JP6036047B2 - Easy-adhesive back surface protection sheet and solar cell module using the same - Google Patents

Description

  The present invention relates to an easily-adhesive back surface protective sheet excellent in adhesiveness with a sealing material in a solar cell module, particularly with a sealing material made of polyethylene resin, and a solar cell module including the back surface protective sheet.

  In recent years, solar cells as a clean energy source have attracted attention due to the growing awareness of environmental issues. Generally, a solar cell module constituting a solar cell has a structure in which each member of a transparent front substrate, a front surface side sealing material, a solar cell, a back surface side sealing material, and a back surface protection sheet is laminated in order from the light receiving surface side. And has a function of generating electric power when sunlight enters the solar battery cell.

  The back surface protection sheet has a role of preventing moisture (water vapor) from entering the back surface side sealing material. Therefore, high adhesion is provided between the laminated back surface protection sheet and the back surface side sealing material. It is required that the adhesive part and the bonded part have high durability.

  As a sealing material used for a solar cell module, ethylene-vinyl acetate copolymer resin (EVA) is most commonly used from the viewpoints of workability, workability, manufacturing cost, etc. Yes. However, EVA resin has a tendency to gradually decompose with long-term use, and deteriorates inside the solar cell module to decrease its strength or generate acetic acid gas that affects the solar cell element. there is a possibility. For this reason, solar cell module sealing materials using polyethylene-based resins such as linear low density polyethylene (LLDPE) instead of EVA resins are increasingly used.

  As a method for integrating the members including the back surface protective sheet in the manufacturing process of the solar cell module, a method of integrating by vacuum heat laminating can be mentioned. Upon integration by such a method, in order to improve the adhesion between the back surface protective sheet and the sealing material, a fluoropolymer, particularly a fluoropolymer (4) containing a tetrafluoroethylene-based curable functional group is provided on one surface. From a backside protective sheet (see Patent Document 1) having improved adhesion by forming a coating film (primer layer) made of a fluororesin), or a mixture of an acrylic resin, a silane coupling agent, and a polyisocyanate curing agent Although the back surface protection sheet (refer patent document 2) which improved adhesiveness by forming the coating film which becomes is disclosed, the back surface protection sheet which has still higher adhesiveness is calculated | required.

  In addition, all of the existing back surface protection sheets that have already been disclosed are based on the premise that EVA is used as a sealing material, and the back surface protection has sufficient adhesion to a sealing material made of polyethylene resin such as LLDPE. The current situation is that there is no sheet yet.

JP 2010-45376 JP 2006-320991 A

  The solar cell module is used outdoors for a long period of time. Therefore, the above-mentioned members constituting the solar cell module are required to have weather resistance that can withstand harsh environments outdoors for a long period of time. In particular, further improvement is required for the adhesion between the back surface protective sheet and the sealing material disposed in the outermost layer of the solar cell module and the durability of the bonded portion, and in particular, a polyethylene resin. When using the sealing material which consists of this, the back surface protection sheet which has sufficient adhesiveness between sealing materials, and sufficient durability of those adhesion parts was calculated | required. The primer layer is exposed on the outermost surface as a product before lamination. For this reason, blocking resistance which is not required in a normal adhesive layer is required.

  This invention is made | formed in view of the above situations, and has high adhesiveness between sealing materials, Especially between back surface side sealing materials for solar cell modules which consist of a polyethylene-type resin. The purpose of the present invention is to provide an easy-adhesive back surface protection sheet for solar cell modules that can withstand use in harsh environments over a long period of time by having extremely high adhesiveness, and also has excellent blocking resistance. To do.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a crosslinkable resin in which a crosslinkable main resin is crosslinked with a polyisocyanate compound on one surface of a back surface protective sheet, and a silane coupling agent By providing an easy-adhesive layer (primer layer) containing an organometallic coordination compound, the adhesion between the back surface protective sheet and the sealing material can be improved, and in particular, a sealing made of polyethylene resin It has been found that the adhesiveness with the material can be remarkably enhanced and that it is further excellent in blocking resistance, and the present invention has been completed.

  (1) That is, in the present invention, an easy-adhesion layer is formed on one side of a back surface protection sheet for a solar cell module composed of one or a plurality of layers, and the easy-adhesion layer includes a) a crosslinkable main resin, and b). An easy-adhesive back surface protective sheet comprising: a crosslinked resin crosslinked with a polyisocyanate compound; c) a silane coupling agent; and d) an organometallic coordination compound.

  (2) Moreover, this invention is an easily-adhesive back surface protection sheet as described in (1) in which the said crosslinked resin is a urethane resin and the said easily bonding layer is formed on the polypropylene resin base material of a back surface protection sheet. is there.

  (3) In addition, the present invention is as described in (1) above, wherein the a) crosslinkable main resin is a crosslinkable substituent-containing acrylic resin, and its glass transition point (Tg) is 25 ° C. or higher and 70 ° C. or lower. It is an adhesive back surface protective sheet.

  (4) Moreover, this invention is an easily-adhesive back surface protection sheet as described in (3) whose glass transition point (Tg) of the said crosslinkable substituent containing acrylic resin is 45 degreeC or more and 60 degrees C or less.

  (5) Moreover, this invention is 0.1 mass% or more and 10 mass% or less of said c) silane coupling agent with respect to the total amount of said a) crosslinkable main ingredient resin and said b) polyisocyanate compound. The easy-adhesive back surface protective sheet according to any one of (1) to (4), which contains 0.1 to 7% by mass of the organometallic coordination compound.

  (6) Moreover, this invention is a manufacturing method of the easily-adhesive back surface protection sheet as described in (4), Comprising: The coating liquid containing the said crosslinked resin and a solvent is apply | coated to the single side | surface of a back surface protection sheet. A step of forming a coating film, a heating and drying step of heating the coating film to evaporate the solvent, and a step of curing the coating film after evaporating the solvent. It is a manufacturing method of the easily adhesive back surface protection sheet whose heating temperature in a process is 70 degreeC or more and less than 100 degreeC.

  (7) Moreover, this invention is a solar cell module with which the easily-adhesive back surface protection sheet in any one of (1) to (5), the sealing material, and the solar cell element are integrated at least. The solar cell module in which the easy-adhesive back surface protection sheet and the sealing material containing a polyethylene resin are integrated with each other through the easy-adhesion layer.

(8) Further, in the present invention, the sealing material is a low density polyethylene (LDPE) having a density of at least 0.900 g / cm ³ or less, and / or a linear low density polyethylene (LLDPE) and an ethylenically unsaturated silane compound. (7) is a solar cell module according to (7), which is a sealing material containing a polyethylene-based resin comprising a silane copolymer obtained by copolymerizing as a comonomer.

  According to the present invention, a back surface protection sheet for solar cell modules that exhibits extremely high adhesiveness and is also excellent in blocking resistance, in particular, with a back surface side sealing material for solar cell modules made of polyethylene resin, and A solar cell module or the like using such a back surface protection sheet is provided.

It is sectional drawing which shows an example of the laminated constitution of the solar cell module of this invention.

  A specific embodiment of the present invention will be described. This embodiment is an easily adhesive back surface protective sheet having an easy adhesive layer and a solar cell module in which the easily adhesive back surface protective sheet is used. The feature of the present invention is that the easy-adhesive back surface protective sheet has an extremely high adhesiveness especially with the sealing material made of polyethylene resin constituting the solar cell module, through the easy-adhesive layer. It is also excellent in blocking resistance.

<Easily adhesive back protection sheet>
The easily adhesive back surface protection sheet which is this embodiment is demonstrated. The easily adhesive back surface protection sheet of this embodiment consists of a back surface protection sheet base material layer and the easy adhesion layer formed in the surface of the single side | surface side of this back surface protection sheet base material layer.

[Configuration of easy-adhesion layer]
The easy adhesion layer is a so-called primer layer, and is formed as a cross-linked resin of a polyisocyanate compound on at least one outermost surface of the back surface protection sheet. This easy-adhesion layer is composed of a mixture containing a) a crosslinkable main resin (hereinafter also simply referred to as main resin), b) a polyisocyanate compound, c) a silane coupling agent, and d) an organometallic coordination compound. The coating liquid is applied to the surface of the substrate, and a film is formed from the applied coating liquid.

  The coating liquid contains a main resin, a curing agent containing a polyisocyanate compound, a silane coupling agent, and an organometallic coordination compound, and optionally contains a solvent and other various additives. Here, the main resin is cross-linked and polymerized by reacting with the polyisocyanate compound. About a main ingredient and a hardening | curing agent, it is preferable that they are a 2 liquid type which mixes these just before use. The polyisocyanate compound is a compound containing a plurality of isocyanate groups in one molecule.

[A) Crosslinkable main resin
As what can be used as the crosslinkable main resin, for example, a crosslinkable substituent-containing acrylic resin, or a polyol compound, a crosslinkable substituent-containing urethane resin, a crosslinkable substitution-containing fluororesin, a crosslinkable substituent-containing vinyl resin, Examples thereof include crosslinkable substituent-containing olefin resins. In the case where the cross-linked resin is a cross-linked acrylic resin, for example, the main resin is a cross-linkable substituent-containing acrylic resin, and the cross-linked acrylic resin is obtained by reacting this with a polyisocyanate compound. When the cross-linked resin is a cross-linked urethane resin, for example, the main resin is a polyol, and a cross-linked urethane resin is obtained by a reaction between this and a polyisocyanate compound (conceptually including a urethane prepolymer terminated with an isocyanate group). In the following description of the present specification, the resin compound before being cured by being crosslinked with a polyisocyanate compound is referred to as “crosslinkable main resin (or simply main resin)”, and is a resin contained in the easy-adhesion layer, that is, cured. Thus, it is distinguished from the resin having the easy-adhesion layer formed. Hereinafter, each constituent material will be described.

[Crosslinkable substituent-containing acrylic resin]
In this case, a crosslinkable substituent-containing acrylic resin (hereinafter also simply referred to as an acrylic resin) as an example of the main resin will be described. The acrylic resin used as the main resin has a plurality of crosslinkable substituents for reacting with the polyisocyanate compound, and is cured by reacting with the polyisocyanate compound to form a firm film. Here, examples of the crosslinkable substituent include a hydroxyl group, an amino group, and a carboxyl group. The main resin is selected from a solvent-soluble resin or a resin dispersible in a solvent. From the viewpoint of availability and crosslinking reactivity, the crosslinkable substituent is preferably a hydroxyl group. A preferred hydroxyl value range is from 5 to 100.

  As the acrylic resin, one or two or more kinds of acrylic acid compound and a monomer having a crosslinkable substituent, one or two or more kinds of acrylic acid compound and a monomer having a crosslinkable substituent, Those obtained by copolymerizing one or more ethylenic monomers are used. Here, in addition to the above monomer, a monomer having a substituent for imparting light resistance to the acrylic resin may be used as a monomer used for obtaining the acrylic resin.

  Such acrylic resins include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-2-hydroxy-3-phenoxypropyl, ethylene glycol mono (meth) ) (Meth) acrylic compounds having hydroxyl groups such as acrylate and propylene glycol mono (meth) acrylate, and (meth) acrylic acid or alkyl groups as methyl, ethyl, n-propyl, i-propyl, n- Examples include those obtained by copolymerizing an alkyl (meth) acrylate monomer having a butyl group, i-butyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, or the like. Further, as a monomer used for copolymerization, (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide (alkyl groups include methyl group, ethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group and the like), N-alkoxy (meth) acrylamide, N, N-di Alkoxy (meth) acrylamide (alkoxy groups include methoxy group, ethoxy group, butoxy group, isobutoxy group, etc.), amide group-containing monomers such as N-methylol (meth) acrylamide, N-phenyl (meth) acrylamide, Contains glycidyl groups such as glycidyl (meth) acrylate and allyl glycidyl ether Monomer, styrene, α-methylstyrene, vinyl methyl ether, vinyl ethyl ether, maleic acid, alkyl maleic acid monoester, fumaric acid, alkyl fumaric acid monoester, itaconic acid, alkyl itaconic acid monoester, (meth) acrylonitrile, chloride Various compounds having an ethylenically unsaturated bond such as vinylidene, ethylene, propylene, vinyl chloride, vinyl acetate, and butadiene may be used. Among these, a copolymer of methyl (meth) acrylate and 2-ethylhexyl acrylate, a copolymer of at least methyl (meth) acrylate, 2-ethylhexyl acrylate, and a hydroxyl group-containing (meth) acrylate is preferably used. Is done. Moreover, 1000-300,000 is mentioned as a preferable mass mean molecular weight of such resin.

  Conventionally, in a primer application using an acrylic resin, from the viewpoint of blocking resistance, the glass transition point (Tg) of the acrylic resin is preferably 50 ° C. or higher, and if the Tg is less than 50 ° C., there is adhesiveness. Since blocking resistance fell, it was not preferable. However, in the back surface protective sheet of the present invention in which the silane coupling agent and the organometallic coordination compound are used in combination for the formation of the easy-adhesion layer, the formation of the easy-adhesion layer has a lower Tg, for example, Tg of 50. Even when an acrylic resin having a temperature lower than 0 ° C. is used as the main resin, a preferable back protective sheet having sufficient blocking resistance can be produced. In the present invention, the Tg of the acrylic resin is preferably 25 ° C. or higher and 70 ° C. or lower, and more preferably 30 ° C. or higher and 70 ° C. or lower. When Tg is less than 25 ° C., even if a silane coupling agent and an organometallic coordination compound are used in combination, the blocking resistance is lowered, which is not preferable. On the other hand, when Tg exceeds 70 ° C., the adhesiveness is lowered, which is not preferable. As will be described later,

[Crosslinked urethane resin]
In this case, the main resin has a plurality of hydroxyl groups for reacting with the polyisocyanate compound, and reacts with the polyisocyanate compound to be cross-linked to be cured to form a strong film. The main resin is selected from a solvent-soluble resin or a resin dispersible in a solvent. A conventional polyol compound can be used as the main resin. For example, polyether type polyol, polyester type polyol, polycarbonate type polyol, etc. are mentioned, and it is used individually or in multiple types. Of these, polycarbonate polyols are preferably used, and polycarbonate polyols that are liquid at room temperature are particularly preferred. Since it has an active hydrogen group as a reactive group in the urethane bond, it can be crosslinked with a lower hydroxyl value compared to other resins. A preferred hydroxyl value range is from 0 to 50.

  Furthermore, polyamines, polyamine alkylene oxide adducts, amide group-containing polyols, polycarboxylic acids, and the like may be contained within a range not departing from the spirit of the present invention. Examples of the polyamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, ethanolamine, propanolamine and other aliphatic polyamines, 1,3- or 1,4-bis (aminomethyl) cyclohexane, Alicyclic polyamines such as 4,4′-, 2,4′- or 2,2′-dicyclohexylmethanediamine, isophoronediamine, norbornanediamine, m- or p-xylylenediamine, 1,3- or 1,4 -Aromatic polyamines such as tetramethylxylylenediamine, aromatic polyamines such as 2,4- or 2,6-tolylenediamine, 4,4'-, 2,4'- or 2,2'-diaminodiphenylmethane Can be illustrated. Examples of the amide group-containing polyol include hydroxyalkylamides. Examples of the polycarboxylic acid include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid, pyromellitic acid and other aromatic polycarboxylic acids, 1,3-cyclohexanedicarboxylic acid, 1 Aliphatic polycarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aliphatic polycarboxylic acids such as malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.

  Here, particularly when a polypropylene resin is used as the base material of the back surface protective sheet, sufficient adhesiveness cannot be obtained if the cross-linked resin forming the easy-adhesion layer is a cross-linked acrylic resin. However, high adhesiveness can be obtained by using a crosslinked urethane resin. Thereby, the adhesiveness between the back surface protection sheet which uses a polypropylene resin as a base material, and a back surface side sealing material layer can be provided to an easily bonding layer.

[B] Polyisocyanate compound]
Next, the polyisocyanate compound will be described. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. As described above, the polyisocyanate compound crosslinks and cures (high molecular weight) the main resin to form a resin contained in the easy adhesion layer. At this time, a polyisocyanate compound becomes a part of resin contained in an easily bonding layer with main ingredient resin. Examples of the polyisocyanate compound include aliphatic, alicyclic, aromatic, and aromatic-aliphatic compounds. The easy-adhesion layer is exposed to the external environment for a long period of time. From the viewpoint of suppressing the accompanying coloring, an aliphatic or alicyclic polyisocyanate compound is preferably used.

  Specific examples of the polyisocyanate compound include aliphatic isocyanates having 3 to 12 carbon atoms such as hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane diisocyanate, and lysine diisocyanate; 1,4-cyclohexane diisocyanate, isophorone diisocyanate ( Alicyclic diisocyanates having 5 to 18 carbon atoms such as IPDI); modified products of these diisocyanates (burettes, isocyanurate modified products, etc.). These can be used alone or in combination of two or more. Further, when the crosslinked resin is a crosslinked urethane resin, it may be a urethane prepolymer having an isocyanate group at the terminal.

[C) Silane coupling agent]
Next, the silane coupling agent will be described. The easy-adhesion layer is required to have high adhesion to the back-side sealing material. In addition to the main resin and the curing agent, a silane coupling agent and an organometallic coordination compound are used in combination. By this, the adhesiveness between the easily adhesive back surface protective sheet and the sealing material can be enhanced, and in particular, the adhesiveness with the sealing material made of polyethylene resin can be remarkably enhanced. In addition, the blocking resistance of the easy adhesion layer can be improved.

  Examples of the silane coupling agent include amino silane coupling agents such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-phenylaminofuropyltrimethoxysilane; ureido systems such as ureidopropyltriethoxysilane. Silane coupling agents; vinyl silane coupling agents such as vinylethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane; methacrylates such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane -Based silane coupling agents; epoxy-based silane coupling agents such as 3-glycidoxypropyltriethoxysilane; and isocyanate-based silane cups such as 3-isocyanatopropyltriethoxysilane Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and 6-mercaptohexatrimethoxysilane; methyl / phenyl such as methyl group and phenyl group-containing methoxysilane oligomer Silane coupling agent; polymer type silane coupling agent such as polyethoxydimethylsiloxane and polyethoxydimethylsiloxane; cationic type such as N- (N-benzyl-β-aminoethyl) -3-aminopropyltrimethoxysilane hydrochloride A silane coupling agent etc. are mentioned. Moreover, the alkoxy oligomer which oligomerized the silane coupling agent can also be used. Among these, an isocyanate silane coupling agent, an epoxy silane coupling agent, a mercapto silane coupling agent, and a methyl / phenyl silane coupling agent can be preferably used.

[D) Organometallic coordination compound]
Next, the organometallic coordination compound will be described. The organometallic coordination compound is also called a chelating agent and is presumed to contribute to curing as a crosslinking agent. In particular, when used in combination with the silane coupling agent, the adhesive strength is remarkably improved. In addition, the blocking resistance of the easy adhesion layer can be improved.

  Examples of organometallic coordination compounds include titanium acetylacetonate, titanium octyl glycolate, titanium triethanolamate, tetra-n-butyl titanate, aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum isopropylate. Examples thereof include rate monosecondary butyrate, aluminum alkyl acetoacetate diisopropylate, aluminum trisacetylacetonate, zirconium acetylacetonate, and acetylacetone zirconium butyrate. Among these, aluminum trisacetylacetonate can be preferably used from the viewpoint of the anti-blocking property and the adhesiveness with the sealing material.

  Here, an easily bonding layer is located in the surface of the outermost layer of the solar cell module in the side which contact | connects the back surface side sealing material layer of a back surface protection sheet base material layer. The easily adhesive back surface protective sheet is also a product that is distributed independently before being integrated as a solar cell module. Therefore, for smooth distribution and storage, it is preferable that the easy-adhesive layer has blocking resistance when completed as an easy-adhesive back surface protective sheet after crosslinking. Thus, it has not been known that the combined use of an organometallic coordination compound and a silane coupling agent is effective for improving blocking resistance, which is an essential requirement unique to an easy-adhesion layer as a primer, This is also a feature of the present invention.

[Other additives]
Other additives are added as necessary to impart weather resistance, light resistance, heat resistance, moisture resistance, flame retardancy, and the like to the easily adhesive layer. Further, the additive is added as necessary to improve the stability, coating property, drying property, blocking resistance and the like of the coating solution.

  Examples of other additives include a dispersant, an antifoaming agent, a light stabilizer, an ultraviolet absorber, a heat stabilizer, and an antioxidant. These can use a well-known thing without a restriction | limiting in particular, According to the performance calculated | required by a coating liquid and an easily bonding layer, it selects suitably.

  In addition, various pigments are often added mainly from the viewpoint of enhancing the design of the solar cell module. In particular, titanium oxide, calcium carbonate, which is a white pigment, carbon black, which is a black pigment, titanium black, a Cu—Mn composite oxide, a Cu—Cr—Mn composite oxide, and the like are usually blended.

[Back protection sheet base material layer]
Next, the back surface protection sheet base material layer which comprises an easily-adhesive back surface protection sheet is demonstrated. A back surface protection sheet base material layer turns into an easily adhesive back surface protection sheet by forming the above-mentioned easy adhesion layer in the surface.

  As the back protective sheet base material layer, a resin sheet obtained by molding a resin into a sheet shape is used. Examples of such resin sheets include polyethylene resins, polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride resins, fluorine Resins, poly (meth) acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamideimide resins, polyaryls Various resin sheets such as phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. It is possible to use. Among these resin sheets, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polycarbonate resin, and polyethylene naphthalate are particularly preferably used. Among them, for example, a biaxially stretched polyethylene terephthalate or a biaxially stretched polypropylene resin film or sheet is particularly preferable. In this specification, the term “resin sheet” is used as the name of a product obtained by processing these resins into a sheet shape, but this term is used as a concept including a resin film. These may be a single layer or a laminate composed of a plurality of layers laminated with a conventionally known adhesive or the like.

  A light shielding layer can be provided as a layer disposed on the outermost side or the entire outer side in the solar cell module among the surfaces of the back surface protective sheet base material layer. By providing this light-shielding layer, it becomes possible to use a resin sheet having somewhat low light resistance as a substrate from the viewpoint of cost. Examples of such a sheet include aluminum foil, aluminum vapor deposition film, polyethylene terephthalate resin colored in black or white, polypropylene resin, polyethylene resin, and the like.

  Moreover, you may provide the weathering layer which consists of a fluorine film etc. in the outermost layer of a back surface protection sheet. As a specific example, a weather resistant layer is provided by dry laminating a white fluorine film or a white polyester film on the surface opposite to the surface of the base layer provided with the easy-adhesion layer using a urethane-based adhesive. be able to.

  What is necessary is just to determine suitably the thickness of a back surface protection sheet base material layer in consideration of the thickness requested | required of an easily-adhesive back surface protection sheet. As an example, the thickness of the back surface protective sheet base material layer may be 10 to 500 μm, but is not particularly limited.

[Formation of coating solution and easy adhesion layer]
The easy-adhesion layer is formed by drying the solvent from the coating liquid applied on the above-mentioned back surface protective sheet substrate, and crosslinking the main resin contained in the coating liquid with a polyisocyanate compound. The coating liquid contains an organic solvent for dissolving or dispersing the main resin. Then, the applied coating liquid is heated to volatilize the solvent. Then, as a curing period for sufficiently carrying out the crosslinking reaction, it is allowed to stand at 40 to 60 ° C. for 3 to 7 days, for example.

  The content of the main resin in the coating liquid is preferably 10 to 60% by mass. When the content of the resin in the coating liquid is 10% by mass or more, the pigment contained in the coating liquid can be favorably dispersed. Further, when the content of the resin in the coating liquid is 60% by mass or less, the coating property of the coating liquid is improved.

  It is preferable that the usage-amount of a polyisocyanate compound is 0.5-75 mass parts with respect to 100 mass parts of main ingredient resin. When the amount of the polyisocyanate compound used is 0.5 parts by mass or more with respect to 100 parts by mass of the main resin, good curability can be imparted to the coating film formed from the coating liquid. A softness | flexibility can be provided to a coating film by being 75 mass parts or less with respect to a mass part. In particular, when a pigment is added, the amount used may be increased in consideration of the isocyanate group consumed in the reaction with other than the main resin due to the reaction with the reactive group on the pigment surface or adsorbed moisture. Moreover, the quantity from which NCO / OH ratio (ratio of NCO number of hardening | curing agent / OH number of main ingredient resin) will be 0.1-10 is preferable. When the pigment is passed through for coloring, the amount of the isocyanate compound used is preferably 1 to 75 parts by mass with respect to 100 parts by mass of the main resin, and the NCO / OH ratio in that case (the NCO of the curing agent) The ratio of the valence / OH ratio of the main resin to 0.1 to 10 is preferable. When almost no pigment is added in an uncolored system, the amount of the isocyanate compound used is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the main resin. In such a case, an amount in which the NCO / OH ratio (ratio of NCO value of the curing agent / OH value of the main resin) is 0.1 to 5 is preferable. When the NCO / OH ratio exceeds the above amount, side reaction products due to the reaction between the remaining isocyanate groups and the moisture in the air increase, and the adhesiveness, heat resistance and durability decrease, but the NCO / OH ratio is If it is in the range, it is preferable because good adhesion, heat resistance and durability can be obtained. In addition, when using the solution containing a polyisocyanate compound as a hardening | curing agent and making it a 2 liquid type coating liquid, a well-known organic solvent is suitably selected and used for a hardening | curing agent. Such a solvent will be described later.

  The content of the silane coupling agent is preferably from 0.1% by weight to 10% by weight, more preferably from 0.5% by weight to 8% by weight, based on the total amount of the main resin and the polyisocyanate compound. Preferably they are 1.0 mass% or more and 8 mass% or less. In particular, when a pigment is added, the amount used may be increased by taking into account the alkoxy groups consumed by the reaction with other than the main resin due to the reaction with the pigment surface. When the content of the silane coupling agent is less than 0.1% by mass, the adhesiveness required as a back surface protective sheet for solar cell modules is not exhibited. Further, even if the content of the silane coupling agent exceeds 10% by mass, there is no further improvement in adhesion and the coating film becomes brittle, which is not preferable.

  The content of the organometallic coordination compound is preferably 0.1% by mass or more and 7% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less based on the total amount of the main resin and the polyisocyanate compound. is there. When the content of the organometallic coordination compound is less than 0.1% by mass, blocking resistance preferable as a back surface protective sheet for a solar cell module cannot be obtained. Further, even if the content of the organometallic coordination compound exceeds 7% by mass, there is no further improvement in blocking resistance and adhesion, which is not preferable. In addition, it is preferable that ratio of content of an organometallic coordination compound and a silane coupling agent is 25: 75-75: 25.

  Next, the solvent used for the coating liquid will be described. A solvent is added in order to provide the coating liquid with the applicability | paintability with respect to a back surface protection sheet base material layer. After the coating liquid is applied to the back surface protective sheet base material layer, the solvent contained in the applied coating liquid is volatilized, and an easy-adhesion layer is formed on the surface of the back surface protective sheet base material layer by the subsequent curing reaction. .

  The solvent is not particularly limited as long as it can dissolve or disperse components such as the main resin and the polyisocyanate compound and does not react with the polyisocyanate compound contained in the coating liquid. Examples of such solvents include water-insoluble solvents such as toluene, xylene, butyl acetate, and ethyl acetate, and water-soluble solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. A solvent is suitably selected according to the resin component used for a coating liquid, and is used individually or in combination of 2 or more types. Further, in order to adjust the drying speed during coating, a high boiling point solvent such as tripropylene glycol dimethyl ether may be added.

  The coating liquid is prepared by mixing a main resin, a solvent, and necessary additives. Of the components contained in the coating liquid, the silane coupling agent, organometallic coordination compound, and polyisocyanate compound, as already mentioned, in order to avoid reacting with the main resin component during storage, Is preferably used as an additive or curing agent which is a separate solution. In this case, the main agent, the additive, and the curing agent are mixed immediately before use to form a coating liquid.

  What is necessary is just to set the viscosity of a coating liquid suitably according to the coating method of a coating liquid. An example of the viscosity of the coating solution is preferably 10 to 100 cPs, more preferably 50 to 80 cPs. The viscosity of the coating solution may be adjusted by adjusting the amount of solvent added to the coating solution.

[Formation of easy adhesion layer]
Next, a method for forming the easy-adhesion layer by applying the coating liquid on the surface of the back surface protective sheet base material layer will be described. The easy-adhesion layer is formed by applying the coating liquid on the surface of the back protective sheet base material layer to form a coating film, evaporating the solvent contained in the coating film, and then evaporating the main resin and the polymer contained in the coating film. It is formed by cross-linking reaction with an isocyanate compound and curing.

  As a method of applying the coating liquid to the surface of the back surface protective sheet substrate, a conventionally known method can be used without any particular limitation. Examples of such a coating method include a printing method, a coating method using a gravure coater, a roll coating method, a spray coating method, a dip coating method, a solid coating method, and a brush coating method.

  As a method for evaporating the solvent contained in the coating film, a conventionally known method can be used without particular limitation. Examples of such an evaporation method include a heating method, a reduced pressure drying method, a hot air drying method, and a natural drying method, but are not particularly limited. The conditions for evaporating the solvent contained in the coating film may be appropriately set according to the solvent used, but the heating time and heating temperature are 15 seconds to 5 minutes when using a gear oven. It is preferably in the range of ~ 200 ° C, more preferably in the range of 70 to 120 ° C for 30 seconds to 2 minutes. By heating in this way, preferable blocking resistance and adhesiveness are exhibited.

  Furthermore, the heating temperature is generally performed at a high temperature of about 120 ° C., but by appropriately selecting the Tg of the crosslinkable main resin used, for example, 70 ° C. or more and less than 100 ° C. The drying treatment may be performed at a low temperature of preferably about 90 ° C. In the case of performing such a low temperature drying treatment, more specifically, a crosslinkable main resin having a Tg of 45 ° C. or more and 60 ° C. or less can be used. By selecting a main resin having a Tg in the above range, the balance between blocking resistance and adhesion can be optimized even when drying is performed at low temperature. By such a specific combination of the main resin and the production conditions, it is possible to reduce the shrinkage and deformation of the resin sheet accompanying the heating operation at a high temperature and contribute to the improvement of the quality and productivity of the back surface protection sheet.

  The coating film obtained by evaporating the solvent is subjected to curing for sufficiently carrying out the crosslinking reaction. Curing conditions may be set as appropriate according to the types of the main resin and polyisocyanate compound used. Examples of the curing conditions include leaving at 40 to 60 ° C. for 3 to 7 days.

  When the solvent is removed by evaporation from the coating film, the base resin, the polyisocyanate compound and the additive added to the coating solution remain on the surface of the substrate to form a film. This film is cured to form an easy adhesion layer. The thickness of the easy-adhesion layer is not particularly limited, and may be determined as appropriate according to the conditions to which the easy-adhesive back surface protective sheet is applied. As a thickness of an easily bonding layer, 0.1-30 micrometers is preferable and 0.5-5 micrometers is more preferable. When the thickness of the easy-adhesion layer is 0.1 μm or more, sufficient adhesion can be imparted. If the thickness of an easily bonding layer is 30 micrometers or less, workability with favorable blocking resistance can be provided and cost can also be suppressed.

<Solar cell module>
Next, an example of the solar cell module of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of the layer structure of the solar cell module of the present invention. In the solar cell module 1 of the present invention, the transparent front substrate 2, the front side sealing material layer 3, the solar cell element 4, the back side sealing material layer 5, and the back surface protection sheet 6 are sequentially formed from the incident light receiving surface side. Are stacked. The solar cell module 1 of the present invention uses the above-mentioned easily adhesive back surface protection sheet for the back surface side sealing material layer 5.

  In the solar cell module 1, for example, the transparent front substrate 2, the front-side sealing material layer 3, the solar cell element 4, the back-side sealing material layer 5, and the back protection sheet 6 are sequentially stacked. It can be manufactured by integration by vacuum suction or the like, and then thermocompression-molding the above-mentioned member as an integral molded body by a molding method such as a lamination method.

  Further, the solar cell module 1 is formed on the front side sealing material layer 3 on each of the front side and the back side of the solar cell element 4 by a molding method usually used in ordinary thermoplastic resins, for example, T-die extrusion molding. And the back surface side sealing material layer 5 are melt-laminated to sandwich the solar cell element 4 with the front surface side sealing material layer 3 and the back surface side sealing material layer 5, and then the transparent front substrate 2 and the back surface protection sheet 6. They may be manufactured by a method of sequentially laminating them and then integrating them by vacuum suction or the like and heat-pressing them.

  In the present invention, an easy-adhesion layer is formed on the bonding surface side with the back surface side sealing material layer 5 in the above back surface protection sheet 6, thereby improving the adhesion with the back surface side sealing material. And especially the adhesiveness between the back surface side sealing materials which consist of a polyethylene-type resin improves notably. For this reason, not only EVA but polyethylene resin can be suitably used as the back surface side sealing material. That is, the easy-adhesive back surface protective sheet of the present invention is particularly preferable for a back surface sealing material made of polyethylene resin, and is characterized in that it has both adhesion to a back surface sealing material made of polyethylene resin and weather resistance. is there. Moreover, since this easily adhesive back surface protection sheet is excellent in blocking resistance, it is excellent also in the handling property as a back surface protection sheet before modularization.

The polyethylene resin is not particularly limited as long as it is mainly composed of polyethylene, but is preferably low density polyethylene (LDPE), more preferably linear low density polyethylene (LLDPE), and particularly preferably metallocene linear low density. Polyethylene. Linear low density polyethylene is a copolymer of ethylene and α-olefin. The density of the polyethylene resin used in the present invention is preferably 0.900 g / cm ³ or less, and more preferably in the range of 0.870 to 0.890 g / cm ³ . If it is this range, favorable transparency and heat resistance can be provided, maintaining sheet workability.

  The polyethylene resin in the present invention includes not only ordinary polyethylene obtained by polymerizing ethylene, but also a resin obtained by polymerizing a compound having an ethylenically unsaturated bond such as α-olefin, ethylenic resin, etc. Resins obtained by copolymerizing a plurality of different compounds having an unsaturated bond, modified resins obtained by grafting different chemical species to these resins, and the like are included. Especially, the polyethylene-type resin containing the silane copolymer formed by copolymerizing at least (alpha) -olefin and an ethylenically unsaturated silane compound as a comonomer can be used preferably. By using such a resin, adhesion between a sealing material and a member such as a transparent front substrate or a solar cell element can be obtained. Examples of the silane copolymer include those described in JP-A-2003-46105.

  The polyethylene resin composition contains a small amount of a polymerization initiator such as t-butylperoxy 2-ethylhexyl carbonate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane. Specifically, it is 0.02 mass% or more and less than 0.5 mass%. Thereby, heat resistance can be imparted without the film forming property being reduced due to the generation of gel during molding, and the transparency being lowered.

  EXAMPLES Hereinafter, although an Example, a comparative example, and a test example are shown and this invention is demonstrated further more concretely, this invention is not limited to the following Examples etc. at all.

The coating liquid which forms an easily bonding layer in the easily adhesive back surface protection sheet of each Example, a comparative example, and a test example was prepared using the following primer materials and solvents.
(Crosslinking main resin)
Crosslinkable main resin 1 (crosslinkable substituent-containing acrylic resin: expressed as “acryl 1” in Table 1): Tg 41 ° C., acid value 5.9, hydroxyl value 19, weight average molecular weight 25000.
Crosslinkable main resin 2 (crosslinkable substituent-containing polycarbonate skeleton urethane resin: expressed as “urethane” in Table 1): Tg of about 30 ° C., hydroxyl value of 20, number average molecular weight of 15000.
Crosslinkable main resin 3 (crosslinkable substituent-containing acrylic resin: expressed as “acryl 2” in the table below): Tg 50 ° C., acid value 3.5, hydroxyl value 19, weight average molecular weight 28000.
(Crosslinking agent: polyisocyanate compound)
Polyisocyanate compound (indicated as “crosslinking agent” in Table 1): (Product name “Coronate HX” manufactured by Nippon Polyurethane Industry Co., Ltd.) For the polyisocyanate compound, the mass ratio with respect to 100 parts by mass of the main resin is shown in Table 1. The ratio was expressed in terms of mass%, and the NCO / OH ratio was blended so as to have the value described in Table 1.
(Organic metal coordination compound)
Organometallic coordination compound (indicated as “chelating agent” in Table 1): Aluminum trisacetylacetonate (Product name: Aluminum chelate A (W), manufactured by Kawaken Fine Chemical Co., Ltd.): For organometallic coordination compounds, crosslinkable main agent It compounded so that the mass ratio with respect to the total amount of resin and a polyisocyanate compound might turn into the ratio represented by the mass% in Table 1.
(Silane coupling agent)
Silane coupling agent 1 (indicated as “Isocyan” in Table 1): 3-isocyanatopropyltriethoxysilane (product name KBE-9007, manufactured by Shin-Etsu Silicone Co., Ltd.).
Silane coupling agent 2 (indicated as “mercapto” in Table 1): 3-mercaptopropyltrimethoxysilane (product name KBM803, manufactured by Shin-Etsu Silicone Co., Ltd.).
Silane coupling agent 3 (indicated as “epoxy” in Table 1): 3-glycidoxypropyltriethoxysilane (product name KBE-403, manufactured by Shin-Etsu Silicone Co., Ltd.).
Silane coupling agent 4 (shown as “methyl / phenyl” in Table 1): Methyl and phenyl group-containing methoxysilane oligomer (product name X-40-9227, manufactured by Shin-Etsu Silicone Co., Ltd.)
Silane coupling agent 5 (indicated as “mixed” in Table 1): A mixture of the following silane coupling agent 6 and silane coupling agent 7 in a ratio of 1: 1.
Silane coupling agent 6 (indicated as “mercapto oligomer” in Table 1): Mercapto group-containing methoxy / ethoxysilane oligomer: (“Product name X-41-1805”, manufactured by Shin-Etsu Silicone Co., Ltd.).
Silane coupling agent 7 (epoxy group-containing methoxy / ethoxysilane oligomer): ("product name X-41-1053", manufactured by Shin-Etsu Silicone Co., Ltd.).
About the silane coupling agents 1-6, it mix | blended so that the mass ratio with respect to the total amount of a crosslinkable main ingredient resin and a polyisocyanate compound might turn into the ratio represented by the mass% in Table 1.
(Coloring agent / Matting agent)
Colorant 1 (indicated as “C1” in Table 1): Carbon black (Product name Special Black 4, manufactured by Evonik Degussa Japan Co., Ltd.): 18% by mass with respect to the total amount of the crosslinkable main resin and the polyisocyanate compound It mix | blended so that it might become.
Colorant 2 (indicated as “C2” in Table 1): Titanium oxide (product name: Taipure R-105, manufactured by DuPont Co., Ltd.): 130% by mass relative to the total amount of the crosslinkable main resin and the polyisocyanate compound It mix | blended so that it might become.
Inorganic filler 1 (indicated as “Si-1” in Table 1): Hydrophobic silica (product name “Silo Hovic 100”, manufactured by Fuji Silysia Ltd.): Mass relative to the total amount of the crosslinkable main resin and the polyisocyanate compound It mix | blended so that a ratio might be 7.3 mass%.
Inorganic filler 2 (indicated as “Si-2” in Table 1): Hydrophobic silica (product name Silo Hovic 200, manufactured by Fuji Silysia Co., Ltd.): Mass ratio to the total amount of the crosslinkable main resin and the polyisocyanate compound It mix | blended so that it might become 6.0 mass%.
(solvent)
Mixture of toluene: methyl ethyl ketone = 1: 1

  The primer material is prepared for each example, comparative example, and test example in the formulation shown in Table 1, and the solvent is added to each of the examples, comparative examples, and test examples, respectively. The liquid was adjusted to a solid content concentration of 60% by mass.

“Sheet of 188 μm thick biaxially stretched polyethylene terephthalate (PET)” (denoted as “PET” in Table 2) or “188 μm thick biaxially stretched polyethylene terephthalate (PET)” and 60 μm thick Sheets obtained by dry-laminating a stretched polypropylene resin (CPP) with a urethane-based adhesive (indicated as “CPP” in Table 2) are used as back surface protection sheet substrates, respectively. Each coating liquid prepared as described above was applied to the surface of the material (on the CPP side for the latter back surface protective sheet base material) with a bar coater, and the coated coating liquids were listed in Table 1, respectively. After drying at the drying temperature and drying time, curing was carried out under the conditions described in Table 1 to form an easy-adhesion layer. Examples 1 to 12, Comparative Examples 1 to 3, and It was used as a sample of Kenrei. About the coating amount of each coating liquid, it was as having indicated with g / m < ² > in the table | surface.

About each sample of produced Examples 1-12, Comparative Examples 1-3, and a test example, the following sealing material sheet 1 or 2 of the solar cell module was applied on the surface which applied the said coating liquid on the following conditions. Lamination was performed using a manufacturing vacuum laminator to obtain a sample for evaluation of adhesiveness and durable adhesiveness.
Sealing material sheet 1 (indicated as “EVA” in Table 2): EVA high-speed cross-linking type, thickness 450 μm (trade name S-11, manufactured by Bridgestone): pressure bonding at 150 ° C. for 15 minutes.
Sealant sheet 2 (indicated as “LL” in Table 2): a resin blended so that the mass ratio of the following silane-modified transparent resin, weatherproof masterbatch, and polymerization initiator compound resin is 20: 5: 80 Weakly crosslinkable LLDPE resin formed to a thickness of 200 μm at an extrusion temperature of 210 ° C .: pressure bonding for 15 minutes at a laminating condition of 150 ° C.
Silane modified transparent resin: vinyl trimethoxy with respect to 98 parts by mass of metallocene linear low density polyethylene (M-LLDPE) having a density of 0.881 g / cm ³ and an MFR at 190 ° C. of 2 g / 10 min. 2 parts by mass of silane and 0.1 part by mass of dicumyl peroxide as a radical generator (reaction catalyst) are mixed, melted and kneaded at 200 ° C., density 0.884 g / cm ³ , MFR at 190 ° C. A silane-modified transparent resin having a weight of 1.8 g / 10 min.
Weatherproof masterbatch: 3.8 parts by mass of benzophenol UV absorber and hindered amine light stabilizer 5 with respect to 100 parts by mass of powder obtained by pulverizing Ziegler linear low density polyethylene having a density of 0.880 g / cm ³ A master batch in which parts by mass and 0.5 parts by mass of a phosphorous heat stabilizer are mixed, melted, processed, and pelletized.
Polymerization initiator compound resin: t-amyl-peroxy-2-ethylhexyl carbonate with respect to 100 parts by mass of M-LLDPE pellets with a density of 0.880 g / cm ³ and MFR at 190 ° C. of 3.1 g / 10 min. Resin impregnated with 1 part by mass and compounded with compound pellets.

<Evaluation of adhesiveness>
The adhesiveness and the durable adhesiveness were evaluated for the samples for evaluating the adhesiveness and the durable adhesiveness using the samples of Examples 1 to 12, Comparative Examples 1 to 3, and Test Examples. Evaluation was performed based on the numerical value measured by the following method.
(Adhesion test)
About each sample for evaluation, peeling strength (N) measured the initial value about adhesiveness, and the value after each endurance test by 180-degree peel of 15 mm width. For the measurement, a peeling test apparatus (manufactured by “A & Day Co., Ltd., trade name“ TENSILON RTA-1150-H ”) was used, and the peeling condition was 50 mm / min at 23 ° C. at 23 ° C. Measurement was performed, and an average value of three measurements was adopted. The results are shown in Table 2.
[Evaluation criteria]
A: 50 N / 15 mm or more B: 26 N / 15 mm or more, less than 50 N / 15 mm C: 16 N / 15 mm or more, less than 26 N / 15 mm D: Less than 16 N / 15 mm (dump heat (DH) test)
In accordance with JIS C8917, each sample was subjected to a durability test for 1000 hours under the conditions of a test chamber temperature of 85 ° C. and a humidity of 85%. An adhesion test was performed on each sample after the test. The results are shown in Table 2.

<Evaluation of blocking resistance>
Each coating liquid consisting of the composition described in Table 1 is applied to the surface of each back surface protective sheet substrate described in Table 2 with a bar coater, and the coated coating liquid is applied at 120 ° C. for 2 minutes, or The film was dried at 90 ° C. for 30 seconds under different conditions to form an easy adhesion layer on the substrate surface. And what laminated | superposed the following films 1 and 2 generally used widely as the outermost layer of a back surface protection sheet on the surface of the easily bonding layer immediately after drying was used as the sample for blocking resistance evaluation.
Film 1: white fluorine film having a thickness of 25 μm: (product name Aflex 25PW, manufactured by Asahi Glass Co., Ltd.): The uneven surface was superimposed on the easy-adhesion layer.
Film 2: White polyester film having a thickness of 50 μm: (Product name VW, manufactured by Teijin DuPont Films Ltd.)
The above sample for evaluating blocking resistance was allowed to stand for 72 hours with a blocking tester (load 3 kg / cm ² , 40 ° C.). Then, the anti-blocking test was evaluated by the method of evaluating the blocking state by peeling off the overlapped portion of the evaluation sample removed from the tester. In addition, when the difference was recognized by the case where the laminated | stacked film is the film 1 and the case where it is the film 2, the lower evaluation result inferior to blocking property was made into the evaluation result of each sample.
[Evaluation criteria]
A: Sheets peel off naturally without transfer of the easy-adhesion layer B: No transfer of easy-adhesion layer, but there is adhesion between sheets, but there is no response C: At the time of peeling between substrates without transfer of the easy-adhesion layer There is a slight adhesion response D: There is a transition of the easy-adhesion layer and / or there is an adhesion response when the substrates are separated from each other

  As shown in Examples 1 to 12, the main resin composed of a crosslinkable substituent-containing acrylic resin contains a crosslinked resin crosslinked with a polyisocyanate compound, a silane coupling agent, and an organometallic coordination compound. It is understood that the easy-adhesive back surface protective sheet that has good adhesion to the EVA sealing material and the LLDPE sealing material and also has good blocking resistance. As for the silane coupling agent, in addition to the isocyanate-based silane coupling agent, epoxy-based silane coupling agent, and mercapto-based silane coupling agent that have been widely used as adhesion improvers, methyl / phenyl-based silane coupling agents have been used. It is understood that a ring agent can also be preferably used, and that a methyl / phenyl silane coupling agent can be particularly preferably used for an EVA sealing material. Further, it is understood that the glass transition point (Tg) of the main resin can be preferably used even if it is a resin having a Tg lower than 50 ° C., which has been conventionally regarded as a general lower limit temperature.

  As shown in Examples 10 to 12, the easy-adhesive back surface protective sheet of the present invention is heated to evaporate the solvent by selecting Tg of the crosslinkable main resin having a glass transition point (Tg) of about 50 ° C. Even when the drying process is performed at a low temperature of about 90 ° C., it is understood that the film has good blocking resistance and adhesion.

  As shown in Example 13, the cross-linked resin is a urethane cross-linked resin, and an easy-adhesive layer containing a silane coupling agent and an organometallic coordination compound is formed on the polypropylene resin substrate of the back protective sheet. It is understood that the easily-adhesive back surface protective sheet that is used has good adhesion to the EVA sealing material and the LLDPE sealing material, and also has good blocking resistance.

DESCRIPTION OF SYMBOLS 1 Solar cell module 2 Transparent front substrate 3 Front side sealing material layer 4 Solar cell element 5 Back side sealing material layer 6 Back surface protection sheet

Claims (5)

An easy-adhesion layer is formed on one side of the back surface protection sheet for solar cell modules composed of one or more layers,
The easy-adhesion layer contains a) a crosslinkable main agent resin, b) a crosslinked resin crosslinked with a polyisocyanate compound, c) a silane coupling agent, and d) an organometallic coordination compound ,
Said a) crosslinkable main ingredient resin is a crosslinkable substituent containing acrylic resin, The glass transition point (Tg) is 25 degreeC or more and 70 degrees C or less,
The easily adhesive back surface protection sheet whose glass transition point (Tg) of the said crosslinkable substituent containing acrylic resin is 45 degreeC or more and 60 degrees C or less . With respect to the total amount of said a) crosslinkable main ingredient resin and said b) polyisocyanate compound,
C) 0.1% by mass or more and 10% by mass or less of the silane coupling agent,
The easy-adhesive back surface protective sheet according to claim 1 , comprising d) an organometallic coordination compound in an amount of 0.1% by mass to 7% by mass. It is a manufacturing method of the easily adhesive back surface protection sheet according to claim 1 or 2 ,
Applying a coating liquid containing the cross-linked resin and a solvent on one side of the back surface protection sheet to form a coating film,
A heating and drying step of evaporating the solvent by heating the coating film;
A step of subjecting the coating film obtained by evaporating the solvent to curing, and
The manufacturing method of the easily-adhesive back surface protection sheet whose heating temperature in the said heat drying process is 70 degreeC or more and less than 100 degreeC. In the solar cell module in which the easy-adhesive back surface protective sheet according to claim 1 or 2 , the sealing material, and the solar cell element are integrated at least.
The solar cell module in which the easy-adhesive back surface protective sheet and the sealing material containing polyethylene resin are integrated via the easy-adhesive layer. The sealing material is formed by copolymerizing at least a low density polyethylene (LDPE) having a density of 0.900 g / cm ³ or less and / or a linear low density polyethylene (LLDPE) and an ethylenically unsaturated silane compound as a comonomer. The solar cell module according to claim 4 , wherein the solar cell module is a sealing material containing a polyethylene resin containing a silane copolymer.

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