TW201221611A - Method for producing flexible solar cell module - Google Patents

Abstract

The objective of the present invention is to provide a method for producing a flexible solar cell module, said method continuously sealing a solar cell element without requiring a cross-linking step, and favorably producing, by a roll-to-roll method, a flexible solar cell module that does not wrinkle or curl and that has superior adhesive properties between the solar cell element and a solar cell sealing sheet. The method for producing a flexible solar cell module has a step for, by means of constriction using a pair of hot rollers, thermocompression bonding a solar cell sealing sheet to at least the light-receiving surface of the solar cell element wherein a photoelectric conversion layer is disposed on a flexible substrate. The solar cell sealing sheet has an adhesion layer comprising a maleic-anhydride-modified olefin resin wherein an a-olefin-ethylene copolymer of which the amount of a-olefin contained is 1-25 wt% has been graft modified by maleic anhydride, the total amount of maleic anhydride contained being 0.1-3 wt%.

Description

201221611 VI. Description of the Invention: [Technical Field] The present invention relates to a method for manufacturing a flexible solar cell module, which can continuously seal a solar cell element without a crosslinking step, and can efficiently manufacture no A flexible solar cell module in which wrinkles or curls are generated and the solar cell element and the solar cell sealing sheet are excellent in adhesion. [Prior Art] As a solar cell, it is known that a rigid solar cell module using glass as a substrate and a flexible polymer material or a stainless steel film using a polyimide or a polyester-based film as a substrate Solar battery module. In recent years, flexible solar cell modules have begun to attract attention due to the ease of handling, construction, or impact resistance due to thinning or weight reduction. The flexible solar battery module is a flexible photoelectric substrate, and has a function of forming a current in a film-like layer by a light-emitting layer, and a photoelectric conversion layer composed of a semiconductor or a compound semiconductor. The upper surface of the solar cell element is sealed by a laminated solar cell sealing sheet. The solar cell sealing sheet is used to prevent the solar cell element from being externally prevented from being formed by the outer layer of the solar cell element. In the above-mentioned adhesive layer, m ( ' G 酉夂 Ethyl vinegar (EVA) tree 曰 曰 (for example, refer to Patent Document 1). However, in the case of using the above-mentioned eva 槲 槲 制造 制造 系 系 系 系 系 系 系 系 系 系In the step, the above-mentioned adhesive layer is used as the above-mentioned adhesive layer of the solar cell sealed 201221611 (for example, see Patent Document 2). ☆The manufacturing method of the above flexible solar cell module has been carried out since the previous method. The flexible solar cell element and the solar cell sealing sheet are previously cut into a desired shape and laminated, and at a standstill. The laminate is formed by vacuum lamination. This vacuum lamination method has the problem that the subsequent steps are time-consuming, and the manufacturing efficiency of the solar cell module is low. In the method of manufacturing a positive battery module, in terms of excellent mass production, a roll to roU meth〇d is used (for example, refer to Patent Document 3). The reel method uses a film-like solar cell sealing sheet. The wound reel is a method of sealing a flexible solar cell module by using a solar cell sealing sheet which is rolled up from the reel by a pair of rolls, and is thermocompression bonded to the solar cell element. According to this reel method, it is expected that the splicable solar cell module can be continuously manufactured with extremely high efficiency. However, by using the previous solar cell encapsulant, the retractable solar cell element is sealed by a reel method to manufacture a flexible In the case of the solar cell (4), there is a problem that a crosslinking step must be performed, and when the above-mentioned flexible solar cell element is thermocompression bonded to the above-mentioned solar cell sealing sheet, wrinkles or curls are generated. The rate drops drastically, or the upper = solar cell component and the above solar cell sealing sheet become two-pointed * # 0 Therefore, the industry's search can fully utilize the high volume of the reel method And it does not produce enemy pleats or curls, and the method of continuously and preferably sealing the solar cell 201221611 battery element can be smashed and smashed by far green. Patent Document 1. Japanese Patent Application Laid-Open No. Hei 7-297439 In the light of the above-mentioned status quo, it is an object of the present invention to provide a continuous process without a cross-linking step, as disclosed in Japanese Unexamined Patent Publication No. Hei. No. Hei. The solar cell element is sealed without wrinkles or sowing, so that solar power can be efficiently manufactured; and the flexible solar cell module of the flexible solar cell module having excellent properties of the solar cell sealing sheet is also used. The invention relates to a method for manufacturing a flexible solar cell module, comprising: a step of using a pair of heat rollers to bring a solar cell sealing sheet close to at least a light receiving surface of a solar cell element, thereby performing thermocompression bonding, which is too % of the battery sealing sheet is provided with a photoelectric conversion layer on a flexible substrate: the solar cell sealing sheet has an adhesive layer composed of a cis-butadiene:texture thin-smoke resin on the gas-based resin sheet The content of the fine-olefin of the cis-butyl dibasic acid ruthenium resin is 25 weights. The resin of the dilute-smoke-diethyl methacrylate is grafted and modified by the cis-butyl dicarboxylic acid, and the cis-butanic acid anhydride The total content is 0 · 1 to 3 weight 〇 / 0. The present invention will be described in detail below. The present invention seals a solar cell element by using an adhesive layer comprising a special component composed of a pull-up #八^"3", and a continuous sealing layer is formed by using a roll to continuously produce no (four) or curl. The above-mentioned solar cell seal: a flexible solar cell module excellent in adhesion to a solar cell element. 5 201221611 That is, the present inventors have found that a specific butylene is formed by using a fluorine-based resin sheet. The solar cell sealing sheet of the adhesive layer composed of the olefin resin after the acid anhydride graft modification is used to seal the solar cell element, and the thermocompression bonding can be realized in a short time at a relatively low temperature without using a crosslinking step, and the reel method can be utilized. The present invention is completed by continuously sealing a solar cell element. The method of manufacturing the flexible solar cell module of the present invention comprises the use of a heat roller to bring the solar cell sealing sheet close to at least the light receiving surface of the solar cell element, thereby performing In the step of thermocompression bonding, the solar cell sealing sheet is formed by disposing a photoelectric conversion layer on a flexible substrate. The solar cell sealing sheet is a fluorine resin sheet. There is an adhesive layer composed of maleic anhydride-modified olefin-based resin. The maleic anhydride-modified olefin-based resin is obtained by using an α-olefin content of 1 to 25 parts by weight of an olefin ethylene copolymer. The resin formed by the grafting of the two (4) grafts, and the total content of the liver of the succinated diacid is 〇1 to 3 by weight in the present invention 'by using a solar cell seal comprising an adhesive layer composed of such a specific resin The flexible solar cell module can be preferably manufactured by the reel method using the 棬 不 不 不. The above-mentioned dilute hydrocarbon-ethylene copolymer is a copolymer of olefinic tobacco, L, and ethylene. Amorphous and low-melting point, 'softening, the upper olefin preferably has a carbon number of 3 to 10, more preferably a carbon number of *~1. Specifically, the above hydrazine: an olefin may be exemplified by hydrazine, =& ene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc. wherein χ t ^ Τ (5) is preferably 1-butene, hexamethylene, 1-octyl 201221611 The above a-olefin-ethylene copolymer is preferably a butene-ethylene copolymer, a hexene-ethylene copolymer, or an octene-ethylene copolymer. In the olefin-ethylene copolymer, the olefin content is i to 25% by weight. If the α-olefin content is less than 5% by weight, the flexibility of the solar cell sealing sheet is lowered, and the melting point of the solar cell sealing sheet becomes high. Therefore, the solar cell element is required to be heated at a high temperature, and wrinkles or curls are easily generated. If the 〇: olefin content exceeds 25% by weight, the crystallinity or fluidity of the solar cell sealing sheet becomes uneven and strain occurs. Or the melting point of the solar cell sealing sheet itself is too low, so that it is difficult to maintain the shape when the solar cell element is kept at a high temperature, and as a result, the solar cell sealing sheet has a decreased adhesion to the solar cell element. Or (4). The preferred lower limit of the above lung content is 10% by weight, and the upper limit is preferably 2% by weight. The content of the above-mentioned "_olefin" in the above α-olefin-ethylene copolymer can be determined by the spectral integral value of 3C-NMR. Specifically, for example, in the case of using 1-butene, it is used in chloroform. The spectral integral value derived from the 丨-butene structure obtained near 1〇·9 ppm or around 261 ppm, around 39.1 ppm, and around 26.9 ppm, around 29.7 ppm, around 3〇2 ppm, 3 3.4 ppm It is calculated from the spectral integral value of the ethylene structure obtained in the vicinity. For the attribution of the spectrum, the known information such as the Handbook of Polymer Analysis (edited by the Analytical Chemistry Society of Japan, issued by Asakura Shoten, 2008) can be used. A known method can be used for the grafting of the above-mentioned α-olefin-ethylene copolymer. Specifically, for example, a method such as a melt reforming method in which the above α·olefin·ethylene is copolymerized can be used. 7 201221611 Into the machine, the composition of the anhydride and the radical polymerization initiator is supplied to the extrusion... 仃 融 融 混 混 混 混 ' 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺 顺Solving f ^ to find the above α-ene The fe-ethylene copolymer is dissolved in a mixture to prepare a solution, and a maleic acid-based polymerization initiator is added to the solution to make the sulfonium-naphthalene & In the above-mentioned copolymer, the above-mentioned melt modification method can be mixed in an extruder. It is excellent in productivity, and the radical polymerization initiator used in the method of graft modification is only required. Since the radical transfer in the radical polymerization has not been particularly limited, the body may be exemplified by: cumene peroxide, cumene hydroperoxide, perylene diisopropyl hydrazine, peroxy ruthenium oxychloride Brewed, perylene isopropyl phenyl acrylate, azobisisobutyronitrile, etc. The total content of the above maleic anhydride modified olefin furnace is "" ~ 3 wt% 2: 曰, cis-succinic acid liver曰3 resets the total content of maleic anhydride above A, and: 1.1 cc/〇', then the solar cell sealing sheet is subsequently lowered by 1± for the solar cell element. The total content of the above maleic anhydride exceeds 3 denier 0/. In the case where the above-mentioned solar cell sealing sheet is produced, gelation occurs when the solar cell sealing sheet is produced, and the sealing sheet is not produced or the extrusion moldability of the solar cell sealing sheet is lowered. A preferred lower limit of the total content of the above cis-succinic acid oxime is 0.2% by weight, and a preferred upper limit is 丨%' more preferably less than 1% by weight. Further, the total content of the above-mentioned maleic anhydride can be measured by using the above-mentioned cis-acid-modified dilute (tetra) resin, and the infrared absorption spectrum of the above test film is calculated based on the absorption intensity near the mow. 201221611 Specifically, the total content of maleic anhydride in the above maleic anhydride-modified olefin-based resin can be, for example, FT_IR (Fourier-converted infrared spectrometer Nicolet 6700 FT_IR), using a polymer analysis manual (Japan) It is measured by a known measurement method described in the Chemicals Association, issued by Asakura Bookstore, 2008). The above-mentioned maleic anhydride-modified olefin-based resin preferably has a maximum peak temperature (Tm) of -125 C as measured by differential scanning calorimetry. If the maximum peak temperature (Tm) of the above endothermic curve is lower than °C, the heat resistance of the solar cell sealing sheet is lowered. If the maximum peak temperature (Tm) of the above endothermic curve is higher than 125t, the heating time of the solar cell sealing sheet becomes longer in the sealing step, the productivity of the solar cell module is lowered, or the sealing of the solar cell element is insufficient. Hey. The maximum peak temperature (Tm) of the above endothermic curve is more preferably 83 〜. Further, the maximum peak temperature (Tm) of the endothermic curve measured by the differential scanning calorimetry described above can be measured in accordance with the measurement method specified in JIS K7121. The maleic anhydride-modified olefin-based resin preferably has a melt flow rate (MFR) of 〇5 g/l 〇 min to 29 g/1 〇 min. If the melt flow rate is less than g5 g/10 min, there is a concern that the seal sheet has residual strain when the solar cell encapsulant is manufactured, and the module is curled after the solar cell module is manufactured. If it exceeds 29 g/l 〇 minutes, there is a concern that it is easy to sag when manufacturing the above solar cell sealing sheet, and it is difficult to manufacture a sheet having a uniform thickness, and the module may still curl after the solar cell module is manufactured, or a solar cell Pinholes and the like are likely to be generated in the sealing sheet, thereby impairing the insulation of the entire solar cell module. The above melt flow rate is more preferably 2 g / 1 〇 min ~ 1 〇 g / 1 〇 minutes. 201221611 The melt flow rate of the maleic anhydride-modified olefin-based resin is a value measured by a load of 2.16 kg of astm D 1 238 ', which is a method for measuring the melt flow rate of the polyethylene-based resin. The above maleic anhydride-modified olefin-based resin preferably has a viscoelastic storage elastic modulus of 3 〇 < t at 2 x 1 () 8 Pa or less. If the viscoelastic storage elastic modulus (4) 2x1 () 8pa under the thief is lower, the flexibility of the solar cell sealing sheet is lowered and the operability is lowered, or the solar cell module is manufactured by using the solar cell sealing sheet and the solar cell element. At the same time, it is necessary to sharply add the above-mentioned solar cell sealing sheet. If the elasticity of the viscoelastic storage of the upper 31 is too low, the solar cell sealing sheet exhibits a decrease in the usability of the solar cell sealing sheet at room temperature, so the lower limit is preferably ixWpa. Further, the upper limit is more preferably 1 5 %. The maleic anhydride-modified olefin-based resin preferably has an elastic storage modulus of 5 x 10 6 or less at i?t. If the above-mentioned adhesive storage elastic modulus exceeds 5xl () 6pa, there is a possibility that the solar cell sealing sheet is lowered in adhesion to the solar cell element. When the above-mentioned viscoelastic storage elastic modulus at 100 ° C is too low, the solar cell module is sealed by the solar cell sealing sheet described above, and the solar cell sealing sheet is greatly pressed by the pressing force. The claw movement 'and thus the thickness unevenness of the solar cell sealing sheet is increased, so the limit is preferably 1×10 〇 4 Pa. Further, the upper limit is more preferably 4xl 〇 6 pa. In the product: the viscoelastic storage modulus of the above-mentioned maleic anhydride-modified olefin-based resin refers to the value determined by the m K6394 < dynamic property test method. . 10

Cv 201221611 The above-mentioned adhesive layer preferably further contains a decane compound. By including the above-described oxime-forming opening, the adhesion between the above-mentioned adhesive layer and the surface of the solar cell element can be further improved. Among them, the above-mentioned adhesive layer preferably contains a decane compound having an epoxy group. By containing a decane compound having an epoxy group, the flexible solar cell module obtained by the reel method can be sufficiently utilized to have a particularly high heat resistance. Further, even if the solar cell in which the surface is preliminarily shaped with an embossed shape is thermoformed to the solar cell element, it is easy to maintain the shape of the flower. And if the decane compound having an epoxy group is formulated, the maleic anhydride is modified to a cis-succinic anhydride group in the dilute-smoke resin and a % oxy group of the epoxidized & The reaction is carried out so that the decane compound is introduced into the side chain 1 of the resin, and further, the (4) compound of the side chain forms a siloxane chain by hydrolysis condensation, and a crosslinked structure is formed between the resins. That is, the above-mentioned anthracene compound having an epoxy group also functions as a crosslinking agent for the above-mentioned diacid diacid-modified olefin-based resin. It is considered that the heat resistance is improved by the increase in the modulus of elasticity at a high temperature due to the formation of a crosslinked structure between resins. The decane compound having an epoxy group may have at least one epoxy group such as an aliphatic epoxy group or an alicyclic epoxy group in the molecule. The decane compound having an epoxy group is preferably a decane compound represented by the following formula (1). [Chemical 1]

R1~Si—(OR^-n 201221611 where R1 represents 3-glycidoxypropyl or 2-(3,4-epoxycyclohexyl)ethyl 'R2 represents an alkyl group having a carbon number of i~3 And r3 represents a carbon group having a carbon number of 3, and η is 0 or 1. R1 represents a 3-glycidoxypropyl group represented by the following formula (II) or 2 of the following formula (III) -(3,4-epoxycyclohexyl)ethyl. [Chemical 2] -ch2ch2och2ch-ch2 < (8) Ο ^ [Chemical Formula 3] Formula (冚) The above R2 is as long as it is a burning group having a carbon number of 1 to 3 In particular, examples thereof include a methyl group, an ethyl group, and a propidium I, preferably a methyl group and an ethyl group, and more preferably a methyl group. The above R3 has no specific p-position as long as it has a carbon number of i~3. For example, a methyl group, an ethyl group, and a propyl group are preferable, and a methyl group is preferable. In the above formula (1), η is 0 or 1, preferably fluorene. The decane compound represented by the above formula (I) For example, glycidoxypropyl decyl decyloxy decane, 3-glycidoxy propyl methyl diethoxy decane, 3-glycidoxy propyl trimethoxy decane, 3 glycidoxypropyl triethoxy zexi, 3_glycidoxypropyl tripropoxy oxime 2-(3,4- Epoxycyclohexyl)ethyltrimethoxydecane, 2 (3,4-epoxycyclohexyl) 12 CO. 201221611, bistriethoxymethane, 2_(3,4-epoxycyclohexyl)ethyltriproperate Oxygen Shi Xi Xuan et al. Among them, 'preferably 3·glycidoxypropyltrimethoxy ketone, 2—(3,4·epoxycyclohexyl)ethyltrimethoxy residue, 3—epoxypropoxy group Propyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane. The decane represented by the above formula (1) Commercially available products of the compound include: D〇w Corning Toray Co., Ltd., 6〇4〇(3_glycidoxypropyltrimethoxydecane), Ζ6043 (2-(3,4·epoxy ring) Hexyl)ethyltrimethoxydecane)' or κβε·4〇3 (3_glycidoxypropyltriethoxydecane) manufactured by Shin-Etsu SiliC0nes Co., Ltd., ΚΒΜ_4〇2. Propylmercaptodimethoxy (tetra), oxime (3_glycidoxypropylmethyldiethoxydecane), and the like. The content of the above-mentioned cerium-sintering compound in the above-mentioned adhesive layer is preferably 5 to 5 parts by weight based on 10 parts by weight of the butyl succinic acid-modified olefin-based resin. If the content of the above-mentioned compound is less than 5 parts by weight, the adhesion of the solar cell sealing sheet may be lowered. When the amount of the above-mentioned compound exceeds 5 parts by weight, the shrinkage of the solar cell sealing sheet may be enhanced to cause pleats or line glue to impair the appearance of the sheet. A more preferred lower limit of the content of the upper calcining compound is 〇1 part by weight, more preferably 1.5 parts by weight. The shape is inversely lower than the above-mentioned adhesive layer containing the above-mentioned time, and sometimes the viscosity of the resin for the layer is adhered to by the above-mentioned methacrylic acid. In this case, it is preferred to crosslink the acid anhydride-modified olefin-based resin to the epoxy group-containing decane compound, and the workability at the time of extrusion molding is lowered. The low-density poly 13 201221611 ethylene is blended in the above-mentioned subsequent layer. By blending low-fat sores with low-twisting polyethylene, it is possible to maintain the ergonomics and improve handling. F-specific properties and further, the above-mentioned low-density polyethylene can be a direct-bonded low-density specifically, in particular, it can be a copolymer of ethylene and olefin. The above-mentioned adhesive layer may also contain an additive such as a stabilizer, an ultraviolet ray, a 哄·^, and further an optical external line, a collector, a heat stabilizer, and the like. The above-mentioned adhesive layer $ f 1 @ enedic anhydride modified olefin " / β 1 + is produced by the following method: the above-mentioned cis-butyl compound compound, and if necessary, the weight ratio of 1 is supplied to the (4) machine for (4) The mixture was mixed in a sheet form from an extruder to produce an adhesive layer. Preferably, the adhesive layer has a thickness of 80 to 700" m. If the US is less than 8 inches, the flexible solar cell module cannot be held. If the thickness exceeds 70 〇, it may adversely affect the flame retardancy of the flexible solar cell module, or the weight of the disposable solar cell module may become heavier, and it is also unfavorable for economy. The preferred lower limit is 15 〇" m, and the upper limit is preferably β m. The solar cell is formed on the sealing sheet-based fluorine-based resin sheet. The gas-based resin sheet is transparent and rich in heat. Further, the flame retardancy is not particularly limited, and is preferably composed of a group consisting of a group of the following: a fluorine-based resin: tetrafluoroethylene-ethylene copolymer (ETFE), ethylene- Gas three a acetal resin (ECTFE), polystyrene triethyl ether resin (PCTFE), polyvinylidene di-ethylene resin (pvDF), tetrafluoroethylene-perfluoroalkane 14 201221611-based vinyl ether copolymer (FAP), poly Fluoroethylene resin (pvF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), partial Ethylene-hexafluoropropylene copolymer (PVDF-HFP), and a mixture of polyvinylidene fluoride and polymethyl methacrylate (PVDF/PMMA), in which the heat resistance and transparency are more excellent. Preferably, it is a polyvinylidene fluoride resin (PVDF), a tetrafluoroethylene-ethylene copolymer (ETFE), or a polyfluoroacetone resin (pVF). The fluorine-based resin sheet preferably has a thickness of 1 〇 to 1 〇〇 #m. If the thickness of the fluorine-based resin sheet is less than 1 〇# m, insulation may not be ensured, or

The flame retardant is impaired. If the thickness of the fluorine-based resin sheet exceeds 丨〇〇 V m', the weight of the flexible solar battery module becomes heavier, which is uneconomical. A lower limit of the thickness of the above fluorine-based resin sheet is 15 " m, and a higher limit is 80 // m. The solar cell encapsulating sheet can be produced by laminating the above-mentioned fluorine-based resin sheet and the layered layer described above. The method for integrating the above-mentioned laminated layer is not particularly limited. For example, (4): a method of extruding a resin sheet on a surface of the adhesive layer and laminating it; and 4 extruding the above-mentioned adhesive layer and the above-mentioned I (four) A method in which a film is formed by a method of forming a fat sheet and the like, and a film is formed at the same time, and the film is processed by an eight-layer film. The extrusion set temperature in the above co-extrusion step is such that the resin and the above-mentioned cis-t-butene _ w A β are π at a melting point of 3 rr or more of the above-mentioned fluoroacid-modified olefin-based resin and less than the decomposition temperature for less than 3 generations. In the above-mentioned solar cell sealing sheet, it is preferred that the above-mentioned fluororesin sheet is simultaneously formed into a film-type laminated body via a co-extrusion step, 15 201221611: Field battery sealing Preferably, the sheet has a desired flower shape. It is particularly preferable that the above-mentioned battery anti-sealing sheet has a surface shape on the light-receiving side when applied. More specifically, it is preferable that the gas system and the surface of the solar cell sealing sheet which is the side of the light-receiving surface of the flexible solar cell module 2 have an embossed shape. By having the embossed shape described above, the reflection loss of sunlight can be reduced, glare is prevented, or the appearance is improved. The above-mentioned invitation flower shape may be a regular concave-convex shape or a convex shape. w The dust shape can be embossed before being attached to the solar cell component. It can also be embossed after bonding to the solar cell component, or simultaneously in the step of bonding with the solar cell component. shape. Among them, the case where the embossing is formed before being bonded to the solar cell element is preferable because the embossed transfer unevenness sentence is obtained and the embossed shape of the uniform sentence can be obtained. When the solar cell sealing sheet having an embossed shape on the surface in advance is used, and the flexible solar cell element is sealed by the reel method, a part of the embossed shape disappears during the thermocompression bonding step at the time of sealing. Therefore, the operation of applying an embossed shape to the surface of the solar cell sealing sheet is usually carried out after sealing the flexible solar cell member. However, in the manufacturing method of the flexible solar cell module of the present invention, even if a solar cell sealing sheet having an embossed shape on the surface is used, the flexible solar cell element is sealed by the reel method, and no embossed shape disappears. The situation. The reason for this is that the above-mentioned adhesive layer has sufficient adhesion (ς.16 201221611 Force' and on the other hand, it has a viscoelastic storage elastic modulus between the knives and the knives. There is no particular limitation on the solar cell seal κ. For example, it is preferably a method of & and a method of performing a film-forming process by simultaneously pressing a U-, /, rat-type resin sheet by co-broadcasting A cooling roll that embosses the surface while cooling the molten resin. The solar cell element is generally composed of a photoelectric conversion layer that generates electrons by receiving light, an electron depletion electrode layer generated by extraction, and a flexible base. The photoelectric conversion layer may be, for example, a layer formed of a single crystal, a single crystal, a polycrystalline stone, a crystalline semiconductor such as a microcrystalline germanium, or the like. Amorphous semiconductors such as germanium, GaAs, InP, A1GaAs, (10), cdTe, (d),

CuInSe2, CuInS2f compound semiconductor, organic semiconductor such as phthalocyanine or polyacetylene. The above photoelectric conversion layer may be a single layer or a plurality of layers. The thickness of the above photoelectric conversion layer is preferably 〇.5 to 1 〇 ym. The flexible substrate is not particularly limited as long as it is flexible and can be used in a flexible solar cell, and examples thereof include a heat resistant resin such as polyimine, polyether ketone or polyether sulfone. The substrate. The thickness of the above flexible substrate is preferably from 10 to 80 / im. The above electrode layer is a layer composed of an electrode material. The electrode layer may be located on the photoelectric conversion layer as needed, or between the photoelectric conversion layer and the flexible substrate, or on the surface of the flexible substrate. The solar cell element may have a plurality of layers of the electrode layers. 17 201221611 The electrode layer on the light-receiving side is preferably a transparent electrode because it needs to transmit light. The electrode material is not particularly limited as long as it is a usual transparent electrode material such as a metal oxide, and ITO, ZnO or the like can be preferably used. When the transparent electrode is not used, the bus electrode or its attached finger electrodes (finger ele...) can be patterned by using a metal such as silver. Since the electrode layer on the back side does not need to be transparent, it is usually used. The electrode material may be configured, and the electrode material is preferably silver. The method for producing the solar cell element described above is not particularly limited as long as it is a known method; and t can be formed, for example, by a known method of disposing the above-described photoelectric conversion layer or electrode layer on the flexible substrate. The solar cell element may be in the form of a strip wound in a reel shape or a rectangular sheet. The flexible solar cell module of the present invention is produced by thermo-compression bonding by using a heat-contacting roller so that the solar cell sealing sheet is close to at least the light-receiving surface of the solar cell element. The light-receiving surface of the solar cell element can be generated by receiving light and the surface of the photoelectric conversion layer can be disposed on the flexible substrate. In the method for producing a flexible solar cell module of the present invention, preferably, the method is such that a surface of the solar cell element on which the photoelectric conversion layer is disposed faces a surface of the solar cell sealing sheet on the side of the adhesive layer. In the state, the solar cell element and the solar cell sealing sheet are laminated, and the pair is brought into close contact for thermocompression bonding using a pair of heat rollers. The temperature of the heat roller is such that the pair of heat rollers are used such that when they are close to each other, 18 201221611 is preferably 70 to 16 (TC. If the temperature of the heat roller is less than 7 〇»c, there is a problem of causing a defect. The temperature of the heat roller exceeds 6 (rc, the valley is liable to wrinkle at the time of thermocompression bonding. The temperature of the above heat roller is preferably 8 〇 15 〇 15 〇. The tumbling speed of the above heat roller is preferably 0.1 〜1 l 〇m/min. If the rotation speed of the above-mentioned heat roller is less than 0.1 m/min, wrinkles are likely to occur after thermocompression bonding. If the rotation speed of the above-mentioned heat roller exceeds 1 〇m/min, it may cause subsequent The rotation speed of the heat roller is preferably 0.3 to 5 m/min. In the method for producing a flexible solar cell module of the present invention, the adhesive layer of the solar cell sealing sheet is made of a specific resin as described above. Since it is configured, the cross-linking step is not required, so that the thermocompression bonding can be performed in a short time. Moreover, the thermocompression bonding can be performed at a low temperature. Therefore, the solar cell element and the solar cell can be sealed without wrinkles or curling. The sheet is fully followed. Therefore, the scroll method can be used efficiently. Flexible solar cell module. The manufacturing method of the flexible solar cell module of the present invention will be specifically described with reference to Fig. 1. As shown in Fig. 1, the solar cell element 8 and the solar cell sealing sheet B are elongated. First, the reel is wound up. First, the reel of the solar cell element A and the solar cell encapsulating sheet B is wound so that the light receiving surface of the solar cell element A and the subsequent layer of the solar cell sealing sheet B are opposed to each other. The state is laminated to form a laminated sheet C.

Next, the laminated sheet C is supplied to a roll and a crucible heated to a certain temperature, and the laminated sheet c is heated while being pressed in the thickness direction to be thermocompression bonded, thereby sealing the solar cell element A and the solar cell. Sheet B 19 201221611 Then integrated, borrowed, t|_, , +. Sealing sheet B sealed solar cell "sealed by the above solar cell, flexible solar cell module can be obtained. Figure 2 shows the flexibility of the present invention. The solar solar module used in the solar cell module, the + 分 々 去 去 去 胄 “ “ “ - - - - - - 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 太阳 太阳 太阳 太阳 太阳 太阳 太阳 太阳A schematic diagram of a longitudinal section of one example. As shown in Fig. 2, the solar cell element Α7 does not go to the U flexible substrate 1 where the photoelectric conversion layer 2 is disposed. Furthermore, since the electrode layers can be variously arranged, they are omitted here. :-: The solar cell sealing sheet of Fig. 3 includes a fluorine-based resin sheet 4 and a connector layer 3. When the solar cell encapsulating sheet (4) is in the form of a clearing of the reel in the form of a reel, the subsequent layer 3 may be the inner side or the outer side. Further, Fig. 4 is a schematic longitudinal sectional view showing an example of a solar cell module obtained by the production method of the present invention. As shown in Fig. 4, the side of the photoelectric conversion layer 2 side of the solar cell element

The solar cell element A and the solar cell sealing sheet B are laminated and integrated by the adhesive layer 3 of the solar cell sealing sheet B to obtain a flexible solar group E. The manufacturing method of the flexible solar cell module of the present invention may further comprise the steps of: thermo-compression bonding the heat-radiating roller so that the solar cell sealing sheet is close to the flexible substrate of the solar cell element. The steps. By sealing not only the surface (surface) on the photoelectric conversion layer side of the solar cell element but also the surface (back surface) on the side of the flexible substrate, the solar cell element can be sealed more satisfactorily, and the production can be stably performed for a long period of time. Recyclable solar cell module for power generation.

20 201221611 The method of thermally connecting the above-described Taichi sealing sheet to the surface (back surface) on the side of the flexible substrate is, for example, the following method: in the same manner as described above, on the flexible substrate side of the solar cell element In the surface (back surface), the solar cell encapsulating sheet is disposed such that the adhesive layer is opposed to the collapsible substrate, and is brought into close contact with each other for thermocompression bonding. Further, since it is not necessary to transmit light when sealing the surface of the solar cell element on the side of the removable substrate, a solar cell sealing sheet composed of an adhesive layer and a metal plate can be used. The above-mentioned adhesive layer may be the same as the adhesive layer of the above-mentioned solar cell sealing sheet. The metal plate may be a plate made of stainless steel or aluminum. The thickness of the above metal plate is preferably 25 to 8 Å/m. When the surface of the flexible battery substrate (back surface) of the solar cell element is sealed by the above-mentioned adhesive layer and a metal plate, for example, a sheet composed of an upper layer and a metal plate is formed in advance, in the same manner as described above. The flexible substrate and the adhesive layer may be thermocompression bonded to the surface (back surface) of the flexible substrate side of the solar cell using a sheet composed of an adhesive layer and a metal plate. a surface of the solar cell element on the side of the flexible substrate (the solar cell encapsulating sheet or the step of forming the sheet by the adhesive layer and the metal sheet may be on the light receiving surface of the solar cell element = the anode cell sealing sheet) It is also possible to carry out the steps before or after the process. It is possible to use, as shown in Fig. 5, the manufacturer of the flexible solar cell of the present invention to, for example, simultaneously seal the surface of the photoelectric conversion layer of the solar cell element ( Table 21: An example of a method of the surface of the flexible substrate side (back surface). The body is made of a long solar cell element that is wound into a reel shape. In addition, a roll of two rolls is prepared. A long strip of solar cell sealing sheet wound in a reel shape. Then, as shown in Figure 5, the long solar cell sealing sheets Β and Β are rolled out, and the long solar cell element A is rolled out to form two suns. In the state in which the adhesive layers of the battery sealing sheets are opposed to each other, the solar cell element A overlaps the solar cell sealing sheets B and B to each other to form a laminated sheet.

Then, the laminated layer C is supplied to one of a certain temperature for heating, and the laminated layer c is heated while pressing between the faces D and D in the thickness direction, thereby making the solar electric power and the sealing sheets B and B mutually integrated. The solar cell module F is sealed by the solar cell sealing sheets b and B to continuously manufacture the flexible solar cell module F. In the above-described manufacturing method of the flexible solar cell module, the solar cell sealing sheets B and B may be stacked on each other to form the laminated sheet C via the solar cell element A, while being pressed in the thickness direction. Further, while heating the laminated sheet, FIG. 6 shows an example of a manufacturing method of a flexible solar battery module in which a rectangular person is used as a solar battery element. / Specifically, S 'prepares a rectangular sheet-shaped solar cell element A of a certain size instead of a long-length solar cell element wound in a reel shape. Then, as shown in Fig. 6, the long-shaped solar cell sealing sheets B and B' wound up in a reel shape are supplied to the solar cell elements a at regular intervals to be disposed, and then the layers are opposed to each other. In the state of the solar cell sealing sheets B and BFa, the solar cell sealing sheets B and B are superimposed on each other via the solar cell element A to form a layer 22 201221611 layer c. Then, the laminated sheet c is supplied to the pair of rolls D and D heated to a certain temperature, and the laminated sheet c is heated while being pressed in the thickness direction, whereby the solar cell sealing sheets B and B are integrated with each other. The solar cell element a is sealed with the solar cell sealing sheets B and B to continuously manufacture the solar cell module F. In the manufacturing method of the flexible solar cell module described above, the laminated sheet C may be heated while being pressed in the thickness direction while forming the laminated sheet C. FIG. 7 and FIG. 8 show the flexible sun using the present invention. A method of manufacturing a battery module is an example of a flexible solar battery module obtained by sealing a surface (surface) on a photoelectric conversion layer side of a solar cell element and a surface (back surface) on a flexible substrate side. 7 is a longitudinal example of a flexible solar battery module F in which the surface of the solar cell element A on the photoelectric conversion layer 2 side and the surface of the flexible substrate 1 are sealed by the adhesive layer B of the solar cell sealing sheet B. Schematic diagram of the section. 8 is a view in which the surface of the solar cell element A on the photoelectric conversion layer 2 side is sealed by the adhesive layer 3 of the solar cell sealing sheet B, and the U-sealed flexible substrate is formed by the adhesive layer 3 and the metal plate 5. A schematic longitudinal cross-sectional view of an example of a flexible solar cell module G. Thus, the manufacturing method of the flexible solar cell module of the present invention is characterized in that the solar cell element is sealed with a solar cell sealing sheet of a specific configuration, and therefore, the solar cell element and the solar cell can be preferably used by the reel method. The sealing manufacture does not produce wrinkles or the flexibility of the crimped sheet is excellent. 23 201221611 Solar cell module. In the manufacturing method of the solar cell module of the present invention, in the manufacture of the solar cell module, the cross-linking step is not required: the solar cell element can be continuously sealed, and the reel method can be preferably manufactured. A flexible solar cell module that is sensitive or curled, and has excellent solar cell elements and solar cell sealing sheets. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. (Examples 1 to 29, Comparative Examples 4, 6, and 7) A T-ethylene copolymer having a content of a dilute component and an ethylene component as shown in Tables 1 to 5 was subjected to maleic anhydride. Graft-modified modified butylene-based resin 10G parts by weight, and the money compound, i.e., the amount of 3-glycidoxypropyltrimethoxydecane (3) manufactured by Corning Toray Co., Ltd., The product for the adhesive layer consisting of the product name "Z 6〇4〇") or 3-propoxymethoxypropyl dimethoxy decane (trade name "KBM-5103", manufactured by Shin-Etsu Chemical Co., Ltd.) is supplied to In the first extruder, melt-kneading was carried out at 250 °C. On the other hand, a certain fluorine resin (polyvinylidene fluoride (trade name "Kynar-72" manufactured by Arkema Co., Ltd.) and tetrafluoroethylene-ethylene copolymer (manufactured by Daikin Industries Co., Ltd.) shown in Tables 1 to 5 are used. , trade name "Neoflon ETFE")' Polyfluoroethylene resin (trade name "Tedlar", manufactured by Dup〇nt Co., Ltd.), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (manufactured by Daikin Industries, trade name "Ne〇" Fl〇n pFAj), ethylene gas three 24 201221611 fluoroethylene resin (manufactured by Solvay, trade name Γ halar ECTFE), gas-dissolved ethylene resin (Daikin Industries, trade name "Neoflon PCTFE"), partial Difluoroethylene·hexafluoropropylene copolymer (manufactured by Paper Co., Ltd., trade name “Kynar-flex 2800”), and a mixture of vinylidene fluoride and polymethyl methacrylate (relative to the trade name “Kynar” manufactured by Arkema Corporation -720" 100 parts by weight, prepared with polymethyl methacrylate (2 parts by weight))) was supplied to a second extruder, and melt-kneaded at the extrusion set temperatures described in Tables 1-5. Then, the composition for the adhesive layer and the fluorine-based resin are supplied to a manifold of the first extruder and the second extruder, and are connected to each other, and then self-connected to the sink mold. In the mold, the thickness of the adhesive layer is 0_3_ and the thickness of the I-based resin layer is 〇〇3_. Moreover, when extruding into a sheet shape from a τ 』 、 目 目 目 , , , , , , , , , τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ τ The concave and convex shape of the rule that P_ 0 does not. Thereby, the area layer of the adhesive layer formed of the composition for the above-mentioned adhesive layer is integrated, and the surface is pressed and has a long shape and has a solid width. Solar cell sealing sheet. In the above solar cell sealing sheet, the 'back layer' may be (four) or outer side. The sheet reel 2 indicates the arrangement of the embossing forming rolls of the sheet manufacturing apparatus. In addition, the use of the temporary (_), by the differential flow h of the smelting flow rate, ^ 9 field ", the quantitative analysis of the measurement of the suction curve t < peak temperature (Tm) shown in the table] Μ times... the largest of the curve is the same as the butt-West m" towel. Further, the total content of benzepene-anthracene anhydride in the modified butylene-based resin is shown in Tables 1-5. 25 201221611 It is recognized that the solar cell encapsulant obtained in the above is used to produce a flexible solar cell module in the following manner. First, as shown in FIG. 6, a rectangular sheet-shaped solar cell element A in which a photoelectric conversion layer made of a film-like amorphous germanium is formed on a flexible substrate made of a flexible polyimide film is prepared. And two rolls of the solar cell sealing sheets obtained in the above-described manner are wound into a reel-shaped solar cell sealing sheet B. Then, as shown in FIG. 6, the long-length solar cell sealing sheets B and B wound in a reel shape are respectively wound up, and the solar cell elements A are supplied to the solar cell sealing sheets provided in a state in which the respective subsequent layers are opposed to each other. Between B and B, the solar cell sealing sheets B and B are superposed on each other via the solar cell element A to form a laminated sheet c. Then, the laminated sheet c is supplied to the pair of rolls D and D heated to the temperature described in Tables 1-5, and the laminated sheet c is heated while being pressed in the thickness direction, thereby sealing the solar cell sealing sheets B and B. The solar cell module A' is then integrated to seal the solar cell element A' to manufacture the flexible solar cell module f. (Comparative Examples 1 and 2) A modified polystyrene (Comparative Example 2) which was replaced with a low-density polyethylene (Comparative Example or Substituted with a butane dicarboxylic acid anhydride) was used instead of the modified D. In addition, the "%% battery sealing sheet obtained by using the decane compound and the Dunnic resin described in Table 5" was sealed at the roll temperature described in 纟5, and was otherwise the same as the Example ,. Flexible solar cell module. (Comparative Example 3) A solar cell seal obtained by using a resin instead of a resin, and a compound obtained by using a fluorine-based resin is obtained in the same manner as in the embodiment. Flexible solar cell module 26 201221611 (Comparative Example 5) A solar cell sealing sheet obtained by using polyethylene terephthalate instead of a fluorine-based resin and using the decane compound contained in Table 5 is described in the table < The sealing was carried out at a temperature of 'in addition to this, a flexible solar cell module was obtained in the same manner as in Example 1. (Comparative Example 8) Using 77.2 parts by weight of ethylene, ethyl acrylate and butadiene 28 liters of dianhydride Ethylene obtained from the polymerization of the base _; 1 member of butenedic anhydride - ethyl acrylate platyrrome a /, eternal (EEAM, Arkema company's Lotader HX8140) instead of the enemy temporarily tauqiushan modified butene The solar cell obtained by the resin is also sealed. In addition to this, a flexible solar cell module can be obtained in the same manner as in Example 1. (Evaluation) Regarding the generation of the flexible solar electric power obtained, The appearance of curling, brother ^ Μ 4 essentials for the sensitivity of the phase and embossed shape with H 'peel strength, high temperature and high humidity resistance 夕 呆 呆 evaluation, and the results are shown in the table necessary conditions, it is not satisfied Evaluation of the solar cell element. The moisture durability and embossed shape of the t-shirt are not sufficient for the peel strength and the conditions, so the high temperature is not high. In the comparative examples 4 and 5, the solar cell is not satisfied. Evaluation of the wet durability of the component. <Production of wrinkles> 27 201221611 The occurrence of wrinkles in the flexible solar cell module obtained above was visually judged and scored by the following score. 5 points: look completely No wrinkles are produced. 4 points · Found 1 / m2 〇. Within 5mm wrinkles alone 3 S · Found 2 ~ 4 / m2 〇. 5mm or less wrinkles. 2 for. Found 5 / m2 The above is less than 5mm wrinkles. 1 point: found large wrinkles of 0.5mm or more. <Production of Curl> Place the above flexible solar cell module of size 500mmx500mm on a flat surface' The height of the end portion from the horizontal plane is measured. ◎: less than 20 mm 〇: 20 mm or more and less than 2 5 mm △ : 25 mm or more and less than 35 mm x : 35 mm or more < peel strength > The obtained flexible solar cell The module measures the peel strength when the solar cell sealing sheet is peeled off from the solar cell element in accordance with JIS K6854. <13⁄4 temperature and high humidity durability (continued)> The obtained flexible solar cell module was placed in an environment of 85 C and a relative humidity of 85% as described in JIC C8991, and every 5 hours after the above-mentioned placement was started. The peeling of the solar cell sealing sheet from the solar cell element was observed once, and the time until peeling was confirmed by the measurement. In the IC IC 8 8 9 0 which is the certification condition for the battery module, the durability of the power generation efficiency is required to be more than 10,000 hours, and the peeler will be confirmed when the time is less than 1 hour 28 201221611. It is judged that the adhesion is insufficient. <Hybrid high humidity and longevity (power generation characteristics)> The obtained flexible solar cell module was placed in an environment of 85 ° C and a relative humidity of 85% as described in C C899, using Nisshin T〇a & The 1116N manufactured by the company measures the amount of change in the maximum power Pmax. In addition, the measurement was not performed for those who had not been removed for 1,000 hours. Further, the evaluation results described in Tables i to 5 indicate the following meanings. 〉3000H: The power is maintained at %% after 3000 hours. 2〇〇〇H: The power is maintained at %% until 2000 hours have elapsed. ιοοοΗ: The power is maintained at 95% by the time of 35100" (JIS-C8991 standard). X: The power cannot be maintained at 95% after 1 hour. Since it has been peeled off after the chest is small, it is impossible to determine the extent of the embossed shape retention > the depth of the wf\y depth, thereby confirming the extent to which the initial 〇i is maintained as shown in Fig. 1 . ◎ : 0.09mm or more 〇: 0.06mm or more and less than 〇.〇9mm △ : 0.03mm or more and less than 〇.〇6mm x : less than 0.03mm 29 201221611 1Example 8 1 I 250〇c I PVDF I 〇 m oo in O 〇ο IT) ◎ 78 N/cm or more 3000 Η or more 2000 Η ◎ 1 Example 7| I 250〇C 1 PVDF T—Η 〇cn IT) 00 tn o 〇§ ο in ◎ 125 N/cm Above 2000 Η 1000 Η ◎ 1 Example 6 I 250〇C PVDF (Ν 〇cn 00 o 〇in ο in ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ | Example 5 1 250〇C 1 PVDF ψ 〇in so 〇ο ◎ 70 N/cm or more 3000 Η or more > 3000 Η ◎ Example 4 1 250 ° C 1 PVDF (N jn 〇o 〇ΙΤ) Ο in 〇 62 N/cm or more 3000 Η or more > 3000 ◎ ◎ Example 3 1 250 ° C | PVDF | ο cn 00 o 〇ο in ◎ 70 N / cm or more 3000 Η or more > 3000 Η ◎ Example 2 | 250〇C | | PVDF I CN (N oo 〇ιη ο inch〇50 N/cm or more 3000 Η or more>3000 Η1 ◎ I Example 1 | 250〇C | PVDF v〇O 00 o 〇ο 〇25 N/cm 1500 Η 1000 Η 1 〇Extrusion set temperature Fluorine resin capacity φ! .Ifhil loaded h ethylene component (% by weight) maleic anhydride total content (% by weight) MFR (g/10 minutes) Tm (t) 3-glycidoxypropyl trioxane Base decane (parts by weight) 3-propenyloxypropyltrimethoxy decane (parts by weight) Roller temperature (°c) Velocity (m/min) Wrinkle generation, peeling strength, high temperature and high humidity durability ( Next) High-temperature and high-humidity durability (power generation characteristics) Embossed shape-maintained butene-ethylene copolymer modified butylene-based resin 201221611 Example 13 250〇C PVDF VO 卜m 00 〇 〇 c>< 78 N/cm or more 3000 Η or more > 3000 Η ◎ Example 12 250 〇 C PVDF 1 < · _ * 卜 m 00 〇〇 〇〇 ο 78 N/cm or more 3000 Η or more > 3000 Η ◎ Example 11 1 250 〇 c 1 PVDF VO f·^ 卜 m 00 (N 〇in ο 〇78 N/cm or more 3,000 Η or more > 3000 Η ◎ Example 10 250 〇C PVDF 卜 00 〇 ◎ 78 N/cm or more 3,000 Η or more >3000 Η ◎ Example ^ | 250〇C | PVDF ΓΟ oo | 0.05 I 〇ίΤ) Ο in 〇25 N/cm I 1500 Η 10 00 Η 〇 Extrusion set temperature Fluororesin butene component (% by weight) Ethylene component (% by weight) Total content of maleic anhydride (% by weight) MFR (g/ΙΟ min) Tm (°C) 3-epoxy Propoxypropyltrimethoxydecane (parts by weight) 3-propenyloxypropyltrimethoxytin (parts by weight) Roller temperature (°c) Velocity (m/min) Generation of wrinkles Peel strength High temperature and high humidity durability (following) High temperature and high humidity durability (power generation characteristics) Embossed shape to maintain butadiene-ethylene copolymer modified butylene resin 201221611 [Γηί 1 Example 2l| 290〇CI ECTFE I ΓΠ 〇00 mo 〇ο ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ Example 20 290 ° C FAP m 〇m in 00 〇〇§ ο in ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ 1 Example 19|250〇C 1 PVF ro Ο iT) 00 o 〇ο ◎ 70 N/cm or more 3000 Η or more > 3000 Η ◎ | Example 18| 1 290 ° C 1 ETFE ΓΛ Ο ro 00 o 〇i 〇d 〇25 N/cm 1500 Η 1000 Η 〇|Example 17” 290〇CI ETFE J VO rn dm uo 00 o 〇in o ◎ 25 N/cm 1500 Η 1000 Η 〇 Example 16 1 250〇c 1 | PVDF | om ο inch 冢 in 〇〇m 〇 ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ | Example 15| 1 250〇c I | PVDF | Ό c\ ο 00 〇〇c> ^T) ◎ 78 N/cm or more 3000 Η or more > 3000 Η ◎ | Example 14 | 1 250〇c 1 | PVDF | VO m ON 00 un o ◎ ◎ 78 N/cm or more 3000 Η or more 1000 Η ◎ Extrusion set temperature fluororesin Jfhil w\ 乙烯 Ethylene component (% by weight) Maleic anhydride total content (% by weight) MFR (g/10 min) Tm (°C) 3-glycidoxypropyltrimethoxydecane (parts by weight) 3-propenyloxypropyltrimethoxydecane (parts by weight) Roller temperature (°c) Speed (m/min) Wrinkle generation curling Peeling strength High temperature and high humidity durability (following) High temperature and high humidity durability (power generation characteristics) Embossed shape retaining device ο & h ^ Modified butylene resin

Vi 201221611 Example 29 230〇C PVDF/PM MA Ο m 00 o 〇〇 ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ 1 Example 28| | 250〇c 1 PVDF-H FP cn 00 00 IT o 〇〇in ◎ 50 N/cm or more 3000 Η or more > 3000 Η | ◎ Example 27 1 250 〇C 1 PVDF VO mdml 〇00 md 〇d ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ Example 26 1 250 〇C PVDF \〇Os d 00 s 〇〇ο iT) 〇70 N/cm or more 3000 Η or more>3000 Η 1 ◎ Example 25 1 250〇C PVDF (N 〇m 00 in 〇〇 In ο m 〇70 N/cm or more 3000 Η or more>3000 Η 〇 Example 24 | 250〇C PVF VO o in 00 o 〇00 ON 〇 〇 70 N/cm or more 3000 Η or more > 3000 Η ◎ Example 23 300°C ETFE o ro yr\ oo o 〇ί〇CN 〇50 N/cm or more 1500 Η 1000 Η 〇Example 22 260°CJ PCTFE Ό dm in 00 mo 〇in Ο in ◎ 50 N/cm or more 3000 Η Above >3000 Η ◎ Extrusion set temperature Fluorine resin ilftiil w\ h1 Ethylene component (% by weight) Total content of maleic anhydride (% by weight MFR (g/10 min) Tm (°C) 3-glycidoxypropyltrimethoxy decane (parts by weight) 3-propenyloxypropyltrimethoxy decane (parts by weight) Roll temperature (°c) Speed (m/min) Wrinkles produce curling Peeling strength South temperature 13⁄4 wet longevity (receiving) High temperature and high humidity durability (power generation characteristics) Embossed shape to keep love ο 1遂爱1 Bu i) mu called rate id ^ 201221611 [s<] 1 comparative example 1 1 250 〇 CI 1 PVDF I EEAM 00 CN ο (Ν § ir> o 〇o 〇 70 N/cm or more XXX 1 Comparative Example 7 1 250〇 C | PVDF | o 〇cn o 00 — \D iT) o 〇in o CO <] 70 N/cm or more 1000 Η 1 X Comparative Example 6| 250〇C | PVDF | s Os 00 O 〇〇〇\ m O 〇70 N/cm or more | 2000 Η 1 X 〇|Comparative Example 5 1 1 | PET | om 00 〇〇o ^T) 〇 not up to 5 N/cm I 1 〇Comparative Example 4 1 250〇c 1 | PVF | oo cn 00 kr> o 〇in 〇 produces bubbles I 〇 is less than 10 N/cm 1 1 X Comparative Example 3 1 290〇C | | ETFE I EVA (VA content 28%) 沄o 〇§ ol produces bubbles IX stripping 1 1 1 |Comparative Example 2| 1 290〇CI | ETFE I oo H oo Ο H in o 〇〇X Peeling 1 1 1 Comparative Example 1 I 290〇CI | ETFE I oo rH o KTi CN in o 〇in m rH in o (NX stripping 1 1 1 extrusion set temperature fluororesin. Imii w\ 爱Η Ethylene content (% by weight) Total content of maleic anhydride (% by weight) MFR (g/10 minutes) Tm (°C) 3-glycidoxypropyltrimethoxy decane ( Parts by weight 3-propenyloxypropyltrimethoxydecane (parts by weight) Roller temperature (°c) Velocity (m/min) Creep of the pleats generated Peel strength High temperature and high humidity durability (continued) High temperature Wet durability (power generation characteristics) Embossed shape retention 玄 • Xuan h modified butylene resin 201221611 (Examples 3 0 to 3 4 ) The use of one of the indicated 纟6 Butene into a knife 3 S &B; If content of the dilute-ethylene copolymer graft modified to a modified TM resin (10) parts by weight, and as a (four) compound shown in Table 6 Jixian + 3-3⁄4虱propoxypropyltrimethoxydecane manufactured by J Dow Corning T〇ray, trade name "z_6〇4〇"), 2 (3,4 _% oxocyclohexyl)ethyltrimethoxy decane (D〇wc〇rning τ〇—manufactured by the company, trade name “Z6043”), 3_glycidoxypropyltriethoxy sulphur (Shin- Manufactured by Etsu Silicones Co., Ltd. under the trade name "kbe 4〇3"), Hiroshi-glycidoxypropylmethyldimethoxyl residue (manufactured by ShinEtsu smc〇nes Co., Ltd., trade name "KBM-402"), < 3 - The same composition as in Example 1 except that the composition for the adhesive layer composed of glycidoxypropylmethyl-ethoxy oxime (manufactured by Shin-Etsu Silicones Co., Ltd., trade name "KBE-402") was used. The flexible solar cell module was obtained and evaluated. The results are shown in Table 6. 35 201221611 [9<] Example 34 250〇C PVDF m 〇00 1 1 1 1 〇§ iTi ο ◎ 50 N/cm or more 3000 Η or more> 3000 Η ◎ Example 33 250〇C PVDF ΓΛ 〇m oo 1 1 1 rn 1 iT) ο ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ Example 32 250 〇 C PVDF VO ro Ο m oo 1 1 〇 1 1 m ο ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ Example 31 250 〇C PVDF Ο m 00 1 ro 〇1 1 1 in ο ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ Example 30 250 〇 C PVDF cn ο ro 00 〇 1 1 1 1 m ο in ◎ 50 N/cm or more 3000 Η or more > 3000 Η ◎ Extrusion set temperature gas-based resin butene component (% by weight) Ethylene component (weight ° / 〇) Total content of maleic anhydride ( % by weight MFR (g/10 min) Tm (°C) 3-glycidoxypropyltrimethoxydecane (parts by weight) 2-(3,4-epoxycyclohexyl)ethyltridecyloxy Decane (parts by weight) 3-glycidoxypropyltriethoxydecane (parts by weight) 3-glycidoxypropylmethyldimethoxydecane (parts by weight) 3-glycidoxy Propylmethyldi Oxydecane (parts by weight) Roller temperature (°C) Velocity (m/min) Wrinkle generation, curling, peeling strength, high temperature, high humidity durability (continued) High temperature and high humidity durability (power generation characteristics) Embossed shape The dilute-acetamidine copolymer modified butene-based resin quantitative polymer was added as the base trimethyl 6040"). The result was 201221611 (Examples 3 5 to 39, Comparative Examples 9 to 11). The dianhydride is a modified olefin-based resin having a content of an α-olefin component and an ethylene component content as shown in Table 7, and a modified olefin resin is used in an amount of 1 part by weight, and a decane compound is shown in Table 7. One of the quantified 3_glycidoxypropoxy decane (manufactured by Dow Corning Toray, trade name "ζ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The solar cell module was evaluated and shown in Table 7. 37 201221611 [Α ΐ Comparative Example 11 | 250〇c 1 1 PVDF I 1 1 〇〇I1 < 卜 (N o ο ◎ 50 N/cm or more 1000 Η 1 X Comparative Example 10 250〇C 1 I PVDF | 1 1 〇〇 m in in 〇〇<n ο m ◎ 50 N/cm or more 1000 Η 1 X |Comparative Example 9 I 1 250〇C 1 PVDF Ο 1 1 〇<N 〇mo in O ο ◎ 50 N/cm or more 1000 Η 1 X | Example 391 j 250 ° C 1 | PVDF | 1 1 oo oo in 〇〇〇 \ c5 ◎ 70 N/cm or more 3000 Η or more > 3000 Η | ◎ Example 38 1 250 ° CI 1 PVDF I 1 1 〇ΓΟ 〇m 00 Os tr> 〇〇ON in 〇〇62 N/cm or more 3000 Η or more>3000 Η ◎ Example 37 | 250〇c 1 | PVDF I 1 1 〇ro 〇ro oo o 〇Os 〇*T) ◎70 N/cm or more 3000 Η or more>3000 Η 1 ◎ |Example 36 j | 250〇C | | PVDF I 1 〇1 〇〇r—Η CN (N o wo o Ο in 〇 inch 〇 50 N/cm or more 3000 Η or more > 3000 Η ◎ | Example 35 | 250〇C j | PVDF | 1 1 gm Ο ΓΠ go in o in 〇25 N/cm 1500 Η 1000 Η 1 〇 Extrusion Setting temperature chaotic resin 1-butene 1 | 1-hexene | | 1-octene | total content of maleic anhydride (% by weight) MFR (g/10 min) Tm CC) 3-epoxypropoxy Propyltrimethoxydecane (parts by weight) Roller temperature re) Speed (m /min) Wrinkle generation, curl generation, peel strength, high temperature, high humidity durability (following), high temperature and high humidity durability (power generation characteristics), embossed shape retention vlC. 4tftlll 〇α - dilute hydrocarbon-ethylene copolymer modification α - Dilute hydrocarbon resin 201221611 (Examples 40, 41) Graft modification using a butene-ethylene copolymer having a content of a dilute component and an ethylene component as specified in Table 8 using maleic anhydride 90 parts by weight of the modified butylene resin, low density polyethylene (Asahi Kasei Chemicals, trade name "L 1 780") or linear low density polyethylene copolymer (the ethylene component amount is 84% by weight) 10 parts by weight of an ethylene-butene copolymer having a 1-butene component of 16% by weight, and 3 -glycidoxypropyltrimethoxy zebra as a compound of the smelting compound (Dow Corning Tor ay) A flexible solar cell module was obtained and obtained in the same manner as in Example 1 except that the composition for the adhesive layer composed of 0,5 parts by weight of the product was produced by the company. Evaluation. The results are shown in Table 8. [Table 8] Example 40 Example 41 Extrusion set temperature 250 〇C 250 〇C Fluorocarbon resin PVDF PVDF Maleic anhydride modified butene-ethylene copolymer blending component (parts by weight) 90 90 Butene component ( % by weight) 16 16 Ethylene content (% by weight) 84 84 Total content of maleic anhydride (% by weight) 0.3 0.3 MFR (g/ΙΟ min) 3 3 Tm (°C) 85 85 Low density polyethylene low density polyethylene 10 - Linear low density polyethylene copolymer - 10 3-glycidoxypropyl trimethoxy decane (parts by weight) 0.5 0.5 Roll temperature (°C) 90 90 Speed (m/min) 0.5 0.5 wrinkle Production of pleats 5 4 Generation of curling ◎ ◎ Peeling strength 50 N/cm or more 50 N/cm or more High temperature and high humidity durability (continued) 3000 Η or more 3000 H or more high temperature and high humidity durability (power generation characteristics) >3000 Η &gt 3000 Η embossed shape retention ◎ ◎ 39 201221611 [Industrial Applicability] The manufacturing method of the flexible solar cell module according to the present invention can be preferably manufactured by the reel method without wrinkles or curling , solar cell components and solar cells come + U β Next were mounted in the flexible solar cell excellent in mold set. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a manufacturing method of a method for manufacturing a flexible solar battery module of the present invention. Fig. 2 is a schematic longitudinal cross-sectional view showing an example of a solar cell element used in the method for producing a flexible solar cell module of the present invention. Fig. 3 is a longitudinal sectional view showing an example of a solar cell sealing sheet used in the method for producing a flexible solar battery module of the present invention. Fig. 4 is a schematic longitudinal cross-sectional view showing an example of a flexible solar battery module obtained by manufacturing the flexible solar battery module of the present invention. Fig. 5 is a schematic view showing an example of a manufacturing method of a method of manufacturing a flexible solar battery module of the present invention. Fig. 6 is a schematic view showing an example of a manufacturing method of a method of manufacturing a flexible solar battery module of the present invention. Figure 7 is a diagram showing the manufacture of a flexible solar cell module by the present invention.

^ I A schematic longitudinal cross-sectional view of an example of a flexible solar cell module. Fig. 8 is a longitudinal sectional view showing an example of a flexible solar battery module which is manufactured by the manufacture of the flexible solar battery module of the present invention. Fig. 9 is a schematic view showing an example of the uneven shape of the surface of the cold portion in an example of the apparatus for producing a solar cell sealing sheet.

40 201221611 Fig. 1 shows a schematic view showing an example of the embossed shape of the surface of a solar cell sealing sheet. Fig. 11 is a view showing an example of an embossing forming device for a solar cell sealing sheet. [Description of main components] 1 Flexible substrate 2 Photoelectric conversion layer 3 Next layer 4 Fluorine resin sheet 5 Metal plate A Solar cell element B Solar cell sealing sheet C Laminated sheet D Roller, F, G flexible sun Battery module 41

Claims (1)

201221611 VII. Patent application scope: ι_ A manufacturing method of a flexible solar cell module comprising using a pair of heat rollers to bring the solar cell sealing sheet close to at least the light receiving surface of the solar cell element, thereby performing thermocompression bonding In the step, the solar cell sealing sheet is provided with a photoelectric conversion layer on a flexible substrate; the solar cell sealing sheet has an adhesive layer composed of a cis-succinic anhydride-modified olefin-based resin on the fluorine-based resin sheet. The maleic anhydride-modified olefin-based resin has a α-olefin content of i to 25% by weight, and the olefin-ethylene copolymer is modified by maleic anhydride graft modification, and the maleic anhydride The total content of the acid needle is 0.1 to 3% by weight. 2. The method for producing a flexible solar cell module according to the invention of the present invention, wherein the fluorine-based resin sheet is composed of at least one fluorine-based resin selected from the group consisting of: PTFE Ethylene-ethylene copolymer, ethylene chlorotrifluoroethylene resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride resin, tetrafluoroethylene-six a fluoropropylene copolymer, a vinylidene fluoride-hexafluoropropylene copolymer, and a mixture of polyvinylidene fluoride and polymethyl methacrylate. 3. The method of manufacturing a flexible solar cell module according to the invention of claim 2 or 2, wherein the subsequent layer is further contained in an amount of 100 parts by weight relative to the maleic anhydride-modified modified hydrocarbon resin. 0.05 to 5 parts by weight of the decane compound represented by the formula (1): [Chemical Formula 1] Μ-Si-(〇R2)3_n (1) (wherein R1 represents 3_glycidoxypropyl or 2_(3,4) _Epoxycyclohexyl) 42 201221611 Ethyl 'R2 represents a C number of 1 alkyl group, and η is 0 or 1). Hyun: The base 'R3' indicates that the flexibility of the carbon number is 1 and the laminate is made of fluorine and is laminated. 4. For the scope of the patent, the first item, the second item or the third anode battery module. A manufacturing method in which a solar cell dense resin sheet and an adhesive layer are simultaneously formed into a film-type laminated body via a co-extrusion step. 5. For example, the method of applying for the patent scope of the first military trap, item 2, item 3 or item 4 of the flexible solar cell module is the Quanyan method, in which the 'solar battery sealing sheet The surface has an embossed shape. 43