WO2012050093A1 - Composition de résine ayant une excellente transparence et d'excellentes propriétés de prévention d'humidité, et feuille obtenue par moulage de la composition - Google Patents

Composition de résine ayant une excellente transparence et d'excellentes propriétés de prévention d'humidité, et feuille obtenue par moulage de la composition Download PDF

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Publication number
WO2012050093A1
WO2012050093A1 PCT/JP2011/073349 JP2011073349W WO2012050093A1 WO 2012050093 A1 WO2012050093 A1 WO 2012050093A1 JP 2011073349 W JP2011073349 W JP 2011073349W WO 2012050093 A1 WO2012050093 A1 WO 2012050093A1
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Prior art keywords
resin
ethylene
solar cell
resin composition
olefin
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PCT/JP2011/073349
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English (en)
Japanese (ja)
Inventor
田中　一也
谷口　浩一郎
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三菱樹脂株式会社
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Priority claimed from JP2010288460A external-priority patent/JP5593215B2/ja
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Publication of WO2012050093A1 publication Critical patent/WO2012050093A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09D123/0815—Copolymers of ethene with aliphatic 1-olefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a resin composition that can be suitably used for applications requiring transparency and moisture resistance, and a sheet formed by molding the resin composition.
  • PVC polyvinyl chloride
  • linear low density polyethylene high density polyethylene, polypropylene and the like have been proposed.
  • the linear low density polyethylene is excellent in transparency, the moisture resistance is not sufficient, and it is difficult to say that it is an optimal resin from the viewpoint of the stability of the contents during long-term storage.
  • polypropylene is superior in moisture resistance as compared to linear low density polyethylene, it has a problem that it does not have sufficient moisture resistance for use in applications where higher moisture resistance is required.
  • Patent Document 1 discloses a resin composition obtained by blending a high density polyethylene having a density of 0.942 to 0.965 g / cm 3 with a nucleating agent. It is disclosed.
  • Patent Document 2 discloses a resin composition comprising a high density polyethylene having a density of 0.94 to 0.97 g / cm 3 and an alicyclic saturated hydrocarbon resin containing no polar group. ing.
  • Patent Document 1 even when a nucleating agent is blended with high-density polyethylene, it is difficult to obtain sufficient transparency when the sheet is molded.
  • Patent Document 2 by blending high-density polyethylene with an alicyclic saturated hydrocarbon resin that does not contain a polar group, moisture resistance is slightly improved, but sufficient transparency is obtained when the sheet is molded. It was difficult to get.
  • an object of the present invention is to provide a new resin composition capable of imparting sufficient transparency and moisture resistance when formed into a sheet, in view of such problems of the prior art.
  • the present invention relates to a resin composition
  • a resin composition comprising a metallocene ethylene polymer (A) having a density of 0.936 to 0.948 g / cm 3 and a heat of crystal fusion of 150 to 200 J / g, and a crystal nucleating agent (B).
  • the present invention proposes a resin composition characterized in that the ratio of (B) in the total content of (A) and (B) is 0.01 to 3.0% by mass.
  • the resin composition of the present invention sufficient transparency and moisture resistance can be imparted when the sheet is molded. Therefore, transparency and moisture resistance are required, for example, for packaging materials such as pharmaceuticals and sweets. It can be used as a packaging material. Further, it can be particularly suitably used as a protective material for an electronic device such as a solar cell encapsulant that requires high transparency and moisture resistance.
  • the present resin composition a resin composition (referred to as “the present resin composition”) as an example of an embodiment of the present invention will be described.
  • the scope of the present invention is not limited to the embodiments described below.
  • This resin composition is a resin composition containing a metallocene ethylene-based polymer (A) and a crystal nucleating agent (B). If necessary, an olefin-compatible resin (C), an olefin-based resin ( It is a resin composition containing D).
  • Metallocene ethylene polymer (A) It is important that the ethylene polymer used in the resin composition is a metallocene ethylene polymer (A), that is, an ethylene polymer that is polymerized using a metallocene catalyst.
  • the metallocene catalyst examples include a single site catalyst in which a metallocene compound and methylaluminoxane are combined.
  • a metallocene catalyst that is, a metallocene ethylene-based polymer, include a narrow molecular weight distribution and a low heat of crystal melting even at the same density.
  • the metallocene ethylene polymer (A) has a molecular weight distribution index (Mw / Mn) of 2.5 to 4.5, particularly 2.6 or more, 4.3 or less, especially 3.0 or more or It is preferably 4.0 or less.
  • Mw / Mn molecular weight distribution index
  • the lower limit of the density of the metallocene ethylene polymer (A) is 0.932 g / cm 3 , preferably 0.936 g / cm 3 , more preferably 0.938 g / cm 3 , and more preferably 0.8. It is 940 g / cm 3 , more preferably 0.941 g / cm 3 .
  • the upper limit is preferably 0.948 g / cm 3 , more preferably 0.947 g / cm 3 , and still more preferably 0.942 g / cm 3 .
  • the density of the metallocene ethylene-based polymer (A) in the present invention is preferably 0.936 ⁇ 0.948g / cm 3, particularly preferably 0.941 ⁇ 0.948g / cm 3 . It is important that the heat of crystal melting of the metallocene ethylene polymer (A) is 150 to 200 J / g, particularly 155 J / g or more or 190 J / g or less, and among them, 160 J / g or more or 185 J / g. It is preferable that: If the density and heat of crystal fusion of the metallocene ethylene polymer (A) are within such ranges, both transparency and moisture resistance can be improved when the sheet is formed.
  • the crystallization peak temperature (Tc) of the metallocene ethylene polymer (A) is preferably 105 to 130 ° C., more preferably 110 ° C. or more and 125 ° C. or less, particularly 112 ° C. or more and 120 ° C. or less. Is preferred.
  • the crystallization peak temperature (Tc) of the metallocene ethylene polymer (A) is within the above range, the crystallization rate is sufficiently high, fine crystals can be formed, and a resin composition excellent in transparency can be obtained. Therefore, it is preferable.
  • the metallocene ethylene polymer (A) may be an ethylene homopolymer, or may be a copolymer of ethylene and an ⁇ -olefin. Moreover, these mixtures can be used. Among these, an ethylene homopolymer or a copolymer of ethylene with at least one ⁇ -olefin of butene-1, hexene-1 and octene-1, specifically ethylene Copolymer of butene-1, copolymer of ethylene and hexene-1, copolymer of ethylene and octene-1, copolymer of ethylene, butene-1 and hexene-1, ethylene and butene- It is preferable to use a copolymer of 1 and octene-1, a copolymer of ethylene, hexene-1 and octene-1, or a copolymer of ethylene, butene-1, hexene-1 and octene-1. preferable
  • the total content of butene-1, hexene-1 and octene-1 in the metallocene ethylene polymer (A) is 0.1 to 3.0. It is preferable that it is mass%, and it is more preferable that it is 0.3 mass% or more or 2.8 mass% or less among these, and 0.5 mass% or more or 2.6 mass% or less is especially preferable. If the ⁇ -olefin is within such a range, a resin composition having excellent transparency and moisture resistance can be provided.
  • a preferred example of the metallocene ethylene polymer (A) is a polymer composed of ethylene, butene-1 and octene-1, and the proportion of butene-1 in the metallocene ethylene polymer (A) is 0.00. 1 to 2.0% by mass, a polymer having a ratio of octene-1 of 0.1 to 2.0% by mass, or a polymer composed of ethylene, hexene-1 and octene-1, and A polymer in which the proportion of hexene-1 in the metallocene ethylene polymer (A) is 0.1 to 2.0% by mass and the proportion of octene-1 is 0.1 to 2.0% by mass is given. be able to.
  • crystal nucleating agent (B) The kind of the crystal nucleating agent (B) used in the resin composition is not particularly limited as long as the effect of improving the transparency of the metallocene ethylene polymer (A) is recognized.
  • dibenzylidene sorbitol (DBS) compound 1,3-O-bis (3,4 dimethyl benzylidene) sorbitol, dialkyl benzylidene sorbitol, diacetal of sorbitol having at least one chlorine or bromine substituent, di (methyl or ethyl substituted benzylidene) ) Sorbitol, bis (3,4-dialkylbenzylidene) sorbitol having substituents forming a carbocycle, aliphatic, alicyclic, and aromatic carboxylic acids, dicarboxylic acids or polybasic polycarboxylic acids, corresponding anhydrides Metal salts of organic acids such as organic and metal salts, bicyclic dicarboxylic
  • fatty acid amides such as oleic acid amide, erucic acid amide, stearic acid amide and ariaic acid amide, and fatty acid metal salts such as magnesium stearate, zinc stearate and calcium stearate are particularly preferable.
  • crystal nucleating agent (B) As specific examples of the crystal nucleating agent (B), the product name “Gelall D” series of Shin Nippon Rika Co., Ltd., the product name “Adeka Stub” series of ADEKA Co., Ltd., the product name “Millad” series of Milliken Chemical Co., Ltd., "Hyperform” series, BASF's product name "IRGACLEAR” series, etc., and as a master batch of crystal nucleating agent, Riken Vitamin Co., Ltd. product name "Rike Master CN” series, Miliken Chemical's product name " HL3-4 "and the like.
  • the products with the highest effect of improving the transparency are the product names of Milliken Chemicals “HYPERFORM HPN-20E” and “HL3-4”, and the product names of Riken Vitamin Co., Ltd. “Rike Master CN-001” “Rike Master CN-002 ”.
  • the proportion of (B) in the total content of the metallocene ethylene polymer (A) and the crystal nucleating agent (B) is 0.01 to 3.0% by mass. Of these, 0.03% by mass or more or 2.0% by mass or less is more preferable, and among them, 0.05% by mass or more or 1.0% by mass or less is even more preferable.
  • the moisture-proof property can be further improved by blending the olefin-compatible resin (C) with the resin composition.
  • the olefin compatible resin (C) is preferably a resin that is compatible with an olefin resin, particularly a metallocene ethylene polymer (A) and has a glass transition temperature higher than that of the metallocene ethylene polymer (A).
  • examples thereof include one resin or two or more resins selected from the group consisting of petroleum resins, terpene resins, coumarone-indene resins, rosin resins, and hydrogenated derivatives thereof.
  • Examples of the petroleum resin include alicyclic petroleum resin from cyclopentadiene or its dimer, aromatic petroleum resin from C9 component, and the like.
  • Examples of the terpene resin include terpene-phenol resin from ⁇ -pinene.
  • Examples of the coumarone-indene resin include a coumarone-indene copolymer and a coumarone-indene-styrene copolymer.
  • Examples of the rosin resin include rosin resins such as gum rosin and wood rosin, and esterified rosin resins modified with glycerin, pentaerythritol, and the like.
  • the olefin-compatible resin (C) is a hydrogenated derivative, particularly a hydrogenation rate (hereinafter referred to as “water”) from the viewpoint of compatibility, color tone, thermal stability and the like when mixed with the metallocene ethylene polymer (A).
  • the ratio of the unsaturated double bond of the conjugated diene based on the phenyl group which may be abbreviated as “addition rate”, which is sometimes abbreviated as “addition rate”) is 95% or more, and is a hydroxyl group, carboxyl group, halogen It is preferable to use a hydrogenated petroleum resin or a hydrogenated terpene resin that substantially does not contain an unsaturated bond such as a polar group or a double bond.
  • the softening temperature Ts (C) measured in accordance with JIS K2207 of the olefin compatible resin (C) is a differential measured in accordance with JIS K7121 of the metallocene ethylene polymer (A).
  • the Tc (A) + 20 ° C. or lower is more preferable, the Tc (A) + 10 ° C.
  • the Tc (A) + 5 ° C. or lower is particularly preferable.
  • the lower limit of Ts (C) is preferably 80 ° C. Since the upper limit of the softening temperature Ts (C) satisfies this condition, the olefin-compatible resin (C) has a high degree of molecular chain freedom in the crystallization process of the metallocene ethylene-based polymer (A). It is preferable because crystallization of the polymer (A) is hardly inhibited, fine crystals are formed, and a resin composition excellent in moisture resistance and transparency can be obtained. Further, when the softening temperature Ts (C) of the olefin compatible resin (C) is 80 ° C.
  • the softening temperature Ts (C) of the olefin-compatible resin (C) can be obtained mainly by selecting the molecular weight.
  • olefin compatible resin (C) examples include, for example, Mitsui Chemical Co., Ltd., trade names “Hi-Lets” series, “Petrogin” series, Arakawa Chemical Industries, Ltd., trade names “Arcon” series, Yasuhara Chemical Co., Ltd. )
  • the content of the olefin compatible resin (C) is preferably 5 to 30% by mass in the present resin composition, more preferably 10% by mass or more and 25% by mass or less, and more preferably 15% by mass or more. Or it is still more preferable that it is a ratio of 20 mass% or less.
  • an olefin resin having a heat of crystal fusion of 0 to 100 J / g, particularly 80 J / g or less, and more preferably 50 J / g or less is preferable.
  • the olefin resin (D) examples include linear low density polyethylene made of a copolymer of ethylene and ⁇ -olefin, polypropylene resin, and cyclic olefin resin. Among these, it is particularly preferable to use a cyclic olefin resin. By using a cyclic olefin resin as the olefin resin (D), the transparency can be improved without substantially reducing the moisture resistance.
  • cyclic olefin-based resin examples include (i) a polymer obtained by hydrogenating a ring-opening (co) polymer of a cyclic olefin as necessary, (ii) an addition (co) polymer of a cyclic olefin, and (iii) a cyclic olefin Random copolymers with ⁇ -olefins such as ethylene and propylene, (iv)
  • the above (i) to (iii) are unsaturated such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, (meth) acrylic acid, etc. Examples thereof include graft copolymers modified with a carboxylic acid or anhydride modifier. These may be used alone or in combination of two or more.
  • the glass transition temperature (Tg) of the cyclic olefin resin is preferably 50 to 110 ° C., more preferably 60 to 90 ° C., and further preferably 65 to 85 ° C.
  • the glass transition temperature (Tg) is within the above range because the transparency of the resin composition of the present invention can be improved without significantly reducing the heat resistance and workability.
  • the average refractive index at room temperature is preferably 1.510 to 1.540.
  • the absolute value of the difference from the average refractive index of the metallocene ethylene polymer (A) used is preferably 0.010 or less, more preferably 0. 0.005 or less, and more preferably 0.003 or less. If the absolute value of the average refractive index difference is within this range, it is preferable because the transparency can be improved without being greatly influenced by the dispersion diameter of the cyclic olefin resin in the resin composition.
  • the average refractive index can be measured using a known method, for example, an Abbe refractometer.
  • the olefin resin (D) as the linear low density polyethylene, Ube Maruzen Polyethylene Co., Ltd. trade name “Umerit” series, Nihon Unicar Co., Ltd. trade name “NUC polyethylene” series, etc. Can be mentioned.
  • the polypropylene resin include a trade name “Novatech PP” series of Nippon Polypro Co., Ltd. and a trade name “Nobrene” series of Sumitomo Chemical Co., Ltd.
  • the cyclic olefin-based resin examples include the product name “TOPAS” series of Polyplastics Co., Ltd., the product name “Apel” series of Mitsui Chemicals, Inc., and the product name “ZEONOR” series of Nippon Zeon Co., Ltd. be able to.
  • the olefin-based resin (D) may be either a single resin or a mixture of a plurality of resins.
  • the content of the olefin resin (D) is preferably 10 to 50% by mass in the resin composition from the viewpoint of further improving transparency without impairing moisture resistance. It is more preferably 20% by mass or more or 45% by mass or less, and more preferably 25% by mass or more or 30% by mass or less.
  • the resin composition includes additives such as a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antibacterial / antifungal agent, an antistatic agent, and a lubricant as long as the effects of the present invention are not impaired. Can be blended.
  • the method for forming a sheet using the resin composition is not particularly limited.
  • metallocene ethylene polymer (A), crystal nucleating agent (B), olefin-compatible resin (C), olefin resin (D) and other additives if necessary, uniaxial or biaxial extrusion
  • An unstretched sheet can be produced by melt-mixing with a machine or the like, extruding with a T-die, quenching with a cast roll, and solidifying.
  • the unstretched sheet means a sheet that is not actively stretched for the purpose of increasing the strength of the sheet.
  • a sheet that has been stretched to less than 2 times by a stretching roll during extrusion molding is included in the unstretched sheet. Shall be.
  • the thickness of the sheet is not particularly limited, but considering workability and practicality, it is preferably 0.01 mm or more and 3 mm or less, and 0.05 mm or more and 2.5 mm or less. More preferably, it is 0.1 mm or more and 2.0 mm or less. Within such a range, the rigidity of the sheet can be made necessary and sufficient, the secondary workability is not inferior, and the handling property when used as various packaging materials does not become a problem, and the transparency. Can also be secured.
  • a plurality of sheets made of the resin composition are laminated by a method such as coextrusion, extrusion lamination, thermal lamination, and dry lamination.
  • resin compositions other than the resin composition of the present invention for example, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polypropylene resins, mixtures of polypropylene resins and petroleum resins, polystyrene resins
  • One or more layers can be laminated on one or both sides of a sheet formed by molding the resin composition.
  • the non-stretched sheet or the laminated sheet it can be stretched uniaxially or biaxially using a roll method, a tenter method, a tubular method, or the like.
  • the internal haze is measured based on JIS K7105 when it is formed into a sheet with a thickness of 0.1 mm from the viewpoints of design properties, contents visibility, and the like. Is preferably 10% or less, more preferably 9% or less, and even more preferably 8% or less. If it is the range which concerns on an internal haze, sufficient visibility will be acquired and the product excellent in the designability can be obtained.
  • Sheets formed by molding this resin composition can be formed into molded products of various shapes by vacuum molding, pressure molding, pressure vacuum molding, press molding, and other thermoforming, and other resins, metals, glass, etc. It can also be used in multiple layers. Since the sheet formed by molding the resin composition has excellent transparency and moisture resistance, it is used in applications requiring transparency and moisture resistance in various fields, for example, medical, food, electronic equipment and energy fields. It can be preferably used.
  • the sheet surface may be processed such as embossing or matting.
  • the cast roll is changed to an embossing roll or a matte roll during extrusion molding. May be.
  • the surface of the sheet may be coated with an antistatic agent, silicone, wax, etc., a film may be formed using a surface protective sheet for the purpose of preventing the adhesion of scratches, or a printing layer may be provided. Is also possible.
  • a well-known arbitrary means is employable as a formation means of a printing layer.
  • seat using this resin composition can be used as a sealing material for solar cells.
  • the solar cell encapsulant in the present invention can be used as a single layer of a sheet using the present resin composition or as a multilayer body laminated with other layers.
  • the other layers laminated with the sheet made of the resin composition (hereinafter sometimes referred to as the resin layer (II)) are not particularly limited, but have sealing properties, heat resistance, and transparency. Therefore, the resin layer (I) containing an ethylene-based resin is preferable.
  • the resin layer (I) containing an ethylene-based resin is preferably the following resin layer (I) -1 and / or the following resin layer (I) -2, and has this as at least one of the outermost layers. It is preferable to use as a solar cell sealing multilayer body.
  • Resin layer (I) -1 an ethylene- ⁇ -olefin random copolymer (P) that satisfies the following conditions (a) and an ethylene- ⁇ -olefin block copolymer that satisfies the following conditions (b)
  • Resin layer containing Q Resin layer (I) -2: Resin layer containing silane-modified ethylene resin (X)
  • B The crystal melting peak temperature measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 100 to 145 ° C., and the crystal melting heat amount is 5 to 70 J / g.
  • the present invention provides moisture resistance sufficient for protection of solar cell elements, excellent transparency and heat resistance, and excellent sealing properties when manufacturing solar cell modules, and handling properties at room temperature. It is possible to provide a solar cell sealing multi-layer body having rigidity for imparting a solar cell module and a solar cell module manufactured using the same.
  • Resin layer (I) -1 includes an ethylene- ⁇ -olefin random copolymer (P) satisfying the condition (a) and an ethylene- ⁇ -olefin block copolymer satisfying the condition (b). (Q) is contained, and the role which expresses the outstanding transparency for providing the outstanding sealing performance, heat resistance for protecting mainly a solar cell element (cell), and sufficient power generation efficiency to a solar cell.
  • the ethylene- ⁇ -olefin random copolymer (P) used in the present invention is not particularly limited as long as the above condition (a) is satisfied. Usually, ethylene and an ⁇ -olefin having 3 to 20 carbon atoms are used. These random copolymers are preferably used. Examples of the ⁇ -olefin copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 3-methyl-butene. -1,4-methyl-pentene-1, etc.
  • propylene, 1-butene, 1-hexene, and 1-octene are preferably used as the ⁇ -olefin copolymerized with ethylene from the viewpoints of industrial availability, various characteristics, and economical efficiency. It is done.
  • the ⁇ -olefin copolymerized with ethylene may be used alone or in combination of two or more.
  • the content of the ⁇ -olefin copolymerized with ethylene is not particularly limited as long as the above condition (a) is satisfied.
  • the content of all units in the ethylene- ⁇ -olefin random copolymer (P) is not limited. It is usually 2 mol% or more, preferably 40 mol% or less, more preferably 3 to 30 mol%, still more preferably 5 to 25 mol%, based on the monomer unit. Within this range, the crystallinity is reduced by the copolymerization component, so that the transparency is improved and problems such as blocking of the raw material pellets are less likely to occur.
  • the type and content of the ⁇ -olefin copolymerized with ethylene can be qualitatively and quantitatively analyzed by a known method, for example, a nuclear magnetic resonance (NMR) measuring device or other instrumental analyzer.
  • NMR nuclear magnetic resonance
  • the ethylene- ⁇ -olefin random copolymer (P) may contain monomer units based on monomers other than ⁇ -olefin as long as the condition (a) is satisfied.
  • the monomer include cyclic olefins, vinyl aromatic compounds (such as styrene), polyene compounds, and the like.
  • the content of the monomer units is 20 mol% or less and 15 mol% or less, assuming that all monomer units in the ethylene- ⁇ -olefin random copolymer (P) are 100 mol%. It is preferable.
  • the steric structure, branching, branching degree distribution and molecular weight distribution of the ethylene- ⁇ -olefin random copolymer (P) are not particularly limited as long as the above condition (a) is satisfied.
  • a copolymer having a branch generally has good mechanical properties, and has an advantage that the melt tension (melt tension) at the time of molding a sheet is increased and the calendar moldability is improved.
  • a copolymer having a narrow molecular weight distribution polymerized using a single site catalyst has advantages such as a low molecular weight component and a relatively low blocking of raw material pellets.
  • the melt flow rate (MFR) of the ethylene- ⁇ -olefin random copolymer (P) used in the present invention is not particularly limited, but is usually MFR (JIS K7210, temperature: 190 ° C., load: 21. 18N) is about 0.5 to 100 g / 10 min, more preferably 2 to 50 g / 10 min, still more preferably 3 to 30 g / 10 min.
  • the MFR may be selected in consideration of molding processability when molding a sheet, adhesion when sealing a solar cell element (cell), a wraparound condition, and the like.
  • the MFR is preferably a relatively low value, specifically about 0.5 to 5 g / 10 minutes, because of the handling properties when the sheet is peeled off from the forming roll.
  • the MFR is preferably 2 to 50 g / 10 min, more preferably 3 to 30 g / 10 min, from the viewpoint of reducing the extrusion load and increasing the extrusion rate. Good.
  • the MFR is preferably 2 to 50 g / 10 minutes, more preferably 3 to 30 g / 10 minutes. Use it.
  • the production method of the ethylene- ⁇ -olefin random copolymer (P) used in the present invention is not particularly limited, and a known polymerization method using a known olefin polymerization catalyst can be employed.
  • a known polymerization method using a known olefin polymerization catalyst can be employed.
  • the ethylene- ⁇ -olefin random copolymer (P) is a relatively soft resin, it has a low molecular weight from the viewpoint of ease of granulation after pelletization and prevention of blocking of raw material pellets.
  • a polymerization method using a single site catalyst capable of polymerizing a raw material with few components and a narrow molecular weight distribution is suitable.
  • the ethylene- ⁇ -olefin random copolymer (P) used in the present invention satisfies the above condition (a), that is, the crystal melting calorie measured at a heating rate of 10 ° C./min in the differential scanning calorimetry is 0 to It is necessary to be 70 J / g, preferably 5 to 70 J / g, more preferably 10 to 65 J / g. If it is in the range of 0 to 70 J / g, flexibility and transparency (total light transmittance) of the multilayer body for sealing solar cells is preferable. In particular, if the heat of crystal fusion is 5 J / g or more, it is preferable because problems such as blocking of raw material pellets hardly occur.
  • general-purpose high-density polyethylene is about 170 to 220 J / g
  • low-density polyethylene resin LDPE
  • linear low-density polyethylene LLDPE
  • the heat of crystal melting can be measured at a heating rate of 10 ° C./min according to JIS K7122 using a differential scanning calorimeter.
  • the crystal melting peak temperature of the ethylene- ⁇ -olefin random copolymer (P) used in the present invention is not particularly limited, but is usually less than 100 ° C. and is often 30 to 90 ° C. .
  • general-purpose high-density polyethylene (HDPE) is about 130 to 145 ° C.
  • low-density polyethylene resin (LDPE) and linear low-density polyethylene (LLDPE) are 100 to 125. It is about °C.
  • the crystal melting peak temperature measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 100 ° C. or higher, and It is difficult to achieve a heat of crystal melting of 5 to 70 J / g.
  • the crystal melting peak temperature can be measured at a heating rate of 10 ° C./min according to JIS K7121 using a differential scanning calorimeter.
  • ethylene- ⁇ -olefin random copolymer (P) used in the present invention include trade names “Engage”, “Affinity” manufactured by Dow Chemical Co., Ltd., Mitsui Chemicals, Inc.
  • the product name “TAFMER A”, “TAFMER ⁇ P”, and the product name “Kernel” manufactured by Nippon Polyethylene Co., Ltd. can be exemplified.
  • the ethylene- ⁇ -olefin block copolymer (Q) used in the present invention is not particularly limited as long as the above condition (b) is satisfied.
  • ethylene and an ⁇ -olefin having 3 to 20 carbon atoms are used. These block copolymers are preferably used.
  • Examples of the ⁇ -olefin copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 3-methyl-butene. -1,4-methyl-pentene-1, etc.
  • propylene, 1-butene, 1-hexene, and 1-octene are preferably used as the ⁇ -olefin copolymerized with ethylene from the viewpoints of industrial availability, various characteristics, and economical efficiency. It is done.
  • the ⁇ -olefin copolymerized with ethylene may be used alone or in combination of two or more.
  • the ethylene- ⁇ -olefin block copolymer (Q) may contain monomer units based on monomers other than ⁇ -olefin as long as the condition (b) is satisfied.
  • the monomer include cyclic olefins, vinyl aromatic compounds (such as styrene), polyene compounds, and the like.
  • the content of the monomer units is 20 mol% or less and 15 mol% or less, assuming that all monomer units in the ethylene- ⁇ -olefin block copolymer (Q) are 100 mol%. It is preferable.
  • the block structure of the ethylene- ⁇ -olefin block copolymer (Q) used in the present invention is not particularly limited as long as the condition (b) is satisfied, but the balance of flexibility, heat resistance, transparency, etc.
  • a structure is preferred. Specific examples include a completely symmetric block, an asymmetric block, and a tapered block structure (a structure in which the ratio of the block structure gradually increases in the main chain).
  • 2005/090425 (WO2005 / 090425), International Publication No. 2005/090426 (WO2005 / 090426), and International Publication No.2005. / 090427 pamphlet (WO2005 / 090427) or the like can be employed.
  • the ethylene- ⁇ -olefin block copolymer having the multi-block structure will be described in detail below.
  • the ethylene- ⁇ -olefin block copolymer having a multiblock structure can be suitably used in the present invention, and an ethylene-octene multiblock copolymer having 1-octene as a copolymerization component as an ⁇ -olefin is preferable.
  • a multiblock copolymer in which two or more highly crystalline hard segments each having a copolymerized crystal melting peak temperature of 100 to 145 ° C. are present.
  • chain length and ratio of these soft segments and hard segments By controlling the chain length and ratio of these soft segments and hard segments, both flexibility and heat resistance can be achieved.
  • trade name “Infuse” manufactured by Dow Chemical Co., Ltd. may be mentioned.
  • the melt flow rate (MFR) of the ethylene- ⁇ -olefin block copolymer (Q) used in the present invention is not particularly limited, but is usually MFR (JIS K7210, temperature: 190 ° C., load: 21. 18N) is about 0.5 to 100 g / 10 min, more preferably 1 to 50 g / 10 min, still more preferably 1 to 30 g / 10 min, and particularly preferably 1 to 10 g / 10 min.
  • the MFR may be selected in consideration of molding processability when molding a sheet, adhesion when sealing a solar cell element (cell), a wraparound condition, and the like.
  • the MFR is preferably relatively low, specifically about 0.5 to 5 g / 10 minutes, because of the handling properties when the sheet is peeled off from the forming roll.
  • an MFR of 1 to 30 g / 10 minutes is preferably used from the viewpoint of reducing the extrusion load and increasing the extrusion amount.
  • those having an MFR of 3 to 50 g / 10 min are preferably used.
  • the ethylene- ⁇ -olefin block copolymer (Q) used in the present invention satisfies the condition (b), that is, the crystal melting peak temperature measured at a heating rate of 10 ° C./min in differential scanning calorimetry is 100. It is necessary that the temperature is ⁇ 145 ° C. and the heat of crystal fusion is 5 to 70 J / g.
  • the crystal melting peak temperature is preferably 105 ° C. or higher, more preferably 110 ° C. or higher, and the upper limit is usually 145 ° C.
  • the heat of crystal fusion is preferably 10 to 60 J / g, more preferably 15 to 55 J / g.
  • the method for measuring the crystal melting peak temperature and the crystal melting heat amount is as described above.
  • a solar cell module is heated to about 85 to 90 ° C. by heat generated during power generation or radiant heat of solar light. If the crystal melting peak temperature is 100 ° C. or higher, the multilayer body for sealing solar cells of the present invention is used. On the other hand, if the upper limit is 145 ° C., it is preferable because it can be sealed without excessively high temperature in the sealing step of the solar cell element. If the heat of crystal fusion is in the range of 5 to 70 J / g, the flexibility and transparency (total light transmittance) of the solar cell sealing multilayer body of the present invention are ensured, and the raw material pellets are blocked. It is preferable because problems such as these are unlikely to occur.
  • the resin layer (I) -1 is a resin layer containing the ethylene- ⁇ -olefin random copolymer (P) and the ethylene- ⁇ -olefin block copolymer (Q).
  • the types of ⁇ -olefins used in each of the copolymer (P) and the copolymer (Q) may be the same or different, but in the present invention, It is preferable that they are the same because the compatibility when mixed and the transparency of the solar cell sealing multilayer body are improved, that is, the photoelectric conversion efficiency of the solar cell is improved.
  • the contents of the ethylene- ⁇ -olefin random copolymer (P) and the ethylene- ⁇ -olefin block copolymer (Q) in the resin layer (I) -1 are flexible, heat resistant, and transparent. From the viewpoint of having an excellent balance such as, it is preferably 50 to 99% by mass, 1 to 50% by mass, more preferably 60 to 98% by mass, and 2 to 40% by mass, and still more preferably. 70 to 97% by mass, and 3 to 30% by mass.
  • the mixed (contained) mass ratio is in the above range because a solar cell sealing multilayer body excellent in balance of flexibility, heat resistance, transparency and the like can be easily obtained.
  • Resin layer (I) -2 is a resin layer mainly composed of silane-modified ethylene resin (X) or a resin layer mainly composed of a mixture of silane-modified ethylene resin (X) and polyethylene resin (F). It doesn't matter.
  • the silane-modified ethylene-based resin (X) can be usually obtained by melt-mixing a polyethylene-based resin, a vinyl silane compound, and a radical generator at a high temperature, and performing graft polymerization. When the polyethylene resin used for using the radical generator is partially crosslinked, gel or fish eye may be mixed in, or the vinylsilane compound or radical generator used may remain unreacted.
  • the polyethylene resin (F) is not particularly limited, but is mixed with the silane-modified ethylene resin (X), and the silane-modified ethylene resin (X) in the resin layer (I) -2.
  • the resin layer (I) -2 is adjusted for various properties such as flexibility, transparency, sealing properties and heat resistance.
  • the same resin as the polyethylene resin used for obtaining the silane-modified ethylene resin (X) that is, low density polyethylene, medium density polyethylene, high density polyethylene, very low density polyethylene, or linear Low density polyethylene is mentioned. These may be used alone or in combination of two or more.
  • the melt flow rate (MFR) of the polyethylene resin (F) used in the present invention is not particularly limited, but usually MFR (JIS K7210, temperature: 190 ° C., load: 21.18 N) is 0.1. What is about 5 to 100 g / 10 min, more preferably 2 to 50 g / 10 min, still more preferably 3 to 30 g / 10 min is used.
  • the MFR may be selected in consideration of molding processability when molding a sheet, adhesion when sealing a solar cell element (cell), a wraparound condition, and the like.
  • the MFR is preferably relatively low, specifically about 0.5 to 5 g / 10 min from the handling property when the sheet is peeled off from the forming roll.
  • MFR is preferably 2 to 50 g / 10 min, more preferably 3 to 30 g / 10 min, from the viewpoint of reducing the extrusion load and increasing the extrusion rate.
  • the MFR is preferably 2 to 50 g / 10 min, more preferably 3 to 30 g / 10 min. Good.
  • the polyethylene resin (F) may be the same resin as the polyethylene resin used when obtaining the silane-modified ethylene resin (X) or a different resin. It is preferable that they are the same resin from the viewpoints of compatibility and transparency when mixed. Moreover, in this invention, since transparency and a softness
  • the polyethylene resin is preferably a density of 0.850 ⁇ 0.920g / cm 3, the density is more preferably a linear low density polyethylene 0.860 ⁇ 0.880g / cm 3. Further, in the linear low density polyethylene, it is particularly preferable that the type of ⁇ -olefin as a copolymerization component is the same as that of the polyethylene resin used for obtaining the silane-modified ethylene resin (X).
  • polyethylene resins having a low density examples include trade names “Engage”, “Affinity”, and “Infuse” manufactured by Dow Chemical Co., Ltd. ”, Trade names“ TAFMER A ”,“ TAFMER P ”manufactured by Mitsui Chemicals, Inc., and“ kernel ”manufactured by Nippon Polyethylene Co., Ltd. it can.
  • the mixing mass ratio when the resin layer (I) -2 is a resin layer mainly composed of a mixture of the silane-modified ethylene resin (X) and the polyethylene resin (F) is not particularly limited.
  • the silane-modified ethylene resin (X) / polyethylene resin (F) ratio is 1 to 99/99 to 1, preferably 2 to 70/98 to 30, more preferably 3 to 40/97 to 60.
  • the content of the silane-modified ethylene resin (X) in the resin layer (I) -2 that is, the silane-modified group concentration can be easily adjusted, and the main role of the resin layer (I) -2 While maintaining the function as an adhesive layer, it is preferable because various properties such as flexibility, transparency, sealing properties and heat resistance as a surface layer and a sealing layer can be adjusted relatively easily.
  • the resin layer (I) -2 has a role of mainly expressing functions as a surface layer, a sealing layer and an adhesive layer in the solar cell multilayer body of the present invention. For this reason, it is preferable that the resin used for the resin layer (I) -2 has flexibility. On the other hand, the resin layer (I) -2 is also required to prevent blocking due to softening as a surface layer.
  • the Vicat softening temperature of the resin layer (I) -2 is preferably 60 ° C. or less, more preferably 30 ° C. or more and less than 60 ° C., 35 More preferably, it is not lower than 55 ° C. and not higher than 55 ° C.
  • the flexibility of the resin layer (I) -2 is sufficiently secured, and it is difficult to block in a normal storage environment (temperature 30 ° C., humidity 50%), which is preferable.
  • the Vicat softening temperature can be measured according to JIS K7206. Specifically, the heat transfer medium is raised at a rate of 50 ° C./hour while applying a total load of 10 N (A method) through a needle-like indenter with a tip cross-sectional area of 1 mm 2 placed perpendicular to the test piece in the heating bath. This is the temperature when the tip of the indenter penetrates 1 mm into the test piece.
  • the mixing method in the case of using a mixture of the silane-modified ethylene resin (X) and the polyethylene resin (F) for the resin layer (I) -2 is not particularly limited. May be supplied to the hopper, or may be supplied after melting and mixing all materials in advance to produce pellets.
  • the vinylsilane compound and radical generator added when obtaining the silane-modified ethylene resin (X) may remain without reacting, the silane-modified ethylene resin
  • the thickness of the resin layer (I) is not particularly limited, but is preferably 0.02 to 0.7 mm from the viewpoint of sealing performance and economic efficiency of the solar cell element (cell), More preferably, the thickness is from 05 to 0.6 mm.
  • the resin layer (II) includes the above-described resin composition, that is, a metallocene ethylene polymer (A) having a density of 0.936 to 0.948 g / cm 3 and a crystal melting heat of 150 to 200 J / g, It consists of the sheet
  • the resin layer (I) constituting the solar cell multilayer body of the present invention has various characteristics (flexibility, rigidity, heat resistance, transparency, adhesiveness, etc.) and the like within a range not departing from the gist of the present invention.
  • Other resins can be mixed for the purpose of further improving the molding processability or economy.
  • other resins for example, other polyolefin resins and various elastomers (olefins, styrenes, etc.), polar groups such as carboxyl groups, amino groups, imide groups, hydroxyl groups, epoxy groups, oxazoline groups, thiol groups, etc. Examples thereof include a resin modified with a group.
  • additives can be added to the resin layer (I) as necessary.
  • the additive include a silane coupling agent, an antioxidant, an ultraviolet absorber, a weathering stabilizer, a light diffusing agent, a nucleating agent, a pigment (for example, a white pigment), a flame retardant, and a discoloration preventing agent.
  • Silane coupling agents are useful for improving adhesion to protective materials for sealing materials (glass, resin front sheets, back sheets, etc.) and solar cell elements, such as vinyl groups, acryloxy groups, Examples thereof include compounds having a hydrolyzable group such as an alkoxy group together with an unsaturated group such as a methacryloxy group, an amino group, and an epoxy group.
  • Specific examples of the silane coupling agent include N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropyltriethoxy.
  • Examples thereof include silane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -methacryloxypropyltrimethoxysilane.
  • silane coupling agent is usually about 0.0 to 5.0 parts by mass with respect to 100 parts by mass of the resin composition constituting each resin layer.
  • a coupling agent such as an organic titanate compound can also be used effectively, but it is preferably not added in the present invention.
  • antioxidant various commercially available products can be applied, and various types such as monophenol type, bisphenol type, polymer type phenol type, sulfur type and phosphite type can be mentioned.
  • monophenols include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, and the like.
  • bisphenols examples include 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4 '-Thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 3,9-bis [ ⁇ 1,1-dimethyl- 2- ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ ethyl ⁇ 2,4,9,10-tetraoxaspiro] 5,5-undecane.
  • Examples of the high molecular phenolic group include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-bidoxybenzyl) benzene, tetrakis- ⁇ methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate ⁇ methane, bis ⁇ (3,3′-bis-4′-hydroxy-3′-tert-butylphenyl) butyric acid ⁇ glycol ester, 1,3,5-tris (3 ′, 5′-di-tert-butyl-4 '-Hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, triphenol (vitamin E) and the like.
  • sulfur-based compounds examples include dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiopropionate.
  • phosphites include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, Crick neopentanetetrayl bis (octadecyl phosphite), tris (mono and / or di) phenyl phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10 pho
  • phenol-based and phosphite-based antioxidants are preferably used in view of the effect of the antioxidant, thermal stability, economy and the like, and it is more preferable to use a combination of both.
  • the addition amount of the antioxidant is usually about 0.1 to 1.0 part by mass with respect to 100 parts by mass of the resin composition constituting each resin layer, and 0.2 to 0.5 part by mass is added. It is preferable.
  • ultraviolet absorbers examples include various types such as benzophenone-based, benzotriazole-based, triazine-based, salicylic acid ester-based, and various commercially available products can be applied.
  • benzophenone ultraviolet absorbers examples include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-n.
  • benzotriazole ultraviolet absorber examples include hydroxyphenyl-substituted benzotriazole compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-butylphenyl).
  • Benzotriazole 2- (2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3-methyl-5-t- Butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, etc. It is done.
  • triazine ultraviolet absorbers examples include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- ( 4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) phenol and the like.
  • salicylic acid esters include phenyl salicylate and p-octylphenyl salicylate.
  • the addition amount of the ultraviolet absorber is usually about 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the resin composition constituting each resin layer, and 0.05 to 0.5 parts by mass is added. It is preferable.
  • Hindered amine light stabilizers are preferably used as the weather stabilizer for imparting weather resistance in addition to the above ultraviolet absorbers.
  • a hindered amine light stabilizer does not absorb ultraviolet rays like an ultraviolet absorber, but exhibits a remarkable synergistic effect when used together with an ultraviolet absorber.
  • hindered amine light stabilizers include dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1 , 3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ 2, 2,6,6-tetramethyl-4-piperidyl ⁇ imino ⁇ ], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3 , 5-Di-tert-4 Hydroxybenzyl) -2-
  • the amount of the hindered amine light stabilizer added is usually about 0.01 to 0.5 parts by mass and 0.05 to 0.3 parts by mass with respect to 100 parts by mass of the resin composition constituting each resin layer. It is preferable to add a part.
  • Multilayer for sealing solar cells It is preferable to use the sheet
  • the multilayer for sealing solar cells is excellent in moisture resistance, and has a water vapor transmission rate of 3.0 g / (m 2 ⁇ 24 hours) or less measured at a total thickness of 0.3 mm, a temperature of 40 ° C., and a relative humidity of 90%. It is preferable that In the present invention, it is more preferably 2.0 g / (m 2 ⁇ 24 hours) or less from the viewpoint of durability and long-term reliability of the solar cell module produced using the multilayer body for sealing solar cells.
  • Such excellent moisture resistance in the present invention is mainly due to the combination of the ethylene resin (A) and the crystal nucleating agent (B), and also the olefin compatible resin (C) and / or the cyclic olefin resin. It can be achieved by adding an olefin resin (D) such as
  • the water vapor transmission rate can be measured by various known methods. In the present invention, the temperature is 40 ° C. using PERMATRAN W 3/31 manufactured by MOCON in accordance with JIS K7129B. The water vapor transmission rate of a multilayer sheet having a total thickness of 0.3 mm was measured under the condition of 90% relative humidity.
  • the multi-layer body for solar cell sealing can appropriately adjust its flexibility and rigidity in consideration of the shape and thickness of the solar cell to be applied, the installation location, and the like. For example, handling property when a solar cell sealing multilayer body is collected in the form of a sheet, prevention of blocking between sheet surfaces, or weight reduction in a solar cell module (usually about 3 mm, thin film glass (about 1.1 mm) ) Is applicable, or a glass-less configuration is applicable), and the storage elastic modulus (E ′) at a vibration frequency of 10 Hz and a temperature of 20 ° C. in the dynamic viscoelasticity measurement is preferably 100 to 1000 MPa, More preferably, it is 250 to 900 MPa, more preferably 300 to 700 MPa, and particularly preferably 400 to 600 MPa.
  • the storage elastic modulus (E ′) can be obtained by measuring a predetermined temperature range at a vibration frequency of 10 Hz using a dynamic viscoelasticity measuring apparatus and obtaining a value at a temperature of 20 ° C.
  • the multilayer body for solar cell sealing has a multilayer structure having the resin layer (I) and the resin layer (II) as at least one of the outermost layers, the characteristics required for the surface layer such as adhesion and flexibility It is possible to balance the properties required for the entire multilayer body such as moisture resistance and handling properties (rigidity) in a well-balanced manner.
  • the solar cell sealing multilayer body employs a soft layer as the resin layer (I) and a hard layer as the resin layer (II).
  • a soft layer as the resin layer (I)
  • a hard layer as the resin layer (II).
  • flexibility and handling properties can be achieved in a well-balanced manner.
  • the solar cell sealing multilayer body may have a laminated structure of two or more layers of the resin layer (I) and the resin layer (II), but the curling prevention (maintaining flatness) and film-forming property as the multilayer body.
  • a symmetrical configuration such as a resin layer (I) / resin layer (II) / resin layer (I), in other words, a soft layer / a hard layer / a soft layer, two-layer / three-layer configuration is preferable.
  • the soft layer is not particularly limited, but is a layer having a storage elastic modulus (E ′) at a vibration frequency of 10 Hz and a temperature of 20 ° C. in dynamic viscoelasticity measurement of preferably 100 MPa or less, more preferably 5 to 50 MPa.
  • the hard layer is a layer having a storage elastic modulus (E ′) preferably exceeding 100 MPa, more preferably 200 to 3000 MPa, and still more preferably 500 to 2000 MPa.
  • the solar cell sealing multilayer body is used as, for example, a solar cell sealing material
  • the protection property (cushioning property) of the solar cell element and the handling property as a whole sealing material It is preferable that both the elastic modulus at room temperature and the like can be realized relatively easily.
  • the total light transmittance at a total thickness of 0.3 mm of the solar cell sealing multilayer body is applied to the type of solar cell to be applied, for example, an amorphous thin-film silicon type or a portion that does not block sunlight reaching the solar electronic element. In some cases, it may not be considered as important, but it is preferably 85% or more, more preferably 88% or more in consideration of the photoelectric conversion efficiency of the solar cell and workability when stacking various members. Preferably, it is 90% or more.
  • the total light transmittance can be measured by various known methods. In the present invention, the “reflection / transmittance” manufactured by Murakami Color Research Laboratory Co., Ltd. is used in accordance with JIS K7105. The total light transmittance of a multilayer sheet having a total thickness of 0.3 mm was measured using a “meter”.
  • the solar cell sealing multilayer body is a solar cell encapsulant that is easy to form a solar cell module, can omit the cross-linking step, and has excellent transparency, moisture resistance, sealing properties, handling properties (rigidity), etc. Is preferably used.
  • the storage elastic modulus (E ′) at a vibration frequency of 10 Hz and a temperature of 20 ° C. in dynamic viscoelasticity measurement is 300. It is preferable that the water vapor transmission rate measured at ⁇ 700 MPa, temperature 40 ° C.
  • the water vapor permeability measured at a vibration frequency of 10 Hz, a storage elastic modulus (E ′) at a temperature of 20 ° C. of 400 to 600 MPa, a temperature of 40 ° C. and a relative humidity of 90% in the dynamic viscoelasticity measurement is 2.0 g / ( m 2 ⁇ 24 hours) and the total light transmittance is 87% or more, and more preferably, the storage elastic modulus (E ′) at a vibration frequency of 10 Hz and a temperature of 20 ° C.
  • the water vapor transmission rate measured at a temperature of 40 ° C. and a relative humidity of 90% is 1.0 g / (m 2 ⁇ 24 hours) or less, and the total light transmittance is 88% or more.
  • the heat resistance of the solar cell sealing multilayer body is affected by various properties (crystal melting peak temperature, crystal melting heat amount, MFR, molecular weight, etc.) of the resin used for the resin layer (I) and the resin layer (II).
  • crystal melting peak temperature crystal melting heat amount, MFR, molecular weight, etc.
  • MFR molecular weight, etc.
  • a solar cell module is heated to about 85 to 90 ° C. due to heat generated during power generation or radiant heat of sunlight, but if the crystal melting peak temperature is 100 ° C. or higher, the heat resistance of the multilayer body for solar cell sealing Can be secured.
  • the total thickness of the solar cell sealing multilayer body is not particularly limited, but is usually about 0.03 to 1.0 mm, preferably from the viewpoint of transparency, moisture resistance, handling properties, and the like. Is used in the form of a sheet of 0.10 to 0.75 mm.
  • the manufacturing method of the multilayer body for solar cell sealing is demonstrated.
  • a method for forming a sheet-like multilayer for sealing solar cells a known method, for example, a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader or other melt mixing equipment, and extrusion using a T die
  • a casting method, a calendar method, an inflation method, and the like can be employed, and are not particularly limited, but in the present invention, an extrusion casting method using a T die is preferably used from the viewpoint of handling properties, productivity, and the like. It is done.
  • the molding temperature in the extrusion casting method using a T-die is appropriately adjusted according to the flow characteristics and film forming properties of the resin composition constituting each resin layer, but is generally 130 to 280 ° C., preferably 150 to 250 ° C. It is.
  • a multilayering method a known method such as a co-extrusion method, an extrusion lamination method, a heat lamination method, a dry lamination method, or the like can be used, but in the present invention, handling property, productivity, etc. From the viewpoint of the above, a coextrusion method is preferably used.
  • various multilayer die can be selected, and examples thereof include a feed block method and a multi-manifold method.
  • a dumbbell base, a capsule base, or the like can be used as appropriate for the purpose of preventing the trimming efficiency of each resin layer and the decrease in transparency during regeneration addition.
  • the thickness ratio to the total thickness of the resin layer (II) is preferably 10% or more and 90% or less, and 20% or more and 60% or less. More preferably, it is 25% or more and 45% or less.
  • a solar cell sealing multilayer body excellent in balance between moisture resistance, rigidity and transparency is preferable.
  • the solar cell sealing multilayer body is excellent in rigidity at room temperature, for example, when used for a flexible type solar cell module, rigidity (waistness) can be imparted, and also used for a rigid type solar cell module.
  • thin glass for example, 1.1 mm
  • a structure such as glassless can be applied, and weight reduction can be expected.
  • the multilayer structure for solar cell sealing preferably uses the above-described two-layer / three-layer structure of the resin layer (I) / resin layer (II) / resin layer (I), but has improved characteristics as a solar cell module. It is also possible to employ other laminated structures for the purpose of adjusting the appearance and improving the warp and curl.
  • the playback layer can be added with scrolls generated by trimming the ears or adjusting the width of the product that are produced when the solar cell sealing multilayer body is formed.
  • the resin layer (II) does not deteriorate moisture resistance, transparency, rigidity, etc., which are the main functions of the resin layer (II). It is preferable to set and add a reproduction layer without adding as much as possible the scroll generated by the width adjustment (slit).
  • the method of mixing various additives such as antioxidants, ultraviolet absorbers, weathering stabilizers, etc. used for the solar cell sealing multilayer body may be dry blended with the resin in advance and then supplied to the hopper. Pellets may be supplied after melting and mixing the materials, or a master batch in which only the additive is previously concentrated in the resin may be prepared and supplied. Moreover, on the surface and / or the back surface of the solar cell sealing multilayer body obtained in the form of a sheet, if necessary, it is possible to prevent blocking between sheets when the sheet is used as a scroll or to seal a solar cell element. Embossing and various irregularities (cone, pyramid shape, hemispherical shape, etc.) may be performed for the purpose of improving the ease of handling and air bleeding.
  • another base film for example, stretched polyester film (OPET), stretched polypropylene film (OPP) or ETFE (tetrafluoroethylene / ethylene copolymer), PVF (polyvinyl fluoride), PVDF (polyvinylidene fluoride) and various weathering films such as acrylic) and the like may be laminated by methods such as extrusion lamination, coextrusion and sand lamination.
  • OPET stretched polyester film
  • OPP stretched polypropylene film
  • ETFE tetrafluoroethylene / ethylene copolymer
  • PVF polyvinyl fluoride
  • PVDF polyvinylidene fluoride
  • various weathering films such as acrylic
  • the solar cell sealing multilayer body is used as a solar cell member, and the portion thereof is not particularly limited, but is mainly a portion as a solar cell sealing material that adheres and protects the solar cell element.
  • the solar cell module is also used for a portion that is not in close contact with the solar cell element for the purpose of adjusting the flexibility, rigidity, curl, thickness and dielectric breakdown voltage of the entire solar cell module.
  • the constituent layer of the upper protective material of the solar cell module such as the upper protective material / sealing material / solar cell element / sealing material / lower protective material
  • the outermost surface layer / multilayer for solar cell sealing / barrier layer outermost surface layer / barrier layer / multilayer for solar cell sealing, outermost surface layer / multilayer for solar cell sealing, outermost surface layer / sun Battery sealing multilayer / barrier layer / solar battery sealing multilayer, and the like.
  • solar cell sealing multilayer / barrier layer / backmost layer As a constituent layer of the lower protective material, solar cell sealing multilayer / barrier layer / backmost layer, other polyolefins Layer (such as CPP) / multilayer body for solar cell sealing / barrier layer / outermost back layer, other polyolefin layer (such as CPP) / barrier layer / multilayer body for solar cell sealing / outermost back surface layer and other polyolefin layers ( CPP etc.) / Multilayer for solar cell sealing / outermost layer etc. It is below.
  • the solar cell sealing material that adheres to and protects the solar cell element includes a solar cell sealing multilayer body, or Commercially available EVA or ionomer type solar cell encapsulant can be used.
  • a solar cell module manufactured using a solar cell sealing multilayer body as a solar cell sealing material that adheres to and protects a solar cell element will be described.
  • a solar cell module can be manufactured by fixing a solar cell element with a front sheet and a back sheet, which are upper and lower protective materials, using a multilayer body for encapsulating solar cells.
  • a solar cell module various types can be exemplified, and preferably a solar cell sealing multilayer body is used as a sealing material, and an upper protective material, a solar cell element, and a lower protective material are used.
  • the solar cell module produced using the material, specifically, the solar cell from both sides of the solar cell element such as upper protective material / sealing material / solar cell element / sealing material / lower protective material.
  • a solar cell element formed on the inner peripheral surface for example, a structure in which an amorphous solar cell element is formed on a fluororesin transparent protective material by sputtering or the like, and a sealing material and a lower protective material are formed. Is mentioned.
  • the solar cell sealing multilayer body when the sealing material is used in two or more parts, the solar cell sealing multilayer body may be used in all parts.
  • a solar cell sealing multilayer body may be used in only one part.
  • the resin layer (I) and the resin layer (II) constituting the solar cell sealing multilayer body used in each part are constituted.
  • the composition of the resin composition and the thickness ratio of the resin layer (I) and the resin layer (II) in the multilayer body may be the same or different.
  • the solar cell module is produced so that the resin layer (I) side of the solar cell sealing multilayer body is in contact with the solar cell element side, which is sufficient for sealing the solar cell element. It is preferable because excellent adhesiveness and sealing properties can be obtained.
  • Examples of the solar cell element arranged and wired between the sealing materials include, for example, III-type such as single crystal silicon type, polycrystalline silicon type, amorphous silicon type, gallium-arsenic, copper-indium-selenium, cadmium-tellurium, etc.
  • III-type such as single crystal silicon type, polycrystalline silicon type, amorphous silicon type, gallium-arsenic, copper-indium-selenium, cadmium-tellurium, etc.
  • Examples include group V and II-VI compound semiconductor types, dye sensitized types, and organic thin film types.
  • each member which comprises the solar cell module produced using the multilayer body for solar cell sealing although it does not specifically limit,
  • glass, an acrylic resin, polycarbonate, polyester examples thereof include a plate material such as a fluorine-containing resin and a single layer or multilayer protective material for a film.
  • the lower protective material is a single layer or multilayer sheet such as metal or various thermoplastic resin films, for example, metals such as tin, aluminum and stainless steel, inorganic materials such as glass, polyester, inorganic vapor deposition polyester, fluorine-containing resin.
  • a single-layer or multilayer protective material such as polyolefin.
  • the surface of the upper and / or lower protective material can be subjected to a known surface treatment such as a primer treatment or a corona treatment in order to improve adhesion to the solar cell sealing multilayer body or other members. .
  • a sealing material (resin layer (I) / resin layer (II) / resin layer (I)) / lower protective material is sandwiched from both sides of the solar cell element with a sealing material. .
  • a sealing material A using a multilayer body for sealing a solar cell (resin layer (I) / resin layer (II) / resin layer (I)), solar cell element, solar cell A sealing material B using a multilayer body for sealing (resin layer (I) / resin layer (II) / resin layer (I)) and a back sheet are laminated, and a junction box ( A terminal box for connecting wiring for taking out electricity generated from the solar cell element to the outside is bonded.
  • the solar cell elements are connected by wiring in order to conduct the generated current to the outside. The wiring is taken out through a through hole provided in the backsheet and connected to the junction box.
  • a known manufacturing method can be applied, and it is not particularly limited, but in general, an upper protective material, a sealing material, a solar cell element, a sealing material, a lower protective material. And a step of vacuum-sucking them and heat-pressing them. Also, batch type manufacturing equipment, roll-to-roll type manufacturing equipment, and the like can be applied.
  • the solar cell module manufactured using the multilayer body for solar cell sealing of the present invention is installed on a small solar cell represented by a mobile device, a roof or a roof, depending on the type and module shape of the applied solar cell. It can be applied to various applications such as large solar cells, both indoors and outdoors.
  • Internal haze means a value obtained by subtracting the external haze value from the haze value of the entire film. The internal haze was measured by applying dioctyl phthalate (DOP) to both surfaces of a 0.1 mm thick sheet (sample) and adjusting the external haze to zero based on JIS K7105. Those having an internal haze of 10% or less were accepted.
  • DOP dioctyl phthalate
  • Moisture resistance (water vapor transmission rate) Based on JIS K7129B, the water vapor transmission rate at a thickness of 0.1 mm was measured in an atmosphere of 40 ° C. and 90% RH using PERMATRAN W 3/31 manufactured by MOCON. A water vapor transmission rate of 1.20 g / (m 2 ⁇ 24 hours) or less was accepted.
  • Crystallization peak temperature (Tc) Using a differential scanning calorimeter “DSC-7” (manufactured by PerkinElmer), according to JIS K7121, about 10 mg of the sample was heated from ⁇ 40 ° C. to 200 ° C. at a heating rate of 10 ° C./min. After holding for 1 minute, the crystallization peak temperature (Tc) (° C.) was determined from the thermogram measured when the temperature was lowered to ⁇ 40 ° C. at a cooling rate of 10 ° C./min.
  • (G) -1 Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM503, ⁇ -methacryloxypropyltrimethoxysilane)
  • Example 1 After dry blending (A) -1 and (B) -1 at a mixing mass ratio of 99.95: 0.05 to obtain a resin composition, 230A was used using a 40 mm ⁇ co-directional twin screw extruder. After kneading at 0 ° C. and then extruding from a T-die, it was quenched with a casting roll at about 50 ° C. to prepare a sheet (sample) having a thickness of 0.1 mm. The obtained sheet (sample) was evaluated for transparency and moisture resistance. The results are shown in Table 1.
  • Example 2 A resin composition and a sheet (sample) were prepared in the same manner as in Example 1 except that the mixing mass ratio of (A) -1 and (B) -1 was 99.9: 0.1. Evaluation was performed in the same manner. The results are shown in Table 1.
  • Example 3 A resin composition and a sheet (sample) were prepared in the same manner as in Example 1 except that the mixing mass ratio of (A) -1 and (B) -1 was 99.8: 0.2. Evaluation was performed in the same manner. The results are shown in Table 1.
  • Example 4 Examples were obtained except that (A) -1, (B) -1, and (C) -1 were dry blended at a mixing mass ratio of 79.9: 0.1: 20 to obtain a resin composition.
  • a sheet (sample) was prepared in the same manner as in No. 1 and evaluated in the same manner. The results are shown in Table 1.
  • Example 5 A resin composition obtained by dry blending (A) -1, (B) -1, (C) -1, and (D) -1 at a mixing mass ratio of 49.9: 0.1: 20: 30 A sheet (sample) was prepared in the same manner as in Example 1 except that the evaluation was performed, and the evaluation was performed in the same manner. The results are shown in Table 1.
  • Example 6 A sheet (A) -2 and (B) -1 were prepared in the same manner as in Example 1 except that a resin composition was obtained by dry blending at a mixing mass ratio of 99.9: 0.1. Sample) was prepared and evaluated in the same manner. The results are shown in Table 1.
  • Example 7 A sheet (A) -3 and (B) -1 were prepared in the same manner as in Example 1 except that a resin composition was obtained by dry blending at a mixing mass ratio of 99.9: 0.1. Sample) was prepared and evaluated in the same manner. The results are shown in Table 1.
  • Example 8 Examples were obtained except that (A) -1, (B) -1, and (C) -2 were dry blended at a mixing mass ratio of 79.9: 0.1: 20 to obtain a resin composition.
  • a sheet (sample) was prepared in the same manner as in No. 1 and evaluated in the same manner. The results are shown in Table 1.
  • Example 2 A sheet (sample) was prepared in the same manner as in Example 1 except that (A) -1 and (C) -1 were dry blended at a mixing mass ratio of 80:20 to obtain a resin composition. The same evaluation was made. The results are shown in Table 1.
  • moisture resistance and transparency can be further improved by further blending an olefin-compatible resin (C) that is compatible with the metallocene ethylene polymer (A) (see Examples 4 and 8). . Furthermore, it was also found that moisture resistance and transparency can be further improved by further blending an olefin resin (D) having a heat of crystal melting of 0 to 100 J / g (see Example 5).
  • Examples of multilayer bodies using the present resin composition are shown below.
  • the following evaluation was performed in addition to the above evaluation.
  • (8) Crystal melting peak temperature (Tm) Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., trade name “Pyris1 DSC”, according to JIS K7121, about 10 mg of sample was heated from ⁇ 40 ° C. to 200 ° C. at a heating rate of 10 ° C./min. After holding at 200 ° C. for 1 minute, the temperature was lowered to ⁇ 40 ° C. at a cooling rate of 10 ° C./min, and again from the thermogram measured from the thermogram measured when the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min. (Tm) (° C.) was determined.
  • Vicat softening temperature Measured according to JIS K7206. That is, the temperature of the heat transfer medium is increased at a rate of 50 ° C./hour while applying a total load of 10 N (A method) through a needle-like indenter having a tip cross-sectional area of 1 mm 2 placed perpendicular to the test piece in the heating bath, The temperature when the tip of the indenter entered 1 mm into the test piece was measured.
  • the storage elastic modulus (E ′) at 20 ° C. is 300 MPa or more and 700 MPa or less ( ⁇ )
  • the storage elastic modulus (E ′) at 20 ° C. is 100 MPa or more and less than 300 MPa, or more than 700 MPa and 1000 MPa or less.
  • Yes ( ⁇ ) Storage elastic modulus (E ′) at 20 ° C. exceeds 1000 MPa
  • a multilayer sheet having a total thickness of 0.3 mm is stacked between a white sheet glass (size: 75 mm length, 25 mm width) and an aluminum plate (size: length 120 mm, width 60 mm) having a thickness of 3 mm, and vacuum is applied.
  • a press machine Using a press machine, a sample which was laminated and pressed at 150 ° C. for 15 minutes was prepared, and the sample was installed at an inclination of 60 ° C. in a constant temperature and humidity chamber of 85 ° C. and 85% RH. was observed and evaluated according to the following criteria.
  • ⁇ Glass deviated from the initial reference position, or the sheet melted
  • Example 9 After dry blending (P) -1, (Q) -1, and (G) -1 at a mixing mass ratio of 94.5: 5: 0.5, using a ⁇ 40 mm co-directional twin screw extruder Extrusion was carried out at a set temperature of 190 to 200 ° C. as a resin layer (I) serving as both outer layers from a two-type, three-layer multi-manifold die. At the same time, after dry blending (A) -1 and (B) -1 at a mixing mass ratio of 99.9: 0.1, an intermediate layer is formed from the same die using a ⁇ 40 mm co-directional twin screw extruder.
  • the resulting resin layer (II) was extruded at a set temperature of 200 to 220 ° C. At this time, the thickness of each layer is such that the resin layer (I) / resin layer (II) / resin layer (I) is 0.1 / 0.1 / 0.1 (mm). Adjusted. Next, this coextruded sheet was quenched with a cast roll of about 20 ° C. to obtain a multilayer sheet having a thickness of 0.3 mm. The obtained multilayer sheet was evaluated for transparency, water vapor transmission rate, and heat resistance. The results are shown in Table 2.
  • Example 10 (Example 10) In Example 9, (A) -1, (B) -1 and (C) -1 were mixed in a resin mass (79.9: 0.1: 20) constituting the resin layer (II). A multilayer sheet was prepared and evaluated by the same method and thickness structure as in Example 9 except that the mixture was mixed at a ratio. The results are shown in Table 2.
  • Example 11 In Example 9, as the resin composition constituting the resin layer (II), (A) -1, (B) -1, (C) -1 and (D) -1 were mixed in a mass ratio of 49.9: A multilayer sheet was prepared and evaluated in the same manner and thickness as in Example 9 except that the mixture was changed to a mixture of 0.1: 20: 30. The results are shown in Table 2.
  • Example 12 Production and evaluation of a multilayer sheet with the same method and thickness as in Example 11 except that (A) -1 in the resin composition constituting the resin layer (II) was changed to (A) -2 in Example 11. Went. The results are shown in Table 2.
  • Example 13 In Example 11, a multilayer sheet was produced by the same method and thickness as in Example 9 except that (P) -1 in the resin composition constituting the resin layer (I) was changed to (P) -2. Evaluation was performed. The results are shown in Table 2.
  • Example 14 In Example 11, a multilayer sheet was produced by the same method and thickness as in Example 11 except that (C) -1 in the resin composition constituting the resin layer (II) was changed to (C) -2. And evaluated. The results are shown in Table 2.
  • Example 15 After dry blending (P) -1, (Q) -1, and (G) -1 at a mixing mass ratio of 94.5: 5: 0.5, using a ⁇ 40 mm co-directional twin screw extruder The resin layer (I) was extruded from a two-type two-layer multi-manifold die at a set temperature of 190 to 200 ° C. At the same time, after dry blending (A) -1, (B) -1, (C) -1, and (D) -1 at a mixing mass ratio of 49.9: 0.1: 20: 30 The resin layer (II) was extruded from the same die at a set temperature of 200 to 220 ° C.
  • Example 16 Using a vacuum laminator LM30 ⁇ 30 manufactured by NPC, hot plate temperature: 150 ° C., processing time: 20 minutes (breakdown, evacuation: 5 minutes, press: 5 minutes, pressure retention: 10 minutes), pressure bonding Speed: Under rapid conditions, in order from the hot plate side, a white sheet glass having a thickness of 3 mm (made by Asahi Glass Co., Ltd., trade name: Solite) as an upper protective material, a multilayer sheet having a thickness of 0.3 mm collected in Example 11 (Sealant, resin layer (I) is solar cell element side), solar cell element (cell) having a thickness of 0.4 mm (manufactured by Photowatt, model: 101 ⁇ 101 MM), the thickness collected in Example 11 0.3 mm multilayer sheet (sealing material, resin layer (I) is solar cell element side), weather-resistant PET film having a thickness of 0.125 mm as a lower protective material (trade name: Lumirror X10S manufactured by Toray Industries, Inc
  • (Example 17) (X) -1 and (F) -1 are mixed at a ratio of 30:70 by using a ⁇ 40 mm same-direction twin screw extruder, and a resin layer (both outer layers) from a two-kind, three-layer multi-manifold die ( Extrusion was performed at a set temperature of 180 to 200 ° C. as I).
  • a resin layer (II) which is an intermediate layer from the same die using (A) -1 and (B) -1 at a mixing mass ratio of 99.9: 0.1 using a ⁇ 40 mm co-directional twin-screw extruder.
  • the obtained multilayer sheet was evaluated for transparency, moisture resistance, heat resistance, and the like. The results are shown in Table 3.
  • Example 18 the resin composition constituting the resin layer (II) was prepared by mixing (A) -1, (B) -1, and (C) -1 in a mixing mass ratio of 79.9: 0.1: 20.
  • a multilayer sheet was obtained by the same method and thickness as in Example 17 except for the change. The obtained multilayer sheet was evaluated for transparency, moisture resistance, heat resistance, and the like. The results are shown in Table 3.
  • Example 19 In Example 18, a multilayer sheet was obtained by the same method and thickness as in Example 17 except that (C) -1 in the resin composition constituting the resin layer (II) was changed to (C) -2. . The obtained multilayer sheet was evaluated for transparency, moisture resistance, heat resistance, and the like. The results are shown in Table 3.
  • Example 20 the resin composition constituting the resin layer (II) was prepared by mixing (A) -1, (B) -1, (C) -1 and (D) -1 with a mixing mass ratio of 49.9: 0.
  • a multilayer sheet was obtained by the same method and thickness as in Example 17 except that the ratio was changed to 1:20:30.
  • the obtained multilayer sheet was evaluated for transparency, moisture resistance, heat resistance, and the like. The results are shown in Table 3.
  • Example 21 In Example 20, a multilayer sheet was obtained by the same method and thickness as in Example 20 except that (A) -1 in the resin composition constituting the resin layer (II) was changed to (A) -2. It was. The obtained multilayer sheet was evaluated for transparency, moisture resistance, heat resistance, and the like. The results are shown in Table 3.
  • Example 22 Using a vacuum laminator manufactured by NPC Corporation, product name “LM30 ⁇ 30”, hot plate temperature: 150 ° C., processing time: 20 minutes (breakdown, vacuuming: 5 minutes, press: 5 minutes , Pressure retention: 10 minutes), pressure bonding speed: obtained under the conditions of rapid, white plate glass (made by Asahi Glass Co., Ltd., trade name: Solite) having a thickness of 3 mm as an upper protective material in order from the hot plate side, in each example.
  • LM30 ⁇ 30 hot plate temperature: 150 ° C.
  • processing time 20 minutes (breakdown, vacuuming: 5 minutes, press: 5 minutes , Pressure retention: 10 minutes)
  • pressure bonding speed obtained under the conditions of rapid, white plate glass (made by Asahi Glass Co., Ltd., trade name: Solite) having a thickness of 3 mm as an upper protective material in order from the hot plate side, in each example.

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Abstract

L'invention concerne une nouvelle composition de résine qui est apte à fournir une feuille qui est obtenue par moulage de la composition de résine ayant une transparence suffisante et des propriétés suffisantes de prévention d'humidité. La composition de résine contient un polymère éthylène métallocène (A) qui a une masse volumique de 0,936-0,948 g/cm3 et une enthalpie de fusion cristalline de 150-200 J/g et un agent (B) de nucléation de cristaux, et est caractérisé en ce que le rapport du composant (B) dans la quantité totale des composants (A) et (B) contenus dans celui-ci est de 0,01-3 % en masse.
PCT/JP2011/073349 2010-10-12 2011-10-11 Composition de résine ayant une excellente transparence et d'excellentes propriétés de prévention d'humidité, et feuille obtenue par moulage de la composition WO2012050093A1 (fr)

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JP2010-229940 2010-10-12
JP2010229940 2010-10-12
JP2010-267013 2010-11-30
JP2010267013 2010-11-30
JP2010288460A JP5593215B2 (ja) 2010-12-24 2010-12-24 太陽電池用多層体及びそれを用いて作製された太陽電池モジュール
JP2010-288460 2010-12-24
JP2011-152756 2011-07-11
JP2011152756 2011-07-11

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