JP5699382B2 - Manufacturing method of solar cell module - Google Patents

Description

  The present invention relates to a method for manufacturing a solar cell module.

  In recent years, solar cells as a clean energy source have attracted attention due to the growing awareness of environmental issues. Currently, various types of solar cell modules have been developed and proposed. Generally, a solar cell module has a configuration in which a transparent front substrate, a solar cell element, and a back surface protection sheet are laminated via a sealing material sheet.

  As illustrated in FIG. 1, the solar cell module 1 includes a transparent front substrate 2, a front sealing material layer 3, a solar cell element 4, a back sealing material layer 5, and a back surface protection sheet from the light receiving surface side of incident light. 6 are laminated in order, and the front sealing material layer 3 is disposed on the light receiving surface side of the solar cell element 4 and the back sealing material layer 5 is disposed on the back surface side of the solar cell element 4 so as to sandwich the solar cell element 4. Has been.

  Here, as a sealing material sheet which comprises said sealing material layer, the structure mainly containing EVA (ethylene-vinyl acetate copolymer) from a transparency or fluidity | liquidity is known. (See Patent Document 1). In this case, the above composition is molded without being cross-linked, and is cross-linked by heating or the like in a modularization step or a subsequent step.

  Further, as a sealing material sheet for another solar cell module, PBR (propylene-butene copolymer), EBR (ethylene-butene copolymer), EPR, which is a low crystalline α-olefin copolymer, The structure containing (ethylene-propylene copolymer) etc. and a crosslinking agent is known (refer patent document 2).

JP 2009-135200 A JP 2006-210906 A

  The EVA of Patent Document 1 has the advantage of being excellent in transparency and fluidity, but has the basic drawback of poor water vapor barrier properties.

  In Patent Document 2, although the water vapor barrier property is improved by using a low crystalline olefin polymer such as PBR as a base, it has a defect that it is also inferior in transparency as compared with EVA.

  As described above, the material for the encapsulant sheet has advantages and disadvantages in the EVA system and the olefin system, respectively, and it has been difficult to satisfy these requirements simultaneously with a single material.

  The present invention has been made to solve the above-mentioned problems, and the object thereof is excellent in light transmittance when considered as a module, and also has excellent olefinic characteristics such as water vapor barrier properties and insulating properties. The object is to provide a solar cell module.

  As described above, the present inventors include the front sealing material layer 3 disposed on the light receiving surface side of the solar cell element 4 and the back sealing material layer 5 disposed on the back surface side of the solar cell element 4. Attention was paid to the difference in the required physical properties of the sealing material sheet. Specifically, transparency is important as the front sealing material layer 3 disposed on the light receiving surface side, while the back sealing material layer 5 disposed on the back surface side is more transparent than Rather, water vapor barrier properties and insulation properties are required. In particular, in the so-called back contact method that is often used in recent years, since all or most of the electrodes are disposed on the back surface in order to improve power generation efficiency, high insulation on the back surface side is particularly required. From such a viewpoint, both the front sealing material layer 3 and the back sealing material layer 5 are not necessarily made of the same material. However, since both layers are integrated by vacuum lamination, both layers are required to have high adhesion. From such a point of view, the inventors have found that the above problems can be solved by using a predetermined EVA resin as the front sealing material layer and a predetermined polyethylene resin as the back sealing material layer, and completing the present invention. It came. More specifically, the present invention provides the following.

(1) A solar cell module including a solar cell element, a first sealing material sheet disposed on the light receiving surface side of the solar cell element, and a second sealing material sheet disposed on the back surface side of the solar cell element. The first sealing material sheet is an ethylene-vinyl acetate copolymer resin, and the second sealing material sheet is a polyethylene resin having a density of 0.900 g / cm ³ or less. A crosslinking step in which an uncrosslinked sealing material sheet comprising a polyethylene resin having a density of 0.900 g / cm ³ or less is crosslinked by irradiation with ionizing radiation to form a crosslinked second sealing material sheet; The manufacturing method of a solar cell module provided with the thermocompression bonding process of laminating | stacking and integrating the member containing the said solar cell element, a said 1st sealing material sheet, and a said 2nd sealing material sheet sequentially.

  (2) The method for producing a solar cell module according to (1), wherein the second sealing material sheet has a polystyrene-equivalent weight average molecular weight of 247,000 g / mol or more and 300,000 g / mol or less.

  (3) The method for manufacturing a solar cell module according to (1) or (2), wherein the solar cell element is a back contact system in which an electrode is disposed on the back surface side.

  According to the method for manufacturing a solar cell module of the present invention, the sealing material layer takes advantage of both the transparency of the EVA resin and the water vapor barrier property and the insulating property of the polyethylene resin, and also the sealing material layer. It is possible to provide a solar cell module having excellent adhesion.

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

  The solar cell module of the present invention is mainly characterized by the material structure of the sealing material layer. First, the overall configuration of the solar cell module and the manufacturing method thereof will be described, the solar cell module encapsulant sheet constituting the encapsulant layer will be described in detail, and other components will be described.

<Solar cell module>
FIG. 1 is a cross-sectional view showing an example of the layer structure of a solar cell module 1 according to an embodiment of the present invention. In the solar cell module 1, a transparent front substrate 2, a front sealing material layer 3, a solar cell element 4, a back sealing material layer 5, and a back surface protection sheet 6 are sequentially laminated from the light receiving surface side of incident light.

  In the present specification, the solar cell element means a minimum structural unit that generates light by receiving light by a photoconductive effect and / or a photovoltaic effect, and has a size of 10 cm × 10 cm square to 20 cm × 20 cm square, for example. Things. Moreover, a solar cell module means what is comprised by connecting this solar cell element in multiple numbers, for example, about 0.5-50 square x-2. The thing about 0 m x 2.0 m square can be mentioned. In the present specification, the solar cell module includes a solar cell panel that is an assembly of modules.

The solar cell module 1 uses a first sealing material sheet made of an ethylene-vinyl acetate copolymer resin having a gel fraction within a predetermined range as the front sealing material layer 3, and the back surface. As the sealing material layer 5, a second sealing material sheet made of a polyethylene resin having a density within a predetermined low density range is used. The first encapsulant sheet has an ethylene-vinyl acetate copolymer resin as a main resin, and has particularly excellent light transmittance while maintaining necessary flexibility and adhesion. The second encapsulant sheet is The main resin is a polyethylene resin having a density of 0.940 g / cm ³ or less, and particularly excellent water vapor barrier properties and insulation properties while maintaining necessary flexibility and adhesion. The solar cell module 1 uses the above-described encapsulant sheets having different physical properties in each layer in the solar cell module, and optimally arranges them by taking advantage of their characteristics to transmit light as a solar cell module. Characteristics, water vapor barrier properties, and insulating properties of the encapsulant layer are simultaneously increased to a preferable range. In addition, the detail of each of a 1st sealing material sheet and a 2nd sealing material sheet is mentioned later.

  About the transparent front substrate 2 and the back surface protection sheet 6 which are members other than the front surface sealing material layer 3 and the back surface sealing material layer 5, a conventionally well-known material can be especially used without a restriction | limiting. As the transparent front substrate 2, glass or the like, and as the back protective sheet 6, a resin sheet such as ETFE or water-resistant PET can be used. In addition, the solar cell module 1 of this invention may also contain members other than the said member.

  The solar cell element 4 is not particularly limited, but is not limited to a crystalline silicon solar cell manufactured using a single crystal silicon substrate or a polycrystalline silicon substrate, and amorphous silicon, microcrystalline silicon, a chalcopyrite compound, or the like is used. The thin-film solar cell (CIGS) is preferably used, and the configuration of the solar cell module is not only the conventional front contact type but also the back contact type in which a plurality of electrodes having different polarities are provided on the non-light-receiving surface side. The solar cell element can be preferably used.

  Among these, as the solar cell element 4, a back contact type solar cell element such as a metal wrap through (MWT) method or an emitter wrap through (EWT) method can be used particularly preferably. In the solar cell module using these back contact type solar cell elements, it is necessary to insulate the electrodes provided on the non-light-receiving surface side to prevent a short circuit. Since the solar cell module 1 uses a second sealing material sheet made of a highly insulating polyethylene-based resin as the back surface sealing material layer 5 in contact with the non-light-receiving surface side of the solar cell element 4, the solar cell element A back contact type solar cell element can be particularly preferably used as 4.

<Sealant sheet for solar cell module>
These 1st sealing material sheets and 2nd sealing material sheets (henceforth "a sealing material sheet" collectively) are the sealing material composition which demonstrates a detail below for normal heat | fever. The sheet is formed into a sheet or film by molding using various molding methods such as injection molding, extrusion molding, hollow molding, compression molding, and rotational molding, which are usually used in plastic resins. In addition, the sheet form in this invention means the film form, and there is no difference in both. Hereinafter, the details of each of the first sealing material sheet and the second sealing material sheet will be sequentially described.

[First sealing material sheet]
The first sealing material sheet used as the front sealing material layer 3 contains an ethylene-vinyl acetate copolymer resin (EVA) and a crosslinking agent as essential components, and further contains a crosslinking aid and other components as necessary. It consists of the 1st sealing material composition to contain. A 1st sealing material sheet can be obtained by forming this 1st sealing material composition into a film by the above-mentioned shaping | molding method, performing a crosslinking process after shaping | molding, and advancing appropriate bridge | crosslinking. The film forming temperature may be 90 ° C. to 120 ° C.

  As a cross-linking method, the cross-linking may be completed by heating at a high temperature of 150 to 250 ° C. at the time of manufacturing the solar cell module, or the cross-linking may be completed by further performing a curing process by heat treatment after modularization.

  The first encapsulant sheet has a gel fraction of 60% or more after completion of the crosslinking after being integrated as the solar cell module 1. When the gel fraction is 60% or more, unnecessary flow in the modularization process can be suppressed. The gel fraction is preferably 80% or more. By setting the gel fraction to 80% or more, preferable heat resistance at 100 ° C. or more and 150 ° C. or less can be obtained.

  Here, the gel fraction (%) means that 0.1 g of a sealing material sheet is put in a resin mesh, extracted with 60 ° C. toluene for 4 hours, taken out together with the resin mesh, weighed after drying, and mass before and after extraction. Comparison is made to measure the mass% of the remaining insoluble matter, and this is used as the gel fraction.

  The thickness of the first sealing material sheet is preferably 100 μm or more and 600 μm or less, and more preferably 300 μm or more and 550 μm or less. If the thickness is less than 100 μm, the impact cannot be sufficiently reduced. Moreover, even if it exceeds 600 micrometers, since the effect beyond it is not acquired and it is uneconomical, it is unpreferable.

  About the color of a 1st sealing material sheet, it is essential that it is transparent. More specifically, the haze value at a thickness of 400 μm at the time of integration as the solar cell module 1 is preferably 10% or less, more preferably 5% or less. Thus, by increasing the transparency on the daylighting surface side, it is possible to contribute to the improvement of the power generation efficiency of the solar cell module.

[First sealing material composition]
(EVA)
EVA used as the main resin of the first encapsulant composition that is the material of the first encapsulant sheet can be a conventionally known one, and is not particularly limited. The gel at the time when the solar cell module 1 is integrated is used. What is necessary is just to be able to make the fraction 60% or more, preferably 80% or more. In order to achieve such a high degree of crosslinking, the vinyl acetate content (VA content) is preferably 24% by mass or more and 35% by mass or less.

  The melt mass flow rate (MFR) of EVA is preferably 1 g / 10 min or more and 40 g / 10 min or less, more preferably 15 g / 10 min or more and 40 g / 10 min or less, at 190 ° C. according to JIS K7210 method. The Vicat softening point of JIS K7206 is preferably in the range of 30 ° C to 40 ° C. When the MFR and softening point are within the above ranges, the resin is excellent in the property of being melted by heating, uniformly fluidized with the additive, and deformed to a constant shape until cooling.

(Crosslinking agent)
The first sealing material composition contains a crosslinking agent. A well-known thing can be used for a crosslinking agent, It does not specifically limit, For example, a well-known radical polymerization initiator can be used. Examples of radical polymerization initiators include hydroperoxides such as diisopropylbenzene hydroperoxide and 2,5-dimethyl-2,5-di (hydroperoxy) hexane; di-t-butyl peroxide, t-butyl Cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-peroxy) hexyne-3, etc. Dialkyl peroxides; diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dichlorobenzoyl peroxide; t-butyl peroxyacetate, t-butyl pero Ci-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxybenzoate, di-t-butyl peroxyphthalate, 2 , 5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, t-butylperoxy-2-ethylhexyl carbonate Oxyesters; organic peroxides such as methyl peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, or azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile), dibutyltin Diacetate, dibutyltin dilaurate It can be mentioned dibutyltin dioctoate, dioctyltin dilaurate, dicumyl peroxide, such a silanol condensation catalyst. These may be used alone or in combination of two or more. Specifically, the fast curing method in the vacuum heating lamination process of solar cell module fabrication (the sealing material is highly crosslinked only by vacuum heating lamination, and is allowed to stand at about 150 to 160 ° C. for 30 minutes to 1 hour to post-crosslink the sealing material. T-butylperoxy-2-ethylhexyl carbonate (TBEC) is preferably used from the viewpoint of adapting to the method of omitting the curing step.

  The 10-hour half-life temperature of the crosslinking agent is preferably an organic peroxide of 100 ° C. to 120 ° C. from the upper limit of the resin temperature at which the crosslinking reaction does not start in the extruder.

  The content of the crosslinking agent is preferably contained in the first sealing material composition in the range of 0.5% by mass to 1.0% by mass. If it is less than 0.5% by mass, the heat resistance at high temperature is inferior due to insufficient crosslinking, which is not preferable.

(Crosslinking aid)
The first sealing material composition may further contain a crosslinking aid. A polyfunctional monomer having a carbon-carbon double bond and / or an epoxy group can be preferably used, and more preferably an allyl group, a (meth) acrylate group or a vinyl group can be used as the functional group of the polyfunctional monomer. This promotes an appropriate crosslinking reaction.

  Specific crosslinking aids include triallyl isocyanurate (TAIC), triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate and other polyallyl compounds, 4-hydroxybutyl acrylate glycidyl ether and two epoxy groups Examples thereof include epoxy compounds such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and trimethylolpropane polyglycidyl ether. These may be used alone or in combination of two or more.

  Among these, triallyl isocyanurate (TAIC) can be preferably used because it has a relatively slow reaction rate and a low shrinkage rate due to the reaction.

  Trimethylolpropane trimethacrylate (TMPT), trimethylolpropane triacrylate (TMPTA), ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1, Poly (meth) acryloxy compounds such as 9-nonanediol diacrylate, glycidyl methacrylate containing a double bond and an epoxy group, and the like are not preferable because of a high reaction rate.

  The content of the crosslinking aid is preferably included in the first sealing material composition in the range of 0.5% by mass to 1.0% by mass. If it is less than 0.5% by mass, the heat resistance at high temperature is inferior due to insufficient crosslinking, and the crosslinking time becomes long and cannot be fast cured. If it exceeds 1.0% by mass, crosslinking is promoted by the annealing treatment described later, and the flexibility of the sealing material is lowered, which is not preferable.

(Radical absorbent)
By using the above-mentioned cross-linking agent as a radical polymerization initiator in combination with the first sealing material composition and the radical absorbent for quenching it, the degree of cross-linking is adjusted to further adjust the gel fraction. May be. Examples of such radical absorbents include hindered phenol-based antioxidants, hindered amine-based weather resistance stabilization, and the like. A hindered phenol-based radical absorbent having a high radical absorbing ability near the crosslinking temperature is preferred. The content of the radical absorbent is preferably included in the first sealing material composition in the range of 0.01% by mass to 3% by mass, more preferably in the range of 0.05% by mass to 2.0% by mass. It is. If it exists in this range, a crosslinking reaction can be suppressed moderately.

(Other ingredients)
The first sealing material composition can further contain other components. For example, components such as a weather resistance masterbatch for imparting weather resistance to the first sealing material sheet, various fillers, a light stabilizer, an ultraviolet absorber, and a heat stabilizer are exemplified. These contents vary depending on the particle shape, density, and the like, but are preferably in the range of 0.001% by mass to 5% by mass in the solar cell module encapsulant composition. By including these additives, it is possible to impart a long-term stable mechanical strength, an effect of preventing yellowing, cracking, and the like to the encapsulant composition for solar cell modules.

  A weatherproof masterbatch is a dispersion of a light stabilizer, ultraviolet absorber, heat stabilizer, and the above-mentioned antioxidants in a resin such as EVA, and this is added to the first sealing material composition By doing, favorable weather resistance can be provided to a 1st sealing material sheet. The weatherproof masterbatch may be prepared and used as appropriate, or a commercially available product may be used. As resin used for a weatherproof masterbatch, EVA used for a 1st sealing material sheet may be sufficient, and other resin may be sufficient. These light stabilizers, ultraviolet absorbers, heat stabilizers and antioxidants can be used alone or in combination of two or more.

  Further, as other components used in the first sealing material composition, in addition to the above, an adhesion improver such as a silane coupling agent, a nucleating agent, a dispersing agent, a leveling agent, a plasticizer, an antifoaming agent, a flame retardant Etc.

[Second encapsulant sheet]
The second sealing material sheet used as the back sealing material layer 5 includes a low density polyethylene-based resin as a main resin, and further contains a crosslinking agent, a crosslinking aid, and other components as necessary. It consists of a material composition. A 2nd sealing material sheet can be obtained by shape | molding this 2nd sealing material composition by the shaping | molding method normally used in a normal thermoplastic resin as above-mentioned.

The density of the second sealing material sheet is 0.940 g / cm ³ or less, preferably in the range of 0.900 g / cm ³ or less, more preferably in the range of 0.870 to 0.890 g / cm ^3. . The low density polyethylene may be a single type of resin or may be composed of a sealing material composition in which a plurality of polyethylene resins are combined. By using the second sealing material sheet as such a low-density polyethylene-based resin, the second sealing material sheet has preferable flexibility and transparency in addition to high water vapor barrier properties and high insulation properties. Can be.

  A 2nd sealing material sheet is good also as a sealing material sheet already bridge | crosslinked by the crosslinking process. As a crosslinking method, the molding temperature may be set to a high temperature of 150 to 250 ° C. so that a crosslinked sheet is formed at the end of molding, and the molding temperature is set to a low temperature of, for example, 90 ° C. to 100 ° C. Then, crosslinking may be completed by heating at a high temperature at the time of manufacturing the solar cell module. The uncrosslinked encapsulant sheet may be a cross-linked encapsulant sheet by a crosslinking treatment with ionizing radiation.

  Regarding the crosslinking treatment by irradiation with ionizing radiation, the individual crosslinking conditions are not particularly limited, and may be appropriately set so that the gel fraction is in the following range as a total treatment result. Specifically, it can be performed by ionizing radiation such as electron beam (EB), α-ray, β-ray, γ-ray, neutron beam, etc. Among them, it is preferable to use an electron beam. The acceleration voltage in electron beam irradiation is determined by the thickness of the sheet that is the object to be irradiated, and the thicker the sheet, the larger the acceleration voltage is required. For example, a 0.5 mm-thick sheet is irradiated with 100 kV or more, preferably 200 kV or more. If the acceleration voltage is lower than this, the crosslinking is not sufficiently performed. The irradiation dose is in the range of 1-100 Mrad, preferably 1-30 Mrad. When the irradiation dose is less than 1 Mrad, sufficient crosslinking is not performed, and when it exceeds 50 Mrad, there is a concern about deformation or coloring of the sheet due to generated heat. In addition, you may irradiate from both sides. Irradiation may be in an air atmosphere or a nitrogen atmosphere.

  The second encapsulant sheet preferably has a gel fraction of 0% or more and 90% or less, more preferably 0% or more and 70% or less, in a state of being integrated as the solar cell module 1. When the gel fraction is 90% or less, high elasticity can be obtained particularly in a low temperature range from 0 ° C. to 70 ° C. Further, when the gel fraction is 70% or more, the fluidity is insufficient at the time of vacuum heating lamination for integration as a solar cell module, and the function of filling an undesired gap space is not sufficiently exhibited. The gel fraction is more preferably 70% or more.

  On the other hand, even when the gel fraction is 0%, by appropriately optimizing the resin density, MFR, cross-linking agent, cross-linking aid content, cross-linking method, etc., shear stress is increased and flow prevention is achieved. It is also possible.

  Moreover, it is preferable that the gel fraction of the 2nd sealing material sheet at the time of integrating as the solar cell module 1 is smaller than the gel fraction of the 1st sealing material sheet. In a general usage state of the solar cell module 1, the front sealing material layer 3 closer to the light receiving surface side of incident light is more sunlight in the daytime than the back sealing material layer 5 far from the light receiving surface side. There is a tendency that the expansion coefficient due to the temperature rise associated with the irradiation is increased. When the difference in expansion coefficient between the front sealing material layer 3 and the back sealing material layer 5 that are closely stacked on top and bottom of the solar cell element 4 increases, the solar cell element 4 undergoes deformation such as warping due to the difference in stress. May occur. This problem is likely to occur particularly when the solar cell element 4 is a thin film solar cell element. However, by making the gel fraction of the second sealing material sheet smaller than the gel fraction of the first sealing material sheet, the expansion of the back sealing material layer 5 with a small temperature rise is moderately promoted, and the front surface The above deformation can be prevented by absorbing the difference in expansion coefficient with the sealing material layer 3.

  In order to make the gel fraction of the second sealing material sheet at the time of being integrated as the solar cell module 1 smaller than the gel fraction of the first sealing material sheet, the first sealing material sheet and the first sealing material sheet It can be realized by appropriately adjusting the crosslinking conditions such as the crosslinking temperature of the two encapsulant sheets and the content of the crosslinking agent in the encapsulant composition. As described above, the solar cell module 1 in which the gel fraction of each sealing material is adjusted to the above-described preferable relative range can be particularly preferably used as a solar cell module including a thin-film solar cell element.

  As will be shown later in Examples, the second sealing material sheet using a polyethylene resin is characterized by having excellent insulating properties. Therefore, the solar cell module 1 in which the second sealing material sheet is disposed as the back surface sealing material layer 5 can be particularly preferably used as a solar cell module including a back contact type solar cell element in which an electrode is disposed on the back surface side. .

  The thickness of the second sealing material sheet is preferably not less than 100 μm and not more than 600 μm, and if it is less than 100 μm, the impact cannot be sufficiently mitigated, and the insulating property becomes insufficient, which is not preferable. Further, if the thickness exceeds 600 μm, no further effect is obtained, and it becomes difficult to form a pattern of a conductive portion for collecting current from a back contact type solar cell element.

  The second encapsulant sheet preferably has a polystyrene-reduced weight average molecular weight of low density polyethylene as a main resin that is 100,000 g / mol or more and 300,000 g / mol or less. When the molecular weight is less than 100,000 g / mol, the heat resistance performance of the solar cell module becomes insufficient, and when it exceeds 300,000 g / mol, vacuum heating lamination for integration as a solar cell module is performed. It is not preferable because sometimes the fluidity is insufficient and the function of filling an undesired gap space is not sufficiently exhibited. The weight average molecular weight can be measured by a conventionally known GPC method after dissolving in a solvent such as THF.

  It does not specifically limit about the color of a 2nd sealing material sheet. The material resin is not particularly colored and may remain colorless and transparent or translucent, or may be colored in any color. For example, by coloring to a color having a high light reflectance such as white, it is possible to reflect incident light and contribute to improving the power generation efficiency of the solar cell module, and by coloring to white or black, The designability of the solar cell module 1 can also be improved.

[Second sealing material composition]
(Low density polyethylene)
As the main resin of the second sealing material composition that is the material of the second sealing material sheet, low density polyethylene (LDPE) having a density of 0.940 or less, preferably linear low density polyethylene (LLDPE) is used. Linear low density polyethylene is a copolymer of ethylene and α- olefin, in the present invention, within the scope thereof density of 0.940 g / cm ³ or less, preferably 0.900 g / cm ³ within the following ranges More preferably, it is the range of 0.870-0.890 g / cm < ³ >.

  In the present invention, it is preferable to use a metallocene linear low density polyethylene. Metallocene linear low density polyethylene is synthesized using a metallocene catalyst which is a single site catalyst. Such polyethylene has few side chain branches and a uniform comonomer distribution. For this reason, molecular weight distribution is narrow, it is possible to make it the above ultra-low density, and a softness | flexibility can be provided with respect to a 2nd sealing material sheet. As a result of the flexibility, the adhesion between the second sealing material sheet and the back surface protective sheet 6 is increased, so that the ingress of moisture into the solar cell module 1 can be suppressed.

  As the α-olefin of the linear low density polyethylene, an α-olefin having no branch is preferably used. Among these, 1-hexene and 1-heptene which are α-olefins having 6 to 8 carbon atoms are preferable. Or 1-octene is particularly preferably used. When the number of carbon atoms of the α-olefin is 6 or more and 8 or less, the second sealing material sheet can be given good flexibility and good strength. As a result, the adhesiveness between the second sealing material sheet and the back surface protective sheet 6 is further increased, and the above problem of moisture intrusion can be further suppressed.

  The Shore D hardness of the low density polyethylene is preferably 80 degrees or less, preferably 15 degrees or more and 40 degrees or less, and more preferably 15 degrees or more and 35 degrees or less. When the Shore D hardness of the linear low density polyethylene is in the above range, the flexibility of the second sealing material sheet can be maintained. The MFR of the linear low density polyethylene is preferably from 0.5 g / 10 min to 40 g / 10 min at 190 ° C., more preferably from 2 g / 10 min to 40 g / 10 min. When the MFR is in the above range, the processability during film formation is excellent.

  The second sealing material composition may further contain a silane-modified polyethylene resin. The silane-modified polyethylene resin is obtained by graft-polymerizing an ethylenically unsaturated silane compound as a side chain to linear low-density polyethylene (LLDPE) or the like as a main chain. Since such a graft copolymer has a high degree of freedom of silanol groups that contribute to the adhesive force, the adhesion of the sealing material to other members in the solar cell module can be improved.

  The silane-modified polyethylene resin can be produced, for example, by the method described in JP-A-2003-46105. By using the resin as a component of the sealing material composition of the solar cell module, strength and durability can be obtained. In addition, it has excellent weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, yield resistance, and other characteristics, and is also affected by manufacturing conditions such as thermocompression bonding for manufacturing solar cell modules. Therefore, it is possible to manufacture solar cell modules having extremely excellent heat-fusibility, stably and at low cost, and suitable for various applications.

  Examples of ethylenically unsaturated silane compounds to be graft polymerized with linear low density polyethylene include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, and vinyltripentyloxysilane. , One or more selected from vinyltriphenoxysilane, vinyltribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane be able to.

  The graft amount, which is the content of the ethylenically unsaturated silane compound, is, for example, 0.001 to 15 masses with respect to a total of 100 mass parts of all the resin components in the sealing material composition containing other polyethylene-based resins described later. What is necessary is just to adjust suitably so that it may become a% grade, Preferably, 0.01 mass% or more and about 5 mass% grade, Especially preferably, it may be 0.05 mass% or more and about 2 mass%. In the present invention, when the content of the ethylenically unsaturated silane compound is large, the mechanical strength and heat resistance are excellent. However, when the content is excessive, the tensile elongation and heat-fusibility tend to be inferior.

  The second sealing material composition may further contain an acid-modified polyethylene resin typified by maleic anhydride modification. The acid-modified polyethylene resin is obtained, for example, by graft polymerization using, for example, maleic anhydride or the like as a side chain on linear low density polyethylene (LLDPE) or the like as a main chain. Such a graft polymer has a high polarity of the acid part which contributes to adhesive force, and can improve the adhesiveness of the sealing material sheet to the metal member in the solar cell module.

The content of the linear low-density polyethylene having a density of 0.940 g / cm ³ or less contained in the second sealing material composition is preferably 10% by mass or more and 99% by mass or less, more preferably in the composition. It is 50 mass% or more and 99 mass% or less, More preferably, it is 90 mass% or more and 99 mass% or less. As long as the density of the second sealing material sheet is 0.940 g / cm ³ or less, other resin may be included. These may be used, for example, as an additive resin, and can be used for masterbatching other components described later.

(Crosslinking agent)
The second encapsulant composition may contain a cross-linking agent as necessary, whereby the second encapsulant sheet may be a cross-linked encapsulant sheet. In this case, the same crosslinking agent as that of the first sealing material composition can be used and is not particularly limited. Specific examples include various organic peroxides, azo compounds, silanol condensation catalysts, and the like. These may be used alone or in combination of two or more.

  When using a crosslinking agent, the content thereof is preferably contained in the second sealing material composition in an amount of 0.01% by mass to 2% by mass, more preferably 0.05% by mass to 1.5% by mass. The range is as follows. If it exists in this range, a crosslinking reaction can be suppressed moderately.

(Crosslinking aid)
When the second sealing material sheet is a crosslinked sealing material sheet, the second sealing material composition may contain a crosslinking assistant. As the crosslinking aid, a polyfunctional vinyl monomer and / or a polyfunctional epoxy monomer can be preferably used. This promotes an appropriate crosslinking reaction so that the gel fraction is 90% or less. The agent reduces the crystallinity of the linear low density polyethylene and maintains transparency. Thereby, a 2nd sealing material sheet can be made into the sealing material sheet which is more excellent in transparency and low temperature flexibility.

  The crosslinking aid can be the same as the first sealing material composition and is not particularly limited. Specifically, in addition to polyallyl compounds such as triallyl isocyanurate (TAIC) that can be used in the first sealing material composition, trimethylolpropane trimethacrylate (TMPT), trimethylolpropane triacrylate (TMPTA), Poly (meth) acryloxy compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, double bonds and epoxy An azo compound such as glycidyl methacrylate containing a group, a silanol condensation catalyst, or the like can also be used. These may be used alone or in combination of two or more.

  Among these, TAIC is preferably used from the viewpoint of good compatibility with low density polyethylene, lowering crystallinity by crosslinking, maintaining transparency, and imparting flexibility at low temperatures.

  When using a crosslinking aid, the content thereof is preferably included in the second sealing material composition in an amount of 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 2.0% by mass. % Or less. Within this range, an appropriate crosslinking reaction can be promoted to make the gel fraction 90% or less.

(Radical absorbent)
When the second encapsulant sheet is used as a cross-linked encapsulant sheet, the degree of cross-linking is obtained by using the above-mentioned cross-linking auxiliary agent serving as a radical polymerization initiator and the radical absorbent for quenching it in combination. To adjust the gel fraction more finely. As a specific radical absorber, the same thing as what can be used for a 1st sealing material composition can be used in the same content range. If it is in the range, a crosslinking reaction can be moderately suppressed.

(Other ingredients)
The second sealing material composition can contain other components such as a weather-resistant masterbatch. About the kind of other component which can be used for a 2nd sealing material composition, content, and the effect by those components, it is the same as that of the case of a 1st sealing material composition. In addition, about a weatherproof masterbatch, it may produce suitably and may use it and a commercial item may be used. The resin used for the weatherproof masterbatch may be a linear low density polyethylene used in the present invention, or other resin.

<Method for manufacturing solar cell module>
The solar cell module 1 includes, for example, the transparent front substrate 2, the front sealing material layer 3 made of the first sealing material sheet, the solar cell element 4, the back sealing material layer 5 made of the second sealing material sheet, And the member which consists of a back surface protection sheet 6 is laminated | stacked one by one, It integrates by vacuum suction etc. Then, said members can be manufactured by thermocompression-bonding as an integral molded object by forming methods, such as a lamination method.

  Further, the solar cell module 1 is obtained by forming a first encapsulant composition on each of the front surface side and the back surface side of the solar cell element 4 by a molding method usually used in a normal thermoplastic resin, for example, T-die extrusion molding. And the second sealing material composition are melt-laminated to sandwich the solar cell element 4 with the front sealing material layer 3 and the back sealing material layer 5, and then the transparent front substrate 2 and the back surface protection sheet 6 are sequentially stacked. Then, they may be manufactured by a method in which these are integrated by vacuum suction or the like and thermocompression bonded.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

<Manufacture of sealing material sheet for solar cell module>
As an example of the first encapsulant sheet and a comparative example of the second encapsulant sheet, as shown below, encapsulant sheets having different main vinyl resins as the vinyl acetate content are formed, and the encapsulant sheets are respectively formed. EVA 1-2.

EVA1: Sealing material sheet EVA1 was created using the sealing material composition mix | blended as follows.
100 parts by mass of EVA (vinyl acetate content 28%, manufactured by Mitsui DuPont Polychemical, trade name EVAFLEX / EV250 grade), 1.0 part by weight of crosslinking agent (trade name TBEC, manufactured by Arkema Yoshitomi Corporation), crosslinking aid 1.0 parts by weight of an agent (Sartomer, trade name: SR350), 0.5 parts by weight of an antioxidant (BASF Japan, trade name Irganox 1076), UV absorber (Kemipro Kasei Co., Ltd., trade name KEMISORB 12) ) 0.3 mass part, weather resistance stabilizer (manufactured by BASF Japan Ltd., trade name Tinuvin 770) 0.1 mass part of a sealing material composition, φ30 mm extruder, film forming machine having 200 mm width T dice Is used, and is molded at an extrusion temperature of 90 ° C. and a take-off speed of 1.1 m / min, and has a thickness of 400 μm. Sheet EVA1 was produced. The gel fraction was 0%.

EVA2: A sealing material sheet EVA2 was prepared using a sealing material composition formulated as follows.
With respect to 100 parts by mass of EVA (vinyl acetate content 33%, manufactured by Mitsui DuPont Polychemical, trade name EVAFLEX / EV150 grade), the same crosslinking agent, crosslinking aid, antioxidant as the EVA1 sealing material composition, A sealing material composition in which a UV absorber and a weathering stabilizer are blended at the same blending ratio (parts by mass) as the above-mentioned EVA1 sealing material composition is molded under the same conditions as EVA1, and the sealing is 400 μm in thickness. A material sheet EVA2 was produced. The gel fraction was 0%.

  As an example of the second encapsulant sheet, an uncrosslinked encapsulant sheet (encapsulant sheet LLDPE2) is formed from an encapsulant composition containing a low-density polyethylene resin as a main resin, as described below, and sealed. The material sheet LLDPE2 is subjected to crosslinking treatment by irradiation with ionizing radiation under different crosslinking conditions as described below (described as “EB irradiation” in Table 1), and each crosslinked sealing material sheet (sealing material sheet LLDPE3 and 4) was made and it was set as the sealing material sheet LLDPE2-4. And the polystyrene conversion weight average molecular weight and gel fraction of each sealing material sheet were measured by the method shown in the following evaluation example.

LLDPE2: A sealing material sheet LLDPE2 was prepared using a sealing material composition formulated as follows.
Silane-modified transparent resin 2: 98 parts by mass of metallocene linear low-density polyethylene (M-LLDPE) having a density of 0.881 g / cm ³ and an MFR of 2 g / 10 min at 190 ° C. 2 parts by mass of methoxysilane 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 , at 190 ° C. A silane-modified transparent resin (hereinafter referred to as “S2”) having an MFR of 1.8 g / 10 min was obtained.
Weatherproof masterbatch 2: 3.8 parts by weight of benzophenol UV absorber and hindered amine light stabilizer with respect to 100 parts by weight of powder obtained by pulverizing Ziegler linear low density polyethylene having a density of 0.880 g / cm ³ 5 parts by mass and 0.5 parts by mass of a phosphorous heat stabilizer were mixed and melted and processed to obtain a pelletized master batch.
Crosslinker compound resin: 2,5-dimethyl-2,5-di (t) with respect to 100 parts by mass of M-LLDPE pellets having a density of 0.880 g / cm ³ and MFR at 190 ° C. of 3.1 g / 10 min. -Butylperoxy) hexane was impregnated with 0.1 part by mass to obtain compound pellets.
S2: 20 parts by mass, weather resistant masterbatch 2: 5 parts by mass, crosslinker compound resin: 80 parts by mass of a composition was molded under the same conditions as the sealing material sheet LLDPE1, and sealed with a thickness of 400 μm Stop material sheet LLDPE2 was produced. The encapsulant sheet LLDPE2 had a polystyrene equivalent weight average molecular weight of 218,000 g / mol and a gel fraction of 0%.

  LLDPE3: Both sides of the encapsulant sheet LLDPE2 were irradiated at an acceleration voltage of 200 kV and an irradiation intensity of 0.5 Mrad using an electron beam irradiation apparatus (product name EC250 / 15 / 180L, manufactured by Iwasaki Electric Co., Ltd.). A cross-linked encapsulant sheet LLDPE3 was obtained by irradiation with 0 Mrad. The polystyrene-converted weight average molecular weight of the crosslinked sealing material sheet LLDPE3 was 247,000, and the gel fraction was 0%.

  LLDPE4: Both sides of the sealing material sheet LLDPE2 were irradiated at an acceleration voltage of 200 kV and an irradiation intensity of 4.0 Mrad using an electron beam irradiation apparatus (product name: EC250 / 15 / 180L, manufactured by Iwasaki Electric Co., Ltd.). A cross-linked encapsulant sheet LLDPE4 was obtained by irradiation with 0 Mrad. The polystyrene-converted weight average molecular weight of the crosslinked sealing material sheet LLDPE4 was 293,000, and the gel fraction was 40%.

<Manufacture of solar cell module evaluation samples>
Samples for solar cell module evaluation of Examples and Comparative Examples are obtained by using the sealing material sheets EVA1 and EVA2 and the sealing material sheets LLDPE2 to 4 as the first sealing material sheet or the second sealing material sheet, respectively. It was created with the configuration shown in Table 1 below.

The solar cell module evaluation sample includes a transparent front glass substrate (blue plate glass), a front sealing material layer made of a first sealing material sheet, a solar cell element, a back sealing material layer made of a second sealing material sheet, and The members made of the back surface protection sheet (Dai Nippon Printing Co., Ltd., model number VPEW280 μm) are sequentially laminated and then manufactured by thermocompression bonding using the above-mentioned members as an integrally formed body by vacuum heating lamination. A solar cell module evaluation sample of a comparative example was used. Regarding the solar cell elements, solar cell elements A to C described below were prepared, and 42 solar cell elements of the same type were electrically connected in series with a connecting member for one solar cell module evaluation sample. As the first sealing material sheet, the second sealing material sheet, and the solar cell element in each evaluation sample, the following three types A, B, and C were used as shown in Table 1. The thermal lamination conditions were as follows.
<Heat lamination conditions> (a) Vacuum drawing: 5.0 minutes
(B) Pressurization (0 kPa to 100 kPa): 1.5 minutes
(C) Pressure holding (100 kPa): 15.0 minutes
(D) Temperature 150 ° C
(Solar cell element)
A: A crystalline silicon solar cell element produced using a polycrystalline silicon substrate. An electrode for collecting current is arranged on the daylighting side. (Q-CELLS, cell Q6LTT-200 / 1520 156mm)
B: Back contact solar cell element. There is no electrode on the surface of the solar cell element, and a P-type electrode and an N-type electrode are provided on the back surface. The P-type electrode and the N-type electrode on the back surface are each formed in a comb shape, and each alternately enter between the combs. A P-type electrode and an N-type electrode on the back surface of an adjacent solar battery cell are connected and sealed with a sealing material.
C: Thin film solar cell element. An n-type transparent conductive film window layer, an n-type high-resistance buffer layer, a p-type CIS-based light absorption layer, a metal back electrode layer, and a thin film power generation element having a device thickness of about 3 μm excluding a glass substrate made of a glass substrate .

  Moreover, as a sample for evaluating the physical properties of each encapsulant layer of the solar cell module, EVA 1-2 and LLDPE 1-4 encapsulant sheets are sandwiched between ETFE films and heated at 150 ° C. for 13.5 minutes and heated. The samples subjected to the crosslinking treatment were used as samples for evaluating the sealing material layers of the solar cell modules of Examples and Comparative Examples, respectively.

<Evaluation Example 1>
About the sample for sealing material layer evaluation of an Example and a comparative example, it measured about the molecular weight, the gel fraction, and the haze value (JIS K7136). The results are shown in Table 2. Each test condition is as follows.

Molecular weight: The sample for evaluation of the sealing material layer was dissolved in o-dichlorobenzene, and the weight average molecular weight in terms of polystyrene of the sample for evaluation of the sealing material layer consisting of the sealing material sheets LLDPE2 to 4 was measured under the following conditions. About the sample for sealing material layer evaluation which consists of sealing material sheet EVA1-2, since it did not melt | dissolve completely but was not measurable, it has not measured.
Measurement model: GPC / V2000 manufactured by Waterers
Column: Shodex AT-G + AT-806MS × 2 Eluent: o-dichlorobenzene (with 0.3% BHT)
Temperature: Column and injector 145 ° C
Concentration: about 1.0 g / L
Flow rate 1.0ml / min
Solubility: Complete dissolution Detector: Differential refractometer (RI)

  Gel fraction (%): 0.1 g of the sample for sealing material layer evaluation was put into a resin mesh, extracted with toluene at 60 ° C. for 4 hours, taken out with the resin mesh, weighed after drying treatment, and compared the weight before and after extraction. The mass% of the residual insoluble matter was measured and this was used as the gel fraction. A gel fraction of 0% means that the residual insoluble matter is substantially 0 and that the crosslinking reaction of the encapsulant composition has not substantially started. More specifically, “gel fraction 0%” means that the above-mentioned residual insoluble matter is not present at all, and that the above-mentioned residual insoluble matter mass% measured by a precision balance is less than 0.05% by mass. Shall be said.

  Haze value (%): Measured by Murakami Color Research Institute Haze / Transmittance HM150 in accordance with JISK7136 in a state where blue sheet glass was laminated on the top and bottom of the sample for evaluation of the sealing material layer.

<Evaluation Example 2>
Water vapor barrier properties and insulation properties were measured for the backside sealing material layers of the examples and comparative examples using the sealing material layer evaluation samples of the examples and comparative examples. The results are shown in Table 3. Each test condition is as follows.

Water vapor barrier property: Measured by JIS-K7129 B method. The measurement conditions are as follows.
40 ° C., 90% RH, unit g / m ² · d, measuring device: MOCON water vapor permeability measuring device PERMATRAN-W

  Insulation: The test for insulation was performed by measuring the volume resistance value of the sample for evaluating the sealing material layer according to JIS K6911. A conductive material is attached to the upper and lower sides of a 50 mm sealing material sample sandwiched between 70 mm below and 30 mm above the aluminum foil. As a measuring instrument, a super insulation meter manufactured by Agilent: model number C4156) was used.

<Evaluation Example 3>
Using the solar cell module evaluation samples of Examples and Comparative Examples, the microcracks generated from the warpage of the solar cell elements were measured. The results are shown in Table 4. The test conditions are as follows.

  Microcrack measurement test of solar cell element: Cell microcracks were observed by EL images for the solar cell module evaluation samples of the above-described Examples and Comparative Examples. The test was performed before and after the cycle test described below. The cycle test used the method based on the temperature cycle test of JIS C8917. Increase from 25 ° C. to 90 ° C. over 45 minutes, hold at this temperature for 90 minutes, then decrease to −40 ° C. over 90 minutes, hold at this temperature for 90 minutes, then increase to 25 ° C. over 45 minutes Let This is one cycle (6 hours). This cycle was repeated 400 cycles to perform a cycle test. Observation of the cell microcrack by the EL image was performed as follows. When current is made to conduct in the forward direction with respect to the solar cell element, electrons of minority carriers are introduced into the p layer, and light emission is generated by recombination of the electrons and holes in the p layer. In the detection step, conventionally known light detection means that can detect the light emission characteristics of light from the solar cell element can be used. In the test, a current of 3 A was passed from the output terminal of the module, EL emission was photographed, and microcracks at a level that could not be confirmed visually or with a microscope were confirmed from the emission image. Then, the number of cells in which microcracks occurred in one solar cell module evaluation sample composed of 42 cells was recorded. The number of microcracks generated before the cycle test was 0 for all microcracks. The number of occurrences shown in Table 4 is the number of occurrences of microcracks in the solar cell module evaluation sample after each cycle test.

  From Tables 1-4, the solar cell module manufactured by the manufacturing method of the solar cell module of this invention is excellent in the light transmittance in the light-receiving surface side by the structure of the original sealing material layer, and the back layer side It turns out that it is the thing excellent in the water vapor | steam barrier property and insulation in.

  From Table 3, the solar cell module manufactured by the manufacturing method of the solar cell module of the present invention has a particularly excellent insulating property of the back sealing material layer in a high temperature environment assumed as an actual use environment of the solar cell module. It turns out that it is excellent, Therefore It turns out that it can be used especially suitably as a solar cell module provided with a back contact type solar cell element.

  Further, from Table 4, the solar cell module manufactured by the method for manufacturing a solar cell module of the present invention is a thin-film type solar cell element that has high protection performance of the solar cell element and is easily affected by the deformation of the sealing material. It turns out that it can be used suitably also as a solar cell module provided.

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

Claims (4)

A solar cell element;
A first sealing material sheet disposed on the light-receiving surface side of the solar cell element;
A second sealing material sheet disposed on the back side of the solar cell element, and a method for producing a solar cell module comprising:
The first encapsulant sheet is composed of a first encapsulant composition containing an ethylene-vinyl acetate copolymer resin and a crosslinking agent,
The second encapsulant sheet comprises a second encapsulant composition comprising a polyethylene resin having a density of 0.900 g / cm ³ or less as a main material resin,
A crosslinking step in which an uncrosslinked sealing material sheet made of the second sealing material composition is crosslinked by irradiation with ionizing radiation to form the crosslinked second sealing material sheet;
Comprising a thermocompression bonding step of sequentially laminating and integrating the members including the solar cell element, the first sealing material sheet, and the second sealing material sheet;
The crosslinking treatment of the uncrosslinked sealing material sheet made of the first sealing material composition is performed by performing a heat treatment in the thermocompression molding process or in another process performed after the thermocompression molding process. There line,
Each crosslinking process of the said 1st sealing material sheet and the said 2nd sealing material sheet so that the gel fraction of the said 2nd sealing material sheet may become smaller than the gel fraction of the said 1st sealing material sheet. The manufacturing method of the solar cell module characterized by performing the process which adjusts the bridge | crosslinking conditions at the time . Method of manufacturing a solar cell module according to claim 1 for the first sealing member composition uncrosslinked crosslinking of the sealing material sheet consisting of a within the heat and pressure molding step. The said 2nd sealing material sheet is a manufacturing method of the solar cell module of Claim 1 or 2 whose polystyrene conversion weight average molecular weights are 247,000 g / mol or more and 300,000 g / mol or less. The method for manufacturing a solar cell module according to any one of claims 1 to 3 , wherein the solar cell element is a back contact system in which an electrode is disposed on a back surface side.

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