stretched in the biaxial direction so that the thermal dimensional stability is good. Further, in the base film, if necessary, surface treatment such as discharge treatment such as corona discharge or plasma discharge or acid treatment may be performed. [Resin Layer] The resin layer laminated in the base film of the present invention comprises: () a fluororesin, (2) a coloring pigment, and (3) melamine cyanurate. In general, the method of improving the light resistance of the resin layer is to use an organic ultraviolet absorber or an inorganic ultraviolet absorber alone, or to mix a plurality of kinds and to mix it in the adhesive resin, thereby further stimulating by the light. Based on the inactivation mechanism, the stabilizer (HALS) is used for the purpose of increasing light stability. However, after that, an ultraviolet absorber or a light stabilizer is added to the resin layer formed in the adhesive resin, or in a high-temperature humidification environment, or with ultraviolet light, the ultraviolet absorber or the light stabilizer will The surface of the coating film flows out of the coating film. Therefore, not only the wettability, the adhesion force of the surface of the coating film, etc., but also the initial occurrence of the ultraviolet filter performance loss will be easily caused. In view of the above, in the present invention, compared with a polyester resin, an olefin resin, an acrylic resin, etc.,

S 201133895 A fluorine-based resin excellent in light resistance is used as an adhesive resin. Therefore, there is no need to add an ultraviolet absorber or a light stabilizer to the adhesive resin, and the problems as described above do not occur. Further, since the fluorine-based resin has excellent flame retardancy, it also has an effect of improving the flame retardancy of the film for sealing the back surface of the solar cell. In addition, in order to improve the adhesion to the base film or to improve the heat resistance of the resin layer, it is preferred to introduce a fluororesin having a curable functional group so as to introduce a suitable crosslinked structure into the resin layer. The solar cell backside sealing sheet using the film for sealing the sheet on the back side of the solar cell is attached to the solar cell module manufacturing step, and the heat resistance is required for the resin layer because it is exposed to high temperature treatment. The functional group to which the fluororesin is imparted with curability is, for example, a hydroxyl group, a carboxyl group, an amine group, a glycidyl group, a decyl group, a decanoic acid group or an isocyanate group, and the ease of production or curability of the resin. The partnership will be appropriately selected. Among them, from the viewpoint of good curing reactivity, a cyano group or a decyl group is preferred, and from the viewpoint of easy availability of the resin or good reactivity, a hydroxyl group is particularly preferred. These curable functional groups are usually introduced into a fluorine-based resin by copolymerization of a monomer having a curable functional group. The monomer having a hydroxyl group can be, for example, 2-hydroxyethyl vinyl ether '3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl group Hydroxy-containing vinyl ethers such as ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2.methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether a hydroxy group-containing allyl ether such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether or glycerol monoallyl ether. Such

In S-10-201133895, from the viewpoint of excellent polymerization reactivity and functional group hardenability, a vinyl ether having a hydroxyl group is preferred; a 4-hydroxybutyl vinyl ether and a 2-hydroxyethyl vinyl group are particularly preferred. ether. Other monomers having a hydroxyl group may, for example, be hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. From the viewpoint of the structural unit, a fluorine-based resin having a curable functional group is introduced, for example, a perfluoroolefin-based resin mainly composed of a perfluoroolefin unit. Specific examples can be exemplified by a single polymer of tetrafluoroethylene (TFE) or a copolymer of TFE with hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (pAVE), and the like. Copolymerized copolymer of other monomers, and the like. Other monomers which are sufficiently copolymerized, for example, ethyl acetate, ethylene propionate, ethylene butyrate, ethylene isobutyrate, trimethylvinyl acetate, ethylene hexanoate, ethylene terephthalate, ethylene laurate, a vinyl carboxylate such as ethylene stearate, ethylene cyclohexylcarboxylate, ethylene benzoate, ethylene terephthalate, etc.; methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, ring An alkyl vinyl ether such as hexyl vinyl ether; a non-fluorinated olefin such as ethylene, propylene, n-butyl or isobutylene; vinylidene fluoride (VdF), chlorotrifluoroethylene (CTFE), or fluorinated A fluorine-based monomer such as ethylene (VF) or fluorovinyl ether, but is not limited to such monomers. Among these monomers, TFE-based resin mainly composed of T F E is preferred from the viewpoint of having excellent pigment dispersibility, weather resistance, copolymerization property, and chemical resistance. S: -11 - 201133895 Specific perfluoroolefin-based resin containing a hardening functional group, for example, a copolymer of TFE/isoprene/hydroxybutyl vinyl ether/other monomer, TFE/tertiary carbonic acid Copolymer of ethylene/hydroxybutyl vinyl ether/other monomer, copolymer of TFE/VdF/hydroxybutyl vinyl ether/other monomer, etc., especially TFE/isoprene/hydroxybutylvinyl Copolymer of ether/other monomer, copolymer of TFE/tertiary ethylene carbonate/hydroxybutyl vinyl ether/other monomer, and the like. The TFE-based curable resin coating material is, for example, a ZEFFLEGK series 歹IJ manufactured by Daikin Industries Co., Ltd., and the like. The thickness of the resin layer is preferably from 2 to 20 μm. The lower limit of the thickness of the resin layer is more preferably 5 μηη or more, and particularly preferably 8 μπι or more. The upper limit of the thickness of the resin layer is more preferably 15 μηη or less, and particularly preferably 10 μηι or less. In the case where the resin layer is formed by a coating method, if the thickness of the resin layer is less than 0.2 μm, the phenomenon of cleaving or film cracking tends to occur at the time of coating, and it becomes difficult to form a uniform coating film. Therefore, there is a case where the adhesion to the base film and the optimum light resistance are not sufficiently found. On the other hand, when the thickness of the resin layer exceeds 20 μm, the light resistance is sufficiently found, but there is a concern that the coating method is limited, the production cost is high, and the coating film on the transfer roller is likely to be adhered or the coating film is accompanied. The idea of stripping and so on. In order to form a solvent of the coating liquid of the resin layer by a coating method, for example, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, and the like can be exemplified. Methylformamide, dimethylacetamide, methanol, ethanol, water, and the like. The characteristics of the coating liquid may be either an emulsified type or a dissolved type.

S -12- 201133895 The method of forming a resin layer on a substrate film is not particularly limited to the conventional coating method. The coating method can be carried out by various methods, such as a roll coating method, a dip coating method, a rod coating method, a die coating method, a gravure roll coating method, or the like, or a combination thereof. Among them, the gravure roll coating method is a preferred method for increasing the stability of the resin layer. [Coloring Pigment] The coloring pigment used in the present invention is used for the following purposes: (1) a colored resin layer, (2) maintenance of color tone (not fading), (3) filtering of ultraviolet rays and/or visible light, (4) ) Improved flame retardancy. From the viewpoint of light reflectivity and conception, the solar cell back sealing sheet is mainly composed of white sheets. In recent years, compared with the above-mentioned white sheets, the gap between the power generating elements has also increased the need for black sheets based on the reason of excellent concept. Further, since these pigments themselves absorb and/or reflect ultraviolet rays of a specific wavelength, the effect of protecting the substrate film of ultraviolet rays and/or visible light can be obtained by coloring. In addition, it has the effect of being able to shield the electrical design pattern in the solar cell module. As the coloring pigment, various coloring pigments such as inorganic pigments and organic pigments can be used. Regarding the white or black which is currently practical, the white pigment is preferably titanium oxide, and the black pigment is preferably carbon black based on the viewpoints of versatility, price, color development property, or ultraviolet resistance. Particularly from the viewpoint of color development, regarding the titanium oxide, the number average particle diameter thereof is preferably from 0.1 to 1.0 μm. More preferably, it is 0.2 to 0.5 μm from the viewpoint of dispersibility or cost with respect to the fluorine-based resin. Similarly,

S -13- 201133895 Regarding carbon black, the number average particle diameter thereof is preferably from 0.01 to 〇·5 μη. From the viewpoint of dispersion or cost, it is more preferably from 至·〇2 to 0.1 μιη. The content of the coloring pigment is preferably adjusted in accordance with the color tone design to be colored. However, when the content of the coloring pigment is too small, the appearance of the color tone having excellent concept, or the lack of ultraviolet light and/or visible light filtering performance cannot be obtained, and when the film is exposed to the outside for a long period of time, the deterioration of the substrate film may occur. The situation of Huang. Further, since the amount of the resin increases, there is a possibility that blockiness will occur. On the other hand, when the content of the coloring pigment is too large, the cost will become high, or the resin layer surface will be poorly caused by the adhesion of the substrate and the terminal box followed by the enamel resin due to the large increase in the hardness of the resin layer. There are concerns about powdering and the like. Further, since the resin layer is reduced, there is a possibility that the adhesion between the resin layer and the substrate film is lowered. In the present invention, a coloring pigment is also used for the purpose of improving the flame retardancy of the film for sealing a sheet on the back side of a solar cell, and the flame retardancy is imparted by increasing the content to some extent. For the above reasons, the content of the coloring pigment is preferably from 30 to 80% by mass based on the entire resin layer. The lower limit of the content is more preferably 50% by mass or more, and particularly preferably 65% by mass or more. The upper limit of the content is more preferably 75% by mass or less, and particularly preferably 70% by mass or less. [melamine cyanurate] The melamine cyanurate of the present invention is used for the purpose of (1) improving the blocking resistance of the resin layer and (2) improving the flame retardancy. Melamine melamine is a non-halogen flame retardant and is also used as a lubricant for £-14-201133895. In the present invention, the addition of melamine cyanurate to the fluororesin has an effect of not only improving the flame retardancy of the resin layer but also reducing the agglomeration property when the fluororesin is used. The mechanism for reducing the agglomeration by the melamine cyanurate in the fluorine-based resin is estimated as follows. When the resin layer is applied to the substrate film and dried by heating, in the resin layer, the melamine cyanurate is separated from the fluorine resin having a low polarity. The low molecular weight melamine cyanurate will migrate to the base. The opposite side of the film. As a result, it is considered that since melamine cyanurate is mostly contained in the surface of the resin layer, agglomeration will be lowered. The content of melamine cyanurate is preferably from 1 to 30% by mass based on the entire resin layer. The lower limit of the content is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit of the content is preferably 20% by mass or less, and particularly preferably 1% by mass or less. When the content is less than 1% by mass, a sufficient effect of not obtaining melamine cyanurate is obtained. When the content exceeds 30% by mass, the cost becomes high, or melamine cyanurate is allowed to flow out on the surface of the coating film to lower the solvent resistance necessary in the resin layer. [Crosslinking Agent] Further, as described above, a crosslinking agent capable of reacting a functional group capable of reacting with a functional group of the fluorine-based resin may be blended for the purpose of improving the properties of the resin layer. In the case of using a crosslinking agent, the adhesion between the base film and the resin layer can be improved, or the effect of improving the solvent resistance and heat resistance of the resin layer can be obtained as the crosslinking structure is introduced. In particular, in the case where the resin layer of the present invention is located at the outermost layer to implement the design of the solar cell sealing sheet, in the solar cell module manufacturing step, specifically, in the glass lamination step ( In the unit charging step, the resin layer is subjected to a heat treatment at a temperature of up to 15 (TC) for a long time, and heat resistance is particularly required due to heat treatment for exposure for 30 minutes or more. In addition, in the manufacturing steps of the solar cell module, Since the cleaning operation is performed by the wiping operation of ethanol or other organic solvent after the module is assembled, solvent resistance is required. From the viewpoint of improving such adhesion, solvent resistance, and heat resistance, it is preferred. In order to blend the crosslinking agent, as described above, since the functional group introduced into the fluorine-based resin is preferably a hydroxyl group, it is preferred to use a crosslinking agent which can react with the hydroxyl group. Such a crosslinking agent is preferably a polyisocyanate. A resin used as a horse hardener to accelerate the formation of a polyurethane bond (crosslinking structure). A polyisocyanate resin used as a crosslinking agent can be exemplified by a fragrance. A polyisocyanate, an aromatic aliphatic polyisocyanate, an alicyclic polyisocyanate, an aliphatic polyisocyanate, or the like, and each of the diisocyanate compounds shown below may be used as a raw material resin. These resins may be used singly or in combination. For the diisocyanate which is a raw material of the aromatic polyisocyanate, for example, m- or p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, and 1,5-naphthalene diisocyanate are exemplified. (NDI), 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), and 4, 4'-diphenyl ether diisocyanate. The diisocyanate which is a raw material of the aromatic polyisocyanate may, for example, be 1,3- or 1,4-xylene diisocyanate (XDI) or 1,3-

S -16 - 201133895 or 1,4-tetramethylxylene diisocyanate (TMXD I). The diisocyanate which is a raw material of the alicyclic polyisocyanate may, for example, be 1,4-cyclohexane diisocyanate, I,3-cyclohexane diisocyanate or 3-cyanate methyl-3,5. 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate: IPDI), 4,4'-, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate (hydrogenated MDI), methyl 4 - cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc., and 1,3- or 1,4-bis(isocyanatemethyl)cyclohexane (hydrogenated XDI). Examples of the diisocyanate which is a raw material of the aliphatic polyisocyanate are, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-extension Isocyanate, 1,2_, 2,3- or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate. The raw material of the polyisocyanate can be used by combining a plurality of such diisocyanates, and can also be used as a modified product such as a B u r a t e modified product or a N u r a t e modified product. The resin containing an aromatic ring having a light-absorbing band in the ultraviolet region is likely to be yellowed by ultraviolet irradiation, and it is preferred to use an alicyclic polyisocyanate and/or an aliphatic polyisocyanate as a hardener. use. Further, from the viewpoint of solvent resistance, the resin layer is preferably a alicyclic polyisocyanate which is hardened by further purification. In addition, from the viewpoint of the ease of crosslinking reaction with the fluorine-based resin, the cross-linking, the degree of kinetics, the heat resistance, the ultraviolet ray resistance, etc., it is preferably hexamethylene diisophthalide Λ π | The Nurate modification of the oxime ester. [Other Additives] -17- 201133895 In addition, thermal stabilizers, antioxidants, enhancers, anti-deterioration agents, weather resistance, and flame retardants may be added to the resin layer containing a fluorine-based resin as long as the properties are not impaired. , plasticizer 'release agent, lubricant, crosslinking aid, pigment dispersant, defoamer, flat agent, UV absorber, light stabilizer, tackifier, adhesion modifier, matting agent. The heat stabilizer, antioxidant, and anti-deterioration agent which can be used, for example, are hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides or a mixture thereof. Examples of reinforcing agents that can be used include clay, talc, calcium carbonate, zinc carbonate', ash, cerium oxide, aluminum oxide, magnesium oxide, calcium citrate, sodium aluminate, sodium aluminosilicate, and strontium. Magnesium silicate, glass sphere, carbon black, zinc oxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate whisker, boron nitride, graphite, glass fiber, carbon fiber. As the crosslinking assistant which can be used, a conventional tin-based, other metal-based, organic acid-based or amine-based crosslinking assistant can be used. [Adhesive layer] A solar cell backside sealing sheet can be obtained by laminating a film for a sheet on the back surface of a solar cell and another resin film. A method of laminating a film and processing it into a sheet shape can utilize a conventional dry lamination method. For the bonding of the resin film using the dry lamination method, it is possible to use a polyether polyurethane-based polyurethane type, a polyester type, a polyepoxy type resin, etc. as the main unit. A polyisocyanate-based resin is a conventional dry laminate for use as a curing agent. However, the adhesive formed by the use of such an adhesive

In the layer of S 18· 201133895, it is necessary to prevent the yellowing caused by the deterioration of the light reflectance due to the deterioration of the light intensity due to the use of the outside of the room for a long period of time. Further, the thickness of the adhesive layer is preferably in the range of 1 to 5 μm. If it is lower than Ιμηι, sufficient adhesive strength cannot be obtained. On the other hand, if it exceeds 5 μm, the speed of application of the adhesive cannot be increased, and it takes a long time to find the adhesion (the acceleration of the crosslinking reaction between the main agent and the hardener), even after The production cost is increased on the grounds that the amount of the agent is increased. As the material for forming the adhesive layer, a conventional dry laminate can be used. In general, the dry laminate adhesive uses two kinds of resins which are diluted with a diluent solvent and blended with a main agent and a cross-linking agent, and the cross-linking agent is reactive with an active hydroxyl group, and it is preferred to use a reaction rate and an initial tightness. The tack was found to be a fast formulation of polymers containing isocyanate groups. In addition to these advantages, it is possible to form an adhesive resin layer having high adhesion strength to the base film and excellent durability and long-term durability even in the subsequent strength. The main component resin to be used in combination with the polymer containing the isocyanate group may, for example, be a urethane resin such as a polyether type, a polyester type or a polyalcohol type, or an epoxy resin, and can be processed according to detailed characteristics. The condition is suitable and used after appropriate selection. Further, according to the structure of the solar cell backside sealing sheet, it is considered that the ultraviolet rays also reach the above-mentioned adhesive layer to induce light deterioration of the resin. From such a viewpoint, the resin used for the formation of the adhesive layer is preferably an aromatic resin or an alicyclic resin which does not contain an aromatic ring or a small amount. [Solar cell back sealing sheet]

S -19-.201133895 A description will be given of a solar cell back sealing sheet using a film for sealing a sheet on the back side of a solar cell. In the solar cell back-sealing sheet, various characteristics represented by water vapor barrier properties, light reflectivity, long-term moisture-proof heat/lightfastness durability, and adhesion to the unit entanglement and electrical insulation are required. In order to meet these required characteristics, various thin-film designs (stacked designs) in which various processing techniques such as functional film, vapor deposition, and wet coating are combined are performed in accordance with the viewpoint of functional division. By laminating more than one layer of a film having hydrolysis resistance, a white film, a film having an inorganic oxide vapor deposition, and a film having thermal adhesion to EVA, on the film for sealing a sheet on the back surface of a solar cell of the present invention A film having a different substrate film can obtain a solar cell back sealing sheet that meets various requirements. In particular, it is preferable to use a film having hydrolysis resistance as a base film on a portion of the solar cell backside sealing sheet which is disposed on the outer side of the solar cell module, and to laminate a solar cell on the substrate film. A film for sealing the sheet on the back side. By arranging a film having hydrolysis resistance, the layer (adhesive layer, film layer, etc.) located on the inner layer side is protected from hydrolysis. In addition, since the resin layer having ultraviolet light and/or visible light properties and flame retardancy is located on the outermost layer side, the inner layer of the resin layer is protected from ultraviolet rays and/or visible light, and the fire can be further reduced. On the other hand, it is preferable to use a white film, a film having an inorganic oxide vapor deposition, and a film having thermal adhesion to EVA in a layer opposite to the surface on which the base film resin layer is laminated. Jiawei has more than one species

S •20- 201133895 Film. In the case of laminating a white film, light reflectivity is imparted; when a film having an inorganic oxide deposited layer is laminated, water vapor barrier properties are imparted; and in the case of a film having thermal adhesion to EVA, a pair of cells is provided. The filling layer is close to the force. The film having thermal adhesion to EVA may, for example, be an olefin-based film such as an EVA film or a polyethylene film. Further, it is not necessary to form a film in the film for sealing a sheet for back surface of a solar cell of the present invention. It is preferable to design a solar cell backside sealing sheet in accordance with the characteristics to be imparted. Further, in the structure of the solar cell backside sealing sheet, if the position on the resin layer in the present invention is removed, it is also possible to form a vapor deposition layer, a sputtering layer, a wet coating layer, etc., which are intended to impart functional properties to any layer. . An example of a method for producing a film for sealing a sheet on the back side of a solar cell can be exemplified by the following methods. For example, the base film can be exemplified by preparing a hydrolysis-resistant polyethylene terephthalate film Rumirror (registered trademark) X10S manufactured by Toray. Then, it is prepared to use a bead mill to disperse/adapt a fluorine-based resin, a coloring pigment and a main component of melamine cyanurate, a crosslinking agent of a Nurate type hexamethylene diisocyanate resin, and a mixed solvent. Agent. This coating agent is applied onto a base film by a gravure roll coating method to obtain a film for a backside sealing sheet of a solar cell. In addition, the solar cell backside sealing sheet is laminated on the surface opposite to the side on which the thin film resin layer for sealing the sheet of the solar cell back surface is laminated, and is laminated with a white film and an inorganic oxide vapor-deposited layer by a dry lamination method. At least one film selected from the group consisting of a film and a film having thermal adhesion to EVA

S -21- •201133895 Yes. When the solar cell back sealing sheet of the present invention is used in a solar cell module, the resin layer of the solar cell back sealing sheet is oriented toward the outside of the solar cell module, and the solar cell back sealing sheet and unit are sealed. The adhesive layer is then assembled into the solar cell module. [Embodiment] Next, a film for a solar cell backside sealing sheet of the present invention and a solar cell backside sealing sheet using the same will be specifically described by way of examples. <Evaluation method of characteristics> The evaluation method of the characteristics used in the present invention is as follows: (1) The coating amount of the resin layer is measured, and after the formation of the resin layer, the solar cell back sealing sheet is cut into a film of 500 cm 2 The area of this test piece was taken as the mass (1) [g]. Then, the test piece was dissolved in methyl ethyl ketone, the resin layer was peeled off, and the mass of the test piece was measured again as mass (2) [g]. Next, the coating amount of the resin layer per unit area was calculated according to the following formula. This coating amount was measured for the three test pieces, and the average enthalpy was used as the coating amount. • Coating amount [g/m2] = {(mass (1)) - (mass (2))} x20. (2) Solvent resistance evaluation of the resin layer The sample was immersed in ethanol for 5 minutes, and then wiped 50 times using Kimwipes. Thereafter, the state of the coating film was observed and classified as follows: A: There was no change in the state of the coating film before the treatment. -22- .201133895 B : Peeling of the substrate and the coating film was observed. (3) Evaluation of ultraviolet filter performance (spectrophotometry) The measurement of the spectroscopic spectrum was carried out in accordance with JIS K7105 (2006 edition). For the measurement device, a visible light near-infrared spectrophotometer UV-3 150 manufactured by Shimadzu Corporation was used. The ultraviolet filter performance of the film for sealing the sheet on the back side of the solar cell was evaluated by measuring the light transmittance at a wavelength of 360 nm. (4) Evaluation of the adhesion strength between the base film and the resin layer The adhesion force between the base film and the resin layer of the film for sealing the back surface of the solar cell produced (the film adhesion force) is described in A cross-cut test was carried out by the method of JIS K 5400 (1990 edition). The results were classified as follows: AA: 100 pieces of film remaining / 100 pieces. A: 81 to 99 pieces of film remain in the /1 block. B: The coating film of 80 or less is left in /100 pieces. (5) Evaluation of ultraviolet resistance Ultraviolet irradiation (ultraviolet irradiation cumulative amount 3 84 kWh/m2) was carried out for 240 hours at an ultraviolet ray intensity of 160 mW/cm 2 in an environment of 60 ° C x 50% RH. The test device was an EYE SuperUV Tester SUV-W151 manufactured by Iwasaki Electric Co., Ltd. The measurement of the color system b値 before and after the ultraviolet irradiation was performed, and Δ b 求出 was obtained according to the following formula. • Ab = (b値 after UV irradiation) 1 (b値 before UV irradiation) In addition, '(3) Evaluation of UV filter performance, '(4) -23- 201133895 Substrate film/resin layer The evaluation of the adhesion strength was carried out in the same manner as in the evaluation of the ultraviolet resistance of the characteristics, and the ultraviolet irradiation was carried out in the same manner as before and after the evaluation. (6) Evaluation of moisture and heat resistance The film for sealing the sheet on the back side of the solar cell was subjected to heat treatment at 48 Hr in an environment of 120 ° C and 10% RH. The test apparatus used was a pressure cooker TPS-21 1 manufactured by ESPEC. After that, "(3) evaluation of ultraviolet filter performance" and "(4) evaluation of adhesion strength between base film/resin layer" of the film for sealing the sheet on the back side of the solar cell, and evaluation of the heat and humidity resistance of the characteristics Implemented for the purpose. (7) Evaluation of flame retardancy The test was carried out according to the horizontal flammability HB test of UL94 specification (2010 edition) and the following classifications were made: A : The HB test passed. B : The HB test failed. (8) Evaluation of anti-caking property The film forming the resin layer was cut into a 5 cm square of one cymbal. These films are superimposed by overlapping the resin layer of the film with the film surface of the other film. Then, using an ink agglomeration tester DG-BT manufactured by DG Engineering Co., Ltd., a load of 5 kg/cin 2 was applied and aging was performed for 3 days in an environment of 4 ° C. Thereafter, the adhesion of the resin layer to the substrate film was evaluated to prepare the following classification: A: The resin layer and the substrate film were not attached. -24- 201133895 B : The resin layer and the substrate film have been attached. (9) Evaluation of chalking property The 3-day aging of the film forming the resin layer was carried out at a temperature of 40 °C. The surface of the resin layer after aging was observed to be classified as follows: A: No pulverization occurred on the surface of the resin layer. B: Powdering has occurred on the surface of the resin layer. (1 〇) Measurement of the adhesive strength with the enamel filler (EVA adhesion) The EVA sheet was superposed on the inner layer side of the solar cell backside sealing sheet (opposite to the surface of the laminated base film resin layer). Further, a semi-reinforced glass having a thickness of 3 mm is overlapped thereon. Subsequently, a commercially available glass laminator was used, and after vacuuming, under a heating condition of 135 ° C, a load of 3 kgf/cm 2 was used for compression for 15 minutes to prepare a pseudo solar cell module sample. The EVA sheet was a 500 μm thick sheet made of San vie. Using this pseudo-like solar cell module sample, the adhesion to the EVA sheet was measured in accordance with JIS Κ 68 54-2 (1,999 edition). Then, the width of the test piece width of the strength test was made 10 mm, and each measurement was performed once for the two test pieces. The average enthalpy of the two measurements is taken as the enthalpy of the strength. Then, the strength is 100 N/50 mm or more, and it is judged that it is practically a problem-free level. (1 1 ) Light reflectance The same as (1 〇), the pseudo solar cell module sample was prepared. Injecting light from the glass side of the sample like the solar cell module, and the inner layer side of the back sealing sheet (with the laminated substrate film resin layer)

The light reflectance was measured on the opposite side of the surface of S-25-.201133895. The measurement of the reflectance is represented by a reflectance at a wavelength of 600 nm. For the measurement device, a spectrophotometer MPC-3 100 manufactured by Shimadzu Corporation was used. (1 2) Measurement of water vapor transmission rate The water vapor transmission rate was measured in accordance with the B method (infrared sensor method) described in Jis K7129 (2000 edition) under the conditions of temperature 4 (TC, humidity 90% RH). For the device, Permatran (registered trademark) W3/3, which is a water vapor transmission rate measuring device manufactured by MOCON, USA, was used. The measurement was performed once for each of the two test pieces, and the average enthalpy of the second measurement was used as the water vapor transmission rate. (Preparation of the coating layer 1 for forming a resin layer) The fluorine-based resin is a ZEFFLE (registered trademark) GK57 (solid content: 65 mass%) of a TFE-based resin coating material of a hydroxyl group manufactured by Daikin Industries Co., Ltd. The fluororesin, the coloring pigment, the melamine cyanurate and the solvent were mixed with the blending amount shown in Table 1, and dispersed using a bead mill to obtain a main component paint having a solid content concentration of 50% by mass. The following products were used for the pigment: • White pigment: titanium oxide particles, JR-7〇9 manufactured by Tayca Co., Ltd. Black pigment: carbon black particles, Special Black 4A manufactured by Degussa Co., Ltd., which became the main coating material/Nurate type Liuya A Bayer's Desmodur (registered trademark) N3300 (solid content concentration: 1 〇〇 mass %) was incorporated into the main product by the mass ratio of isocyanate resin = 10 0 / 2 to the Nurate type hexamethylene diisocyanate resin. In the paint, further

S -26- 201133895 To obtain a coating of a solid concentration of 4 〇 mass% (resin solid concentration), add a diluent of n-butyl acetate and stir for 15 minutes. In this manner, the coating material 1 for forming a resin layer having a solid content concentration of 40% by mass (resin solid content) was obtained. (Preparation of the coating material 2 for forming a resin layer) is shown in Table 1 except that the content of the coloring pigment with respect to the resin solid content is 80% by mass, and the content of the melamine cyanurate is i% by mass. In addition to the blending amount, the coating material 2 for forming a resin layer is obtained by the same method as the preparation of the coating liquid 1 for forming a resin layer. (Preparation of the coating material 3 for resin layer formation) / is shown in Table 1 except that the content of the coloring pigment with respect to the resin solid content is 30% by mass, and the content of melamine cyanurate is 30% by mass. In addition to the blending amount, the coating material 3 for forming a resin layer is obtained by the same method as the preparation of the coating liquid 1 for forming a resin layer. (Preparation of the coating material 4 for forming a resin layer) The content shown in Table 1 is formed so that the content of the coloring pigment with respect to the resin solid content is 85% by mass and the content of the melamine cyanurate is 1% by mass. In the same manner as in the preparation of the coating liquid 1 for forming a resin layer, a coating material for forming a resin layer (preparation of the coating material for forming a resin layer 5) is obtained, except that the content of the coloring pigment with respect to the resin solid content is 20 The mass % and the content of the melamine cyanurate were 30% by mass, and the amount shown in Table 1 was used to form a resin layer.

S-27-201133895 The coating liquid 5 for forming a resin layer was obtained by the same method as the preparation of the coating liquid 1. (Preparation of the coating material for forming a resin layer 6) The content shown in Table 1 is formed so that the content of the coloring pigment with respect to the resin solid content is 30% by mass and the content of the melamine cyanurate is 40% by mass. In the same manner as the preparation of the coating liquid 1 for forming a resin layer, the coating material 6 for forming a resin layer was obtained. (Preparation of the coating layer 7 for forming a resin layer) The content shown in Table 1 is formed so that the content of the coloring pigment with respect to the resin solid content is 80% by mass and the content of the melamine cyanurate is 0.5% by mass. In the same manner as the preparation of the coating liquid 1 for forming a resin layer, the coating material for forming a resin layer 7» (modulation of the resin layer forming coating material 8) is used in addition to the use of the Burate type hexamethylene diisocyanate resin. Desmodur (registered trademark) N3200 (solid content: 1% by mass) manufactured by Bayer Co., Ltd. is obtained by the same method as the preparation of the coating liquid 1 for forming a resin layer, in place of the Nurate type hexamethylene diisocyanate resin. The coating layer 8 for forming a resin layer. (Preparation of Resin Layer Forming Coating Material 9) A resin in which an ultraviolet absorber and a light stabilizer (HALS) are added to an acrylic resin using methyl methacrylate and 2-hydroxyethyl methacrylate as raw materials is used. (solid content: 40% by mass) to replace ZEFFLE (registered trademark) GK570 (solid content: 65 mass%) of a hydroxyl group-containing TFE-based resin coating agent manufactured by Daikin Industries Co., Ltd.

In the same manner as the preparation of the coating liquid 1 for forming a resin layer, a coating material 9 for forming a resin layer was obtained. (Preparation of the resin layer-forming coating material 10) The resin layer-forming coating material 1 was obtained by the same method as the preparation of the coating liquid 1 for forming a resin layer, except that the coloring pigment was not blended and the amount shown in Table 1 was used. 0. (Preparation of the coating material for forming a resin layer 1) The resin was obtained by the same method as the preparation of the coating liquid 1 for forming a resin layer, except that the melamine melamine was not blended and the amount shown in Table i was used. The layer forming coating 1 i.

S -29- 201133895 〔I嗽〕 Coating 11 25.0 75.0 〇〇100.0 50.0 Ρ — 56.0 40.0 Coating 10 70.0 〇d 30.0 100.0 50.0 11.0 66,5 40.0 Coating 9 25.0 70.0 〇100.0 50.0 ρ 56.0 40.0 Coating 8 25.0 70.0 〇uS 100.0 50.0 P 56.0 40.0 Coating 7 19.5 80.0 in ο 100.0 50.0 〇cn 54.5 40.0 Coating 6 30.0 30.0 40.0 100.0 50.0 ο 57.5 40.0 Coating 5 50.0 20.0 30.0 100.0 50.0 ο od 62.0 40.0 Coating 4 14.0 85.0 ρ 100.0 50.0 Ο CN 53.0 40.0 Coating 3 40.0 30.0 30.0 100.0 50.0 Ο 59.0 40.0 Coating 2 19.0 80.0 ρ ^Η 100.0 50.0 ο CO 54.5 40.0 Coating 1 25.0 70.0 Ο 100.0 50.0 ρ 56.0 40.0 parts by mass parts by mass parts by mass parts by mass parts by mass parts by mass parts by mass parts by mass Quality % Fluorine resin*1 Acrylic resin*2 Coloring pigment melamine cyanurate I_ Ethyl acetate 1_ Main agent coating solid content isocyanate*3 Isocyanate*4 Solid content concentration of n-propyl acetate blending coating Thinner|& 莸 呍 呍 氍跋 氍跋 氍跋 氍跋 氍跋 氍跋 氍跋 α α α α α α α銶擗銶擗吕腾|^※ οίνο (Fun boat +H_)31dPH3zl; (^)撇Hui>nBa I ※ 00(ΝεΝ (Fun 暇电? Festival: 口一^口一^口镰陌^-^^ ^坦^李莸莸莸:^&冏忆到^一^^寸※ οοΓηεΝ (short light sa) JnpomsaQ 铋ίΜ«1-Ι3ΛΒΗ^ϊ}·ΝιΠΙΙ3莸 Distillate: Tffl-冏<To 312- ε ※ , 201133895 (Preparation of dry laminate with an adhesive) 16 parts by mass of DIC (dry) dry build-up agent DicDry (registered trademark) LX-903, 2 parts by mass as a hardener KL-75 manufactured by Dainippon Ink Chemical Industry Co., Ltd., and 29.5 parts by mass of ethyl acetate were stirred for 15 minutes. In this manner, an adhesive for a dry layering agent having a solid content of 20% by mass was obtained. (Preparation of coating for layer formation) 12 parts by mass of a dry laminating agent, Takelac (registered trademark) A-310 (polyester polyurethane resin), manufactured by Mitsui Chemical Polyurethane Co., Ltd. 1 part by mass of Takenate (registered trademark) A-3 of an aromatic polyisocyanate resin manufactured by Mitsui Chemicals Polyurethane Co., Ltd., and 212 parts by mass of ethyl acetate were stirred for 15 minutes. In this manner, a coating material for forming an adhesive layer having a solid content of 3 mass% was obtained. (Preparation of Coating for Thermal Adhesive Resin Layer Formation) 20 parts by mass of Aquatex (registered trademark) MC-3800, 10.8 mass of an aqueous emulsion coating containing EVA-based 3 copolymerized resin manufactured by Central Chemical Industry Co., Ltd. A portion of isopropyl alcohol and 22.6 parts by mass of water were stirred for 15 minutes. In this manner, a coating material for forming a thermal adhesive resin layer having a solid content concentration of 15% by mass was obtained. (Example 1) Hydrolyzable polyethylene terephthalate film Rumirror (registered trademark) X10S (125 μπι) prepared by Tor ay (manufactured by Tor ay) having a content of 1% by mass or less. ). On the side of the base film, the coating material 1 for forming a resin layer was applied by using a metal wire rod, and dried at 150 ° C for 60 seconds to provide a resin layer having a coating amount of 15.5 g/m 2 after drying.

S-31-201133895 In this manner, a film 1 for a solar cell backside sealing sheet was produced. (Example 2) A film 2 for solar cell backside sealing sheet was produced in the same manner as in the method described in Example 1 except that the coating material 2 for forming a resin layer was used instead of the coating material 1 for forming a resin layer. (Example 3) A solar cell backside sealing film 3 was produced in the same manner as in the method described in Example 1 except that the resin layer-forming coating material 3 was used instead of the resin layer-forming coating material 1. (Example 4) A film 4 for solar cell backside sealing sheet was produced in the same manner as in the method described in Example 1 except that the coating material for forming a resin layer 4 was used instead of the coating material 1 for forming a resin layer. (Example 5) A film 5 for sealing a solar cell backside sealing sheet was produced in the same manner as in the method described in Example 1 except that the coating material for forming a resin layer 5 was used instead of the coating material 1 for forming a resin layer. (Example 6) A solar cell backside sealing film 6 was produced in the same manner as in the method described in Example 1 except that the resin layer-forming coating material 6 was used instead of the resin layer-forming coating material 1. (Example 7) The solar cell backside sealing sheet film 7 was produced in the same manner as in the method described in Example 1 except that the coating material for forming a resin layer 7 was used instead of the coating material 1 for forming a resin layer. -32-201133895 (Example 8) A film for sealing a solar cell backside sealing sheet was produced in the same manner as in the method described in Example 1 except that the coating material for forming a resin layer 8 was used instead of the coating material 1 for forming a resin layer. 8. (Comparative Example 1) A solar cell backside sealing sheet film 9 was produced in the same manner as in the method described in Example 1 except that the coating material for forming a resin layer 9 was used instead of the coating material 1 for forming a resin layer. (Comparative Example 2) A film 10 for solar cell backside sealing sheet was produced in the same manner as in the method described in Example 1 except that the coating material 1 for forming a resin layer was used instead of the coating material 1 for forming a resin layer. (Comparative Example 3) A film 11 for solar cell backside sealing sheet was produced in the same manner as in the method described in Example 1 except that the coating material 1 for forming a resin layer was used instead of the coating material 1 for forming a resin layer. (Comparative Example 4) The resin film was not formed, and Rumirror (registered trademark) X10S (manufactured by Toray Co., Ltd., 125 μm) was used as a film for solar cell backside sealing sheet 12°. The above Examples 1 to 8 were used for comparison. The films for solar cell back sealing sheets of Examples 1 to 4 were evaluated for characteristics by the above evaluation method. The results are shown in Tables 2 and 3.

S -33- 201133895 〔Z撇〕 times>_f hang black 1 i get m ^ 雀 | S m 键 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线〇1 or less 1 after the damp heat test 1 or less 1 or less 1 or less 1 or less 1 or less 1 or less 1 or less 1 or less 1 initial 1 or less 1 or less 1 or less 1 or less 1 or less 1 or less 1 or less 1 or less 1 Tightness between the film/resin layer After UV irradiation ΑΑ 1 After the damp heat test ΑΑ <;< C < 1 Initial ί ί 1 Solvent resistance initial c < 3 < 3 CQ < ( 3⁄4 <<< Deletion layer coating amount (g/m2) 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 1 Formation coating material 1 coating 2 coating 3 coating 4 coating 5 coating 6 coating 7 coating 8 coating 9 Ο Gong Shovel Coating 11 1 mm 驷嫩爱昍 if dc 龆 4< Film 1 Film 2 Film 3 | Film 4 Film 5 Film ό Film 7 Film 8 Film 9 Film 10 Film 11 Film 11 Example 1 Example 2 Example 3丨Example 4 Example 5 EXAMPLES Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 201133895 [Table 3] UV resistance Δb Flame retardant Anti-caking property Anti-micronization Initial initial stage Example 1 0.5 AAA implementation Example 2 0.2 "--One AAA Example 3 1.0 AA - - A Example 4 0.2 AAB Example 5 1.5 ·~ I. BBA Example 6 1.0 AAA Example 7 0.2 ABA Example 8 0.5 AAA Comparative Example 1 2.0 -------- BAA Comparative Example 2 25.0 BBA Comparative Example 3 0.3 ABA Comparative Example 4 29.9 BAA (Evaluation of the Examples 1 to 8) The film 1 for solar cell back sealing sheets of Examples 丨 to 8 All of the 8 series have excellent UV resistance (Δ1) 値), wet film test and film adhesion after UV irradiation, damp heat test and UV filter performance after UV irradiation. (Evaluation of Examples 1 to 3) In particular, the color pigment content in the film 1 to 3 resin layer for the solar cell backside sealing sheet of Examples 1 to 3 is 3 to 80% by mass, melamine cyanurate The content is in the range of 1 to 30% by mass, and has excellent flame retardancy, blocking resistance, powdering resistance, and solvent resistance. Further, it was observed that the content of the colored pigment was as close as 80% by mass, and the tendency of the coating film adhesion force after the damp heat test was lowered by the decrease in the amount of the resin or the hardening of the coating film. In addition, it is also observed that the content of the coloring pigment is closer to 30% by mass, and the increase in the ultraviolet absorbing performance of the film is caused by the decrease in the substrate film Ab ,, that is, the substrate film Ab 紫外线 after the ultraviolet ray irradiation. Increase the tendency. (Evaluation of Examples 4 and 5) The film 4 for solar cell backside sealing sheet of Example 4 contains 85% by mass of a color pigment in the resin layer, and powdering is observed on the surface of the resin layer due to the large amount of the coloring pigment. . Further, since the amount of the resin component in the resin layer was small, the coating film adhesion force after the damp heat test was slightly lowered. In the film 5 for sealing the back surface of the solar cell of Example 5, since the coloring pigment in the resin layer was as small as 20% by mass, the flame retardancy was deteriorated as compared with Examples 1 to 3. Further, agglomeration occurs due to the amount of the resin component in the resin layer of up to 5% by mass. (Evaluation of Examples 6 and 7) The film 6 for solar cell backside sealing sheet of Example 6 contains 40% by mass of melamine cyanurate in the resin layer, and since the amount of melamine cyanurate is large, In comparison with Examples 1 to 3, the solvent resistance was deteriorated. The film 7 for back-sealing sheet of the solar cell of Example 7 was agglomerated because the melamine cyanurate in the resin layer was as small as 0.5% by mass. Further, since the amount of the resin component in the resin layer was small, the coating film adhesion force after the damp heat test was slightly lowered. (Evaluation of Example 8) The film 8 for solar cell backside sealing sheet of Example 8 was changed from a Nurate type to a Burate type by a hardener hexamethylene diisocyanate resin, and solvent resistance was insufficient due to insufficient hardening of the coating film. Getting worse. (Evaluation of Comparative Example 1)

S. 36-.201133895 The solar cell back sealing sheet film 9 of Comparative Example 1 is used. An acrylate resin having a UV absorber and a light stabilizer (HALS) is added instead of the fluorine resin as a resin layer. Therefore, as the ultraviolet ray is irradiated, the ultraviolet ray absorbing agent or the light stabilizer is discharged from the resin layer on the surface of the resin layer, and the ultraviolet ray-removing performance is lowered, and the Ab 基材 of the base film is increased. In addition, the flame retardancy also deteriorates. (Evaluation of Comparative Example 2) The film 10 for solar cell backside sealing sheets of Comparative Example 2 did not contain a coloring pigment. Therefore, the ultraviolet filter performance is lacking, and after the ultraviolet irradiation, the Ab 値 of the base film increases to cause yellowing. In addition, since the colored pigment is not contained, the flame retardancy is also deteriorated. Further, agglomeration occurs due to a large amount of the resin component in the resin layer. (Evaluation of Comparative Example 3) The film 1 1 for solar cell backside sealing sheets of Comparative Example 3 was not contained in the resin layer and contained no melamine cyanurate. Therefore, agglomeration occurs. In addition, the adhesion of the coating film after the damp heat test was also slightly lowered. (Evaluation of Comparative Example 4) The film 1 2 for a solar cell backside sealing sheet of Comparative Example 4 (Rumirror (registered trademark) X10S film itself without a resin layer) has no ultraviolet filter performance, and no adjustable film tone is formed. The color pigment layer. Therefore, as the ultraviolet ray is irradiated, the Ab 値 of the base film increases to cause yellowing. Therefore, in the case of the outermost layer of the solar cell back sealing sheet, cracks, pinholes, and the like occur in the film in an extreme case, and are required not only for the sealing sheets such as electrical insulating properties and water vapor barrier properties. The loss of function, but also worried about the adverse effects of the operation of the solar cell module. Further, -37-201133895, a resin layer containing a coloring pigment is not formed, and flame retardancy is also obtained (Example 9) A light-reflective film is prepared by Toray (manufacturing) white polyethylene film Rumirror (registered trademark) E20F (50) The gas-shielding film is prepared by Toray processing of the ethylene oxide phthalate film Barrier Rocks (registered trademark (1 2 μιη) on the opposite side of the alumina evaporation layer, and is directly photographed in the following double-headed tandem type. Coating for coating and thermal adhesive resin layer forming coating by gravure coater. • Coating conditions for the subsequent layer: dry film thickness target 0.2 μm, dry temperature 1 2 0 ° C. • Thermal adhesive resin layer coating conditions: drying Film thickness target 1. | Oven setting temperature 1 〇〇 ° C. • Coating speed: 100 m / min. • Aging: After coating/winding, aging at 40 ° C for two days. Sealed with solar cell backing of Example 1. The surface of the base film on the opposite side of the sheet resin layer was dried by an adhesive for a wire rod layer at 80 ° C for 45 seconds to form a 3.5-layer layer. Next, a light-reflective film was formed using a manual roll. Patch layer. Further, on the surface of the film opposite to the resin layer of the laminated film, the dry layer was coated with a metal wire rod and dried for 45 seconds to form a 3.5 μm adhesive layer. Then, the water vapor permeable film was formed by a roll. Alumina vapor-deposited layer of the patch layer. The three sheets of the film produced in this manner were placed in an oven heated to 40 t, and aged for three days to obtain too bad. Terephthalic acid μιη). Platinum plating) 1 01 3HGTS conditions, using a backing layer to form a dry oven setting 0 μηη, drying film 1 and applying dry μιη followed by the subsequent light-reflecting agent, at 80 ° C, using manual combination This is followed by a thin sheet, a solar battery back-38-201133895 face sealing sheet 1. (Example 1 〇) The same procedure was carried out except that a white polyethylene film (150 μm) made of Tor ay processed (E) was used in place of the EVA sheet to replace the E20F and the water vapor barrier film. The solar cell backside sealing sheet 2 was obtained by the method of Example 9. (Comparative Example 5) The solar cell backside sealing was carried out in the same manner as in the method of Example 9 except that the film for solar cell backside sealing sheet 10 of Comparative Example 2 was used instead of the film 1 for solar cell backside sealing sheet. Sheet 3. (Comparative Example 6) A solar cell obtained by the same method as in Example 9 was used except that the film 1 for solar cell backside sealing sheet of Comparative Example 4 was used instead of the film 1 for sealing the solar cell backside film. The back side seals the sheet 4. -39- 201133895 [Inch] Resin layer coating amount C g/m2 ] 15.0 15.0 15.0 1 Forming coating material 1 Coating 1 Coating 10 1 Sheet structure 薆 ( (7) — ® g S a ® ®® g $ § _ gfg _ s sg | £区惣_ 1 Polyethylene film/adhesive layer / Rurnirror X10S/resin layer: am tEQ 婺〇><S 〇5 1 〇1 IS ^ fs Xiangfan [χ, 田ο $ w W Sf | am ΧΠ 〇ί >< ® .3⁄4 S 1 ^蘅目婴^ ω 槲b _ _ am pi Μ Λ 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能 太阳能2 Solar cell back sealing sheet 3 Solar cell back sealing sheet 4 Example 9 Example 10 Comparative Example 5 Comparative Example 6 [S嗽] The outermost layer side is resistant to ultraviolet rays Δb Ο ^Τ\ 〇 25.0 29.9 m § 嫉, f P (g/(m2 · day)] inch Ο ^•Η inch inch light reflectance (600 nm) 1 1 (Ν (Ν 1〇EVA close force (N/50 mm ) 390 490 390 390 solar energy Battery back sealing sheet solar battery back sealing sheet 1 solar battery back sealing sheet 2 solar battery back Locking the back sheet of the solar cell sealing sheet 3 4 Example 9 Example 10 Comparative Example 5 Comparative Example 6 10 inch -

S 201133895 (Evaluation of Examples 9, 1) The solar cell back sealing sheets 1 and 2 of Examples 9 and 10 are all in the solar cell module structure, with the resin layer positioned on the outer layer side. On the side of the ultraviolet ray, no decrease in the adhesion between the substrate film and the resin layer was observed. Further, the yellowing of the resin layer and the base film is extremely small. In addition, the characteristics required for the solar cell backside sealing sheet and the enamel filler (EVA resin) also have excellent adhesion. Further, the sealing sheet 1 containing a water vapor-blocking film in the structure also has excellent water vapor barrier properties. (Evaluation of Comparative Example 5) The film 3 for solar cell backside sealing sheet of Comparative Example 5 does not contain a coloring pigment in the resin layer of the outermost layer, and the effect of shielding the wiring pattern on the inner surface of the module is not obtained. A change in the hue of the appearance of the blocked sheet with the ultraviolet irradiation (an increase in Ab値) was observed. Therefore, if exposed to ultraviolet rays for a long period of time, it is expected that the resin of the base film is deteriorated. (Evaluation of Comparative Example 6) The film 4 for solar cell backside sealing sheets of Comparative Example 6 was not formed with a resin layer in the outermost layer. That is, since the resin layer which removes ultraviolet rays is not formed, it is completely free from ultraviolet rays. Therefore, it cannot be used for a solar battery module that is intended to be exposed to an ultraviolet radiation reflection type such as a field setting type or the like. [Industrial Applicability] The film for solar cell backside sealing sheet of the present invention has excellent light resistance and moist heat resistance, and can be applied to a solar cell backside sealing sheet. Further, the film for solar cell backside sealing sheet of the preferred embodiment of the present invention has excellent flame retardancy and can be applied to a solar cell backside sealing sheet. These solar cell back sealing sheets can be applied to solar cell modules. -41 - 201133895 [Simplified illustration] Μ 〇 \\ [Main component symbol description] 〇 y»\\ s -42-

Claims (1)

201133895 VII. Patent Application Range: 1. A film for sealing a sheet for a back surface of a solar cell, which is a resin layer containing a fluorine-based resin, a coloring pigment, and a cyanurate in a single-layered substrate. 2. The solar cell backside sealing sheet of claim 1, wherein the resin layer contains 30 to % of the color pigment, and 1 to 30% by mass of melamine cyanurate 3 with respect to the integral resin layer. The solar cell backside sealing film according to claim 1 or 2, wherein the resin layer contains an aromatic polyisocyanate tree aliphatic polyisocyanate resin or an alicyclic polyisocyanate tree polyisocyanate resin. At least the isocyanate resin selected from the group formed. 4. A solar cell backside sealing sheet comprising a solar cell backside sealing sheet for use in any one of claims 1 to 3, wherein the solar cell back sealing sheet is attached to The surface of the solar cell back sealing thin resin layer of any one of the range of items 1 to 3 is laminated on the opposite side, and a white film, a film having an evaporation layer, and a copolymer with ethylene-vinyl acetate are laminated. At least one film selected from the group consisting of the film of matter. 6. A solar cell module comprising a solar cell backside sealing sheet and a unit ruthenium layer as described in the patent application scope, and an anode solar cell back sealing sheet and the unit 塡 filling layer film For melamine film, I 80 mass ester. Thin slices of fat, aroma and fat are a kind of desert. Patent application Film for film Inorganic oxidation Heat adhesion 4 or 5 items This is the same -43 - 201133895 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: