TW201139137A - Solar cell sealing material and solar cell module produced using the same - Google Patents

Abstract

The problem of the present invention is to provide a solar cell sealing material which is easier to form a solar cell module and excellent in water vapor barrier property, flexibility, flowability and the like, and a solar cell module produced using the same. The solution of the present invention is the production of a solar cell sealing material constituted by laminating a (I) layer composed of a resin composition having a cyclic olefinic polymer as the main component, and a (II) layer composed of a resin composition having a polyolefinic polymer that has lower storage elastic modulus (E') and shear elastic modulus (G') in a specific temperature range than the resin composition which constitutes the (I) layer.

Description

201139137 VI. Description of the Invention: [Technical Field] The present invention relates to a sealing material for a solar cell element in a solar cell module and a solar cell using the same, and more particularly, relates to making solar power A easier A solar cell sealing material that is excellent in water vapority, impurities, and fluidity, and a solar cell module produced using the same. [Prior Art] A solar cell is a power generating device that directly converts solar light energy directly. Solar power generation in recent years due to the fact that it does not have to burn petroleum materials when generating electricity, and does not produce the characteristics of the gas (such as c〇2, etc.) and hazardous waste (such as crude oil ash and heavy putty) caused by the reduction. It is one of the green energy sources and has attracted attention. In order to obtain electric power from a solar cell, the structure is a straight line arrangement of 7L pieces (cells) of a plurality of solar cells. Moreover, since the solar cell is placed outside the house, the solar cell element is sealed in the resin, and the outside is protected by glass and sheet to avoid the influence of moisture and dust, and can withstand hail and small gravel, etc. Crash, or wind pressure. Such a structure is called a solar cell mold, and the structure is as follows. The surface that is in contact with sunlight is covered with a transparent substrate (glass/translucent solar cell sheet; front sheet) as an upper protective material, and is heated. A sealing material (sealing resin layer) made of a plastic plastic (for example, an ethylene-vinyl acetate copolymer) is buried in a gap, and the back surface is protected by a back sealing sheet (a back sheet such as a polyvinyl fluoride resin film). The protective material is as described above. Since the solar cell module is mainly used for a long time outside the house, it must have various characteristics such as 100106861 201139137 ==. In each of the above-mentioned protective members, the visibility of the solar cell element is protected, the flowability of the solar cell element is required, the flow characteristics of the solar cell, and the solar energy of the solar cell group are made to reach the sun ulU0 (four). Etc.) Adhesion, durability, ruler, insulation, etc. with the soil and the back sheet and the unit. Size 疋 = Sealing material used as a solar cell element in a solar cell module, for example, 夂^4丨, body (hereinafter, omitted as EVA) (Example Patent Document 丨). Further, Saki EVA imparts heat resistance as a main purpose, and crosslinks using an organic peroxide as a crosslinking agent. Therefore, a step of preliminarily making a hidden sheet which has been added with a cross-linking (organic peroxide) and a crosslinking assistant and using the obtained sheet to seal the solar cell element is employed. When using the EVA >; material to manufacture a solar cell module, according to the conditions such as heating and pressure bonding, there are the following problems: acetic acid gas is generated by thermal decomposition of EVA, which has a good influence on the working environment and the manufacturing device. Further, circuit corrosion of the solar cell occurs, or peeling occurs at an interface with each member such as a solar cell element, a front sheet, and a back sheet. Furthermore, EVA has the following problems: water vapor barrier properties are insufficient (for example, water vapor permeability in a thickness of 0.45 mm, a temperature of 40 ° C, and a humidity of 90% RH. 25 to 35 g / (m 2 · day)) When used in high humidity and other environments, moisture reaches the solar cell components, causing adverse effects, which becomes the cause of the deterioration of solar cell efficiency and power generation efficiency. Therefore, in order to solve the above problem _, the functional sealing material. For example, a cyclic olefin-based polymer which exhibits higher performance than EVA and which introduces a cyclic olefin into a known molecular chain generally has heat resistance and high transparency, and the sheet of the cyclic polymer is per unit area. The water money rate is low and the water vapor barrier property is excellent. For the aeronautical ___polymerization (four) domain battery sealing material, Patent Document 2 discloses a ring-opening polymerization of a mono-complex composed of a monomer or a monomer containing a substituent and a substituent-containing monomer. (10) The solar cell sealing material composed of the resin composition of the ring-opening polymer hydride obtained by nitriding the carbon ray as described above (4). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. SHO-58-61-579 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei No. Hei. In the resin composition used for the sealing material described in Patent Document 2, there is no description and suggestion regarding the flexibility at room temperature in this document t, and the impact on the solar cell element is not considered at all. Protective. In the general outdoor temperature (for example, 25 〇 ' 'If the storage of the resin composition used in the sealing material is too high (7) is too high, riding against external impact, etc., 100106861 201139137 solar cell components are damaged. In the above Patent Document 2, there is no mention of the sealing property of the sealing of the solar cell element, and (4), the general temperature region 8 when the solar cell element is sealed is not considered at all (rc~15 (rc When the shear modulus (G,) in the above temperature region is too high, the resin cannot be buried in the gap of the solar cell element, and the resin cannot be sufficiently sealed. The pressure is increased, but on the other hand, there are new possibilities for solar cell components and wiring deterioration caused by South Temperature, and damage to solar cell components caused by excessive pressure. For example, in batch manufacturing equipment, In the normal layer σ machine used in the sealing step, the pressure applied to the solar cell module is about atmospheric pressure (about lG1325Pa) because of the pressure difference using the vacuum degree of the vacuum system. In order to increase the pressure at the time of sealing the solar cell element, it is necessary to change the pressure-bonding method into a hydraulic type, and the production cost is high, etc., in order to increase the pressure of the sealing material as described in the above-mentioned Patent Document 2. The problem is that the previous technical towel does not provide a solar cell sealing material that is more compatible with the solar cell module, and has excellent gas barrier properties, flexibility, and fluidity, and a solar cell module using the same. The purpose of the present invention is to provide a solar cell module produced by using a solar cell sealing material which is easy to form a solar cell module and which is excellent in water vapor barrier properties, flexibility, and fluidity. 100106861 201139137 The inventors of the present invention repeated the results of the research and found that the (1) layer consisting of a resin composition having a ring-shaped thin, a condensed & a body as a main component, and a storage in a special 'soil area' The elastic modulus (E,) and the shear modulus (G,) are lower than the composition of the composition of the composition of the composition of the polyolefin-based polymer constituting the resin composition of the (I) layer as a main component. (8) The layer is laminated to satisfy the water vapor barrier 11, softness, fluidity, etc., and the present invention is completed. That is, the present invention is a solar cell sealing material characterized by having at least ()e and the following ( II) layer, and satisfying the following condition (1) and the following condition (2): "(I) layer: a layer composed of a resin composition containing a cyclic olefin as a main component (a) The layer condition (1) of the resin composition containing the ethylenic polymer as a main component is (1) at 25. (The storage elastic modulus (£,) is Ε, ι > Ε, 2. Condition (2): 8 (TC~15 (the temperature range of rc, the shear elastic modulus (7) continuously becomes the GAG, and the temperature region exists in the range above the machine. (When K and 匕 are respectively composed of the (1) layer, (_ resin composition) The storage modulus of the object, %, G, and 2 are the shear elastic modulus of the constituents, respectively. (Effect of the Invention) According to the present invention, it is possible to provide a solar cell module which is easy to form, and has water vapor depletion property, sisterness, fluidity, and durability (4) solar cell sealing material 100106861 201139137 and a solar cell using the same. Module. In particular, a solar cell sealing material and a solar cell module which are excellent in unit protection both in flexibility at room temperature and fluidity in the above temperature range are provided. If the solar cell sealing material of the present invention is used, the problem of deterioration of the wiring solar aging water caused by the wrong acid can be reduced, and the adverse effects on the working environment and the manufacturing device, and the solar cell mode can be prevented. Degradation of the group and reduction in power generation efficiency. Further, the manufacturing apparatus for the solar cell module can be applied to a manufacturing apparatus of a passenger roll type in addition to the batch type preparation. Further, since the solar cell sealing material of the present invention is excellent in water vapor barrier property, it is possible to suitably use a solar cell element which is susceptible to moisture such as power generation efficiency and durability, and for example, power generation using a CIGS system or an organic system. Sealing material for the next generation solar cell of components. [Embodiment] Hereinafter, a solar cell sealing material which is an example of an embodiment of the present invention and a solar cell module produced using the same will be described. However, the scope of the present invention is not limited to the embodiments described below. In the present specification, the term "main component" means that other components are allowed to be contained in a range that does not interfere with the action and effect of the resin constituting each layer of the solar cell sealing material of the present invention. In addition, this term does not limit the specific content rate, and is 50% by mass or more, preferably 65% by mass or more, more preferably 80% by mass or more, and more preferably 1% by mass of the constituent component of the resin composition. 〇〇106861 9 201139137 Quantities below the range of ingredients. Hereinafter, the present invention will be described in detail. The solar cell sealing material of the present invention is composed of a resin composition containing a cyclic olefin polymer as a component and has excellent water vapor barrier properties. (1) A resin composition containing a polyene-based polymer as a main component. The (H) layer which is excellent in the sealing performance and the flexibility, the fluidity, and the heat resistance is formed by the combination of the following conditions (1) and the following condition (2). Condition (1): The storage elastic modulus (E') at 25 ° C is e, i > e, 2. Condition (2): In the temperature range, the temperature range in which the shear modulus 1 (g,) continuously becomes GVG'2 exists in the range of 3 〇ΐ or more. (where 'EW, respectively, is the storage elastic modulus of the resin composition constituting the (1) layer and the (11) layer, and A, G, and 2 are the shear elastic modulus of the resin composition constituting the (1) layer, respectively. In the layer of the solar cell sealing material of the present invention, _ is composed of a resin composition containing a ring-shaped flue-cured polymer as a main component, as the above-mentioned cyclic olefin system. The type of the polymer is not particularly limited, and specific examples thereof include a cyclic olefin polymer obtained by combining one or more kinds of rings (four) and a hydride product thereof, and a linear phase and a cyclic solution. a combination of a mixture of hydrocarbons and a mixture of hydrocarbons and a mixture of hydrocarbons, and the like, which is industrially easy to obtain; t, which has a linear balance of a hydrocarbon and a cyclic olefin from the viewpoint of a good balance of transparency and flexibility. It is preferred that the aggregate polymer is 100106861 10 201139137 _ which constitutes the ring (tetra) hydrocarbon of the above-mentioned cyclic hydrocarbon-based polymer, and there is no particular P艮t ', which may be exemplified by bicycloheptan-2-ene (2_仏_

From the viewpoints of availability and various characteristics and economics, it is suitable to use (4) and 4th ring. > ), ιυ-dimercaptotetrayl_3_dodecene, and the like. a primary olefin, and tetracyclo-3·dodecene and cyclo-3-dodecene, 8-ethyltetracyclo-3~, 10-didecyltetracyclo-3-dodecene, in the present invention The type of the linear-smoke which is industrially easy to be copolymerized with the above-mentioned cyclic olefin is not particularly limited. Usually, a straight-chain α·smoke having a carbon number of 2 to 2 Å is suitable for use: Examples of the linear α-olefin copolymerized with the cyclic olefin include ethylene, propylene, 1, butyl, 1-pentane, 1-hexene, 1-g-heptene, octene, 1-decene, , 1 · 癸 thin and so on. In the case of the company, it is suitable for use as a linear hydrocarbon compound copolymerized with a cyclic olefin from the viewpoint of easy availability, various characteristics, economy, and the like. The linear OJ-olefin copolymerized with the cyclic dilute hydrocarbon may be used singly or in combination of two or more. Further, the content of the cyclic olefin copolymerized with the linear α·olefin is not particularly limited to “normally, the ratio of the linear α-olefin to the cyclic olefin is < The above is preferably 1% by mole or more, more preferably 20% by mole or more, and is usually 70% by mole or less, preferably 60% by mole. 100106861 11 201139137 or less, more preferably 5 〇 mole %the following. When the content of the cyclic olefin is increased, the heat resistance, the water vapor barrier property, and the transparency can be improved, and if the content is small, the flexibility can be improved, which is suitable. When the content of the cyclic olefin is within this range, the crystallinity is lowered by the copolymerization component to exhibit transparency, and it is also difficult to cause discomfort such as agglomeration of the raw material particles. Further, the type and content of the cyclic olefin copolymerized with the linear oxime-olefin can be qualitatively and quantitatively analyzed by a known method, for example, a nuclear magnetic resonance (NMR) measuring apparatus or another apparatus for analyzing the apparatus. The above-mentioned cyclic olefin-based polymer, for example, is disclosed in JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, and JP-A-61-115916. It is produced by a known method described in, for example, JP-A-61-271308, JP-A-61-272216, and JP-A-62-252. As a specific example of the above cyclic olefin-based polymer, Mitsui Chemicals can be exemplified

The product name "TOPEL" made by the brand name "APEL" and the TOPAS ADVANCED POLYMERS (stock) system. The water vapor barrier property of the composition of the above-mentioned ring (tetra) hydrocarbon-based polymer as a main component can be determined as long as the shape and thickness of the solar cell element and the solar cell module of the test application and the installation place are difficult. For example, regarding a sheet made of a thickness of 〇.3 mm or 〇.45 mm, the water vapor transmission rate in the temperature 仞ΐ, humidity (d) RH (measuring method: ^κ7ΐ27) is preferably less than lg/(m2). ·天), preferably less than G 8 coffee 2 • day), then good 100106861 12 201139137 is less than 0.6g / (m2 · day). When the water vapor transmission rate is in the above range, corrosion of the wiring and deterioration of the solar cell element can be suppressed, which is suitable. For example, by adjusting the ring-shaped _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Frequency: ihz, temperature increase: 3 ° C / min, strain 〇. 1% of the measured storage elastic modulus (hereinafter, referred to as E '1), as long as the application of the solar cell shape and thickness, installation location The adjustment may be appropriately performed, and is usually 1 MPa (lxl 〇 7 Pa) or more and 5000 MPa (5 x 10 〇 9 Pa) or less. Here, considering the cushioning property and flexibility of the impact on the solar cell module, and the rigidity of the solar cell module support and the operability at the time of manufacturing the solar cell module, the resin composition of the layer (7) is formed. The storage elastic modulus (E'!) is preferably 5 〇 MPa (5×10 〇 7 Pa) or more and 3000 MPa (3×10 9 Pa) or less, and more preferably i 〇〇 Mpa (ixl 〇 8 Pa) or more and 2000 MPa (2×10 9 Pa) or less. (11) The layer of the solar cell sealing material of the present invention, wherein the layer (11) is a layer composed of a resin-based polymer having a polystyrene-based polymer as a main component, and is characterized in that The storage elastic modulus of the resin composition at 25 C (hereinafter referred to as &) is lower than the above E, (condition (1)), and in the temperature range of 8 〇〇 c 15 (rc), the resin The shear modulus of the composition (hereinafter referred to as G, 2) is continuously lower than the shear modulus of the resin composition constituting the layer (1) (hereinafter, '', 卜, called G'i) 100106861 13 201139137 In the range of the above-mentioned temperature range, the condition (2) is given. Specific examples of the preferred polyolefin-based polymer are exemplified below, and the resin may be used singly or in combination of two or more. The layer composed of the resin composition containing the polyolefin-based polymer as a main component may be a single layer, and two or more layers may be laminated. The polyolefin-based polymer used in the layer (II) of the present invention may be used. Kind, as long as the (9) layer satisfies the above-mentioned storage elastic modulus (E,) and shear elastic modulus (G,) The above conditions (1) and (2) are not particularly limited, and at least one selected from the group consisting of a polyethylene polymer, a polypropylene polymer, and a modified polyolefin polymer is preferred. The type of the polyethylene-based polymer is not particularly limited, and specific examples thereof include ultra low density polyethylene, low density polyethylene, linear low density polyethylene (ethylene-α-olefin copolymer), and medium density polyethylene. High-density polyethylene, ultra-high-density polyethylene, etc. Among them, linear low-density polyethylene (ethylene-α-olefin copolymer) has low crystallinity and excellent transparency and flexibility, so it is difficult to hinder solar cell elements. It is preferable that the power generation characteristics are excessive stress on the solar cell element and cause discomfort such as damage. The ethylene-α-olefin copolymer may be a random copolymer and may be a block copolymer. The type of the terpene olefin to be copolymerized is not particularly limited. Usually, an α-olefin having 3 to 20 carbon atoms is suitably used. Here, examples of the olefin copolymerized with ethylene include propylene and 1-butene. , 1-pentene, 1-hexaped, 1-heptacene, 1-octyl, 1-indene, 1-indene, 3-mercapto-100106861 14 201139137 Dingsib 4_methyl.pentene· i. In the present invention, it is suitable for the co-olefins with Ethylene: i.e., propylene, i, butene, b, and bismuth, from the viewpoints of industrial availability, various characteristics, economy, and the like. It is also possible to use a mixture of two or more of the olefins, and it is also possible to combine two or more kinds of the olefins. The content of the α-olefin to be copolymerized with ethylene is not particularly limited.合! - The total amount of olefins is 2 moles / 〇 or more, preferably 3 mole % or more, more preferably 5 mole % or more, and usually 2 mole % or less, preferably 30 moles. Less than or equal to the ear, and preferably less than 25 mol%. When it is in this range, the crystallinity is lowered by the copolymerization component to improve the transparency, and it is also difficult to cause discomfort such as agglomeration of the raw material particles. Further, the type and content of α-cationic hydrocarbon copolymerized with ethylene can be qualitatively and quantitatively analyzed by a known method, for example, a nuclear magnetic resonance (N M R) measuring apparatus or other machine analysis. The method for producing the polyethylene-based polymer is not particularly limited, and a known polymerization method using a known catalyst for olefin polymerization can be employed. For example, a multi-site catalyst represented by a Ziegler-Natta type catalyst, and a single site catalyst represented by a metallocene catalyst and a post-metallocene catalyst may be used. A polymerization method, a polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like, and a block yarn mixture of a (four) based initiator is used. As a solar cell, the (10)·_hydrocarbon mixture is preferably softer than __, and is easy to use after the polymerization (filtration) and prevent the purity of the raw material. 100106861 1<: 201139137 A polymerization method using a single site catalyst which is polymerizable with a raw material having a small molecular weight component and a narrow molecular weight distribution is suitable. Specific examples of the polyethylene include the trade names "Hizex", "Neozex", "Ultzex" manufactured by Prime Polymer, and the trade name "Novatec HD" manufactured by Japan Polyethylene / Co., Ltd., and "N〇vatec". TL", "Novatec LL", "Karnel", Dow Chemical ("Engage", "Affinity", "Infuse", Mitsui Chemicals Co., Ltd. under the trade names "TAFMER A", "TAFMER P" "Umedt" manufactured by Ube Maruyama P〇iyethylene Co., Ltd., and the trade name "rcliolex" manufactured by Asahi Kasei Chemicals Co., Ltd.". The type of the polypropylene-based polymer is not particularly limited, and specific examples thereof include a homopolymer of propylene, a copolymer of (4), a reactor-type polypropylene-based thermoplastic elastomer, and a mixture thereof. Examples of the propylene copolymer include a random copolymer of propylene and ethylene or other aliphatic hydrocarbons (random polypropylene), or a block copolymer (year-old polypropylene), and a block containing a rubber component. a copolymer or a graft copolymer or the like. As another α·smoke which can be copolymerized with the above propylene, it is preferred that the number of carbon atoms is 4 to 12, for example, ?butene, ι pentene, hexene, and heptene 1 octene 4-mercapto pentacene, ruthenium or the like may be used, or a mixture of two or more thereof may be used. In addition, the content of the rare smoke which is copolymerized with the propylene is not particularly limited, and is usually 2 mol% or more, preferably 3 mol% or more, and more preferably the total amount of the propylene and the slope. It is preferably more than 45% by mole, and usually 100,106,861, 201139137 is 40 mol% or less, preferably 30 mol% or less, more preferably 25 mol or less. If it is recorded _, the age of the copolymer is reduced to a high degree of transparency, and it is also difficult to cause discomfort such as agglomeration of the raw material particles. Further, the type and content of the Of-olefin copolymerized with propylene can be qualitatively and quantitatively analyzed by a conventional method such as a nuclear magnetic resonance (NMR) measuring apparatus or another machine analysis. The method for producing the above-mentioned polypropylene-based polymer is not particularly limited, and a known method for using a known catalyst for olefin polymerization can be employed. For example, a multi-site catalyst represented by a Ziegler Natta type catalyst, and a single-site catalyst represented by a metallocene catalyst and a post-metallocene catalyst may be used for slurry polymerization or solution polymerization. A bulk polymerization method, a gas phase polymerization method, or the like, and a bulk polymerization method using a radical initiator. The propylene-α-olefin copolymerization system used as a solar cell sealing material is preferably a softer resin, and is used from the viewpoints of easiness of granulation (granulation) after polymerization and prevention of agglomeration of raw material particles. A polymerization method of a single site catalyst in which a raw material having a low molecular weight component and a narrow molecular weight distribution is polymerizable is suitable. 'As a specific example of the above-mentioned polypropylene-based polymer, the product name "Novatec PP", "Wintec", and Prime Polymer (product) manufactured by 曰本 pl〇lypr0 (share) can be exemplified as "Prime Polypro", " Prime ΤΡΟ", Sumitomo Chemical Co., Ltd.'s trade name "No brene", etc. The type of the modified polyolefin-based polymer is not particularly limited, and is composed of EVOH (ethylene-vinyl alcohol copolymer), E-MMA (ethylene-mercapto acrylate, 100106861 17 201139137 polymer), E-EAA (ethylene). - ethyl acrylate copolymer), propylene-glycidyl acrylate copolymer, ionic polymer resin (ethylene-mercapto-acrylic acid copolymer, ion-crosslinkable ethylene-dividing polymer), decane It is preferred that the crosslinkable polyolefin and the maleic anhydride are grafted with at least one selected from the group consisting of the above. ", poly. The method for producing the modified polyolefin-based polymer is not particularly limited, and the ionic polymer resin and the decane cross-linking polyolefin described below are in addition to the "Bertin-I-anhydride graft copolymerization". A well-known polymerization method using a known olefin polymerization, for example, a solution of a single site catalyst represented by a Ziegler nata type catalyst, a catalyst of a ceramsite, and a metallocene catalyst is used. A polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like can be obtained by a bulk polymerization method using a mouth-based initiator. The ionic polymer resin is a metal ion or an organic amine which is at least a part of the unsaturation of a silky body composed of ethylene, an unsaturated acid, and other non-fresh compounds as an optional component. At least one of them - obtained from Zhonghe. Further, the ionic polymer resin may be formed by condensing ethylene, ? = ester, and other unsaturated compounds as optional components. At least part of the body's disability and test ingredients are obtained and verified. In the case of the smouldering of the smoky smog, it is obtained by melt-mixing a poly-smoke-based resin, a squid, and a radical generating agent, which will be described later, at a high temperature, and graft polymerization. 100106861 18 201139137 The maleic anhydride graft copolymer can be obtained by melt-mixing a polyolefin resin, maleic anhydride, and a radical generating agent described later at a high temperature and graft polymerization. Specific examples of the modified polyolefin-based resin used in the present invention include a "NUC" series manufactured by Uni本 Uniker Co., Ltd., and an EVOH (ethylene-vinyl alcohol copolymer) exemplified by 曰本合成化学(股) The product name "Aval" manufactured by Sumitomo Chemical Co., Ltd., as the product name "Eval" manufactured by CURALE, and the product name "Acrift" manufactured by Sumitomo Chemical Co., Ltd., as the E-MMA (ethylene-methacrylate acrylate copolymer) The E-EAA (ethylene-ethyl acrylate copolymer) can be exemplified by the product name "REXPEARL EEA" manufactured by Sakamoto Polyethylene Co., Ltd., and the E-GMA (ethylene-glycidyl methacrylate copolymer) can be exemplified by Sumitomo Chemical Co., Ltd. The product name "BONDFAST" manufactured by the company (M) is exemplified as the product name "Himilan" manufactured by Mitsui Dupont Polychemical Co., Ltd., and the trade name of Mitsubishi Chemical Co., Ltd. as a decane crosslinkable polyolefin. "Linchrone" and the maleic anhydride graft copolymer are exemplified by "Adomer" manufactured by Mitsui Chemicals Co., Ltd., and the like. The preferred melt flow rate (MFR) of the above polyolefin-based polymer, for example, 'in the case of polyethylene,' MFR (JIS K721 〇, temperature: 19 〇 ° C, load: 21.18 N) is preferably 〇. 5 g / 10 min or more, more preferably 2 g/1 〇 min or more, still more preferably 3 g/10 min or more, and more preferably 3 〇 g / 1 〇 min or less, more preferably 25 g/10 min or less, and still more preferably 2 〇 g / 1〇min or less. Further, the MFR is selected in consideration of the moldability at the time of producing a sealing material and the degree of attachment, expansion, and the like when sealing the solar cell element of 100106861 19 201139137. For example, when the sheet is formed by a pulverizing machine, the MFR is preferably lower than the operability when the sheet is stretched and pulled, specifically, 〇5 yi 〇 min or more, and 5 g/10 min or less. Further, when extrusion molding is performed using a τ-type mold, mfr is preferably 2 g/10 min, more preferably 3 g/1 〇 min or more, and is preferably from the viewpoint of reducing the crushing load and increasing the amount of extrusion. It is 30 g/10 min or less, more preferably 2 〇 g / 1 〇 min or less. Further, from the viewpoint of the adhesion at the time of sealing the solar cell element (unit) and the ease of expansion filling, the MFR is preferably 2 g/l 〇 min, more preferably 3 g/min or more, and preferably 30 g. /10 min or less, more preferably 2 〇 g / 1 〇 min or less. <Other resins used in the (1) layer and the (II) layer> The resin composition constituting each of the (1) layer and the (11) layer of the solar cell sealing material of the present invention does not deviate from the gist of the present invention. In the range, the above-mentioned cyclic olefin-based polymer and polyolefin-based polymerization may be contained for the purpose of further improving physical properties (softness, heat resistance, transparency, adhesion, etc.) and moldability, economy, and the like. Resin other than body. The resin may be mixed only in the (1) layer or only in the (II) layer, and may also be mixed in both the (1) layer and the (11) layer. Examples of the resin include other polyolefin-based resins and various elastomers (olefin-based, styrene-based, etc.), an ester group, an amine group, an acrylamido group, a thiol group, an epoxy group, and a carbazole. A polar group-modified resin such as a phenyl group or a thiol group, or an adhesion-providing resin. Examples of the adhesion-imparting resin include petroleum resin, (iv) resin, coumarin 100106861 201139137 ketone, a section resin, a rosin-based resin, or a hydrogenated derivative thereof. Specifically, = petroleum resin, an alicyclic petroleum tree cerium derived from cyclopentadiene or a dimer thereof, and an aromatic petroleum resin derived from a C9 component, and a terpene derived from a terpene resin. The resin and the terpene-phenol resin, and the rosin-based resin may, for example, be a rosin resin such as rosin gum or turpentine, or an esterified rosin resin modified with glycerin or pentaerythritol. Further, the adhesion-imparting resin mainly has various softening temperatures depending on the molecular weight, and is compatible with the polyolefin-based polymer component, the compatibility, the bleed property, the color tone, the thermal stability, and the like. The particularly preferred softening temperature is preferably 1 Torr or more, more preferably 12 〇〇 c or more, and is preferably a hydrogenated derivative of an alicyclic petroleum resin having 15 or less, more preferably 140 〇 c or less. When the resin other than the above-mentioned polyolefin-based polymer is mixed, usually, when the target layer to be mixed, that is, the resin composition of each layer is 1 part per mu, it is preferably 20 parts by mass or less, and more preferably 1 part by mass or less. In addition, in the resin composition constituting each of the (1) and (H) layers of the solar cell sealing material of the present invention, various additives may be added as needed. For example, a free radical generator (crosslinking agent/crosslinking aid), a decane coupling agent, an antioxidant, a UV absorber, a fuel stabilizer, a light diffusing agent, a nucleating agent, a pigment (for example, a white pigment), and a flame retardant. Agent, anti-discoloration In the present invention, it is preferable to use at least one additive selected from the group consisting of a radical generating agent, a sulphur coupling agent, an ultraviolet absorber, and a weathering stabilizer, such as the reason described later, etc. 100106861 21 201139137. It may be added only to the above (1) layer or to the above (8) layer, and may be added to both the above (I) layer and the above (II) layer. [Free radical generating agent] Free radical generating agent (crosslinking) When the above-mentioned polyfluorene-based polymer is used for a solar cell sealing material, it has a cross-linking structure for the purpose of achieving heat resistance and mechanical strength, and is a free radical. The generating agent is not particularly limited, and examples thereof include an organic peroxide; an azo compound such as azobisisobutyronitrile (鸠N) or a polymer azo compound, an organometallic compound such as propylpropyltin or triethylguanidin Among them, in terms of the reaction rate and the safety at the time of blending, 'organic peroxide, _ is at 100. 〇 generates radicals' and the decomposition temperature at a half-life of 10 hours is 7 〇 (the above is suitable for use). As such a free radical As the green agent, for example, 2,5-dimercaptohexane, _2'5-monohydroperoxide, 2,5-dimercapto-2,5-di(t-butylperoxy) can be preferably used. Benzene; 3-di-tert-butyl peroxide; third-diisopropylphenyl peroxide; 2'5-dimercapto-2,5-di(t-butylperoxy) Block; triisopropylphenyl peroxide, α,α-bis(t-butylperoxyisopropyl)benzene; n-butyl-4,4-bis(t-butylperoxy)butane 2,2-bis(t-butylperoxy)butane;^-bis(t-butylperoxy)cyclohexane; U•bis(t-butylperoxy)3,3, 5 tridecylcyclohexane; tert-butylperoxy succinate; benzoquinone peroxide, etc. The amount of the radical generator added, in order to suppress the increase in resin pressure, and When a foreign matter such as a gel or a white spot is generated, and in order to suppress the residue (such as oozing out of the product), it is set to (10) parts by mass, and the resin composition constituting each layer is (10) parts by mass, and 5f is used. The following parts are preferred and are preferably 3 〇 2: 2: more preferably. In addition, in order to carry out the crosslinking reaction efficiently, it is preferable to use G·5 parts by mass or more, and more preferably 0.75 parts or more. [Centane coupling agent] A stone coupling agent is used to improve the protection of solar cell sealing materials (glass, resin, front, back, etc.) and solar cell trees. , alkoxy group, an unsaturated group of a methyl group, an amine group, an epoxy group, etc., and a compound such as a oxy group. As a specific example of the mixture of the gift, it can be exemplified by propyl propyl methoxy, NI amine ethyl, methacryl dimethyl dimethyl phthalate, γ propyl propyl ethoxylate, γ epoxide Propoxypropionate dimethoxy Wei, Τ·methacryl oxiranyl trimethoxy Wei and the like. In the present invention, it is more expensive to use 7•epoxypropoxylate three? Oxygen and ^ methyl propyl methacrylate methoxy mechanical, due to good mixing, and yellow discoloration. The amount of the addition agent to be added is equal to the target layer to be added, that is, the amount of the reading layer f of each layer is formed, and in order to suppress an increase in the resin pressure and generate foreign matter such as gel or white spots, it is also unsuitable for suppression or the like. The lower part is better, and the amount is 3f or less to become the opening: =, in order to express the adhesion, it is better to use more than 5% by mass, and more preferably in parts by mass. Acidic acid 100106861 23 201139137 Compounds and other coupling agents can also be effectively used. [Ultraviolet absorber] As a UV absorber, various commercial products can be used, including diphenyl _ series: Benzene, three saliva, three lectures Various types, such as a benzophenone-based ultraviolet absorber, for example, 2·min·4·methoxybenzophenone 2 H4-methoxy 2,_yl group Benzophenone, 2_transyl-4 octyloxybenzophenone 2, keto-4-n-dodecyloxy, adipic, 2, keto-n-butyl oxo-oxybenzene Base _4_ oxy benzophenone, 2 _ _ _ _ _ _ _ _ _ _ _ benzoic benzophenone, 2 · thiol _ 5 chloro benzophenone, 2, 4- Dibenzophenone, 2, 2, '_ dipyridyl 4. methoxybiphenyl, 2, 2, _ two meals: methoxy benzophenone, 2,2,4,4,-tetracarboxylic benzophenone, etc., as benzodiazepine ultraviolet The absorbent may, for example, be a benzotriphenyl compound substituted with a phenyl group, for example, 2-(2-carbyl-5-fluorenylphenyl)benzotrisole, 2-(2-hydroxy-5-butylphenyl)benzene And three saliva, 2 · (2_ mercapto_3,5-didecylphenyl) benzotriene, 2 methyl ketone by phenyl) benzotrisodium, 2 pucosyl winter methyl Butyl phenyl) benzodiazepine, 2 (2-carbyl-3,5-di-tert-decylphenyl) benzo-spin 2 (2-carbyl- 3,5-di-t-butyl phenyl Base) benzotriazine and the like. Further, as a three-spray ultraviolet absorber, 2_[4,6-bis(2,4-didecylphenyl)_1,3,5-tris-2-yl]-5-(octyloxy) can be cited. Benzene, 2_(4,6 diphenyl-1,3,5-tris 4-2-yl)-5-(hexyloxy)phenol, and the like. Examples of the salicylic acid vinegar system include salicylic acid benzene and salicylic acid. The amount of the ultraviolet absorber to be added is usually 0.01 parts by mass or more, preferably 〇〇 5 parts by mass or more with respect to the target layer to be added, that is, the resin composition constituting each layer 100106861 24 201139137 10 parts by mass. It is preferably added in an amount of 20 parts by mass or less, preferably 5% by mass or less. [Weather-Resistant Stabilizer] A weather-resistant stabilizer that imparts weather resistance to the ultraviolet absorber other than the above-mentioned ultraviolet absorber is suitably used as a parent-resistant fee-based light stabilizer. The hindered amine light stabilizer does not absorb ultraviolet rays like an external absorbent, but exhibits a remarkable synergistic effect by being used in combination with an ultraviolet absorber. In addition to the hindered amine system, it also functions as a photosensitizer, but it has many coloring conditions and is inferior to the solar cell sealing material of the present invention. As the hindered amine-based light stabilizer, didecyl succinate-1 - (2-hydroxyethyl M-carbyl-2,2,6,6-tetramethylpiperidine polycondensate, polymethylbutyl group) Amino-1,3,5_3 4_2,4_diyl}{(2,2,6,6-tetra-yl-4-bryridinyl)imido}hexamethylene { {2, 2,6,6 tetramethyl-4(piperidinyl sulfoximine iodide'-bis(7)aminopropylated diamine-recognized butyl-butyl-pentamethyl-4-piperidinylamine ]]·6_Chloro·trientene condensate, double 0.01 parts by mass... parts by weight, (2,2,6,6-tetramethyl-4-exidyl) sebacate, 2_(3, 5_2rd third_4_ succinctyl)-2-n-butylmalonic acid bis (1,2,2,6,6-pentamethyl·4·Nylon bite mask. etc. The amount of the silking agent added is usually 1 part by mass based on the target layer to be added, that is, the resin composition constituting the above (I) layer or the above (11) layer.

100106861 25 201139137 The above-mentioned ultraviolet absorber and coffee stabilizer, (10) is more likely to cause yellowing, so the minimum amount of heart in the county (4) is more than the above (8) layer to form the above-mentioned series _ polymer body fat composition of the soft Secret, can (4) set the material state _ knife tree rate, heating rate 3t / min, strain 〇 1% of the vibration frequency of the storage bomb (four) number (E, such as Kazaki estimates, important shirt lighter than ^ said (1) The resin composition of the layer in the hunger storage _ number (the storage elastic modulus (E,) in the formation of hunger, through the satisfaction of ~ even if ^ ice and small shirts and other materials from the external material will When the solar cell element enclosed in the (four) tree = is damaged, the impact resistance is excellent. From the above viewpoint, when the storage elastic modulus (E) is marked in MPa units, the above E, 2 satisfies EV20 (four), and 2 is preferable, and Satisfy e, Okazaki η is better' and E'r800^E, 2 is particularly good. 25. (: The storage elastic modulus of the resin composition of the (9) layer (Ey, as long as the solar cell is considered Appropriate adjustment with thickness, installation location, etc. 'Normally, 0.1 MPa (lxl 〇 5pa) or more, 5 〇〇 Mpa (5xl 〇 8p) a) In the following, the storage elastic modulus of the resin composition constituting the (1) layer is considered in consideration of the cushioning property and flexibility of the impact on the solar cell module, and the operability in the manufacture of the solar cell module. (E, 2) is preferably 5 MPa (5xl 〇 5 Pa) or more and 300 MPa (3 x 108 Pa) or less, and more preferably 1 MPa (1 χ 1 〇 6 Pa) or more and 200 MPa (2 x 10 08 Pa) or less. The fluidity of the resin composition of the layer can be set according to the rheometer 100106861 26 201139137. The flow rate is set to the oscillation frequency: 1 Hz, the temperature increase rate is 3 〇 c / minute, and the strain is 0.5%. 8 (TC ~ 150 °) The shear elastic modulus (G'2) in the temperature range of c is evaluated, and it is important that it is continuously lower than the temperature region of the shear elastic modulus (G, !) of the resin composition constituting the above (1) layer. It is present in the range of 30 ° C or more. In the range of 80 ° (: 15 °C, the shear elastic modulus (G') continuously becomes g'ag, and the temperature range of 2 is 30 ° C. The above range exists, and it is difficult to be affected by temperature oscillations and the like in the sealing step, presenting stability and for solar cell elements and The sealing property of the concavities and convexities in the wire detail is good. In these cases, the shear elastic modulus (G,) is continuously set to G, i > G, and the temperature range of 50 is more preferably 50 ° C or more. In order to make the shear elastic modulus (G') continuously become the temperature range of G'pG'2, the maximum value is 80 ° c ~ 15 〇! 5 (: the temperature range ' is mainly set to 7 〇〇 c. °C to 150. (: The shear modulus of the resin composition of the (11) layer in the temperature range (G'2) can be appropriately adjusted by considering the shape, thickness, and installation location of the solar cell to be applied. It is preferably M1 Mpa (lxl 〇 3 Pa) or more, more preferably 0.005 MPa (5×10 3 Pa) or more, further preferably 〇〇 1 Μ ρ & (1×10 Pa) or more, and preferably 1 MPa (lxl 〇 6 Pa). The following is more preferably -0.5 MPa (5xl 〇 5 Pa) or less, and further preferably 〇 2 MPa (2 x l 〇 5 Pa) or less. When the upper limit of the shear modulus (G, 2) is in the above range, the sealing property of the unevenness in the solar cell element and the wiring detail is appropriate, and the lower limit of the shear modulus (G'2) is appropriate. If it is in the above range, it is difficult to cause damage to the solar cell element due to excessive stress or damage to the solar cell module, and it is preferable that the solar cell element 100100861 27 201139137 is damaged. The storage elastic modulus (e, 2) and the shear elastic modulus (G'2) of the resin composition constituting the above (π) layer are within the range specified by the invention, for example, as long as the resin composition is used. The crystallinity of the main component polyolefin-based polymer and the mfr (melt flow rate) may be selected as appropriate standards. More specifically, for example, the polyolefin-based polymer used in the above (II) layer can be subjected to the condition (2) specified in the present invention by selecting the α-olefin content and the MFR to the above range. ~15 (In the temperature range of TC, the shear modulus (σ) is continuously G'PG, and the temperature range is 3〇. (The above range is fully achieved, but it is not limited to such a means.) Solar cell sealing material The solar cell sealing material of the present invention is obtained by laminating the above (1) layer and the above-mentioned shell). The layer (1) and the layer (11) are layered as long as at least i layers. Although it is not particularly limited, it is preferable that the surface layer of at least one of the above-mentioned (II) layer is used as the sealing material for the purpose of improving the sealing performance when manufacturing the solar cell module using the solar cell sealing material of the present invention. Specifically, it is of course possible to adopt two kinds of two layers of the (I) layer/(II) layer (Fig. 2), and two kinds of three layers of the (II) layer/(I) layer/(II) layer can be used. Two types of four-layer structures (not shown) of the (Fig. 3) and (11) layers/(1) layers/(11) layers/(I) layers are formed. In the case of such a configuration, It is preferable to apply the solar cell sealing material of the present invention in such a manner that the above (II) layer is on the side of the solar cell module of the present invention. [100106861 28 201139137 The solar cell sealing material of the present invention The film forming method is not particularly limited, and a known method can be employed, for example, a melt mixing device having a single screw extruder, a multi-screw extruder, a Banbury mixer, a kneader, etc., and using a τ-type mold Extrusion (four) method (4) photo method, etc. For example, the above (I) layer and the above (9) layer are respectively formed into a film according to the above method, and the layers are laminated by a known method such as thermal lamination, and the present invention may be applied. The solar cell sealing material is formed into a film. In particular, in the aspect of workability and productivity, a co-extrusion method using a plurality of multi-layer molds is suitably used. To the funnel, the material is melt-mixed and pelletized (4) and then supplied to the co-extrusion method using the laminated mold. The forming temperature is appropriately adjusted depending on the flow characteristics and the crucible properties of the resin composition to be used. , about 8 〇ΐ or more, preferably HKTC or more, more preferably 12 (rc or more, more preferably 14 or more generations) and A 300 ° C or less, preferably 2 or less, more preferably the following, and more preferably 18GX: The following is the case where a radical generator and a Wei coupler are added. In order to suppress the increase in the resin pressure and the white point with the crosslinking reaction, the molding temperature is preferably lowered. The radical generator, the money coupling/ Various additives such as antioxidants, ultraviolet absorbers (4), weathering stabilizers, etc.

100106861 It is also possible to perform embossing processing and various concavities (cone and pyramid shapes and hemispheres, etc.) for the purpose of (4) roll-to-roll (four) materials, battery elements in the sealing operation, and the ease of extraction of air 29 201139137. )machining. In addition, when the film is formed into a film, in order to improve the workability in film formation, etc., it is also possible to use other substrates (elongated poly(tetra) film (OPET) and extended polypropylene film ((10)). Further, the total thickness of the solar cell sealing material of the present invention is not particularly limited, and it is usually 0.05 mm or more, preferably 〇 linm or more, more preferably ^^ . The above 'and 'lmm or less, preferably 〇8 or less, more preferably 〇'2 or less. The total thickness is set to the above range, in addition to water vapor barrier properties, workability and operability The water vapor barrier property of the solar cell sealing material of the present invention may be appropriately adjusted in consideration of the type of the solar cell element to be applied, the shape and thickness of the solar cell module, the installation place, and the like, for example, ' Solar cell sealing material: thickness: water vapor permeability in 〇.3mm, temperature thief, humidity 9〇% RH (measured: method: JIS K 7127) is preferably less than 4g / (m2 · day), more Jia is less than 2g/(m2 · day)' and then better than less than lg/(m2·day). The water vapor transmission rate (measuring method: jisk · 7127) in the thickness of 〇45 surface, temperature iron, humidity 90% RH is preferably less than 4g/(m2.day), more preferably less than city, day ), again. Jia is less than l / (m2 • day). When the water vapor barrier property is in the above range, it is possible to suppress wiring clogging and deterioration of the solar cell element. The thickness of the (1) layer and the (11) layer in the solar cell sealing material of the present invention is in the thickness of the solar cell sealing material of too 100106861 30 201139137, that is, when the total thickness of each layer is set to 1 GG%, the thickness of the (1) layer is The limit value is preferably 1 G%, more preferably war, and more preferably 4% by weight, and the 'upper limit value is preferably 90%, more preferably 8 % by weight, and still more preferably 6 % by weight. If the lower limit of the thickness of the layer (1) is the above range, the hydro-blocking property is appropriate. • If the upper limit of the thickness of __ is the domain flip, the sealing performance of the solar cell component and the wiring detail is suitable. . The heat resistance of the solar cell sealing material of the present invention. In general, the solar panel group rises by about 85 90 C by the heat generated during power generation and the heat of the sun. In addition, the long-term shadow caused by poor soldering and falling leaves causes the resistance of the solar cell element to rise, and there is also a fever to the vicinity of i〇〇°c (hot spot phenomenon, in order to suppress the flow of the sealing material, etc., a method of forming a crosslinked structure by using the above-mentioned radical generating agent, a Wei coupling agent, or the like; a method of using a mixed crystal to dissolve a crystalline resin having a high peak temperature; and a method of using or mixing a resin having a high glass transition temperature. In the invention, there is no special addition, but (4) the method of forming a crosslinked structure and mixing a crystalline resin having a high peak temperature of crystal melting, from the viewpoints of balance between flexibility and heat resistance of the warm towel and economy. The method is suitable for use. Here, the temperature of the surface crystal cleavage peak of the ❹ crystalline resin is 10 (TC or more 'more preferably, it is more than the above machine, and more preferably U (rc or more. Further, 160 ° C or less). Preferably, it is preferably 15G or less, and preferably 145 (the following is more preferably below uet. If the upper limit temperature is above _, the sealing step of the solar cell component can be sealed at a high temperature, so it is preferable, and The lower limit temperature 100106861 31 201139137 degrees is appropriate if it is in the above range. The shaft of the solar cell which is not the solar cell sealing material of the present invention, such as the flow of the sealing material in long-term use, for example, is not required to be worn. The application is too close to the solar cell element's cut light (4) and the like, and does not obscure the surface of the patch, etc. (for example, the solar cell element and the back are sometimes not too shameful: the operation efficiency when changing the efficiency and the various components overlap Etc.: Considering that the solar cell is better and more than 9〇% is a better inferior 'usually 85% or more> solar cell module> using the solar cell of the present invention _ the surface element of the protective material by means of upper and lower =Module. As such a (four) pool module ^ to make a solar power lift, for example, to protect the case from the above, not to all types. Can be listed as a sealed shaft coffee break cell battery component / Si::- her,: at == ^ In the solar cell module using the solar cell sealing material of the present invention, the solar cell module using the solar cell sealing material of the present invention is sealed only by the positive battery of the present invention. Material can also be used 1 or only in the area When the sealing material is used in two or more parts of the invention, the H-cell battery sealing material of the present invention is used in all the parts, and the Japanese-made 100106861 32 201139137 constitutes a sealing material. When the sealing material is used in two or more places, The composition of the present invention may be phased or different. The battery component is disposed between the sealing layers of the tree, for example, multi-junction amorphous (tetra), gallium- Kun-, organic film type, etc. Cattle-conductor type, dye-sensitized type, and money parts constituting a solar cell module produced by using the solar cell sealing material of the present invention, for example, glass protective material fluorine = Layer or multi-layer protective material. As a lower protective material, it is a single layer of enamel layer such as gold 2 various heat-resistant ship resin films, such as: tin, inscription, non-recorded steel, etc., inorganic materials such as glass, and poly Ester, inorganic vapor deposition, S, fluororesin, polydisperse # Λ a,, in 兮 μ μ + η Μ "layer of protective material", the surface of the lower protective material, in order to improve the solar cell seal of the present invention Adhesion of materials and other components, Of Li and other known surface treatment. The solar cell module produced by using the solar cell sealing material of the present invention at the bottom of the coating process and the solar cell component by the above-mentioned protective material/sealing material/solar cell component/sealing material/underlying protective material The structure in which the side is sandwiched by the sealing material is described. As shown in Fig. 1, the sealing resin layer 12α of the solar cell sealing material of the present invention is sequentially laminated from the light receiving side of the sunlight. 100106861 33 201139137 Solar cell elements 14A, 14B, solar cells using the present invention The sealing resin layer 2B, the back sheet 16, and the lower bonding box 18 of the back sheet 16 (connecting a terminal box for connecting the wiring from the solar cell element to the outside). The solar cell elements W and (10) are connected by a wiring 2B for conducting a current to the outside of the power generation current, and are taken out to the outer casing 2 through a through hole (not shown) provided on the back surface 46, and are connected to Connect the box 18. ^ ' As a manufacturing method of a solar cell module, a known method applicable, particularly limited, generally, a step of sequentially laminating a protective material, a sealing layer, a solar cell element, a sealing resin layer, and a lower protective material And ^ are the steps of vacuum suction and heat pressing. Further, it is also possible to apply a manufacturing apparatus and a stick-type to a light-type manufacturing apparatus. The solar cell module manufactured by using the solar cell sealing material of the present invention can be applied to a small solar cell represented by a portable machine, a roof and a large plastic sun set on a house according to the type of solar cell applied and the shape of the module. Various uses such as batteries and indoors. [Examples] The following examples are further described in detail, but are not intended to limit the invention in any way. Further, various measured values and evaluations of the sheets shown in the present specification were carried out as follows. Here, the flow direction of the sheet from the extruder is referred to as the longitudinal direction, and the vertical direction thereof is referred to as the transverse direction. (1) Water vapor barrier property (water vapor transmission rate) 100106861 34 201139137 Using a water vapor penetration tester (manufactured by MOCON Corporation, type: PERMATRAN W3/33) 'The sheet is sealed with a thickness of 33mm or n45nim. As a sample, the water vapor transmission rate in temperature 4 (rc, humidity 9〇% RH) was measured. The results were evaluated on the basis of the following criteria. (Ο) The water vapor transmission rate was less than 4 g/(m2 · day) (X ) Water vapor transmission rate is 4 g / (m 2 · day) or more (2) Flexibility (storage elastic modulus (E,)) Dynamic viscoelasticity measuring machine (IT measurement and control system), trade name: viscoelasticity Spectrometer DVA-200), with vibration frequency: 1 Hz, heating rate: 3. 〇/knife, strain 0.1%, starting from _1 〇〇. 贮 began to measure the storage elastic modulus for '), and obtained Data, estimated for storage elastic modulus (Ε,) in 25t:. (3) Fluidity (shear modulus (G,)) Using a rheometer (manufactured by Rheology Co., Ltd., type: Rhe〇meter MR-300T), vibration frequency: 1 Hz, temperature increase rate: 3 ΐ/min, strain 〇 5% of the condition, the shear elastic modulus (G') of the sample placed on the parallel plate of the (four) plane measured by _1 () (rC to 2 ( (the sample prepared by the example or the comparative example) The temperature was dispersed and measured at _150 to 150. (: Shear-elastic modulus (G,) in the temperature range, and the results were evaluated on the basis of the following criteria. (〇) Shearing of the resin composition constituting the layer (II) The elastic modulus (G, 剪切 and the shear elastic modulus (G, i) of the resin composition constituting the (I) layer are continuously formed in a temperature range of 30 ° C or more. 2 (X) Composition (Π The shear elastic modulus of the resin composition of the layer (o. The shear elastic modulus (G, !) of the resin composition constituting 100106861 201139137 (I) continuously becomes G'pG, and the temperature region is not full The range of 30 ° C. (4) The sealing property is based on the use of a vacuum laminator (manufactured by NPC, trade name: LM30X30), with a hot plate temperature: 150 ° C, processing time: 20 minutes (details, Vacuum: 5 minutes, pressurization: 5 minutes, holding pressure: 10 minutes), pressure-adhesive speed: conditions of rapids. 3mm thick whiteboard glass (made by Asahi Glass Co., Ltd., trade name: Solight) was implemented in order from the hot plate side. A sealing material produced in an example or a comparative example, a 0.4 mm thick solar cell element (manufactured by France Photo watt Co., Ltd., trade name: ΙΟΙχΙΟΙΜΜ), a sealing material produced in the examples or the comparative examples, and a ruthenium-resistant 125 Å thick weather resistant PET film (East) The appearance of a solar cell module (dimensions: 150 mm x 150 mm) produced by vacuum-pressing five layers of Lililar X10S) was visually observed and evaluated according to the following criteria. The sealing material is filled with no gap around the solar cell element and fully expanded. (X) The sealing material is not fully expanded and filled around the solar cell element, and bubbles and floats are generated. (5) Heat resistance in 3 mm thick whiteboard glass (a size of 75 mm in length and 25 rnm in width) and a 5 mm thick aluminum plate (dimensions: 120 mm in length and 60 mm in width), the sheet-like sealing materials produced in the examples or the comparative examples were superposed, and a vacuum presser was used. Plate temperature 100106861 36 201139137 degrees: 150C, pressure bonding time · 2 〇 minutes, pressure: 〇 iMPa conditions to make a laminated pressurized sample, and the sample is tilted at 60 degrees in a constant temperature bath of l ° ° C, The state after the lapse of the hour was observed and evaluated based on the following criteria: (〇) The glass was not moved from the initial reference position (X) The glass was moved from the initial reference position, and the sheet was melted (Example 1) The cyclic olefin system was used. A mixture of ethylene and decylene in a polymer (Polyplastics, trade name: TOPAS 9501x1, reduced fat content: 22% by mole, hereinafter referred to as COC1) 1 part by mass as (1) layer, After performing single-layer extrusion molding at a set temperature of 260 ° C by a τ-type mold method, the film was formed by rapid cooling at 25 ° C > 尧 casting rolls. Secondly, 'Used in ethylene-propylene-hexene 3-membered random copolymer (manufactured by Japan Polyethylene Co., Ltd., trade name: canel KJ640T, propylene content: 7.4 mol% (10 mass%), hexene content: 4.4 Molar% (10% by mass), MFR: 30g/10min, Tm: 53〇C, hereinafter abbreviated as P01) Addition of a third butylperoxy 2-ethylhexyl carbon as a crosslinking agent in 1 part by mass • Acid ester (Arkema Co., Ltd., trade name: Luperox TBEC) 1.0 part by mass of the resin composition as the (II) layer, and a single layer extrusion molding at a set temperature of 1 〇〇C by the T-die method. Thereafter, the film was formed by casting at 25 ° C. Further, 'the state in which the (I) layer and the (II) layer are overlapped, and laminated under heat and pressure to obtain a total thickness of 〇.3 mm ((1)/(11)=0.15111111/〇丨The sheet-like sealing material. The results of evaluation using the obtained sample are shown in Table 1. 100106861 37 201139137 (Example 2) The thickness of the (1) layer and the (8) layer was changed except for the Example i towel ((D/dlhOJmm/CUnnn) In the same manner as in the examples, a sheet-like sealing material having a total thickness of 0.3 mm was obtained. The results of evaluation using the obtained samples are shown in Table 1. (Example 3) Using COCH乍 as the (I) layer, and using Ethylene-octene random copolymer of E. coli and dilute tobacco copolymer (manufactured by D〇w Chemical Co., Ltd., Enzyme 8200, octene content: 1〇1 mol% (31% by mass) ,: 5g/10min (manufactured by Dow Chemical Co., Ltd., trade name: Infuse 91〇〇, octat content. 12.8 mol% (37%), MFR: lg/min, Tm: 119. 〇5 parts by mass a resin composition (hereinafter abbreviated as p〇2) in a ratio of 1 part by mass, and a 3-mercaptopropenyloxypropyltrimethoxy group as a decane coupling agent is added. Base decane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBM_5〇3) i 〇 mass part of the resin composition as the (II) layer 'and the resin composition of the (I) layer and the (Π) layer are respectively The extruder is supplied to the feeding mechanism' and is extruded by a τ-type mold method at a resin temperature of 180 to 220 C, and then the film is formed by 2 〇. The sheet was subjected to treatment to obtain a sheet-like sealing material having a total thickness of 〇3 mm ((1)/(11) = 0.15 mm/0.15 mm). The results of evaluation using the obtained sample are shown in Table 1. (Example 4) 100106861 38 201139137 In addition to changing the '(II) layer in Example 3 to a modified polyolefin resin, a decane crosslinkable polyolefin (a decane graft modified resin of ethylene-hexene random copolymer) (Mitsubishi Chemical Co., Ltd.) System name: Lincrone XLE815N, MFR: 〇.5g/l〇min, Tm: 124°C, hereinafter referred to as P03), and the thickness of (I) layer and (II) layer is changed ((I)/ (n) = 0.28 mm / 0.02 mm), the same procedure as in Example 3 was carried out to obtain a sheet-like sealing material having a total thickness of 〇3 mm. The results of evaluation using the obtained sample are shown in 1. (Comparative Example 1) In Example 1, the unused layer (II), to obtain a thickness formed of COC1 as the 〇.3mm ⑴ single layer sheet-like sealing material layer. The results obtained using the obtained samples are shown in Table 1. (Comparative Example 2) In the third embodiment, the layer (1) was not used, and a single-layer sheet-like sealing material having a thickness of 〇 and 3 mm (II) composed of P 〇 2 was obtained. The results of evaluation using the obtained samples are shown in Table 1. 100106861 39 201139137 [Table i] Comparative Example 2 | P〇2 I CO o ¢33⁄4 Ύ-· T* l〇CD o 0.3 (80°C) 0.03 (130°〇X 5 \ 〇〇Example 3 4 Comparative Example 1 COC1 CO 2 (80°C) 0.2 (150°C) 〇S \ X 〇COC1 CO CM 〇1371 2 (80°C) 0.2 (150°C) P03 I so Si T~ s 3.7 (80 °C) 0.04 (150°〇〇S 〇co in T* 〇〇COC1 LO 5 1371 2 (80°C) 0.2 (150°C) P02 m T— o 65. 119 o 0.3 (80°C) 0.03 ( 130°〇〇5 〇80°C ~150oC 〇〇Example 2 COC1 CM ο 2 (80°C) 0.2 (150°C) i poi 5 § s 0.2 (150°C) 0.01 (125°G) 〇5 〇I 80°C~148°C ' i 〇〇Example 1 COC1 in 5 £ 2 (80°C) 0.2 (150°C) POI in Τ Ο g 8 0.2 (150°C) 0.01 (125°〇〇 2 〇l 80°C ~148°C 〇〇 material thickness (mm) — storage elastic modulus at 25°C (E' (MPa) I_ 〇〇SO r- P 〇00 跌铁 a P Ο 00 material Thickness (mm) Crystal melting peak temperature (Tm) (°C) Storage modulus at 25°C (E'2) (MPa) -β-Σ 〇ϋΧ ο ο° Ο 00 8 0°C~1 Shear modulus of elasticity (G'2) (MPa) at 50 °C Small value ε ε CO ^ d curtain \ 硙 二硙. \ Fluidity £ (4) 〇υ 5 〇 § 5 Sealing heat resistance (I) layer ► - t evaluation 100106861 40 201139137 (Example 5) In addition to the example 1 In the case of using a cyclic olefin-based polymer, an ethylene-nanoolefin random copolymer (manufactured by Polyplastics Co., Ltd., trade name: T〇PAS99〇3D-10, reduced box content: 22 mol%, hereinafter abbreviated as c 〇C2) 丨 (9) parts by mass, as the layer (1), and the thickness of the (1) layer and the (Π) layer are changed ((I) / (II) = 0.225 mm / 0.225 mm), and the same as in the first embodiment, A sheet-like sealing material having a total thickness of 0 45111111 was obtained. The results of evaluation using the obtained samples are shown in Table 2. (Example 6) The same as Example 5 except that the thickness of the '(1) layer and the (π) layer in Example 5 was changed ((I) / (II) = 0.3 mm / 0.15 mm), the total thickness was obtained. It is a sheet seal of 0.45 mm. The results of the evaluation using the obtained samples are not shown in Table 2. (Example 7) Except that in Example 3, C〇C2 was used as the layer (1), and the thicknesses of the (1) layer and the (π) layer were changed ((I)/(II)=〇.225 mm/0.225 mm). The same procedure as in Example 3 was carried out to obtain a sheet-like sealing material having a total thickness of 〇45 mm. The results of the evaluation using the obtained samples are shown in Table 2. * (Example 8) Except that in Example 7, P03 was used as the (II) layer, and the thicknesses of the (1) layer and the (11) layer were changed ((I) / (II) = 〇.36 mm / 0.09 mm) The same procedure as in Example 7 was carried out to obtain a sheet-like sealing material having a total thickness of 〇45 mm. The results of the evaluation using the obtained samples are shown in Table 2. 100106861 41 201139137 (Comparative Example 3) In Example 5, a single-layer sheet-like sealing material having a layer (1) having a thickness of 0.45 mm composed of COC2 was obtained without using the layer (II). The results of evaluation using the obtained sample are shown in Table 2. (Comparative Example 4) In Example 5, the (I) layer was not used, and a single-layer sheet-like sealing material having a thickness of 0.45 mm (II) composed of p〇2 was obtained. The results of the evaluation using the obtained sample are shown in Table 2. (Comparative Example 5) In the fifth embodiment, the layer (II) was changed to a high-density polyethylene of a polyethylene resin (manufactured by Prime Polymer, trade name: Hizex 3600F, acetylated content, 100% by mole ( 100% by mass), MFR: lg/l〇min, Tm: 134 ° C, hereinafter abbreviated as P〇4), and treated in the same manner as in Example 5 to obtain a sheet-like sealing material having a total thickness. The results of evaluation using the samples of 77 samples are shown in Table 2. 100106861 42 201139137 [Table 2] Comparative Example 5 CGC2 0.225 1371 2 (80°〇0.2 (150°C) P04 to CM CNI Inch CO 1500 150 (80°C) 0.015 (150°C) o SX o^>〇 0 LO l〇CO Ί— t— X 〇Comparative Example 4. \ I P02 I lO inch o 65, 119 o •V* 0.3 (80°C) 0.03 (130°C) x S \ 〇〇Comparative Example 3 1 COC2 I 1〇〇2 (80°〇0.2 (150°C) 〇S \ X 〇Example 8 | C.OC2 | CO CO 2 (80°G) 0.2 (150°C) | P03 go § 3.7 (80 °C) 0.04 (150°C) o 2 〇co m 〇〇 Example 7 | COC2 | 0.225 2 (80°C) 0.2 (150°C) P02 0.225 〇> r— t〇_ <〇o 0.3 (80 ° C) 0.03 (130 ° C) o S 〇 80 ° C ~ 150 ° C 〇〇 Example 6 | COC2 | CO 2 (80 ° C) 0.2 (150 ° C) P01 ir? T-· oss 0.2 (150 ° C) 0.01 (125 ° C) 〇S 〇 80 ° C ~ 1483⁄4 〇〇 I Example 5 | COC2 | 0.225 2 (80 ° C) 0.2 (150 ° C) P01 | 0.225 | o CO s 0.2 ( 150 ° C) 0.01 (125 ° C) o § 〇 803⁄4 ~ 1480C 〇〇 material! Thickness (mm) 弹性 弹性 elastic modulus in 25 ° C (EVOVIPa) 80 ° C ~ 1 50 ° C shear elasticity The maximum modulus (G,) (MPa) is 80 ° C ~ 150 ° C Shear modulus of elasticity (G,) (MPa) minimum material E crystal melting peak temperature (Tm) (°C) Storage modulus in 25°c (E'2) (MPa) 80°C The maximum value of the shear modulus (G'2) (MPa) in ~150 °C is the minimum value of the shear modulus (G'2) (MPa) in 80 °C ~ 150 °C. ό ^. ^ \ 1~~l 涟$ \ »_52 Mobility οϋ ϋ w 7遽t oiib 〇ettL ^ Sealing heat resistance (1) Layer 1-1 *—* Evaluation i ' 1 43 100106861 201139137 From Table 1 and Table 2' It is confirmed that the solar cell, which has a layer of the resin composition defined by the present invention, is excellent in water-based properties, visibility, fluidity, and heat resistance (Examples 1 to 8). On the other hand, in the case of a layer composed of a resin composition which is not specified, the characteristics are sufficiently sufficient. In Comparative Example 1 and Comparative Example 3, although it is green, it is excellent in water vapor barrier property, but it does not have the requirements of the present invention (clear, so the storage elastic modulus (E') at normal temperature is passed against the impact from the outside. When the solar cell element is damaged, and the shear modulus (G,) of the sealing temperature region is too high, the sealing property of the solar cell element is deteriorated. Next, in Comparative Example 2 and Comparative Example 4, It was confirmed that the sealability and the heat retention were good, but the (1) layer which is not provided in the present invention was inferior in gas barrier property. The silver was produced in comparison with the sheet produced in Example 5, and it was confirmed that the sheet was not simultaneously satisfied. The conditions specified in the invention (1) "the storage elastic modulus (e,) in 25 Ε is Ε, ι > ρ, and the condition (7) "in the temperature range of ah ~ (10), the shear elastic modulus (=,) continuously becomes G> The temperature range of G'2 is inferior to the above range, so the fluidity and the sealing property are inferior. [Simplified Schematic] A schematic cross-sectional view of an example of a solar cell module of the invention. A schematic cross-sectional view of two types of two layers of the layer configuration - examples. Fig. 3 is a schematic cross-sectional view showing two types of three-layer structures of an example of a layer configuration of a solar cell sealing material of the present invention. [Description of Main Element Symbols] 10 Transparent Substrate 12A > 12B Sealing Resin Layer 14A, 14B Solar Cell Component 16 Back Sheet 18 Connection Box 20 Wiring 100106861 45

Claims (1)

201139137 VII. Patent application scope: 1. A solar cell sealing material characterized by having at least the following (1) layer and the following (II) layer and satisfying the following condition (1) and the following conditions ( 2): (1) layer, layer (II) layer composed of a resin composition containing a cyclic olefin polymer as a main component: layer conditions composed of a resin composition containing a polyolefin-based polymer as a main component (1) The storage elastic modulus (E,) at 25eC is E'pE, and the condition (2) is at 8 (rc~15〇〇c), the shear elastic modulus (g,) is connected, and only becomes The temperature region of 〇1>G 2 exists in the range of 30 ° C or more (E1 E 2 is the storage elastic modulus of the resin composition constituting the (I) layer and the (π) layer, respectively, G, 1, G And 2 are the shear elastic modulus of the resin composition constituting the (I) layer and the (II) layer, respectively. 2. The solar cell sealing material according to the first aspect of the patent application, wherein the solar cell company and the sealing device are In the material, the water 蒸 〇 轴 轴 叱 叱 叱 叱 叱 叱 叱 叱 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 湿度 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. Cell seal member, wherein said upper seal material in the loose solar cell 'square 45_Degree thickness, thief temperature, humidity, water vapor transmission rate of generous cents under • day). 4. A solar cell module, which uses the patent application scope! Made of solar cell sealing material to any of S items. 100106861 46