TW201226463A - Sealing material for solar cell, solar cell protective sheet and process for producing solar cell module - Google Patents

Abstract

Disclosed is a sealing material for a solar cell, which can seal a solar cell element in a solar cell within a short time in the production of a solar cell module to produce the solar cell module with high efficiency. The sealing material for a solar cell is characterized by comprising: 100 parts by weight of a modified butane resin which is produced by the graft modification of a butene-ethylene copolymer having a butene content of 1 to 25 wt% with maleic anhydride and contains maleic anhydride in the total amount of 0.1 to 3 wt%; and 0.1 to 15 parts by weight of a silane compound having an epoxy group.

Description

201226463 VI. Description of the Invention: [Technical Field] The present invention relates to a solar cell sealing material, a solar cell protective sheet, and a solar cell module manufacturing method. [Prior Art] A solar cell module consisting of a semiconductor wafer of a crucible or a crucible is manufactured by the following method: an 11-semiconductor (a piece of semiconductor in which an electric light is generated by using an interconnecting feed line) Or a wafer of semiconductor elements _ joint or combined solar cell element upper surface layer solar cell sealing material: on the solar cell. The sealing material is superposed on the transparent upper side protective material and stacked underneath The lower side protective material is combined, and the obtained laminated body is degassed and heated under reduced pressure, and the protective material is laminated on the upper surface of the solar cell element via a sealing material for the solar cell. Further, it is integrated on the substrate. In a solar cell having a structure in which a solar cell element composed of ruthenium or a compound semiconductor or the like is laminated, a solar cell sealing material is used for sealing a solar cell element. A sealing material for a solar cell, for example, Patent Document 1 proposes a protective sheet for a solar cell module, which is characterized in that it contains organic The protective sheet for a solar cell module comprising an ethylene oxide copolymer comprising at least a dialkyl peroxide and at least one selected from the group consisting of alkyl peroxyalkyl esters and peroxy ketals. A peroxide (Β) is blended with a weight ratio of (A) / (Β) of 〇 1〇/9〇~9〇/1〇 to form an organic peroxide. The protective sheet is formed of an ethylene copolymer, and 201226463, in order to provide heat, contains an organic peroxide, and after forming a laminated sheet or a laminated body with a protective sheet for a solar cell module on a solar cell element, The laminated sheet or the laminated body is pressed in the thickness direction by vacuum lamination, and the organic peroxide/knife in the protective sheet for a solar cell module is heated while being heated to crosslink the ethylene copolymer to impart heat resistance. And the solar cell module and the solar cell module protective sheet are used to form the solar cell module 0. Therefore, if the cross-linking of the solar cell module protective sheet is unevenly ordered, the following problem occurs: the sun One of the protective sheets for the battery module Part of the financial heat has become insufficient, resulting in a decrease in the durability of the obtained solar cell module. To prevent this problem from happening, it is not in the state of transport that there is a solar cell module protection sheet on the solar cell component. In the state of the laminated sheet or the laminated body, heating is carried out, but a cross-linking step is required: "after the laminated sheet or the laminated body is cut into a desired shape in advance, the laminated layer is laminated in the thickness direction by vacuum lamination in a stationary state. The sheet or laminate is applied with a pressure for two to ten minutes to temporarily carry it out, and then heated to a temperature at which the organic peroxide is decomposed, which is officially followed by tens of minutes to one hour, thereby producing a solar cell module. The problem of low manufacturing efficiency. In addition, heat resistance is applied to the protective sheet for a solar cell module, and the organic peroxide is used for the fourth (fourth). However, the following problems occur: protection for manufacturing a solar cell module. At the time of the month, the organic peroxide is decomposed, resulting in failure to form a film for the solar cell module protective sheet, or a solar cell mold, and a protective sheet. Significantly decreased; or subsequently to cause the knife through the interface generator of the organic peroxide 201,226,463 ' »· resultant solution was led to decrease solar cell module using the protective sheet. $ That is, since the solar cell component is a precision component, when manufacturing or using a solar cell module, there is a concern that a gas generated by a decomposition product of an organic peroxide is generated from a protective sheet for a solar cell module, resulting in The battery performance of solar cells is degraded. SUMMARY OF THE INVENTION The present invention provides a solar cell sealing material, a solar cell protective sheet using the same, and a solar cell module manufacturing method, and the solar cell sealing material can be used. When manufacturing a solar cell module, the solar cell element of the solar cell is sealed in a short time to efficiently manufacture the solar cell module. The sealing material for a solar cell of the present invention is characterized in that 100 parts by weight of the modified butadiene-based resin and decane compound 〇i~i5 having an epoxy group are damaged, and the 5-modified butadiene-based resin is made of cis-butene. The dianhydride is graft-modified with a butadiene-ethylene copolymer having a butyl sulfonate content of 1 to 25% by weight, and the total content of the cis-succinic anhydride is 0.1 to 3% by weight. The modified butene-based sapphire spear, which constitutes the sealing material for solar cells of the present invention, is grafted with a butadi-diethylene hydride to form a butadiene-ethylene copolymer. If the content of butene is small, the solar power: the flexibility of the sealing material is lowered, and high-temperature heating is required when the solar cell element is sealed with a sealing material for a solar cell. If there is more, the solar energy is also crystallized with a sealing material. The property or fluidity becomes uneven, and the sealing material for the solar cell is strained. As a result, the sealing property of the solar cell sealing material is lowered, so it is limited to 1 to 25% by weight, preferably 10 to 20% by weight. . In addition, the butene content in the butene-ethylene copolymer was determined by dissolving the butene-ethylene copolymer into the deuterated gas, and measuring the nc_nMR spectrum (nuclear magnetic resonance spectrum) The spectral integral value of the olefin structure is calculated from the spectral integral value derived from the ethylene structure. Furthermore, the light δ derived from the 1-butene structure is usually obtained near 1 〇.9 ppm, near 26.1 ppm, and near 39.1 ppm. The spectrum derived from the ethylene structure is usually around 26.9 ppm, around 29.7 ppm, and 30.2 ppm. Nearby, near 33.4 ppm. Further, regarding the assignment of the 13C-NMR spectrum, reference may be made to the use of a polymer analysis manual [Edited by the Japan Analytical Society, issued by Asakura Bookstore, (2008), page 〜 01 to page 11]. Further, if the total content of maleic anhydride in the modified butylene-based resin is small, the adhesion of the solar cell sealing material is lowered. If the amount is large, the modified butadiene-based resin is crosslinked and the sun is caused. The adhesiveness of the sealing material for a battery is lowered or the extrusion moldability of the sealing material for a solar cell is lowered, and thus it is limited to 0.1 to 3% by weight, preferably 15 to 15% by weight, more preferably 5% by weight or more. When the total content of maleic anhydride in the butene-based resin is changed, the test film can be produced by using a modified butylene-based resin constituting a sealing material for a solar cell. The infrared absorption spectrum of the test film was measured and calculated from the absorption intensity in the vicinity of 丨79〇cm. Specifically, the total content of the term butylene anhydride in the modified butylene-based resin can be, for example, FT-IR (Fourier transform infrared spectrometer, Nic〇let 6700 FT-IR) and by polymer analysis hand 201226463 [Measured by the method described in the Japanese Society of Analytical Chemistry, issued by Asakura Bookstore, (Wrap-page ~ page 154). The 152th modified butene-based resin is based on the content of terpene butadiene anhydride. The ene-B, the method is based on the general point;: the material: the person, but the graft modification is straightforward. The butyl bis can be exemplified: (1) the melt modification method, the second system will be the butyl-ethylene copolymerization The 'succinic acid dilute liver starter is supplied to the extruder to carry out the melting reaction. The strain 7 κ u is trained to graft copolymerize maleic anhydride with the butadiene-ethylene copolymer; (2) Solution modification method, which transmits = ethylene copolymer dissolved in a solvent to make ', add cis-butanic acid liver and self-...!: solution, to the solution in the liver ... base polymerization initiator, and so Grafting polymerization modification method of butadiene dianhydride and butene-ethylene copolymer. 衩佳 is the melting of the above (1) Based on the point of the above-mentioned melt-modified ice method or the above-mentioned solution modification method, the production of the succinimide 秘 秘 又 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Ding, Μ, 竖, the modified butene-ethylene copolymer in the polymer: two ... total content, can also be modified by adding no maleic anhydride to the modified dilute-ethylene Mix and feed... [The total content of acetamethylene copolymer and dilute nt Xuan, to make the total content of cis-butylic acid anhydride 0.1~3 by weight ^ & ^ Lili / 〇 modified butene resin 》,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Caprylic acid (tetra) diisopropyl _, peroxy neodymium cumene, cumene, azobisisobutyronitrile, etc. Also, the modified butyl resin 201226463 is determined by differential scanning calorimetry. If the maximum peak temperature (Tm) of the obtained endothermic curve is low, the heat resistance of the sealing material for solar cells is lowered, if higher When a solar cell module is sealed with a solar cell sealing material to produce a solar cell module, the heating time of the solar cell sealing material is prolonged, the productivity of the solar cell module is lowered, or the heating of the solar cell sealing material is insufficient. The sealing of the solar cell element is insufficient. Therefore, it is preferably 8 to 12 generations, more preferably 83 to uo ° C. In the present invention, the heat absorption curve of the synthetic resin obtained by differential scanning calorimetry is When the melt flow rate of the modified butylene-based resin is low, the extrusion moldability of the solar cell sealing material is lowered, and if it is high, there is a sun. The extrusion molding property of the sealing material for a battery is lowered, and the thickness precision of the sealing material for a solar cell is lowered. Therefore, it is preferably 0'5 to 29 gm_', more preferably 2 to 1 Gg/1 Gmin. Further, the melt flow rate of the & slag-based resin is a value measured in accordance with ASTM D1238 under a load of 2.16 kg. / If the modified butadiene-based resin has a high viscoelastic storage modulus under 3 ,, the flexibility of the solar cell sealing material is lowered to cause a decrease in operability, or the solar t-cell is sealed with a sealing material. ·The cell component is required to rapidly heat the solar cell sealing material when manufacturing the solar cell module, so it is preferably 2 χ 1 〇pa or less. If it is too low, the solar cell sealing material exhibits adhesion at room temperature, resulting in adhesion. The operability of the sealing material for solar cells is lowered, and thus it is more preferably lx1〇7~15xl〇8pa. Further, if the viscoelastic storage modulus of the modified butylene-based resin at 1 〇〇 «C is higher at 201226463, the adhesion of the solar cell sealing material is lowered, so that it is preferably "ΙΟ6 Pa or less, and if it is too low, When a solar cell module is sealed with a sealing material for a solar cell to produce a solar cell module, the sealing material for a positive electrode is strongly flown by a pressing force, which causes an unevenness in the degree of sealing of the solar cell, which is preferable. Further, in the present invention, the viscoelastic storage number of the modified butylene-based resin is a value measured by a dynamic property test method according to JIS K6394: and 'Solar sealing material for solar cells In the case of a solar cell sealing material for a solar cell module, which is used for graft modification of cis-succinic anhydride or cis-succinic acid, There are components such as poles or wires contained in the solar cell module of the S-acid Sf or the S-T-H rot #, which cause the power generation performance of the solar cell module to decrease, not to be long in the high temperature and high humidity environment: :::Γ成的太阳电In the case of the pool module, the modified butadiene resin contained in the second is hydrolyzed to form a cis-butanic anhydride or a maleic acid. The combination: two = money with an epoxy group The compound can be trapped/added with cis-tautic acid or cis-succinic acid by the # library, and the cis-succinic acid field can be captured. Or a decane compound, as long as it has at least one epoxy group such as r earth or alicyclic epoxy group in the molecule, that is, a compound of the formula (1): ... a decane compound which is not in the formula (1). 201226463

. . . (1) where R represents 3-glycidoxypropyl (giyeidGXypr〇p^) or 2-(3,4-epoxycyclohexyl)ethyl, and r2 represents a carbon number of 3 Indicates that the carbon number is the base of Bu 3 and that 〇 is 〇 or n. R1 above represents "3_glycidoxypropyl group represented by the following chemical formula ("), or 2-(3,4-epoxycyclohexyl)ethyl group represented by the following chemical formula (111). -CH2CH2CH2OCH2CH- Ch2 0

(Π) <DI) The R2 is not particularly limited as long as it is an alkyl group having a carbon number of 3, and examples thereof include a methyl group, an ethyl group, and a propyl group, preferably a methyl group and an ethyl group. Good for methyl. The alkyl group of 1 to 3 is not particularly limited to a propyl group, and is preferably a methyl group. For example, as the above-mentioned R3, the above-mentioned R3 may be, for example, a methyl group or an ethyl group, and as a compound of the above formula (I), Methyl-dimethoxyxanthine, 3-glycidoxypropyl:diethoxy residue; 3-glycidoxypropyltrimethoxy-, 3-glycidoxypropyl Triethoxy oxalate, 3_glycidoxypropyltripropoxy ketone, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy ketone, 2_(3,4-epoxy ring Hexyl)ethyltriethoxydecane, 2_(3,4-epoxycyclohexane 201226463)ethyltripropoxydecane, and the like. The above formula (1)+, preferably n is a money compound, and particularly preferably 3-glycidoxypropyltrimethoxydecane. When the content of the above-mentioned Shi Xixuan compound in the sealing material for a solar cell is small, the adhesion of the sealing material for a solar cell is lowered, and if it is large, the adhesion of the sealing material for the solar cell may be lowered, thereby being compared with the modified Ding (4) (10) parts by weight and parts by weight, preferably 〇·ι to 1.5 parts by weight. In addition, the sealing material for solar cells can also contain a light-receiving agent, a material (4) (4), and a heat stabilizer additive in a range that does not impair the physical properties thereof. Further, the gas resin sheet layer may be integrated into the surface of the solar cell sealing material to be used as a solar cell protective sheet. Examples of the fluororesin constituting the gas resin sheet include polytetraethylene, polytrifluoroethylene, polydisperse: chaotic ethylene, polyvinyl fluoride, perfluoroalkoxy resin, and fluoroethylene. The μ propylene copolymer 'ethylene __ tetraethylene ethylene copolymer, ethylene _ gas trifluoroethylene copolymer, etc., preferably polyvinylidene fluoride. Next, a method of manufacturing the above-mentioned solar cell sealing material will be described. The method for producing the solar cell sealing material is not particularly limited, and examples thereof include the following production methods: a modified butylene-based resin, an epoxy group-containing decane compound, and optionally an additive added in a specific weight ratio It is supplied to an extruder, melted and kneaded, and extruded in a sheet form from an extruder to produce a sealing material for a solar cell. In the case where an additive to be added as needed is used in the above method, the above additive may be used as a masterbatch (10) containing it. Example-11 - 201226463 If the additive can be added to the polyolefin resin by steam, Cao, Tian, * 丄 ^ ^ 问 而 添加剂 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 The weight ratio of IL balance and decane compound having a % oxygen group is supplied to an extruder, and the machine is extruded in a sheet form to produce a sun φ a kneading, and a self-extruding mother m sealing material. By doing so, it is possible to provide a sealing material for a solar cell in which the addition is cut. As the above-mentioned polyolefin-based polyethylene for the masterbatch, the middle-density band is given by the R^J, and the low-preciousness 'B...::. =::= Key: Polyethylene phthalide resin, homopolypropylene, polypropylene resin containing more than % by weight = two: copolymer. As the olefin-olefin, for example, propylene '1-butanthene, 4-methyl decene, 1 hexanol, i-octyl^^ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ Examples of the olefin include: "thin, diarrhea, 卜辛浠, etc.... T埽, 4-methyl-p-pentyl-based tree r-poly(tetra)-based resin is preferably polyethylene-based tree 曰 曰Good for low density polyethylene. Wen Jia is a linear low density. The density of the low density polyethylene is preferably ... In the present invention, the 〇: = degree is based on the value measured by still training 2. _ Low-density polyethylene is dense, and the method of deuterating the fluororesin sheet as a surface for laminating the sealing material for a solar cell is not particularly limited, and one of the sealing materials for the cell is extruded on one side of the sealing material. The method of the film is to coextrude the sealing material for the solar cell with the resin sheet. Method, Solar Power Next, the main points of the solar cell -12-201226463 pool module using the above-mentioned solar cell tea sealing material will be described. The sealing material for a solar cell of the present invention is different from the sealing material for a solar cell of the prior art, which does not need to be heated for decomposing the organic peroxide, and does not need to ensure the necessary time for crosslinking the resin, and can be sealed in a short time. Solar battery components. In particular, the sealing of a solar cell of a solar cell in which a thin film-shaped solar cell element composed of a ruthenium or a compound semiconductor is formed on a flexible strip-shaped substrate can be wound by a roll. 〇1b t.—r〇u) can improve the manufacturing efficiency of the solar cell module. Specifically, as shown in Fig. 1, a solar cell A is prepared in which an electric i-film solar cell 2 is formed by light irradiation on a long strip substrate 1 having flexibility. In addition, the flexible strip-shaped substrate 1 is not particularly limited, and examples thereof include a sheet made of a heat-resistant resin such as polyimine, polyether ether or polyethersulfone. In addition, some of the thin-film solar cells are made of a crystalline semiconductor such as a single crystal germanium, a single crystal germanium, a polycrystalline germanium or a microcrystalline germanium, or an amorphous semiconductor such as an amorphous germanium, ?aAs, InP, AlGaAs, or CdS. Compound semiconductors such as CdTe, Cu2S, CuInSe2, and CuInS2, and organic semiconductors such as anthracycline and polyacetylene. Further, on the upper surface and the lower surface of the thin film solar cell element, an electrode made of a oxidized oxidized layer such as a oxidized silica, an indium tin oxide (IT 〇) & oxidized _ (Zn 〇) layer, or the like is formed. As shown in FIG. 2, the long-length solar cell A is wound into a roll shape, and the long-sealed solar cell sealing material B is also wound into a roll shape, and the solar cell A and the solar cell seal are wound up. In the material B, the solar cell sealing material B is laminated on the substrate of the solar cell A to form a laminated sheet c in a state opposed to the solar cell-13·201226463 element 2, and thereafter, the laminated sheet c is supplied. The solar cell sealing material B is applied to the substrate 1 of the solar cell a while heating the laminated sheet C while pressing the laminated sheet c in the thickness direction between the rolls D and D. Then, it is integrated, whereby the solar cell element 2 can be sealed and the solar cell module E can be continuously manufactured. When the solar cell protective sheet B' in which the resin sheet B1 is integrated in one surface of the solar cell sealing material B is used, the solar cell element is laminated on the solar cell element of the solar cell A by the solar cell protective sheet B'. In the state in which the solar cell sealing material B and the solar cell element 2 are opposed to each other, the solar cell module E can be manufactured, and the fluororesin sheet B1 having excellent gas barrier properties is laminated in the outermost layer of the solar cell module. As a protective material, a solar cell module capable of generating electricity for a long period of time can be obtained (refer to FIG. 3). Since the sealing material B for a solar cell of the present invention has excellent heat resistance even without cross-linking using an organic peroxide, it is not necessary to strictly control the heating of the sealing material B for a solar cell, as described above, in a solar cell. The solar cell element 2 of A is laminated on the solar cell sealing material B and is pressure-bonded in a heated state. By such a simple procedure, the solar cell element 2 can be reliably sealed by the solar cell sealing material B, and can be manufactured. A solar cell module that remains stable for a long time. In the above, the case where the solar cell module 2 is formed by sealing only the surface of the solar cell element 2 on the substrate 1 of the solar cell A by the solar cell sealing material B has been described. However, as shown in FIG. The battery sealing materials B and B are sealed from above and below the solar cell A to manufacture a solar cell module. • 14- 201226463 Specifically, a long-length solar cell A wound in a roll shape is prepared, and on the other hand, two long-sealed solar cell sealing materials B° are prepared, which are wound into rolls, and then rolled out separately. The strip-shaped solar cell sealing materials b and b are simultaneously wound out of the long-length solar cell A'. The solar cell sealing materials B and B are superposed on each other via the solar cell A to form a laminated sheet c, and then the laminated layer is formed. The sheet C is heated to a specific temperature between the pair of rolls d and d, and while the laminated sheet C is pressed in the thickness direction thereof, the laminated sheet c is heated, whereby the solar cell sealing materials B and B are integrated with each other. The solar cell module E can be continuously manufactured by using the solar cell for the sealing material B and B to seal the solar cell A. The solar cell sealing materials b and b may be stacked one upon another to form a laminated sheet C, and the laminated sheet c may be heated while pressing the laminated sheet c in the thickness direction thereof. In the case where the solar cell protective sheet B' in which the fluororesin sheet B1 is laminated on one side of the solar cell sealing material B is used, in the above manufacturing method, the solar cell protective sheet B' is used instead of the solar cell. The solar cell protection sheets b, and B are superposed on each other by the sealing material B to be equal to the solar power; the sealing material is also used for the bucket B, b. At this time, the fluorochemical resin sheet B i of the λ positive battery protection sheet B, B, or any of the sun 1: & 成为 成为 becomes the transparent upper side protective material, and the other side of the solar cell material sheet B, the fluorine The resin sheet β1 & is a lower protective material. Further, the above description has been made on the case where the solar battery module A is continuously wound while the long solar battery A is being wound out, but the solar power is also not required to be elongated, and may be rectangular or the like. A solar cell A of -15 - 201226463 is formed on a sheet-like flexible substrate ι by forming a thin film-shaped solar cell element 2 which is generated by light irradiation. In the case of using such a solar cell, as shown in Fig. 5, two long sealing materials B for solar cells wound in a roll shape are prepared. In addition, the long-length solar cell sealing material B'B is wound out, and the solar cell A is supplied between the solar cell sealing materials b and b at regular intervals, and the solar cell sealing material b is interposed between the solar cells A. After b is joined to each other to form a laminated sheet C, the laminated sheet C is heated to a temperature between one of the rolls D and D, and the laminated sheet C is pressed in the thickness direction thereof while heating the laminated layer. In the sheet c, the solar cell sealing materials B and B are integrated with each other, and the solar cell a is sealed by the solar cell sealing materials b and b, whereby the solar cell module E can be continuously manufactured. Further, in the case where the solar cell protection of the solar cell sealing material B-face resin sheet B1# is used, in the above manufacturing method, the solar cell protection sheet B' is used instead of the solar cell. Sealing (4) B, the solar cell protection sheets B, B, and Φ are combined so that the sealing materials B and b for the solar cells are opposite to each other. At this time, 'solar battery protection # B, B, Zhong Ren - The fluororesin sheet B1 of the solar cell protection sheet becomes the transparent upper side protective material, and the fluororesin sheet of the other solar cell protection sheet B1 is the lower side protective material. As the solar cell, for use, The case where the film-forming solar cell and the solar cell which generate electricity by light irradiation are formed on the levisable sheet 1 is described, but the solar electric sealing material of the present invention can also be used as the right.. ^ A sealing material for a solar cell module having a configuration other than the above-described configuration. As such a solar cell, for example, (1) a substrate having no flexibility such as a glass plate is formed by irradiation with -16 · 201226463 A solar cell formed by an electric film-like solar cell element, or (2) a solar cell element formed by a stellite semiconductor element or a selenium semiconductor element having a function of generating a current after light irradiation is connected in series or in parallel using an interconnecting feed line. In the case of the solar cell having the above configuration (1), when the solar cell sealing material is used to seal only the surface of the solar cell element on the substrate of the solar cell, the solar cell module is manufactured. When a solar cell in which a thin film-shaped solar cell element that generates electricity is generated by light irradiation is formed on a flexible substrate, a solar cell sealing material can be laminated on the solar cell to face the semiconductor element. After the laminated sheet is produced in a state, the laminated sheet is supplied between the pair of rolls, and is pressed in the thickness direction while being heated, thereby integrating the solar cell sealing material on one of the substrate layers of the solar cell. Sealing solar cell components to manufacture solar cell modules. The solar cells that make up the

Seal ' to make a solar cell module. Further, in the case of the solar cell sealing material having the above configuration (1), when the solar cell module is mounted from the solar cell, the solar cell module can be used.

Between the solar cell 3 and the upper surface protective material 4' of the solar cell 3, the solar cell sealing material B is placed under the solar cell 3 under the surface layer under the protective material 5, In order to manufacture the laminated body, it is preferable to apply a pressing force to the laminated body along the thickness direction thereof under reduced pressure, and to heat the solar cell 3 by using the solar cell (four) materials #B and B, and the solar cell can be manufactured. Battery module (see Figure 6). The transparent upper protective material 4 is, for example, a glass substrate such as bismuth silicate glass or a fluororesin sheet. Examples of the lower protective material 5 include a fluororesin sheet, a polyethylene terephthalate (ρΕτ) sheet, a polyethylene naphthalate (yttrium) tablet, and a polybutyl butyrate tablet. sheet. The fluorine: lipid 4 is, for example, the same as the above-mentioned Dunshu Mooncake for solar cell protective sheets. In particular, 'as the transparent upper side protective material 4 and the lower side protective material 5, it is preferable to use a fluororesin sheet, and it is more preferable to use the polydisperse 2 in the above method, so that _ % 丨 丨 电 〜 ～ 川 川 川啊' When the bamboo fluororesin sheet is integrated with the solar cell protection sheet, the flute _ + m π is applied to the solar cell protection sheet (one of the sealing materials for the solar cell = the gas resin sheet layer as the transparent upper side protective material) - the body becomes the upper side of the solar cell and the solar cell is in a state opposite to the above-mentioned solar cell 2 material' and the second solar cell protection sheet (the one side of the sealing material for the first time will be used as the lower side protection) The fluororesin of the material is integrated. The layer is laminated on the underside of the above solar cell and is in the upper yang battery. · · Μ Μ ' 4 The solar cell sealing material is in a relative state, and the temperature is preferably under reduced pressure. The solar cell module can be manufactured by sealing the solar cell 3 with the solar cell sealing materials B and b by heating the above-mentioned laminated body along the thickness -18·201226463, and sealing the solar cell 3 by the solar cell sealing materials B and b. The degassing step of removing the gas contained in the laminated body by heating the laminated body to a specific temperature in advance by applying a pressing force in the thickness direction of the laminated body. Further, in the degassing step, when the laminated body is heated When it is not necessary to apply a pressing force to the laminated body along its thickness direction. In the degassing step, it is preferred to add the laminated body, preferably to a temperature of 8 or more. If you add the teaching, the ®4^ .../the degree of the right is too good, you can't remove the gas contained in the layer. ^ Ν _ Right too low, the gas is fully removed from the layer during the degassing step. The heating time of the laminate in the de-milking step is preferably from 1 to 10 minutes', more preferably from 2 to 5 minutes. If the heating time of the laminate in the degassing step is short, there is no possibility When the gas contained in the laminated body is sufficiently removed, if it is too long, the time required for the gas to be sufficiently removed from the laminated body in the degassing step is prolonged. The human TM side applies a pressing force to the laminated body along the thickness direction thereof. When heating, it is better to heat the laminate 1〇〇〜"Ο.., more preferably heated to 〇〇120C. X ' while applying pressure to the laminate along its thickness direction - the heating time is preferably Μ0 minutes, more preferably 2 to 5 minutes - the step of heating while applying pressure to the laminate in the thickness direction thereof is preferably carried out under a reduced pressure environment of 1000 Pa or less, more preferably under a reduced pressure environment of 〇〇〇Pa. Heating the laminate in a reduced pressure environment can obtain the solar cell stack without the surface curvature of the obtained solar cell module, or the solar cell 201226463 pool sealing material does not produce wrinkles or bubbles. The step of heating the laminate to a specific temperature and the step of heating the laminate while applying a pressing force in the thickness direction thereof can be carried out by using a conventionally known device such as a vacuum laminator. In the above method of manufacturing a solar cell module by heating a laminate body in which a sealing material B for a solar cell is disposed on both surfaces of the solar cell 3, the solar cell module can be used, and the solar cell sealing can be used even if the heating time of the laminated body is shortened. Material B positively seals the solar cell 3. Therefore, by the above method, the time required for the sealing step of sealing the solar cell 3 by the solar cell sealing material B can be shortened, and the solar cell module which can stably emit volatile electric power for a long period of time can be efficiently manufactured. Further, in the above method, since the solar cell sealing material B does not contain an organic peroxide, it is not necessary to strictly control the heating temperature of the laminate, and even if the heating temperature of the laminate is lowered, the sealing material B for the solar cell can be used. The solar cell 3 is sealed. Further, P can prevent the solar cell sealing material B from being oozing out from the side surface of the laminated body by the melted flow of the sealing material B for the solar cell, and the solar cell sealing material B does not have the appearance characteristics of the solar cell module. Or the decline in power generation performance. In the above, a solar cell module is manufactured using the solar cell having the above configuration (2), but a solar cell having the above configuration (7) may be used instead of the rectangular battery. A solar cell A in which a film-like solar cell element that generates electricity by light irradiation is formed on a flexible substrate such as a sheet, or a sheet-like shape such as a rectangular shape, which is not flexible. A solar cell A (see FIG. 7) in which a thin film-shaped solar cell element that generates electricity is generated by light irradiation is formed on the substrate. The sealing material for a solar cell of the present invention has the above-described configuration, and does not need to contain an organic peroxide. When the solar cell module is sealed and the solar cell module is sealed, it is not necessary to strictly control the solar cell in order to control the decomposition of the organic peroxide. Heating with a sealing material, by sealing the solar cell to the solar cell element in a state where the solar cell has been heated by the sealing material, or by sealing the solar cell sealing material which is placed below the solar cell. The sealing of the solar cell elements can be carried out in a straightforward and simple manner. In particular, when sealing a solar cell element of a solar cell in which a film-shaped solar cell element is formed on a flexible substrate, the solar cell wound in a roll shape is rolled up and wound up. A solar cell sealing material is formed on a surface of a solar cell on a substrate of a solar cell, and a sealing sheet for a solar cell is laminated to form a laminated sheet, and the laminated sheet is supplied between a pair of rolls. By heating and pressing along the thickness side, the solar cell element can be sealed according to the above-mentioned simple points, and the solar cell module can be easily and efficiently manufactured by roll-to-roll. In addition, even if the solar cell module is sealed by sealing the solar cell with a solar cell sealing material by vacuum laminating the laminated body of the solar cell sealing material on the upper and lower surface layers of the solar cell, the sealing step can be shortened. The time required does not require strict control of the heating of the laminate. Therefore, even with the above method, the solar cell module can be efficiently manufactured. Further, even if the laminate is heated under reduced pressure, the sealing material for the solar cell can be largely prevented from oozing out from the side surface of the laminate. • 21 201226463 and the fact that the sealing material for a solar cell of the present invention does not contain an organic peroxide as described above, it is also possible to increase the speed of extrusion at the time of manufacture and to improve the production efficiency, and to incorporate a solar cell module. After that, there is no gas generated by the organic peroxide caused by the sealing material for the solar cell. Further, the sealing material for a solar cell of the present invention contains a decane compound having an epoxy group, and even if the sealing material for a solar cell contains maleic anhydride or maleic acid which is not used for graft modification, Corrosion of components such as electrodes or wires inside the solar cell module by maleic anhydride or maleic acid can be greatly suppressed. Therefore, the sealing material for a solar cell of the present invention can maintain the battery performance of the solar cell module at a high level for a long period of time. [Embodiment] Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the embodiments. (Examples 1 to 16 'Comparative Examples 1, 2, 6 to 7, and 1 to 14>) The content of butene contained in the specific amount shown in Table 丨4 and ethylene was modified by grafting with maleic anhydride. 100 parts by weight of the modified butylene-based resin of the content of the butene-ethylene copolymer and the specific amount of t 3-glycidoxypropyltrimethoxy-infraline as shown in Table 1-4 of the decane compound (manufactured by D〇w Coming Toray, trade name "z-6〇4〇") or 3_propylene oxypropyltrimethoxysilane (3 ((acryl〇xypr〇pchuan trimethoxysilane) (Shin-Etsu Chemical Industry) The company manufactures a composition for a sealing material for solar cells of 'product name "kbm-5103") for melt-kneading at 230 t in a first extruder, and on the other hand, a polyethylene-based ethylene (manufactured by Arkema Co., Ltd., The product name "KYNAR 72〇" is supplied to the second extrusion-22· 201226463. The melt-kneading is carried out at 230 °C, and the composition for sealing materials for solar cells and polyvinylidene fluoride are used to connect the first extrusion. The merged die of the outlet and the second extruder is used to extrude the merged T-die connected by the merged die into A sheet-like shape obtained by integrating a polyvinylidene fluoride sheet having a thickness of 〇 mm on a surface of a sealing material for a solar cell having a thickness of 0.2 mm, which is composed of a composition for a sealing material for a solar cell. A strip of solar cell protection sheet with a special width. In addition, it will change the melting flow rate of the butadiene resin and the endothermic heat of the butadiene resin. The maximum peak temperature (Tm) of the curve, and 3 (the viscoelastic (four) of the TC and l〇Gt

The number is shown in Table 4. The total content of maleic anhydride in the modified butylene-based resin is also shown in Tables 1 to 4. W used in Example 1 and Comparative Example - Teambethene-based resin was marketed by Mitsui Chemicals Co., Ltd. under the trade name "Admer XE(R) 7" (Comparative Example 3), except that it was used in combination with Example 1. A solar cell protective sheet was obtained in the same manner as ethylene instead of the modified butylene-based resin. (Comparative Examples 4 and 8) The same as Example 1 except that the specific amount shown in Table 4 of the modification polymerization using Tables 3 and 4 was used, (Comparative Example 5) A specific amount of maleic anhydride is added to ethylene instead of the modified butylene-based resin, and the glycidoxypropyltrimethoxydecane is obtained in such a manner as to obtain a solar cell protective sheet. In addition to the butene-ethylene copolymer -23-201226463, which has been modified with a specific amount of butene-containing dianhydride which is not modified by the use of cis-butyl, and has an ethylene content of Tables 3 and 4, instead of the modified butylene resin. A solar cell protective sheet was obtained in the same manner as in Example 1 except for the same. (Comparative Example 9) Except that an ethylene-vinyl acetate copolymer (vinyl acetate content: 28% by weight) was used instead of the modified butylene-based resin, and a specific amount of 3-glycidoxypropane shown in Table 4 was used. A solar cell protective sheet was obtained in the same manner as in Example 1 except for the tris-methoxydecane. (Comparative Example 1 5) A terpolymer obtained by radical polymerization of 77.2 parts by weight of ethylene, 20 parts by weight of ethyl acrylate, and 2.8 parts by weight of maleic anhydride (manufactured by Arkema Co., Ltd., Lotader HX8140) A solar cell protective sheet was obtained in the same manner as in Example 1 except that instead of the modified butadiene resin. Further, in the following Tables 1 to 1, the above terpolymer is simply referred to as "EEAM". (Comparative Example 1 6) A copolymer containing ethylene monovinyl acetate (vinyl acetate content: 28% by weight) 1 part by weight, an organic peroxide} (tertiary butyl peroxycarbonate 2-ethylhexyl) Ester) 35·35 parts by mass, crosslinking auxiliary (triallyl isocyanurate) 0.5 parts by mass, and decane coupling agent (3-nonyl propylene methoxy propyl tridecyloxy decane ( 3~ methacryloxypropyhrimethoxysilane)) 0.5 parts by weight of the resin composition was supplied to an extruder and melt-kneaded at 90 ° C from a T-die of 90 at the tip of the extruder. (: extrusion was carried out to obtain a solar cell sealing material having a thickness of 〇. 2 mm. -24- 201226463 (Production of solar cell module: roll-to-roll) Using Examples 1 to 16 and Comparative Examples 1 to 1 5 The solar cell protection sheet produced in the 'made solar cell module E' is formed according to the following points. First, a film is formed on the substrate 1 composed of a flexible polyimide film as shown in FIG. The solar cell element 2 is formed and wound into a roll-shaped solar cell A'. On the other hand, two solar cell protection sheets B' wound in a roll shape are prepared. Next, as shown in Fig. 4, the solar cell is rolled out. a and two solar cell protection sheets B' and B', and the solar cell sealing materials b' and B· are superimposed on each other via the solar cell a to form a laminated sheet C. Further, the solar cell sealing material B' The B1 is laminated so that the sealing materials for the solar cells are opposed to each other. Thereafter, the laminated sheet C is heated to 140 by the atmospheric pressure in an unpressurized and decompressed atmosphere. Between the rolls D and d, while the laminated sheet C is pushed in the thickness direction thereof, The laminated sheet c is used to integrate the solar cell protective sheets B' and B, and the solar cell sealing materials B and B are integrated with each other', thereby continuously manufacturing the sun by sealing the solar cell element 2 with the solar cell protective sheets B' and B'. The battery module E was taken up to a take-up reel (not shown). The solar cell module obtained by the above-described roll-to-roll method was used to measure the peel strength and the high temperature and high wet durability according to the following points. Moreover, the occurrence of bleeding of the sealing material for solar cells in the solar cell module was confirmed based on the following points. The results are shown in Tables 44. (Peel Strength &lt; Substrate-Solar Cell Protection Sheet&gt;) In the obtained solar cell module, the peel strength of the solar cell protective sheet deposited on the solar cell element side from the substrate of the solar cell 25-201226463 was measured in accordance with JIS K6854. Further, the solar cell protective sheet was peeled off and could not be removed. The evaluator of the solar cell module and the peeling strength of the solar cell module was recorded as "_". (Peel strength &lt; solar cell sealing material _ polyvinylidene fluoride Sheets> The peeling strength of the solar cell module obtained by peeling the polyvinylidene fluoride sheet B1 from the solar cell sealing material of the solar cell protective sheet laminated on the side of the solar cell element was measured in accordance with JIS K6854. The solar cell module is peeled off and the solar cell module cannot be produced, and the evaluation of the peel strength of the solar cell module cannot be performed as "_". (咼温高湿 durability<Next>) The solar cell module of Aberdeen is taught in the order of JIS C8990 in an environment of 85% relative humidity. Every 5 (10) hours, observe the solar power from the solar cell module on the side of the solar cell component. The time from the time when the sheet is peeled off from the substrate of the solar cell, and the time for the determination of the solar cell module is required to be 1000 hours for the durability of the claws of the solar cell module. 1 is the case where the adhesion is not the same. In Table 4, the solar cell is peeled off from 11 and the solar cell module cannot be fabricated, and the adhesion of the solar cell module cannot be achieved. The program recorded by the evaluator of high temperature and high humidity durability (high temperature and high humidity durability & power generation characteristics) The solar cell module obtained is placed in an environment of m C89 -26 · 201226463 85C and a relative humidity of 85%. The decrease rate of the maximum power Pmax after placement with respect to the maximum power PmaxG before placement (Pmax/Pmax0xl 〇〇 [%]) is calculated for 〇〇〇 hours. Further, the power measurement system used 1116N manufactured by Nisshin Ding (10) Strand Injury Limited A Division. In the table, the rate of decrease in the maximum power after the hour is 95% or more, which is regarded as "exceUent", which is less than 95 /. Person 5 is "bad". In addition, the solar cell protection sheet was peeled off and the solar cell module could not be produced, and the evaluation of the durability to the high-humidity durability of the solar cell module was not described as "-" ° (sea battery sealing) The occurrence of bleed out of the material) For the solar cell module immediately after manufacture, it is visually confirmed whether the sealing material for the solar cell oozes from the side of the solar cell module. The solar cell sealing material is not exuded from the side of the solar cell module as "excellent", and the solar cell used in and the sealing material b is exuded from the side of the solar cell module as "bad" (bad). . In addition, the evaluator who is unable to perform the production of the solar cell sealing material by peeling off the solar cell protective sheet and making it impossible to produce the solar cell module is referred to as "_". (Anti-corruption property 1) The solar cell protective sheet produced in Examples 1 to 16 and Comparative Examples 1 to 5 was subjected to a corrosion promotion test according to the following points to evaluate the solar cell protective sheet. Corrosion resistance of solar cell sealing materials. Forming a transparent conductive film made of zinc oxide by a sputtering method on a flat rectangular glass substrate (the entire surface of the first surface of the thickness 〇·7 μη〇). Secondly, the second on the glass substrate On the surface, by applying a silver electrode -27-201226463 paste and drying it to form two strip-shaped collector electrodes having a certain width, a simulated solar cell element is obtained. In the simulated solar cell element, the collector electrode is respectively The longitudinal direction of the collector electrode is parallel to the short side direction of the glass substrate and covers the entire length of the short side of the glass substrate. The collector electrode is extended to the first side of the glass substrate at both ends in the longitudinal direction. Further, the end faces of the short-side direction of the coated glass substrate and the both ends of the transparent conductive film connected to the end faces are formed. Further, the two collector electrodes are formed at a predetermined interval in the longitudinal direction of the glass substrate. Between the two solar cell protective sheets, the solar cell sealing material is placed in a state opposed to the pseudo solar cell element, and a pseudo solar cell element is provided to obtain a laminated body. Among the two solar cell protection sheets, the solar cell protection sheet disposed on the second surface of the glass substrate of the pseudo solar cell element has a square frame shape by providing a flat rectangular opening portion in the center portion thereof. The solar cell protection sheet is placed on the second surface of the analog solar cell element such that the two collector electrodes formed on the second surface of the glass substrate of the pseudo solar cell element are exposed to the outside through the opening of the solar cell protection sheet. On the other hand, the laminate was heated at 80 ° C for 2.5 minutes using a vacuum laminator (spi- LAMINATOR 350), and then heated at 12 Torr for 5 minutes. Make a simulated solar cell module. According to JIS C8990, the simulated solar cell module is placed in an environment of 85 ° C and a relative humidity of 8 5 / %. The test machine is used to measure the simulated sun before and after placement. The resistance value between the two collector electrodes of the battery module. The resistance value Ri ( Ω ) of the simulated solar battery module after placement is compared to the -28-201226463 simulated solar power before placement. The power supply module based on the dry〗 square to 5.5 Ω) ratio (R Shu / R ()) in Table 1 ~ 4 Table no. Furthermore, in the table 丨~4 ^ ^ will be placed after the simulation of the solar power, the mold and the transparent conductive film and too;, + &amp; electric core used in the sealing material is peeled off ..., the method of evaluation It is recorded as "- 啻汕田-, the transparent conductive film of the heart is corroded by the sealing material of the solar cell, and the resistance of the simulated T vapor m π I 苟 battery module becomes high, and the resistance value ratio (l/Ro) becomes High. (Anti-corruption 2) The evaluation of the comparative example was carried out according to the following points. The corrosion resistance test of the solar cell made of K was made into a flat rectangular glass substrate (thickness 〇 7). /m) The entire surface of the first side of the first surface is formed by a sputtering method to form a transparent conductive film composed of zinc oxide (Zn〇). Secondly, on the second side of the glass substrate, by coating a silver electrode The paste is dried and formed into two strip-shaped collector electrodes having a certain width to obtain a simulated solar cell element. In the simulated solar cell element, the collector electrodes are respectively in the longitudinal direction of the collector electrode and the short side direction of the glass substrate. Parallel and cover the full length of the short side of the glass substrate The current collecting electrode is formed by extending both end portions in the longitudinal direction to the first surface side of the glass substrate, and forming an end surface of the coated glass substrate in the short side direction and two transparent conductive films connected to the end surface. Further, the two collector electrodes are formed at a certain interval in the longitudinal direction of the glass substrate. Next, the sealing material and thickness of the solar cell are sequentially laminated on the first surface of the glass substrate simulating the solar cell element. 〇3 mm of polyethylene dioxide sheet' and on the second side of the glass substrate simulating the solar cell element, sequentially sealing the solar cell sealing material and the thickness of 聚.〇3 mm 201226463 A vinyl fluoride sheet is used to obtain a laminate. Further, a solar cell sealing material and a polyvinylidene fluoride sheet which are laminated on the second surface of the glass substrate simulating the solar cell element are used in advance by the central portion of the a rectangular rectangular opening is formed to form a square frame shape, and the two collector electrodes formed on the second surface of the glass substrate simulating the solar cell element are passed through the solar cell sealing material. The mouth is exposed to the outside, and a solar cell sealing material and a polyvinylidene fluoride sheet are laminated on the second surface of the simulated solar cell element. And 'by using a vacuum laminator (SpIRE, spi - LAMmATORSSO) ) 'The above laminated body was degassed by heating at 8 rc for 2·5 minutes, and then heated at 12 (TC for 5 minutes to make a simulated solar cell module. According to JIS C8990, the solar cell module was simulated at 85 &lt;;t, the relative humidity of 85% environment for 1000 hours. Use the test machine to measure the resistance between the two collector electrodes of each simulated solar cell module before and after placement. The resistance value of the simulated solar cell module after placement Rl The ratio (Ri/Rq) of (Ω) to the resistance value R〇(25.5i2) of the simulated solar cell module before placement is 14. As the transparent conductive film is corroded by the solar cell sealing material, the resistance of the simulated solar cell module becomes high, and the resistance value ratio (Ri/r〇) becomes high. (Production of Solar Cell Module: Vacuum Lamination Condition 1) The solar cell protective sheet produced in Example 1, '2, 6, 10, 12, 14, 16 and Comparative Example 1, 2' 4 5 13 1 5 was used. The solar cell module shown in Fig. 7 was produced according to the following points. First, a solar cell protective sheet and a solar cell A in which a film-shaped solar cell element is formed on a substrate made of a flexible polyimide film are prepared. The solar cell is laminated on the solar cell element of the solar cell A, and the solar cell element and the solar cell sealing material B are opposed to each other, and the solar cell protective sheet is laminated on the solar cell A. The polyimide film B is in a state in which the sealing material B for the solar cell and the polyimide film are opposed to each other. In this way, a laminate having the above-described configuration is obtained in which the polyvinylidene fluoride sheet 4 is laminated on the solar cell element 2 of the solar cell A via the solar cell sealing film B as a transparent upper protective material, and in the solar cell A. On the polyimide film, a polyvinylidene fluoride sheet 5 is laminated on the solar cell sealing film B as a lower protective material. Next, by using a vacuum laminator (SPI_ LAMINATOR 350), the laminate was heated at 80 ° C for 2 minutes and then degassed under a reduced pressure of 133 Pa at 100 ° C. After heating for 3 minutes, the laminate is heated in the thickness direction, and the laminate is heated, and the solar cell a is sealed by the solar cell sealing materials B and B, and the solar cell A is sealed via the solar cell sealing materials B and B. And the polyvinylidene fluoride sheets 4 and 5 are then integrated to manufacture the solar cell module shown in Fig. 7. (Production of solar cell module: vacuum lamination condition 1)

The solar cell module shown in Fig. 7 was produced in accordance with the following points using the sealing material for a solar cell produced in Comparative Example 16. First, a Φ sealing material for a solar cell, a polyvinylidene fluoride sheet having a thickness of 〇Q3 mm, and a solar cell element formed on a substrate formed of a flexible polyimide film are prepared. 2 made of solar battery A. On the solar cell component of the solar cell A, a solar cell sealing material B and a polyvinylidene fluoride sheet 4 as a transparent upper protective material are sequentially laminated, and on the solar nanotube film of the solar cell A • 31·201226463 A laminated body for a solar cell sealing material B and a polyvinylidene fluoride sheet 5 as a lower protective material is sequentially laminated. Next, by using a vacuum laminator (spl _ LAMINATOR 350, manufactured by SpIRE), the laminate was heated under a sail for 2 minutes to degas, and then under a reduced pressure of 133 Pa at 1 〇〇〇c After heating for 3 minutes, the laminate is heated in the thickness direction, and the laminate is heated, and the solar cell A is sealed by the solar cell sealing materials B and B, and the solar cell is sealed by the solar cell sealing materials B and B. a and the polyvinylidene fluoride sheet 4' 5 are then integrated to produce the solar cell module shown in Fig. 7 (the fabrication of the solar cell module: vacuum lamination condition 2) using the examples 1, 2, and 6, 1 〇, 12, 14, 16 and the solar cell protective sheets produced in Comparative Examples 1, 2, 4, 5, 1 3, and 1 5, the solar cell module shown in Fig. 7 was produced according to the following points. First, a solar cell protective sheet and a solar cell element in which a solar cell element is formed on a substrate made of a flexible polyimide film, and a solar cell protective sheet are laminated on the solar cell. In the solar cell element of A, the solar cell element and the solar cell sealing material B are opposed to each other, and the solar cell protective sheet is laminated on the polyimide film of the solar cell A to form a solar cell sealing material B and The polyimide film is relatively in a state of being oriented. In this way, a laminate body is formed in which the polyvinylidene fluoride sheet 4 is laminated on the solar cell element 2 of the solar cell A via the solar cell sealing film B as a transparent upper side protective material' On the polyimide film of Battery A, a polyvinylidene fluoride sheet 5 was laminated as a lower protective material via a sealing film B for a solar cell. ° •32· 201226463 Next, secondly, by using a vacuum laminator (manufactured by SPIRE, 35〇), the laminate was degassed by heating at 80 ° C for 2 minutes, and then decompressed at 133 Pa after gas. Under the environment, add at 12〇&lt;t

The LAMINATOR i was used for 3 minutes, B sealed the solar cell A, and the solar cell A and the polypyramidic tablets 4 and 5 were integrated next to each other to manufacture the solar cell module shown in Fig. 7. (Production of Solar Cell Module: Vacuum Lamination Condition 2) Using the sealing material for a solar cell produced in Comparative Example 1, the solar cell module shown in Fig. 7 was produced in accordance with the following points. First, a solar cell sealing material, a polyvinylidene fluoride sheet having a thickness of 〇〇3 mm, and a solar cell element 2 formed on a substrate formed of a flexible polyimide film are prepared. Made of solar cells a. On the solar cell element of the solar cell A, a solar cell sealing material B and a polyvinylidene fluoride sheet 4 as a transparent upper protective material are sequentially laminated, and sequentially laminated on the polyimide film of the solar cell A. A sealing material B for a solar cell and a polyvinylidene fluoride sheet 5 as a lower protective material were obtained to obtain a laminate. Secondly, by using a vacuum laminator (SPIRE company, SPI - LAMINATOR 3 50), the laminate was heated at 8 ° C for 2 minutes to degas, and then under a reduced pressure of 133 Pa, at 12 (When the laminate is heated for 3 minutes, the laminate is heated while being pressed in the thickness direction, and the laminate is heated, and the solar cell A is sealed by the solar cell sealing materials B and B, and the sealing materials B and B for the solar cell are interposed. The solar cell module A and the polyvinylidene fluoride sheets 4 and 5 are then integrated to manufacture the solar cell module shown in Fig. 7. -33- 201226463 For the solar cell module obtained by the above vacuum lamination, according to the above In the solar cell module, the peeling strength <the sealing material for solar cells—polyvinylidene fluoride sheet> is measured according to the following points, and the appearance is confirmed according to the following points. The results are shown in Tables 5 and 6. (Peel strength &lt; solar cell sealing material - polyvinylidene fluoride sheet &gt;) For the obtained solar cell module, it was determined according to Jis κ6854 The peeling strength of the solar cell sealing material Β when the polyvinylidene fluoride sheet 4 is peeled off. Further, the solar cell protective sheet is peeled off, and the solar cell module cannot be produced, and the peeling strength of the solar cell module cannot be performed. The evaluator remembers that the solar cell sealing material is used to visually confirm the solar cell seal in the solar cell module that is paid for: whether the material generates bubbles or wrinkles or pleats. The solar cell sealing material does not produce bubbles and pleats. For "exeellent", the solar cell sealing material "gGGd" is produced without the occurrence of air bubbles, but the solar cell sealing material is used to generate bubbles and enemy. It is marked as "bad". In addition, the solar cell protection sheet is peeled off and the solar cell module cannot be produced, and the evaluation of the solar cell module cannot be performed as "one". -34· 201226463

[II Example 8 \q 〇〇〇r4 v〇o 70 or more 3000 or more 2.03 Example 7 in &lt;N 〇〇〇§ 0 01 〇vd ^T) o 62 or more CN 2000 2.05 Example 6 Ο CN § m ο 〇〇m 00 (N &lt; N inch vd o 62 or more (N 3000 or more 2.01 Example 5 Ο m ο 〇m 卜 &lt;N ON o 70 or more 3000 or more 1.98 Example 4 σ\ inch ο 〇〇m &lt N Os rn ... o 1 70 or more 0C ro 2000 2.04 Example 3 m ο 〇〇m 00 inch CN v〇&lt;5 V〇o 70 or more 〇s ro 3000 or more OS ON Example 2 (N 〇&lt;N Oo 10.1 O 50 or more | 卜ro 3000 or more 2.04 Example 1 σν ο 〇〇cn in (N 卜o 70 or more | inch 3000 or more 00 Ο) Butene component (% by weight) Ethylene component (% by weight) Butylene Total content of acid anhydride (% by weight) Content (parts by weight) Fractional flow rate (g/l〇min) Maximum peak temperature (°C) CU ? II] X 'w- o Ph oO o 3-epoxypropoxypropyl Base trimethoxy decane (parts by weight) Peel strength (N/cm) &lt;Substrate-solar battery protection sheet&gt; Λ Ο Ο 1 i 1 ladder ζ 龌 冢 冢V high High-humidity durability &lt;Next&gt; (hours) High-temperature and high-humidity durability &lt;Power generation characteristics&gt; Exudation resistance value of solar cell sealing material ratio Ri/Ro Viscoelastic storage modulus Butene-ethylene copolymer modification Butene resin resin physical properties 201226463 -ΐ Example 16 S VO 〇〇〇00 inch CN vd 78 or more 00 rn 3000 or more 1.99 Example 15 〇〇〇in 00 inch (N v 〇 (N o 78 or more ro 3000 or more 2.01 implementation) Example 14 v〇〇〇〇〇00 Tf CN v〇d 50 or more CN — 2000 2.01 Example 13 ν〇On 〇〇〇οο 〇 〇 oi 00 in o 70 or more — 3000 or more 2.03 i Example 12 | ν〇〇 Rn 〇α\ 00 o (N 00 »r! o 78 or more - 1500 2.02 | Example 11 | in 〇〇 m 00 〇cs 〇·&gt; oo | 78 or more I Ο rn 2000 2.04 Example 10 〇ο ο 00 inch CN in 〇 | 25 or more 1 rn inch · 2000 OS Ο) «·« |Example 9 I ν〇CN 〇ο ο in 00 inch (N v〇〇50 or more | 〇\ cn 3000 or more | 2.00 Butene Composition (% by weight) Ethylene component (% by weight) Total content of maleic anhydride % by weight) Content (parts by weight) Fractional flow rate (g/l〇min) Maximum peak temperature (°c) Gh XP Oh o X '—^ P oo 3-glycidoxypropyltrimethoxy decane (parts by weight) Peel strength (N/cm) &lt;substrate-solar battery protection sheet&gt; Λ 装 t0 Ί i 友 C' ^ 1 ^ 2 K _ vehicle 1 娥螌糠 4 &lt; tea V high temperature and high humidity durability &lt; And then (hours) high temperature and high humidity durability &lt; power generation characteristics&gt; solar cell sealing material exudation resistance value ratio Ri/R〇 viscoelastic storage modulus butene-ethylene copolymer modified butene resin resin Physical properties -9e- 201226463 [ε ΐ 1 Comparative Example 7 1 Ον 〇〇〇ΓΠ 00 in CN Ο 1 1 1 Bad 1 Comparative Example 6 g 〇〇〇 6 〇〇 (N 00 VO ON VO o Ο 1 00 rn 1 1 1 Comparative Example 5 〇〇| 67.0 00 卜 〇 〇 o 1 〇 〇 1 1 Bad 1 Comparative Example 4 1 〇〇〇〇〇a\ mv〇o ο 1 — 1 1 1 Comparative Example 3 1 〇ί —Η 〇〇〇〇rn (N 1 21.2 | v〇o ο 1 ΓΟ 1 1 Bad 1 Comparative Example 2 S Os 〇〇〇ο CO 00 ^T) CN Bu v〇o ο rn 1000 1 Bad 4.55 Comparative Example 1 〇\ 〇〇〇ο ΓΟ 00 CN o vd o ο (N 〇 1000 1 bad 4.41 butene component (% by weight) ethylene component (% by weight) maleic anhydride total content (% by weight) content ( Parts by weight) Flow rate (g/10min) Maximum peak temperature (°c) (XXS—XP 〇ro /^N cd CLh X 〇/^s _ «ifftii S—^ 3-Acryloxypropyl trimethyl Oxydecane (parts by weight) Peel strength (N/cm) &lt;Substrate-Solar cell protection sheet&gt; Λ $ Decoration Ί ii Silver recording 慕 Mu V High temperature and high humidity durability &lt;Next &gt; (hours) High temperature Wet Durability &lt;Power Generation Characteristics&gt; Exudation resistance value ratio of solar cell sealing material Ri/Ro viscoelastic storage modulus isf ®- 'Ί 幽 CO butyl ethylene dilute copolymer modified butene resin resin physical property 201226463 Inch ΐ Comparative Example 15 ΕΕΑΜ 100 parts by weight § ι&gt; ν 〇Ο 70 or more CN (N 3000 bad | 10.5 Comparative Example 14 ΓΟ 〇〇〇 00 inch CS SS 00 1 00 1 1 bad | 1 Comparative Example 13 〇ΓΟ 〇 〇〇p Os ir! ο 70+〇\ ro 1000 1 1 Comparative Example 12 ν〇〇〇〇Ο \ 00 Ο ο | 70 or more | — 3000 or more bad | &lt;N (&gt; Comparative Example 11 ν〇m ο 〇ο ΓΟ 00 inch CS Ό vd 0.02 5 or less 〇 1000 1 Bad 1 Comparative Example 10 0.01 〇Ο ΓΛ 00 (N Bu vd ο 10 or more 〇 1000 1 Bad 1 Comparative Example 9 EVA 100 parts by weight 1 104 I ο V) ο 1 〇 1 1 1 bad | 1 | Comparative Example 8 1 1 〇 1 o. oi 1 〇 ο inchο 1 〇1 1 bad | 1 butene component (% by weight) ethylene component (% by weight) maleic anhydride total content (% by weight) content (parts by weight) swell flow rate (g/10min) P S—✓ 〇, X. . /—Ν CQ CU X Ρ ο 3-glycidoxypropyltrimethoxydecane (parts by weight) Peel strength (N/cm) &lt;Substrate-solar battery protection sheet&gt; Λ 〇Ί i Ben 1 Z SE镟¥ ^ V High temperature and high humidity durability &lt;Next&gt; (hours) High temperature and high humidity durability &lt;Power generation characteristics&gt; Exudation resistance ratio of solar cell sealing material R^/Ro -κ Viscoelastic storage modulus Butene-ethylene copolymer modified butene resin resin physical property-se- 201226463 [II] Example 16 VO 〇〇kD 00 inch oi VO 70 or more 70 or more Example 14 so VO 〇〇〇m 00 呀 CN v〇vd O 70 or more 70 or more Example 12 〇 1 « - ^ Os 00 &lt; N 00 d 70 or more 70 or more Example 10 Η m 00 inch &lt; N mv〇o 1 70 or more 70 or more Example 6 g ΓΛ 〇〇00 &lt;N (N inch 〇 70 or more 70 or more Example 2 §: &lt; Ν 〇 (N OO oo 70 or more 70 or more embodiment 1 v〇Ο) ο 〇〇 inch 00 oi 卜 v〇o 70 or more 70 or more butene component (% by weight) ethylene component (% by weight) maleic anhydride total content Amount (% by weight) Content (parts by weight) Flow rate (g/l〇min) Maximum peak temperature (°c) /-&quot;S ed £X r~-_^ » _ X Sw^ P 〇N cd CU XP o 3-glycidoxypropyltrimethoxydecane (parts by weight) Exudation of solar cell sealing material π 袈Ο si »si Ί ύ 1 step ζ Κ History gorge m V Appearance characteristics Exudation of solar cell sealing material Λ μ: Dare Ο »Si Ί 1 silver ζ K Μ 赢 Win V Appearance characteristics Viscoelastic storage modulus Butene-ethylene copolymer modified butene resin 1 Resin physical property 4&lt; w /—N (N 4: 刼漤^ (3⁄4) 201226463 [9&lt;] Comparative Example 16 EVA 100 parts by weight ο ΓΛ ο 〇1 1 1 1 1 1 Comparative Example 15 EEAM 100 parts by weight s ν*ϊ ν〇ο 〇 〇 〇 〇〇 〇〇 On On On On On On On On On On On On On On On On On 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良 不良Example 4 1 〇Η 〇〇宕0\ ΓΛ so ο 〇1 1 1 〇|Comparative example 2 1 Os Ο 〇00 yr\ &lt;N 卜vd ο νο 〇|bad| 〇1 Poor I 〇Comparative Example 1 ON ο 〇00 &lt;N 卜vd ο 〇1 Poor I 〇1 Poor 1 〇 Butene component (% by weight) Ethylene component (% by weight) Total content of maleic anhydride (% by weight Content (parts by weight) Fractional flow rate (g/10min) Maximum peak temperature (°c) cu X Vw/ P om /—\ CQ CU XP ο »—Η 3-glycidoxypropyltrimethoxy Decane (parts by weight) 3-propenyloxypropyltrimethoxydecane (parts by weight) Exudation of solar cell sealing material π ο ο i §Throw Z SE Green ¥ V V Appearance characteristics Solar cell sealing material Exudation Λ π 装 Ί 1 i 1? Q ^ 1 throw z field record ¥ Μ V Appearance characteristics viscoelastic storage modulus butene-ethylene copolymer modified butene resin resin physical property (N 刼漤 ^ 13⁄4) Suo Fan ^ 圆 Circle 6 is a schematic longitudinal cross-sectional view showing another example of using the solar cell anode battery module of the present invention.

201226463 [Industrial Applicability] The solar cell sealing material according to the present invention can provide a solar cell module which can maintain a high temperature for a long period of time. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a longitudinal sectional view showing an example of a solar battery. Fig. 2 is a schematic view showing an example of manufacturing points of a solar battery module for a solar battery according to the present invention. Fig. 3 is a schematic longitudinal sectional view showing an example of a solar battery module for a solar battery according to the present invention. Fig. 4 is a schematic view showing an example of manufacturing points of a solar battery module for a solar battery according to the present invention. The circle 5 shows a schematic diagram of an example in which the manufacturing points of the solar battery module of the present invention are used. Fig. 7 is a schematic longitudinal sectional view showing another example of the use of the solar battery module of the present invention. [Main component symbol description] Substrate 1 Solar cell component 3 Solar cell 4 Upper protective material 5 The underlying protective material efficiently manufactures the battery performance too. The sealing material is too much in the 'sealing material too sealing material too sealing material Too, sealing material too sealing material too 41, 201226463 A solar cell B solar cell sealing material B 1 fluororesin sheet B' solar cell protection sheet C laminated sheet D roller E solar battery module -42-

Claims (1)

201226463 VII. Applicable Patent Range: l A solar cell sealing material containing 0.1 parts by weight of modified butyl and 0.1 to 15 parts by weight of (4) compound having epoxy group: 曰 modified butyl resin Grafting of cis-succinic acid anhydride to humans: weight /. a butadiene-ethylene copolymer, and the total content of cis-butyl is 〇.1~3 by weight to phthalic anhydride. 2. The sealing material for solar cells according to claim 1 of the patent scope, wherein the decane compound is as follows As shown in the general formula (I), R3n (I) R1 - Si - (〇R2) 3.n (wherein R1 represents 3-glycidoxypropyl (3 - giyCid〇xypropyi) or 2_( 3,4_ ring-salt cyclohexyl)ethyl, Han 2: The number of the courtyards of the number 1 to 3 'r3 indicates that the carbon number is Η^ or 1). And η is a solar cell protective sheet, which is a method for manufacturing a solar cell module by laminating a fluororesin sheet on one of the sealing materials for the first solar cell of the patent application scope. The utility model has the following steps: a ruthenium layer step, which is a transparent upper side protective material on the surface layer of the solar cell by means of a sealing material of the application scope 丨 双 双 电池 battery, and the sun is separated by the patent application scope 帛i The sealing material for the battery is used to protect the material under the surface layer of the solar cell to form a laminated crucible; the sealing step is performed by pressing the laminated body along the thickness direction thereof, and heating the sealing material with the solar cell The solar cell. -43- 201226463 5 - The manufacturing method of the solar cell module of claim 4, wherein the step of laminating is a step of depositing a first solar cell protection sheet on top of the solar cell to present the solar cell and The solar cell sealing material is opposed to the state, and the second solar cell protection sheet is laminated under the solar cell to face the solar cell and the solar cell sealing material to form a laminate; A solar cell protection sheet, which is formed by integrating a fluororesin sheet of a transparent upper protective material, is formed by a solar cell sealing material according to the scope of the patent application, and the second solar cell protection sheet is attached to One of the sealing materials for solar cells of the first application of the patent scope is integrated with a fluororesin sheet layer as a lower protective material. (6) A method of manufacturing a solar cell module, comprising the steps of: laminating a solar cell sealing material of the first application of claim 1 to continuously laminate a solar cell element to form a laminated sheet, the solar cell The component is a solar cell element in a solar cell in which a solar cell element is formed into a film shape on a flexible strip substrate; the sealing step is performed by applying the laminated sheet along its thickness direction The solar cell element of the solar cell is sealed with the solar cell sealing material by pushing the pressure while heating. 7 · The manufacturing method of the solar cell module according to item 6 of the patent application scope is the following steps: the solar cell protection sheet is laminated on the solar cell element to present the solar cell element and the solar cell The sealing material is oppositely oriented to produce a laminated sheet; the solar cell protective sheet is one of the sealing materials for solar cells according to the first application of the patent scope. • 44· 201226463 The solar cell element is formed in 70 pieces of the battery. A solar cell element in which a fluororesin sheet is integrated into a film-like surface; a solar cell element in a solar cell in which a sun is formed on a flexible strip-shaped substrate. 8. A solar cell module according to claim 6 The manufacturing method of the group, wherein the step of laminating is performed on the substrate and continuously laminating the sealing material for the solar cell of the first application of the patent scope 1 to produce a laminated sheet; the step of sealing is to use a solar cell laminated on the solar cell element The step of sealing the solar cell with a sealing material and a sealing material for a solar cell laminated on the substrate. •45-