WO2017150217A1 - Resin sheet, laminated glass, and solar cell module - Google Patents

Resin sheet, laminated glass, and solar cell module Download PDF

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Publication number
WO2017150217A1
WO2017150217A1 PCT/JP2017/005905 JP2017005905W WO2017150217A1 WO 2017150217 A1 WO2017150217 A1 WO 2017150217A1 JP 2017005905 W JP2017005905 W JP 2017005905W WO 2017150217 A1 WO2017150217 A1 WO 2017150217A1
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Prior art keywords
resin sheet
mass
vinyl acetate
ethylene
parts
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PCT/JP2017/005905
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French (fr)
Japanese (ja)
Inventor
理恵 大土井
洋文 善光
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三井化学東セロ株式会社
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Publication of WO2017150217A1 publication Critical patent/WO2017150217A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • 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 sheet, a laminated glass, and a solar cell module.
  • An ethylene / vinyl acetate copolymer is widely used for an interlayer film for laminated glass, a solar cell encapsulant, a building material and the like because of its excellent insulation and high transparency.
  • Patent Document 1 International Publication No. 2005/090504.
  • Patent Document 1 discloses a sheet-like adhesive containing an ethylene / vinyl acetate copolymer and an organic peroxide.
  • An organic peroxide is used as the crosslinking agent, and a cyanurate-based or acrylate-based compound is generally used as the crosslinking assistant.
  • a laminated glass or a solar cell module using a conventional resin sheet using an ethylene-vinyl acetate copolymer has poor transparency (haze), bubbles are generated, and a resin sheet is not formed. It has become clear that there are problems such as gelation during molding. As described above, the present inventors have found that there is still room for improvement in terms of achieving compatibility of transparency, bubble prevention and gel suppression with a resin sheet using a conventional ethylene-vinyl acetate copolymer. It was.
  • the present invention has been made in view of the above circumstances, and provides a resin sheet made of an ethylene / vinyl acetate copolymer that is excellent in transparency and bubble-preventing properties and in which the generation of gel is suppressed.
  • the inventors of the present invention have intensively studied in order to achieve the above-mentioned problems.
  • the inventors have found that it can be improved and have reached the present invention.
  • the following resin sheet, laminated glass and solar cell module are provided.
  • a resin sheet used for an interlayer film for laminated glass or a solar cell sealing material An ethylene / vinyl acetate copolymer; A carbonate-based organic peroxide as a crosslinking agent; A cyanurate compound which is a crosslinking aid; Including The content of the carbonate organic peroxide in the resin sheet is 1.0 part by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer, The resin sheet whose content of the said cyanurate compound in the said resin sheet is 1.2 mass parts or more and 1.5 mass parts or less with respect to 100 mass parts of said ethylene-vinyl acetate copolymers.
  • An intermediate film for glass comprising the resin sheet according to any one of the above [1] to [8]; Transparent substrates provided on both surfaces of the interlayer film for laminated glass, Laminated glass with.
  • Transparent substrates provided on both surfaces of the interlayer film for laminated glass, Laminated glass with.
  • a resin sheet made of an ethylene / vinyl acetate copolymer that is excellent in transparency and bubble prevention properties and suppresses the generation of gel.
  • Resin sheet The resin sheet according to the present embodiment is a resin sheet used for an interlayer film for laminated glass or a solar cell encapsulant, and an ethylene / vinyl acetate copolymer and a carbonate organic peroxide that is a cross-linking agent. And a cyanurate compound which is a crosslinking aid. And the content of the carbonate organic peroxide in the resin sheet is 1.0 part by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer, The content of the cyanurate compound in the resin sheet is 1.2 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer.
  • the inventors of the present invention have made extensive studies in order to provide a resin sheet made of an ethylene / vinyl acetate copolymer that is excellent in transparency and bubble prevention properties, and in which the generation of gel is suppressed.
  • a resin sheet made of an ethylene / vinyl acetate copolymer that is excellent in transparency and bubble prevention properties, and in which the generation of gel is suppressed.
  • a carbonate organic peroxide and a cyanurate compound as constituents of the resin sheet, and by setting the blending ratio thereof within the above range, transparency, bubble prevention and gel suppression are well balanced. I found that it can be improved. That is, the resin sheet according to the present embodiment is excellent in transparency and bubble prevention properties and can suppress the generation of gel.
  • the mass ratio of the content of the cyanurate compound to the content of the carbonate organic peroxide in the resin sheet according to the present embodiment is preferably 0.9 or more and 1.5 or less.
  • the total content of the carbonate organic peroxide and the cyanurate compound in the resin sheet according to the present embodiment is preferably 2.3 parts by mass or more with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer. It is 2.8 parts by mass or less.
  • the average film thickness of the resin sheet according to this embodiment is not particularly limited, but is preferably 0.2 mm or more and 2.0 mm or less.
  • the average film thickness of the resin sheet is equal to or more than the above lower limit value, the mechanical strength of the resin sheet can be further improved, and thermal shrinkage of the resin sheet can be suppressed.
  • the average film thickness of the resin sheet is not more than the above upper limit value, damage of other members such as a transparent substrate can be suppressed in the laminating step, and the laminate can be formed on the transparent substrate even at a relatively low temperature.
  • sufficient light transmittance can be ensured as the average film thickness of a resin sheet is below the said upper limit, and the solar cell module using it has a high photovoltaic power generation amount.
  • the content of the ethylene / vinyl acetate copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% when the entire resin component contained in the resin sheet is 100% by mass. It is at least 100% by mass, and particularly preferably 100% by mass. Thereby, it is possible to obtain a resin sheet excellent in balance of various properties such as transparency, adhesiveness, heat resistance, flexibility, appearance, cross-linking properties, electrical properties and extrusion moldability.
  • the content of the resin component is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass, when the resin sheet as a whole is 100% by mass. That's it. Thereby, it is possible to obtain a resin sheet excellent in balance of various properties such as transparency, adhesiveness, heat resistance, flexibility, appearance, cross-linking properties, electrical properties and extrusion moldability.
  • the resin sheet according to the present embodiment contains an ethylene / vinyl acetate copolymer as a main component.
  • the ethylene / vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and is usually a random copolymer.
  • the melt flow rate (MFR) of the ethylene / vinyl acetate copolymer measured at 190 ° C. under a load of 2.16 kg is preferably 10 to 50 g / 10 min, more preferably. Is 10 to 40 g / 10 min, more preferably 10 to 30 g / 10 min.
  • the MFR of the ethylene / vinyl acetate copolymer can be adjusted by adjusting the polymerization temperature during the polymerization reaction, the polymerization pressure, and the molar ratio of the monomer concentration and the hydrogen concentration of the copolymerization monomer in the polymerization system. it can.
  • the MFR is not less than the above lower limit
  • the fluidity of the ethylene-based resin composition containing the ethylene / vinyl acetate copolymer is improved, and the moldability of the resin sheet becomes better.
  • the MFR is not more than the above upper limit value
  • the molecular weight is increased, so that adhesion to a roll surface such as a chill roll can be suppressed, and therefore, peeling is unnecessary and the resin sheet can be formed with a more uniform thickness.
  • a thick resin sheet of 0.1 mm or more can be easily formed.
  • a crosslinking characteristic improves, it can fully bridge
  • the content of vinyl acetate units in the ethylene / vinyl acetate copolymer is preferably 25% by mass to 35% by mass, more preferably 28% by mass to 35% by mass, and even more preferably 28% by mass to 33% by mass. % Or less.
  • the content of the vinyl acetate unit is within this range, the balance of crosslinkability, flexibility, weather resistance, and transparency is further improved.
  • the vinyl acetate content can be measured according to JIS K6730.
  • the resin sheet according to the present embodiment is used as a solar cell encapsulant, if the vinyl acetate content is within the above range, crosslinkability, flexibility, solar cell encapsulating sheet adhesion, and weather resistance. , Better balance of transparency and mechanical properties. In addition, when the solar cell encapsulating sheet is formed, the film formability is good.
  • the ethylene / vinyl acetate copolymer is preferably a binary copolymer consisting only of ethylene and vinyl acetate.
  • ethylene and vinyl acetate for example, vinyl formate, vinyl glycolate, vinyl propionate, vinyl benzoate.
  • a vinyl ester monomer such as acrylic acid, methacrylic acid, ethacrylic acid, or an acrylic monomer such as a salt or alkyl ester thereof; Good.
  • the amount of the copolymer component other than ethylene and vinyl acetate in the ethylene / vinyl acetate copolymer may be 0.5 mass% or more and 5 mass% or less. preferable.
  • Two or more kinds of ethylene / vinyl acetate copolymers having different vinyl acetate contents and MFR may be used in combination.
  • the total amount of these is preferably within the above range.
  • the method for producing the ethylene / vinyl acetate copolymer is not particularly limited, and can be produced by a known method.
  • a radical generator copolymerization of ethylene, vinyl acetate, and other copolymerization components as necessary in the presence or absence of a solvent or chain transfer agent at 500 to 4000 atm and 100 to 300 ° C Can be manufactured.
  • the resin sheet which concerns on this embodiment contains the carbonate type organic peroxide which is a crosslinking agent.
  • the crosslinking rate of the ethylene / vinyl acetate copolymer is improved by containing a carbonate-based organic peroxide.
  • the content of the carbonate-based organic peroxide in the resin sheet according to this embodiment is 1.0 part by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer, preferably 1.1 parts by mass or more and 1.3 parts by mass or less.
  • the content of the carbonate-based organic peroxide is not less than the above lower limit, the cross-linking property of the resin sheet becomes good, and the heat resistance of the resin sheet is improved.
  • the graft reaction of the silane coupling agent to the main chain of the ethylene / vinyl acetate copolymer is improved, and the heat resistance and adhesiveness are further improved. Furthermore, the transparency of the resin sheet is improved.
  • the content of the carbonate-based organic peroxide is not more than the above upper limit value
  • the above cross-linking characteristics, heat resistance, and adhesiveness are good, and gelation during sheet molding can be suppressed, and the sheet appearance is good. Can be obtained.
  • the generation amount of decomposition products of carbonate-based organic peroxides can be reduced, and the generation of bubbles in the resin sheet can be suppressed.
  • the scorch resistance of the resin sheet can be improved.
  • Examples of the carbonate organic peroxide include t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-amyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexyl carbonate, and the like. Can be mentioned. Of these, t-butylperoxy-2-ethylhexyl carbonate is preferred.
  • the carbonate organic peroxides may be used alone or in a combination of two or more.
  • the resin sheet which concerns on this embodiment contains the cyanurate compound which is a crosslinking adjuvant from a viewpoint of improving crosslinking
  • the cyanurate compound for example, one or more selected from triallyl cyanurate, triallyl isocyanurate, and the like can be used. Among these, it is preferable that triallyl isocyanurate is included as a cyanurate compound.
  • Content of the cyanurate compound in the resin sheet which concerns on this embodiment is 1.2 mass parts or more and 1.5 mass parts or less with respect to 100 mass parts of ethylene-vinyl acetate copolymers, Preferably it is 1.2. It is not less than 1.4 parts by mass.
  • the content of the cyanurate compound is not less than the above lower limit
  • the cross-linking property of the resin sheet becomes good and the heat resistance of the resin sheet is improved.
  • the graft reaction of the silane coupling agent to the main chain of the ethylene / vinyl acetate copolymer is improved, and the heat resistance and adhesiveness are improved.
  • the transparency of the resin sheet is improved.
  • the content of the cyanurate compound is not more than the above upper limit value, the above-mentioned crosslinking characteristics, heat resistance, and adhesiveness are good, and further, the gelation at the time of sheet molding can be suppressed, and a resin sheet having a good sheet appearance can be obtained. Obtainable.
  • the scorch resistance of the resin sheet can be improved.
  • the resin sheet according to the present embodiment may further include a silane coupling agent.
  • the content of the silane coupling agent in the resin sheet according to this embodiment is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer, and preferably 0.1 to 4 parts.
  • the amount is more preferably part by mass, and particularly preferably 0.1 to 3 parts by mass.
  • Adhesiveness improves that content of a silane coupling agent is more than the said lower limit.
  • the content of the silane coupling agent is not more than the above upper limit value, the balance between cost and performance is good, and deterioration of moisture permeability can be prevented.
  • adhesiveness with a surface side transparent protection member, a cell, an electrode, and a back surface side protection member becomes favorable, and adhesiveness also improves.
  • a conventionally well-known silane coupling agent can be used, and there is no restriction in particular.
  • vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxysilane), ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane Etc. can be used.
  • Preferred examples include ⁇ -glycidoxypropylmethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and the like, which have good adhesion.
  • the resin sheet according to the present embodiment may further contain at least one additive selected from ultraviolet absorbers, light stabilizers, and heat stabilizers.
  • the amount of these additives is preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer.
  • the blending amount of the additive is within the above range, it is possible to sufficiently secure the effect of improving weather resistance stability and heat stability, and to prevent deterioration of transparency and adhesion to a glass plate. Therefore, it is preferable.
  • the ultraviolet absorber examples include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy.
  • Benzophenone ultraviolet absorbers such as -4-carboxybenzophenone and 2-hydroxy-4-N-octoxybenzophenone; 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2 Benzotrialisol ultraviolet absorbers such as -hydroxy-5-methylphenyl) benzotriazole; salicylic acid ester ultraviolet absorbers such as phenylsalicylate and p-octylphenylsalicylate are used.
  • Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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 ⁇
  • Hindered amine light stabilizers, hindered piperidine light stabilizers and the like are preferably used.
  • heat-resistant stabilizers include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester.
  • Phosphorous acid tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, and bis (2,4-di-tert-butylphenyl) Phosphite heat stabilizers such as pentaerythritol diphosphite; lactone heat stabilizers such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene; 3,3 ′, 3 ′′, 5,5 ′, 5 ′′ -hexa-tert-butyl-a, a ′, a ′′-(methylene-2,4,6-triyl) tri-p-cresol, 1,3 , 5-Trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, pentaerythritol te
  • hindered phenol-based heat stabilizers examples thereof include hindered phenol-based heat stabilizers, sulfur-based heat stabilizers, amine-based heat stabilizers, etc. In addition, these can be used alone or in combination of two or more. A heat resistance stabilizer and a hindered phenol heat resistance stabilizer are preferred.
  • the resin sheet which concerns on this embodiment can contain suitably various components other than the various components detailed above in the range which does not impair the objective of this invention.
  • examples thereof include various polyolefins other than the ethylene / vinyl acetate copolymer, styrene-based, ethylene-based block copolymers, and propylene-based polymers. These may be contained in an amount of preferably 0.0001 to 50 parts by mass, more preferably 0.001 to 40 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer.
  • the above additives can be appropriately contained.
  • a stirring mixer such as a Henschel mixer, tumbler or super mixer.
  • the obtained resin composition is put into, for example, a hopper of an extrusion sheet molding machine, and the resin composition is extruded into a sheet form from a T-die of the extrusion sheet molding machine while performing melt kneading to obtain a resin sheet.
  • the extrusion temperature range for example, the extrusion temperature is 100 to 250 ° C. When the extrusion temperature is within the above range, a better sheet can be obtained.
  • Laminated glass The use of the resin sheet according to this embodiment is not particularly limited, but it is preferably used as an interlayer film for laminated glass.
  • the laminated glass of this embodiment should just use the resin sheet which concerns on this embodiment as an intermediate film for laminated glasses.
  • the laminated glass according to the present embodiment is a laminated glass that is less likely to cause poor appearance.
  • FIG. 1 is a cross-sectional view schematically showing one embodiment of a laminated glass 100 of the present invention.
  • the laminated glass 100 includes an intermediate film 101 for laminated glass including the resin sheet according to the present embodiment, and a transparent substrate 103 provided on both surfaces of the intermediate film 101 for laminated glass.
  • the resin sheet according to the present embodiment is used as the laminated glass intermediate film 101, and the laminated glass intermediate film 101 is interposed between the two transparent substrates 103.
  • a method of heating and pressurizing is used. These processes are performed using, for example, a vacuum bag method, a nip roll method, or the like.
  • the interlayer film for laminated glass 101 is cured, and the interlayer film for laminated glass 101 and the two transparent substrates 103 can be bonded and integrated.
  • the above laminate is pre-pressed at a temperature of 80 to 120 ° C., and heat-treated at 100 to 150 ° C. for 10 minutes to 1 hour to crosslink the ethylene / vinyl acetate copolymer. Further, the heat treatment may be performed under pressure.
  • the transparent substrate 103 is, for example, a glass plate such as a green glass plate, a silicate glass plate, an inorganic glass plate, or an uncolored transparent glass plate; polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene butyrate, polymethyl methacrylate
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PMMA polyethylene butyrate
  • a plastic substrate such as (PMMA) or a film can be used.
  • a glass plate is preferable in terms of weather resistance, impact resistance and the like.
  • the thickness of the transparent substrate 103 is generally about 1 to 20 mm.
  • the same transparent substrate 103 may be used for each of the transparent substrates 103 disposed on both surfaces of the laminated glass 100, or different base materials may be used in combination. The combination is determined in consideration of the strength of the base material and the use of the laminated glass.
  • Laminated glass 100 is used for various applications such as materials for buildings and vehicles (automobiles, railcars, ships); electronic devices such as plasma displays; doors and walls of various devices such as refrigerators and heat insulation devices. Can be used. Among these, it can be particularly suitably used for buildings.
  • Solar cell module The application of the resin sheet according to the present embodiment is not particularly limited, but is preferably used as a solar cell sealing material.
  • a solar cell encapsulant also referred to as a solar cell encapsulant sheet
  • a solar cell module is usually a crystal solar cell in which solar cell elements formed of single crystal silicon, polycrystalline silicon or the like are sandwiched between solar cell encapsulant sheets, and both front and back surfaces are covered with a protective sheet. Module.
  • a typical solar cell module includes a solar cell module protective sheet (front surface side transparent protective member) / light-receiving surface side sealing layer / solar cell element / back surface side sealing layer / solar cell module protective sheet (back surface side). (Protective member).
  • the solar cell encapsulant of the present embodiment is used to form one or both of the light-receiving surface side sealing layer and the back surface side sealing layer, and these sealing layers are made of a resin sheet. It can be formed by crosslinking.
  • the solar cell module which is one of the preferred embodiments of the present invention is not limited to the above-described configuration, and a part of each of the above layers is appropriately omitted or the above-described range within a range not impairing the object of the present invention.
  • Other layers can be provided as appropriate. Examples of the layer other than the above include an adhesive layer, a shock absorbing layer, a coating layer, an antireflection layer, a back surface rereflection layer, and a light diffusion layer. These layers are not particularly limited, but can be provided at appropriate positions in consideration of the purpose and characteristics of each layer.
  • the solar cell module 10 includes a plurality of solar cell elements 13, a pair of light-receiving surface side solar cell sealing material sheets 11 and back surface side solar cell sealing material sheets 12 that are sealed with the solar cell elements 13 interposed therebetween, and a front surface side.
  • a transparent protective member 14 and a back surface side protective member (back sheet) 15 are provided.
  • solar cell element 13 examples include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and III-V and II-VI compound semiconductor systems such as gallium-arsenic, copper-indium-selenium, and cadmium-tellurium. Various solar cell elements can be used. In the solar cell module 10, the plurality of solar cell elements 13 are electrically connected in series via an interconnector 16 having a conducting wire and a solder joint.
  • Examples of the surface-side transparent protective member 14 include a glass plate; a transparent substrate such as a resin plate formed of an acrylic resin, polycarbonate, polyester, fluorine-containing resin, or the like.
  • the solar cell encapsulant sheet of this embodiment exhibits good adhesion to the surface side transparent protective member 14.
  • back surface side protection member (back sheet) 15 examples include single or multilayer sheets such as metals and various thermoplastic resin films. Examples thereof include metals such as tin, aluminum, and stainless steel; inorganic materials such as glass; various thermoplastic resin films formed of polyester, inorganic material-deposited polyester, fluorine-containing resin, polyolefin, and the like.
  • the back surface side protection member 15 may be a single layer or a multilayer.
  • the solar cell encapsulant sheet of this embodiment exhibits good adhesion to the back surface side protection member 15.
  • the manufacturing method of the solar cell module in this embodiment is not specifically limited, For example, the following method is mentioned.
  • a plurality of solar cell elements 13 that are electrically connected using the interconnector 16 are sandwiched between a pair of light receiving surface side solar cell sealing material sheets 11 and a back surface side solar cell sealing material sheet 12, and these light receiving surface sides are further sandwiched between them.
  • a laminated body is produced by sandwiching the solar cell encapsulant sheet 11 and the back side solar cell encapsulant sheet 12 between the front side transparent protective member 14 and the back side protective member 15.
  • the laminate is heated to receive the light-receiving surface side solar cell sealing material sheet 11 and the back surface side solar cell sealing material sheet 12, the light receiving surface side solar cell sealing material sheet 11 and the front surface side transparent protective member 14, and the back surface side.
  • the solar cell sealing material sheet 12 and the back surface side protection member 15 are bonded.
  • a resin sheet is prepared in advance, and is subjected to pressure bonding at a temperature at which the resin sheet melts.
  • the lamination temperature is 145 to 170 ° C.
  • the vacuum pressure is 10 Torr or less. Heat for 5-10 minutes under vacuum.
  • pressurization by atmospheric pressure is performed for about 2 to 30 minutes, and a module having the configuration as described above can be formed.
  • the resin sheet has excellent cross-linking properties by containing a specific cross-linking agent, and it is not necessary to go through a two-step bonding process in forming the module, and can be completed in a short time at a high temperature. This can greatly improve module productivity. It is also possible to go through a two-step bonding process using an oven or the like. In the case of going through a two-step bonding process, for example, the module is produced by heating at 120 to 170 ° C. for 1 to 120 minutes. It is also possible.
  • Example 1 Production of Resin Sheet For Examples 1 to 6 and Comparative Examples 1 to 6, resin compositions were prepared as follows. First, an ethylene / vinyl acetate copolymer (EVA), a crosslinking agent, a crosslinking aid, a silane coupling agent, a light stabilizer, an ultraviolet absorber, and a heat stabilizer are blended in the formulation shown in Table 1 to form a resin composition. Got.
  • EVA ethylene / vinyl acetate copolymer
  • each component in Table 1 is a mass part.
  • the detail of each component in Table 1 is as follows.
  • EVA1 Ethylene / vinyl acetate copolymer (vinyl acetate content 28% by mass, MFR: 15 g / 10 min)
  • EVA2 ethylene-vinyl acetate copolymer (vinyl acetate content 28 mass%, MFR: 30 g / 10 min)
  • Crosslinking agent t-butylperoxy-2-ethylhexyl carbonate
  • Crosslinking aid triallyl isocyanurate
  • Silane coupling agent ⁇ -methacryloxypropyltrimethoxysilane
  • Light stabilizer bis (2,2,6 , 6-tetramethyl-4-piperidyl) sebacate /
  • UV absorber 2-hydroxy-4-normal-octyloxybenzophenone / heat stabilizer: octadecyl-3- (3,5-di-tert-but
  • the laminated body of the resin sheet and glass plate obtained by scorch-proof evaluation was produced.
  • Lamination was performed using a vacuum laminator (manufactured by NPC: LM-110 ⁇ 160-S) at a hot plate temperature of 130 ° C., a vacuum time of 3 minutes, and a pressurization time of 30 minutes.
  • the obtained laminate was put into an oven set at 100 ° C. (manufactured by Tabai Espec: PHH-401).
  • the resin sheets of Examples 1 to 6 were excellent in transparency and bubble prevention properties, and the generation of gel was suppressed.

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Abstract

The resin sheet according to the present invention is employed as an interlayer film in laminated glass or as a solar cell sealing member, and contains an ethylene/vinyl acetate copolymer, a carbonate-based organic peroxide, which serves as a cross-linking agent, and a cyanurate compound, which serves as a cross-linking aid. The amount of the carbonate-based organic peroxide contained in the resin sheet is 1.0 parts by mass to 1.5 parts by mass, inclusive, per 100 parts by mass of the ethylene/vinyl acetate copolymer, and the amount of the cyanurate compound contained in the resin sheet is 1.2 parts by mass to 1.5 parts by mass, inclusive, per 100 parts by mass of the ethylene/vinyl acetate copolymer.

Description

樹脂シート、合わせガラスおよび太陽電池モジュールResin sheet, laminated glass and solar cell module
　本発明は、樹脂シート、合わせガラスおよび太陽電池モジュールに関する。 The present invention relates to a resin sheet, a laminated glass, and a solar cell module.
　エチレン・酢酸ビニル共重合体は、絶縁性に優れ、高い透明性を有することから、合わせガラス用中間膜や太陽電池封止材、建材用途等に広く用いられている。 An ethylene / vinyl acetate copolymer is widely used for an interlayer film for laminated glass, a solar cell encapsulant, a building material and the like because of its excellent insulation and high transparency.
　このようなエチレン・酢酸ビニル共重合体を用いた樹脂シートに関する技術としては、例えば、特許文献１（国際公開第２００５／０９０５０４号）に記載のものが挙げられる。 Examples of the technology relating to the resin sheet using such an ethylene / vinyl acetate copolymer include those described in Patent Document 1 (International Publication No. 2005/090504).
　特許文献１には、エチレン／酢酸ビニル共重合体および有機過酸化物を含有してなるシート状接着剤が開示されている。 Patent Document 1 discloses a sheet-like adhesive containing an ethylene / vinyl acetate copolymer and an organic peroxide.
国際公開第２００５／０９０５０４号International Publication No. 2005/090504
　エチレン－酢酸ビニル共重合体を用いた樹脂シートの各種特性について要求される技術水準は、ますます高くなっている。本発明者らは、従来のエチレン－酢酸ビニル共重合体を用いた樹脂シートに関し、以下のような課題を見出した。
　まず、エチレン・酢酸ビニル共重合体シートを用いて、合わせガラスや太陽電池モジュールを製造する場合は、架橋剤を含むエチレン・酢酸ビニル共重合体シートと透明基板とを積層し、加熱加圧によりエチレン・酢酸ビニル共重合体シートを硬化させることにより各層を接着一体化させる。架橋剤としては有機過酸化物が用いられ、架橋助剤としてはシアヌレート系やアクリレート系の化合物が一般的に用いられている。
　本発明者らの検討によれば、従来のエチレン－酢酸ビニル共重合体を用いた樹脂シートを用いた合わせガラスや太陽電池モジュールは、透明性（ヘイズ）が劣る、気泡が生じる、樹脂シートを成形する際にゲル化が生じる、等の問題点を抱えていることが明らかになった。
　このように、本発明者らは、従来のエチレン－酢酸ビニル共重合体を用いた樹脂シートは透明性と気泡防止性とゲル抑制とを両立するという観点においてまだまだ改善の余地があることを見出した。 The technical level required for various properties of resin sheets using ethylene-vinyl acetate copolymer is becoming higher and higher. The present inventors have found the following problems regarding a resin sheet using a conventional ethylene-vinyl acetate copolymer.
First, when producing a laminated glass or a solar cell module using an ethylene / vinyl acetate copolymer sheet, an ethylene / vinyl acetate copolymer sheet containing a crosslinking agent and a transparent substrate are laminated and heated and pressurized. The layers are bonded and integrated by curing the ethylene / vinyl acetate copolymer sheet. An organic peroxide is used as the crosslinking agent, and a cyanurate-based or acrylate-based compound is generally used as the crosslinking assistant.
According to the study by the present inventors, a laminated glass or a solar cell module using a conventional resin sheet using an ethylene-vinyl acetate copolymer has poor transparency (haze), bubbles are generated, and a resin sheet is not formed. It has become clear that there are problems such as gelation during molding.
As described above, the present inventors have found that there is still room for improvement in terms of achieving compatibility of transparency, bubble prevention and gel suppression with a resin sheet using a conventional ethylene-vinyl acetate copolymer. It was.
　本発明は上記事情に鑑みてなされたものであり、透明性と気泡防止性に優れるとともにゲルの発生が抑制されたエチレン・酢酸ビニル共重合体からなる樹脂シートを提供するものである。 The present invention has been made in view of the above circumstances, and provides a resin sheet made of an ethylene / vinyl acetate copolymer that is excellent in transparency and bubble-preventing properties and in which the generation of gel is suppressed.
　本発明者らは、上記課題を達成するために鋭意研究を重ねた。その結果、樹脂シートの構成成分として、カーボネート系有機過酸化物とシアヌレート化合物とを用い、かつ、これらの配合割合を高度に制御することで、透明性と気泡防止性とゲル抑制とをバランスよく向上できることを見出し、本発明に至った。 The inventors of the present invention have intensively studied in order to achieve the above-mentioned problems. As a result, the use of carbonate-based organic peroxides and cyanurate compounds as constituents of the resin sheet, and by highly controlling the blending ratio of these, the transparency, bubble prevention and gel suppression are well balanced. The inventors have found that it can be improved and have reached the present invention.
　本発明によれば、以下に示す樹脂シート、合わせガラスおよび太陽電池モジュールが提供される。 According to the present invention, the following resin sheet, laminated glass and solar cell module are provided.
［１］
　合わせガラス用中間膜または太陽電池封止材に用いられる樹脂シートであって、
　エチレン・酢酸ビニル共重合体と、
　架橋剤であるカーボネート系有機過酸化物と、
　架橋助剤であるシアヌレート化合物と、
を含み、
　当該樹脂シート中の上記カーボネート系有機過酸化物の含有量が、上記エチレン・酢酸ビニル共重合体１００質量部に対して、１．０質量部以上１．５質量部以下であり、
　当該樹脂シート中の上記シアヌレート化合物の含有量が、上記エチレン・酢酸ビニル共重合体１００質量部に対して、１．２質量部以上１．５質量部以下である樹脂シート。
［２］
　上記［１］に記載の樹脂シートにおいて、
　上記カーボネート系有機過酸化物が、ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネートを含む樹脂シート。
［３］
　上記［１］または［２］に記載の樹脂シートにおいて、
　上記シアヌレート化合物がトリアリルシアヌレートおよびトリアリルイソシアヌレートから選択される少なくとも一種を含む樹脂シート。
［４］
　上記［１］乃至［３］いずれか一つに記載の樹脂シートにおいて、
　ＡＳＴＭ　Ｄ１２３８に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定される上記エチレン・酢酸ビニル共重合体のＭＦＲが１０ｇ／１０分以上５０ｇ／１０分以下である樹脂シート。
［５］
　上記［１］乃至［４］いずれか一つに記載の樹脂シートにおいて、
　上記エチレン・酢酸ビニル共重合体中の酢酸ビニル単位の含有量が２５質量％以上３５質量％以下である樹脂シート。
［６］
　上記［１］乃至［５］いずれか一つに記載の樹脂シートにおいて、
　当該樹脂シート中の上記カーボネート系有機過酸化物の含有量に対する上記シアヌレート化合物の含有量の質量比が０．９以上１．５以下である樹脂シート。
［７］
　上記［１］乃至［６］いずれか一つに記載の樹脂シートにおいて、
　当該樹脂シート中の上記カーボネート系有機過酸化物および上記シアヌレート化合物の合計含有量が、上記エチレン・酢酸ビニル共重合体１００質量部に対して、２．３質量部以上２．８質量部以下である樹脂シート。
［８］
　上記［１］乃至［７］いずれか一つに記載の樹脂シートにおいて、
　上記エチレン・酢酸ビニル共重合体の含有量が、当該樹脂シートに含まれる樹脂成分の全体を１００質量％としたとき、８０質量％以上である樹脂シート。
［９］
　上記［１］乃至［８］いずれか一つに記載の樹脂シートを含むガラス用中間膜と、
　上記合わせガラス用中間膜の両面に設けられた透明基板と、
を備える合わせガラス。
［１０］
　上記［９］に記載の合わせガラスにおいて、
　建築物に使用される合わせガラス。
［１１］
　表面側透明保護部材と、
　裏面側保護部材と、
　太陽電池素子と、
　上記［１］乃至［８］いずれか一つに記載の樹脂シートの架橋体であり、かつ、上記太陽電池素子を上記表面側透明保護部材と上記裏面側保護部材との間に封止する封止層と、
を備えた太陽電池モジュール。 [1]
A resin sheet used for an interlayer film for laminated glass or a solar cell sealing material,
An ethylene / vinyl acetate copolymer;
A carbonate-based organic peroxide as a crosslinking agent;
A cyanurate compound which is a crosslinking aid;
Including
The content of the carbonate organic peroxide in the resin sheet is 1.0 part by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer,
The resin sheet whose content of the said cyanurate compound in the said resin sheet is 1.2 mass parts or more and 1.5 mass parts or less with respect to 100 mass parts of said ethylene-vinyl acetate copolymers.
[2]
In the resin sheet according to the above [1],
A resin sheet in which the carbonate-based organic peroxide contains t-butylperoxy-2-ethylhexyl carbonate.
[3]
In the resin sheet according to the above [1] or [2],
A resin sheet containing at least one kind of the cyanurate compound selected from triallyl cyanurate and triallyl isocyanurate.
[4]
In the resin sheet according to any one of [1] to [3],
A resin sheet having an MFR of 10 g / 10 min or more and 50 g / 10 min or less of the ethylene / vinyl acetate copolymer measured under conditions of 190 ° C. and 2.16 kg load in accordance with ASTM D1238.
[5]
In the resin sheet according to any one of [1] to [4] above,
The resin sheet whose content of the vinyl acetate unit in the said ethylene-vinyl acetate copolymer is 25 to 35 mass%.
[6]
In the resin sheet according to any one of the above [1] to [5],
The resin sheet whose mass ratio of content of the said cyanurate compound with respect to content of the said carbonate type organic peroxide in the said resin sheet is 0.9-1.5.
[7]
In the resin sheet according to any one of [1] to [6] above,
The total content of the carbonate organic peroxide and the cyanurate compound in the resin sheet is 2.3 parts by mass or more and 2.8 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer. A resin sheet.
[8]
In the resin sheet according to any one of [1] to [7],
The resin sheet whose content of the said ethylene-vinyl acetate copolymer is 80 mass% or more when the whole resin component contained in the said resin sheet is 100 mass%.
[9]
An intermediate film for glass comprising the resin sheet according to any one of the above [1] to [8];
Transparent substrates provided on both surfaces of the interlayer film for laminated glass,
Laminated glass with.
[10]
In the laminated glass according to [9] above,
Laminated glass used in buildings.
[11]
A surface-side transparent protective member;
A back side protection member;
A solar cell element;
A sealed resin body according to any one of [1] to [8], wherein the solar cell element is sealed between the front surface side transparent protective member and the rear surface side protective member. Stop layer,
Solar cell module with
　本発明によれば、透明性と気泡防止性に優れるとともにゲルの発生が抑制されたエチレン・酢酸ビニル共重合体からなる樹脂シートを提供することができる。 According to the present invention, it is possible to provide a resin sheet made of an ethylene / vinyl acetate copolymer that is excellent in transparency and bubble prevention properties and suppresses the generation of gel.
　上述した目的、およびその他の目的、特徴および利点は、以下に述べる好適な実施の形態、およびそれに付随する以下の図面によってさらに明らかになる。 The above-described object and other objects, features, and advantages will be further clarified by a preferred embodiment described below and the following drawings attached thereto.
本発明の合わせガラスの一実施形態を模式的に示す断面図である。It is sectional drawing which shows typically one Embodiment of the laminated glass of this invention. 本発明の太陽電池モジュールの一実施形態を模式的に示す断面図である。It is sectional drawing which shows typically one Embodiment of the solar cell module of this invention.
　以下に、本発明の実施形態について、図面を用いて説明する。なお、すべての図面において、同様な構成要素には共通の符号を付し、適宜説明を省略する。また、図は概略図であり、実際の寸法比率とは一致していない。数値範囲の「Ａ～Ｂ」は特に断りがなければ、Ａ以上Ｂ以下を表す。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not match the actual dimensional ratio. “A to B” in the numerical range represents A or more and B or less unless otherwise specified.
１．樹脂シート
　本実施形態に係る樹脂シートは、合わせガラス用中間膜または太陽電池封止材に用いられる樹脂シートであって、エチレン・酢酸ビニル共重合体と、架橋剤であるカーボネート系有機過酸化物と、架橋助剤であるシアヌレート化合物と、を含む。
　そして、当該樹脂シート中の上記カーボネート系有機過酸化物の含有量が、上記エチレン・酢酸ビニル共重合体１００質量部に対して、１．０質量部以上１．５質量部以下であり、当該樹脂シート中の上記シアヌレート化合物の含有量が、上記エチレン・酢酸ビニル共重合体１００質量部に対して、１．２質量部以上１．５質量部以下である。 1. Resin sheet The resin sheet according to the present embodiment is a resin sheet used for an interlayer film for laminated glass or a solar cell encapsulant, and an ethylene / vinyl acetate copolymer and a carbonate organic peroxide that is a cross-linking agent. And a cyanurate compound which is a crosslinking aid.
And the content of the carbonate organic peroxide in the resin sheet is 1.0 part by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer, The content of the cyanurate compound in the resin sheet is 1.2 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer.
　本発明者らは、透明性と気泡防止性に優れるとともにゲルの発生が抑制されたエチレン・酢酸ビニル共重合体からなる樹脂シートを提供するために鋭意研究を重ねた。その結果、樹脂シートの構成成分として、カーボネート系有機過酸化物とシアヌレート化合物とを用い、かつ、これらの配合割合を上記範囲とすることで、透明性と気泡防止性とゲル抑制とをバランスよく向上できることを見出した。
　すなわち、本実施形態に係る樹脂シートは透明性と気泡防止性に優れるとともにゲルの発生を抑制することができる。 The inventors of the present invention have made extensive studies in order to provide a resin sheet made of an ethylene / vinyl acetate copolymer that is excellent in transparency and bubble prevention properties, and in which the generation of gel is suppressed. As a result, by using a carbonate organic peroxide and a cyanurate compound as constituents of the resin sheet, and by setting the blending ratio thereof within the above range, transparency, bubble prevention and gel suppression are well balanced. I found that it can be improved.
That is, the resin sheet according to the present embodiment is excellent in transparency and bubble prevention properties and can suppress the generation of gel.
　また、本実施形態に係る樹脂シート中の上記カーボネート系有機過酸化物の含有量に対する上記シアヌレート化合物の含有量の質量比が、好ましくは０．９以上１．５以下である。 Moreover, the mass ratio of the content of the cyanurate compound to the content of the carbonate organic peroxide in the resin sheet according to the present embodiment is preferably 0.9 or more and 1.5 or less.
　また、本実施形態に係る樹脂シート中の上記カーボネート系有機過酸化物および上記シアヌレート化合物の合計含有量が、エチレン・酢酸ビニル共重合体１００質量部に対して、好ましくは２．３質量部以上２．８質量部以下である。 The total content of the carbonate organic peroxide and the cyanurate compound in the resin sheet according to the present embodiment is preferably 2.3 parts by mass or more with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer. It is 2.8 parts by mass or less.
　本実施形態に係る樹脂シートの平均膜厚は特にされないが、好ましくは０．２ｍｍ以上２．０ｍｍ以下である。樹脂シートの平均膜厚が上記下限値以上であると、樹脂シートの機械的強度をより良好なものとすることができ、樹脂シートの熱収縮を抑制することができる。また、樹脂シートの平均膜厚が上記上限値以下であると、ラミネート工程において、透明基板等の他の部材の破損を抑制でき、比較的低温でも透明基板へのラミネート成形ができる。また、樹脂シートの平均膜厚が上記上限値以下であると、十分な光線透過率を確保でき、それを用いた太陽電池モジュールは高い光発電量を有する。 The average film thickness of the resin sheet according to this embodiment is not particularly limited, but is preferably 0.2 mm or more and 2.0 mm or less. When the average film thickness of the resin sheet is equal to or more than the above lower limit value, the mechanical strength of the resin sheet can be further improved, and thermal shrinkage of the resin sheet can be suppressed. Further, when the average film thickness of the resin sheet is not more than the above upper limit value, damage of other members such as a transparent substrate can be suppressed in the laminating step, and the laminate can be formed on the transparent substrate even at a relatively low temperature. Moreover, sufficient light transmittance can be ensured as the average film thickness of a resin sheet is below the said upper limit, and the solar cell module using it has a high photovoltaic power generation amount.
　上記エチレン・酢酸ビニル共重合体の含有量は、当該樹脂シートに含まれる樹脂成分の全体を１００質量％としたとき、好ましくは８０質量％以上、より好ましくは９０質量％以上、さらに好ましくは９５質量％以上、そして、特に好ましくは１００質量％である。これにより、透明性、接着性、耐熱性、柔軟性、外観、架橋特性、電気特性および押出成形性等の諸特性のバランスにより優れた樹脂シートを得ることができる。 The content of the ethylene / vinyl acetate copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% when the entire resin component contained in the resin sheet is 100% by mass. It is at least 100% by mass, and particularly preferably 100% by mass. Thereby, it is possible to obtain a resin sheet excellent in balance of various properties such as transparency, adhesiveness, heat resistance, flexibility, appearance, cross-linking properties, electrical properties and extrusion moldability.
　上記樹脂成分の含有量は、当該樹脂シートの全体を１００質量％としたとき、好ましくは５０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、特に好ましくは９０質量％以上である。これにより、透明性、接着性、耐熱性、柔軟性、外観、架橋特性、電気特性および押出成形性等の諸特性のバランスにより優れた樹脂シートを得ることができる。 The content of the resin component is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass, when the resin sheet as a whole is 100% by mass. That's it. Thereby, it is possible to obtain a resin sheet excellent in balance of various properties such as transparency, adhesiveness, heat resistance, flexibility, appearance, cross-linking properties, electrical properties and extrusion moldability.
＜エチレン・酢酸ビニル共重合体＞
　本実施形態に係る樹脂シートはエチレン・酢酸ビニル共重合体を主成分として含む。
　上記エチレン・酢酸ビニル共重合体は、エチレンと酢酸ビニルとの共重合体であり、通常はランダム共重合体である。 <Ethylene / vinyl acetate copolymer>
The resin sheet according to the present embodiment contains an ethylene / vinyl acetate copolymer as a main component.
The ethylene / vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and is usually a random copolymer.
　ＡＳＴＭ　Ｄ１２３８に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定される上記エチレン・酢酸ビニル共重合体のメルトフローレ－ト（ＭＦＲ）は、好ましくは１０～５０ｇ／１０分であり、より好ましくは１０～４０ｇ／１０分、さらに好ましくは１０～３０ｇ／１０分である。エチレン・酢酸ビニル共重合体のＭＦＲは、重合反応の際の重合温度、重合圧力、並びに重合系内の共重合モノマーのモノマー濃度と水素濃度のモル比率等を調整することにより、調整することができる。 According to ASTM D1238, the melt flow rate (MFR) of the ethylene / vinyl acetate copolymer measured at 190 ° C. under a load of 2.16 kg is preferably 10 to 50 g / 10 min, more preferably. Is 10 to 40 g / 10 min, more preferably 10 to 30 g / 10 min. The MFR of the ethylene / vinyl acetate copolymer can be adjusted by adjusting the polymerization temperature during the polymerization reaction, the polymerization pressure, and the molar ratio of the monomer concentration and the hydrogen concentration of the copolymerization monomer in the polymerization system. it can.
　ＭＦＲが上記下限値以上であると、エチレン・酢酸ビニル共重合体を含むエチレン系樹脂組成物の流動性が向上し、樹脂シートの成形加工性がより良好となる。
　一方、ＭＦＲが上記上限値以下であると、分子量が大きくなるため、チルロール等のロール面への付着を抑制できるため、剥離を不要とし、より均一な厚みの樹脂シートに成形することができる。さらに、「コシ」がある樹脂組成物となるため、０．１ｍｍ以上の厚い樹脂シートを容易に成形することができる。また、架橋特性が向上するため、十分に架橋させて、耐熱性の低下を抑制することができる。 When the MFR is not less than the above lower limit, the fluidity of the ethylene-based resin composition containing the ethylene / vinyl acetate copolymer is improved, and the moldability of the resin sheet becomes better.
On the other hand, when the MFR is not more than the above upper limit value, the molecular weight is increased, so that adhesion to a roll surface such as a chill roll can be suppressed, and therefore, peeling is unnecessary and the resin sheet can be formed with a more uniform thickness. Furthermore, since it becomes a resin composition with “koshi”, a thick resin sheet of 0.1 mm or more can be easily formed. Moreover, since a crosslinking characteristic improves, it can fully bridge | crosslink and it can suppress a heat resistant fall.
　上記エチレン・酢酸ビニル共重合体中の酢酸ビニル単位の含有量は、好ましくは２５質量％以上３５質量％以下、より好ましくは２８質量％以上３５質量％以下、さらに好ましくは２８質量％以上３３質量％以下である。酢酸ビニル単位の含有量がこの範囲にあると、架橋性、柔軟性、耐候性、透明性のバランスにより一層優れる。
　酢酸ビニル含有量は、ＪＩＳ　Ｋ６７３０に準拠して測定可能である。 The content of vinyl acetate units in the ethylene / vinyl acetate copolymer is preferably 25% by mass to 35% by mass, more preferably 28% by mass to 35% by mass, and even more preferably 28% by mass to 33% by mass. % Or less. When the content of the vinyl acetate unit is within this range, the balance of crosslinkability, flexibility, weather resistance, and transparency is further improved.
The vinyl acetate content can be measured according to JIS K6730.
　本実施形態に係る樹脂シートを太陽電池封止材として用いた場合には、酢酸ビニルの含有量が上記範囲内にあると、架橋性、柔軟性、太陽電池封止シートの接着性、耐候性、透明性、機械的性質のバランスにより一層優れる。また、太陽電池封止シートを成膜する際にも、成膜性が良好となる。 When the resin sheet according to the present embodiment is used as a solar cell encapsulant, if the vinyl acetate content is within the above range, crosslinkability, flexibility, solar cell encapsulating sheet adhesion, and weather resistance. , Better balance of transparency and mechanical properties. In addition, when the solar cell encapsulating sheet is formed, the film formability is good.
　なお、エチレン・酢酸ビニル共重合体は、エチレンおよび酢酸ビニルのみからなる二元共重合体が好ましいが、エチレンおよび酢酸ビニルの他に、例えばギ酸ビニル、グリコール酸ビニル、プロピオン酸ビニル、安息香酸ビニル等のビニルエステル系単量体；アクリル酸、メタクリル酸、エタクリル酸、或いはこれらの塩もしくはアルキルエステル等のアクリル系単量体；等から選択される一種または二種以上の共重合成分として含んでもよい。上記エチレンおよび酢酸ビニル以外の共重合成分を含む場合、エチレン・酢酸ビニル共重合体中の上記エチレンおよび酢酸ビニル以外の共重合成分の量を０．５質量％以上５質量％以下とすることが好ましい。 The ethylene / vinyl acetate copolymer is preferably a binary copolymer consisting only of ethylene and vinyl acetate. In addition to ethylene and vinyl acetate, for example, vinyl formate, vinyl glycolate, vinyl propionate, vinyl benzoate. A vinyl ester monomer such as acrylic acid, methacrylic acid, ethacrylic acid, or an acrylic monomer such as a salt or alkyl ester thereof; Good. When a copolymer component other than ethylene and vinyl acetate is included, the amount of the copolymer component other than ethylene and vinyl acetate in the ethylene / vinyl acetate copolymer may be 0.5 mass% or more and 5 mass% or less. preferable.
　酢酸ビニル含有量や、ＭＦＲ等が異なる２種以上のエチレン・酢酸ビニル共重合体を併せて用いてもよい。２種以上のエチレン・酢酸ビニル共重合体を用いる場合には、これらの総量を上記範囲とすることが好ましい。 Two or more kinds of ethylene / vinyl acetate copolymers having different vinyl acetate contents and MFR may be used in combination. When two or more kinds of ethylene / vinyl acetate copolymers are used, the total amount of these is preferably within the above range.
　上記エチレン・酢酸ビニル共重合体の製造方法は特に限定されず、公知の方法により製造することができる。例えば、ラジカル発生剤の存在下、５００～４０００気圧、１００～３００℃で溶媒や連鎖移動剤の存在下または不存在下で、エチレン、酢酸ビニル、必要に応じて他の共重合成分を共重合させることにより製造することができる。 The method for producing the ethylene / vinyl acetate copolymer is not particularly limited, and can be produced by a known method. For example, in the presence of a radical generator, copolymerization of ethylene, vinyl acetate, and other copolymerization components as necessary in the presence or absence of a solvent or chain transfer agent at 500 to 4000 atm and 100 to 300 ° C Can be manufactured.
＜架橋剤＞
　本実施形態に係る樹脂シートは、架橋剤であるカーボネート系有機過酸化物を含む。
　本実施形態に係る樹脂シートにおいて、カーボネート系有機過酸化物を含有することにより、上記エチレン・酢酸ビニル共重合体の架橋速度が向上する。 <Crosslinking agent>
The resin sheet which concerns on this embodiment contains the carbonate type organic peroxide which is a crosslinking agent.
In the resin sheet according to the present embodiment, the crosslinking rate of the ethylene / vinyl acetate copolymer is improved by containing a carbonate-based organic peroxide.
　本実施形態に係る樹脂シート中のカーボネート系有機過酸化物の含有量は、エチレン・酢酸ビニル共重合体１００質量部に対し、１．０質量部以上１．５質量部以下であり、好ましくは１．１質量部以上１．３質量部以下である。
　カーボネート系有機過酸化物の含有量が上記下限値以上であると、樹脂シートの架橋特性が良好となり、樹脂シートの耐熱性が向上する。また、シランカップリング剤のエチレン・酢酸ビニル共重合体の主鎖へのグラフト反応を良好にして、耐熱性、接着性がより良好となる。さらに、樹脂シートの透明性が良好となる。
　また、カーボネート系有機過酸化物の含有量が上記上限値以下であると、上記の架橋特性、耐熱性、接着性が良好な上に、シート成形時のゲル化を抑制でき、シート外観が良好な樹脂シートを得ることができる。さらに、カーボネート系有機過酸化物の分解生成物等の発生量が低下し、樹脂シート中に気泡が発生するのを抑制することができる。さらにカーボネート系有機過酸化物の含有量が上記上限値以下であると、樹脂シートの耐スコーチ性を良好なものとすることができる。 The content of the carbonate-based organic peroxide in the resin sheet according to this embodiment is 1.0 part by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer, preferably 1.1 parts by mass or more and 1.3 parts by mass or less.
When the content of the carbonate-based organic peroxide is not less than the above lower limit, the cross-linking property of the resin sheet becomes good, and the heat resistance of the resin sheet is improved. In addition, the graft reaction of the silane coupling agent to the main chain of the ethylene / vinyl acetate copolymer is improved, and the heat resistance and adhesiveness are further improved. Furthermore, the transparency of the resin sheet is improved.
In addition, when the content of the carbonate-based organic peroxide is not more than the above upper limit value, the above cross-linking characteristics, heat resistance, and adhesiveness are good, and gelation during sheet molding can be suppressed, and the sheet appearance is good. Can be obtained. Furthermore, the generation amount of decomposition products of carbonate-based organic peroxides can be reduced, and the generation of bubbles in the resin sheet can be suppressed. Furthermore, when the content of the carbonate-based organic peroxide is not more than the above upper limit value, the scorch resistance of the resin sheet can be improved.
　カーボネート系有機過酸化物としては、例えば、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネート、ｔ－アミルパーオキシイソプロピルカーボネート、ｔ－アミルパーオキシ－２－エチルヘキシルカーボネート等が挙げられる。これらの中でもｔ－ブチルパーオキシ－２－エチルヘキシルカーボネートが好ましい。
　上記カーボネート系有機過酸化物は、一種単独で用いてもよく、二種以上を混合して用いてもよい。 Examples of the carbonate organic peroxide include t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-amyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexyl carbonate, and the like. Can be mentioned. Of these, t-butylperoxy-2-ethylhexyl carbonate is preferred.
The carbonate organic peroxides may be used alone or in a combination of two or more.
＜架橋助剤＞
　本実施形態に係る樹脂シートは、架橋性を向上させる観点から、架橋助剤であるシアヌレート化合物を含む。
　シアヌレート化合物としては、例えば、トリアリルシアヌレート、トリアリルイソシアヌレート等から選択される一種または二種以上を用いることができる。これらの中でも、シアヌレート化合物としてはトリアリルイソシアヌレートを含むことが好ましい。 <Crosslinking aid>
The resin sheet which concerns on this embodiment contains the cyanurate compound which is a crosslinking adjuvant from a viewpoint of improving crosslinking | crosslinked property.
As the cyanurate compound, for example, one or more selected from triallyl cyanurate, triallyl isocyanurate, and the like can be used. Among these, it is preferable that triallyl isocyanurate is included as a cyanurate compound.
　本実施形態に係る樹脂シート中のシアヌレート化合物の含有量は、エチレン・酢酸ビニル共重合体１００質量部に対して、１．２質量部以上１．５質量部以下であり、好ましくは１．２質量部以上１．４質量部以下である。 Content of the cyanurate compound in the resin sheet which concerns on this embodiment is 1.2 mass parts or more and 1.5 mass parts or less with respect to 100 mass parts of ethylene-vinyl acetate copolymers, Preferably it is 1.2. It is not less than 1.4 parts by mass.
　シアヌレート化合物の含有量が上記下限値以上であると、樹脂シートの架橋特性が良好となり、樹脂シートの耐熱性が向上する。また、シランカップリング剤のエチレン・酢酸ビニル共重合体の主鎖へのグラフト反応を良好にして、耐熱性、接着性が良好となる。さらに、樹脂シートの透明性が良好となる。
　また、シアヌレート化合物の含有量が上記上限値以下であると、上記の架橋特性、耐熱性、接着性が良好な上に、シート成形時のゲル化を抑制でき、シート外観が良好な樹脂シートを得ることができる。さらにシアヌレート化合物の含有量が上記上限値以下であると、樹脂シートの耐スコーチ性を良好なものとすることができる。 When the content of the cyanurate compound is not less than the above lower limit, the cross-linking property of the resin sheet becomes good and the heat resistance of the resin sheet is improved. Further, the graft reaction of the silane coupling agent to the main chain of the ethylene / vinyl acetate copolymer is improved, and the heat resistance and adhesiveness are improved. Furthermore, the transparency of the resin sheet is improved.
In addition, when the content of the cyanurate compound is not more than the above upper limit value, the above-mentioned crosslinking characteristics, heat resistance, and adhesiveness are good, and further, the gelation at the time of sheet molding can be suppressed, and a resin sheet having a good sheet appearance can be obtained. Obtainable. Furthermore, when the content of the cyanurate compound is not more than the above upper limit value, the scorch resistance of the resin sheet can be improved.
＜シランカップリング剤＞
　本実施形態に係る樹脂シートは、さらにシランカップリング剤を含んでもよい。
　本実施形態に係る樹脂シート中のシランカップリング剤の含有量は、エチレン・酢酸ビニル共重合体１００質量部に対して、０．１～５質量部であることが好ましく、０．１～４質量部であることがより好ましく、０．１～３質量部であることが特に好ましい。 <Silane coupling agent>
The resin sheet according to the present embodiment may further include a silane coupling agent.
The content of the silane coupling agent in the resin sheet according to this embodiment is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer, and preferably 0.1 to 4 parts. The amount is more preferably part by mass, and particularly preferably 0.1 to 3 parts by mass.
　シランカップリング剤の含有量が上記下限値以上であると、接着性が向上する。
　一方、シランカップリング剤の含有量が上記上限値以下であると、コストと性能のバランスがよく、透湿性の低下も防止できる。また、太陽電池封止材として用いた場合に、表面側透明保護部材、セル、電極、裏面側保護部材との密着性が良好となり、接着性も向上する。また、シランカップリング剤自体が縮合反応を起こし、太陽電池封止材に白い筋として存在し、製品外観が悪化することを抑制できる。 Adhesiveness improves that content of a silane coupling agent is more than the said lower limit.
On the other hand, when the content of the silane coupling agent is not more than the above upper limit value, the balance between cost and performance is good, and deterioration of moisture permeability can be prevented. Moreover, when it uses as a solar cell sealing material, adhesiveness with a surface side transparent protection member, a cell, an electrode, and a back surface side protection member becomes favorable, and adhesiveness also improves. Moreover, it can suppress that a silane coupling agent itself raise | generates a condensation reaction, exists as a white stripe | line in a solar cell sealing material, and a product external appearance deteriorates.
　シランカップリング剤は、従来公知のものが使用でき、とくに制限はない。具体的には、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス（β－メトキシエトキシシラン）、γ－グリシドキシプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン等が使用できる。好ましくは、接着性が良好なγ－グリシドキシプロピルメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、ビニルトリエトキシシラン等が挙げられる。 A conventionally well-known silane coupling agent can be used, and there is no restriction in particular. Specifically, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxysilane), γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane Etc. can be used. Preferred examples include γ-glycidoxypropylmethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and the like, which have good adhesion.
＜紫外線吸収剤、光安定化剤、耐熱安定剤＞
　本実施形態に係る樹脂シートは、紫外線吸収剤、光安定化剤、および耐熱安定剤から選択される少なくとも一種の添加剤をさらに含有してもよい。これらの添加剤の配合量は、エチレン・酢酸ビニル共重合体１００質量部に対して、０．００５～５質量部であることが好ましい。さらに、上記三種から選ばれる少なくとも二種の添加剤を含有することが好ましく、とくに、上記三種の全てが含有されていることが好ましい。上記添加剤の配合量が上記範囲内にあると、耐候安定性および耐熱安定性を向上する効果を十分に確保し、かつ、透明性や、ガラス板との接着性の低下を防ぐことができるので好ましい。 <Ultraviolet absorber, light stabilizer, heat stabilizer>
The resin sheet according to the present embodiment may further contain at least one additive selected from ultraviolet absorbers, light stabilizers, and heat stabilizers. The amount of these additives is preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer. Furthermore, it is preferable to contain at least two kinds of additives selected from the above three kinds, and it is particularly preferred that all of the above three kinds are contained. When the blending amount of the additive is within the above range, it is possible to sufficiently secure the effect of improving weather resistance stability and heat stability, and to prevent deterioration of transparency and adhesion to a glass plate. Therefore, it is preferable.
　紫外線吸収剤としては、具体的には、２－ヒドロキシ－４－ノルマル－オクチルオキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２，２－ジヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－メトキシ－４－カルボキシベンゾフェノン、２－ヒドロキシ－４－Ｎ－オクトキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤；２－（２－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール等のベンゾトリアリゾール系紫外線吸収剤；フェニルサルチレート、ｐ－オクチルフェニルサルチレート等のサリチル酸エステル系紫外線吸収剤等が用いられる。 Specific examples of the ultraviolet absorber include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy. Benzophenone ultraviolet absorbers such as -4-carboxybenzophenone and 2-hydroxy-4-N-octoxybenzophenone; 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2 Benzotrialisol ultraviolet absorbers such as -hydroxy-5-methylphenyl) benzotriazole; salicylic acid ester ultraviolet absorbers such as phenylsalicylate and p-octylphenylsalicylate are used.
　光安定化剤としては、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ポリ［｛６－（１，１，３，３－テトラメチルブチル）アミノ－１，３，５－トリアジン－２，４－ジイル｝｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝］等のヒンダードアミン系光安定化剤、ヒンダードピペリジン系光安定化剤等が好ましく使用される。 Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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} Hindered amine light stabilizers, hindered piperidine light stabilizers and the like are preferably used.
　耐熱安定剤としては、具体的には、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、ビス［２，４－ビス（１，１－ジメチルエチル）－６－メチルフェニル］エチルエステル亜リン酸、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）［１，１－ビフェニル］－４，４'－ジイルビスホスフォナイト、およびビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト等のホスファイト系耐熱安定剤；３－ヒドロキシ－５，７－ジ－ｔｅｒｔ－ブチル－フラン－２－オンとｏ－キシレンとの反応生成物等のラクトン系耐熱安定剤；３，３'，３"，５，５'，５"－ヘキサ－ｔｅｒｔ－ブチル－ａ，ａ'，ａ"－（メチレン－２，４，６－トリイル）トリ－ｐ－クレゾール、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）ベンジルベンゼン、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］等のヒンダードフェノール系耐熱安定剤；硫黄系耐熱安定剤；アミン系耐熱安定剤等を挙げることができる。また、これらを一種単独でまたは二種以上を組み合わせて用いることもできる。中でも、ホスファイト系耐熱安定剤、およびヒンダードフェノール系耐熱安定剤が好ましい。 Specific examples of heat-resistant stabilizers include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester. Phosphorous acid, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, and bis (2,4-di-tert-butylphenyl) Phosphite heat stabilizers such as pentaerythritol diphosphite; lactone heat stabilizers such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene; 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(methylene-2,4,6-triyl) tri-p-cresol, 1,3 , 5-Trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], etc. Examples thereof include hindered phenol-based heat stabilizers, sulfur-based heat stabilizers, amine-based heat stabilizers, etc. In addition, these can be used alone or in combination of two or more. A heat resistance stabilizer and a hindered phenol heat resistance stabilizer are preferred.
＜その他の添加剤＞
　本実施形態に係る樹脂シートは、以上詳述した諸成分以外の各種成分を、本発明の目的を損なわない範囲において、適宜含有させることができる。例えば、上記エチレン・酢酸ビニル共重合体以外の各種ポリオレフィン、スチレン系やエチレン系ブロック共重合体、プロピレン系重合体等が挙げられる。これらは、上記エチレン・酢酸ビニル共重合体１００質量部に対して、好ましくは０．０００１～５０質量部、より好ましくは０．００１～４０質量部含有されていてもよい。また、ポリオレフィン以外の各種樹脂、および／または各種ゴム、可塑剤、充填剤、顔料、染料、帯電防止剤、抗菌剤、防黴剤、難燃剤、架橋助剤、および分散剤等から選ばれる一種以上の添加剤を適宜含有することができる。 <Other additives>
The resin sheet which concerns on this embodiment can contain suitably various components other than the various components detailed above in the range which does not impair the objective of this invention. Examples thereof include various polyolefins other than the ethylene / vinyl acetate copolymer, styrene-based, ethylene-based block copolymers, and propylene-based polymers. These may be contained in an amount of preferably 0.0001 to 50 parts by mass, more preferably 0.001 to 40 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer. One kind selected from various resins other than polyolefins and / or various rubbers, plasticizers, fillers, pigments, dyes, antistatic agents, antibacterial agents, antifungal agents, flame retardants, crosslinking aids, dispersants, etc. The above additives can be appropriately contained.
２．樹脂シートの製造方法
　以下、本実施形態に係る樹脂シートの製造方法の一例について説明する。
　はじめに、エチレン・酢酸ビニル共重合体と、カーボネート系有機過酸化物と、シアヌレート化合物と、必要に応じて、シランカップリング剤と、紫外線吸収剤と、光安定化剤と、耐熱安定剤と、さらに必要に応じてその他添加剤とを、例えば、ポリ袋等の袋の中で人力でのブレンドや、ヘンシェルミキサー、タンブラー、スーパーミキサー等の攪拌混合機を用いてブレンドする。次いで、得られた樹脂組成物を、例えば、押出シート成形機のホッパーに投入し、溶融混練を行いつつ押出シート成形機のＴダイから樹脂組成物をシート状に押出して樹脂シートを得る。 2. Hereinafter, an example of the manufacturing method of the resin sheet which concerns on this embodiment is demonstrated.
First, an ethylene / vinyl acetate copolymer, a carbonate-based organic peroxide, a cyanurate compound, and if necessary, a silane coupling agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, Further, if necessary, other additives are blended by hand in a bag such as a plastic bag or by using a stirring mixer such as a Henschel mixer, tumbler or super mixer. Next, the obtained resin composition is put into, for example, a hopper of an extrusion sheet molding machine, and the resin composition is extruded into a sheet form from a T-die of the extrusion sheet molding machine while performing melt kneading to obtain a resin sheet.
　押出温度範囲としては、例えば、押出温度が１００～２５０℃である。押出温度が上記範囲内であると、より一層良好なシートが得られる。 As the extrusion temperature range, for example, the extrusion temperature is 100 to 250 ° C. When the extrusion temperature is within the above range, a better sheet can be obtained.
３．合わせガラス
　本実施形態に係る樹脂シートの用途は特に限定されないが、合わせガラス用中間膜として用いることが好ましい。
　本実施形態の合わせガラスは、本実施形態に係る樹脂シートを合わせガラス用中間膜として用いていればよい。本実施形態に係る合わせガラスは、外観不良が生じ難い合わせガラスである。 3. Laminated glass The use of the resin sheet according to this embodiment is not particularly limited, but it is preferably used as an interlayer film for laminated glass.
The laminated glass of this embodiment should just use the resin sheet which concerns on this embodiment as an intermediate film for laminated glasses. The laminated glass according to the present embodiment is a laminated glass that is less likely to cause poor appearance.
　図１は、本発明の合わせガラス１００の一実施形態を模式的に示す断面図である。
　合わせガラス１００は、本実施形態に係る樹脂シートを含む合わせガラス用中間膜１０１と、合わせガラス用中間膜１０１の両面に設けられた透明基板１０３と、を備える。
　合わせガラス１００を製造するには、例えば、図１に示すように、本実施形態に係る樹脂シートを合わせガラス用中間膜１０１として用い、合わせガラス用中間膜１０１を２枚の透明基板１０３の間に狭持した後、加熱加圧する方法等が用いられる。
　これらの工程は、例えば、真空袋方式、ニップロール方式等を用いて行われる。これにより、合わせガラス用中間膜１０１が硬化して、合わせガラス用中間膜１０１と２枚の透明基板１０３とを接着一体化することができる。製造条件としては、例えば、上記積層体を８０～１２０℃の温度で予備圧着し、１００～１５０℃で１０分～１時間加熱処理することによりエチレン・酢酸ビニル共重合体を架橋させる。また、加熱処理は加圧下で行ってもよい。 FIG. 1 is a cross-sectional view schematically showing one embodiment of a laminated glass 100 of the present invention.
The laminated glass 100 includes an intermediate film 101 for laminated glass including the resin sheet according to the present embodiment, and a transparent substrate 103 provided on both surfaces of the intermediate film 101 for laminated glass.
In order to manufacture the laminated glass 100, for example, as shown in FIG. 1, the resin sheet according to the present embodiment is used as the laminated glass intermediate film 101, and the laminated glass intermediate film 101 is interposed between the two transparent substrates 103. After nipping, a method of heating and pressurizing is used.
These processes are performed using, for example, a vacuum bag method, a nip roll method, or the like. Thereby, the interlayer film for laminated glass 101 is cured, and the interlayer film for laminated glass 101 and the two transparent substrates 103 can be bonded and integrated. As the production conditions, for example, the above laminate is pre-pressed at a temperature of 80 to 120 ° C., and heat-treated at 100 to 150 ° C. for 10 minutes to 1 hour to crosslink the ethylene / vinyl acetate copolymer. Further, the heat treatment may be performed under pressure.
　透明基板１０３は、例えば、グリーンガラス板、珪酸塩ガラス板、無機ガラス板、無着色透明ガラス板等のガラス板；ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリエチレンブチレート、ポリメチルメタクリレート（ＰＭＭＡ）等のプラスチック製の基板又はフィルム等を用いることができる。耐候性、耐衝撃性等の点でガラス板が好ましい。
　透明基板１０３の厚さは、１～２０ｍｍ程度が一般的である。合わせガラス１００において両面に配置されるそれぞれの透明基板１０３は、同一のもの用いてもよく、異なる基材を組み合わせて用いてもよい。基材の強度と合わせガラスの用途とを考慮して、組み合わせを決定する。 The transparent substrate 103 is, for example, a glass plate such as a green glass plate, a silicate glass plate, an inorganic glass plate, or an uncolored transparent glass plate; polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene butyrate, polymethyl methacrylate A plastic substrate such as (PMMA) or a film can be used. A glass plate is preferable in terms of weather resistance, impact resistance and the like.
The thickness of the transparent substrate 103 is generally about 1 to 20 mm. The same transparent substrate 103 may be used for each of the transparent substrates 103 disposed on both surfaces of the laminated glass 100, or different base materials may be used in combination. The combination is determined in consideration of the strength of the base material and the use of the laminated glass.
　合わせガラス１００は、建築物や乗り物（自動車、鉄道車両、船舶）用の材料；プラズマディスプレイ等の電子機器；冷蔵庫や保温装置等のような各種装置の扉や壁部等；の種々の用途に使用することができる。これらの中でも建築物に特に好適に使用することができる。 Laminated glass 100 is used for various applications such as materials for buildings and vehicles (automobiles, railcars, ships); electronic devices such as plasma displays; doors and walls of various devices such as refrigerators and heat insulation devices. Can be used. Among these, it can be particularly suitably used for buildings.
４．太陽電池モジュール
　本実施形態に係る樹脂シートの用途は特に限定されないが、太陽電池封止材として用いることが好ましい。
　本実施形態に係る樹脂シートにより構成された太陽電池封止材（太陽電池封止材シートとも呼ぶ。）は、太陽電池モジュールにおいて、太陽電池素子を封止するために用いられる。
　太陽電池モジュールは、例えば、通常、単結晶シリコン、多結晶シリコン等により形成された太陽電池素子を太陽電池封止材シートで挟み積層し、さらに、表裏両面を保護シートでカバーした結晶型太陽電池モジュールが挙げられる。すなわち、典型的な太陽電池モジュールは、太陽電池モジュール用保護シート（表面側透明保護部材）／受光面側封止層／太陽電池素子／裏面側封止層／太陽電池モジュール用保護シート（裏面側保護部材）という構成になっている。ここで、本実施形態の太陽電池封止材は上記受光面側封止層および裏面側封止層のいずれか一方、あるいは両方を形成するために用いられ、これらの封止層は樹脂シートを架橋させることにより形成することができる。
　ただし、本発明の好ましい実施形態の１つである太陽電池モジュールは、上記の構成には限定されず、本発明の目的を損なわない範囲で、上記の各層の一部を適宜省略し、または上記以外の層を適宜設けることができる。上記以外の層としては、例えば接着層、衝撃吸収層、コーティング層、反射防止層、裏面再反射層、および光拡散層等を挙げることができる。これらの層は、とくに限定はないが、各層を設ける目的や特性を考慮して、適切な位置に設けることができる。 4). Solar cell module The application of the resin sheet according to the present embodiment is not particularly limited, but is preferably used as a solar cell sealing material.
A solar cell encapsulant (also referred to as a solar cell encapsulant sheet) constituted by the resin sheet according to the present embodiment is used for encapsulating solar cell elements in a solar cell module.
For example, a solar cell module is usually a crystal solar cell in which solar cell elements formed of single crystal silicon, polycrystalline silicon or the like are sandwiched between solar cell encapsulant sheets, and both front and back surfaces are covered with a protective sheet. Module. That is, a typical solar cell module includes a solar cell module protective sheet (front surface side transparent protective member) / light-receiving surface side sealing layer / solar cell element / back surface side sealing layer / solar cell module protective sheet (back surface side). (Protective member). Here, the solar cell encapsulant of the present embodiment is used to form one or both of the light-receiving surface side sealing layer and the back surface side sealing layer, and these sealing layers are made of a resin sheet. It can be formed by crosslinking.
However, the solar cell module which is one of the preferred embodiments of the present invention is not limited to the above-described configuration, and a part of each of the above layers is appropriately omitted or the above-described range within a range not impairing the object of the present invention. Other layers can be provided as appropriate. Examples of the layer other than the above include an adhesive layer, a shock absorbing layer, a coating layer, an antireflection layer, a back surface rereflection layer, and a light diffusion layer. These layers are not particularly limited, but can be provided at appropriate positions in consideration of the purpose and characteristics of each layer.
　図２に、本実施形態の太陽電池モジュールの断面図の一例を示す。
　太陽電池モジュール１０は、複数の太陽電池素子１３と、太陽電池素子１３を挟んで封止する一対の受光面側太陽電池封止材シート１１と裏面側太陽電池封止材シート１２、および表面側透明保護部材１４および裏面側保護部材（バックシート）１５とを備える。 In FIG. 2, an example of sectional drawing of the solar cell module of this embodiment is shown.
The solar cell module 10 includes a plurality of solar cell elements 13, a pair of light-receiving surface side solar cell sealing material sheets 11 and back surface side solar cell sealing material sheets 12 that are sealed with the solar cell elements 13 interposed therebetween, and a front surface side. A transparent protective member 14 and a back surface side protective member (back sheet) 15 are provided.
（太陽電池素子）
　太陽電池素子１３としては、単結晶シリコン、多結晶シリコン、アモルファスシリコン等のシリコン系、ガリウム－砒素、銅－インジウム－セレン、カドミウム－テルル等のＩＩＩ－Ｖ族やＩＩ－ＶＩ族化合物半導体系等の各種太陽電池素子を用いることができる。
　太陽電池モジュール１０においては、複数の太陽電池素子１３は、導線および半田接合部を備えたインターコネクタ１６を介して電気的に直列に接続されている。 (Solar cell element)
Examples of the solar cell element 13 include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and III-V and II-VI compound semiconductor systems such as gallium-arsenic, copper-indium-selenium, and cadmium-tellurium. Various solar cell elements can be used.
In the solar cell module 10, the plurality of solar cell elements 13 are electrically connected in series via an interconnector 16 having a conducting wire and a solder joint.
（表面側透明保護部材）
　表面側透明保護部材１４としては、ガラス板；アクリル樹脂、ポリカーボネート、ポリエステル、フッ素含有樹脂等により形成された樹脂板等の透明基板が挙げられる。
　本実施形態の太陽電池封止材シートは、表面側透明保護部材１４に対して良好な接着性を示す。 (Front side transparent protective member)
Examples of the surface-side transparent protective member 14 include a glass plate; a transparent substrate such as a resin plate formed of an acrylic resin, polycarbonate, polyester, fluorine-containing resin, or the like.
The solar cell encapsulant sheet of this embodiment exhibits good adhesion to the surface side transparent protective member 14.
（裏面側保護部材）
　裏面側保護部材（バックシート）１５としては、金属や各種熱可塑性樹脂フィルム等の単体もしくは多層のシートが挙げられる。例えば、錫、アルミ、ステンレススチール等の金属；ガラス等の無機材料；ポリエステル、無機物蒸着ポリエステル、フッ素含有樹脂、ポリオレフィン等により形成された各種熱可塑性樹脂フィルム等が挙げられる。
　裏面側保護部材１５は、単層であってもよく、複層であってもよい。
　本実施形態の太陽電池封止材シートは、裏面側保護部材１５に対して良好な接着性を示す。 (Back side protection member)
Examples of the back surface side protection member (back sheet) 15 include single or multilayer sheets such as metals and various thermoplastic resin films. Examples thereof include metals such as tin, aluminum, and stainless steel; inorganic materials such as glass; various thermoplastic resin films formed of polyester, inorganic material-deposited polyester, fluorine-containing resin, polyolefin, and the like.
The back surface side protection member 15 may be a single layer or a multilayer.
The solar cell encapsulant sheet of this embodiment exhibits good adhesion to the back surface side protection member 15.
＜太陽電池モジュールの製造方法＞
　本実施形態における太陽電池モジュールの製造方法は特に限定されないが、例えば、以下の方法が挙げられる。
　まず、インターコネクタ１６を用いて電気的に接続した複数の太陽電池素子１３を一対の受光面側太陽電池封止材シート１１と裏面側太陽電池封止材シート１２で挟み、さらにこれら受光面側太陽電池封止材シート１１と裏面側太陽電池封止材シート１２を表面側透明保護部材１４と裏面側保護部材１５とで挟んで積層体を作製する。次いで、積層体を加熱して、受光面側太陽電池封止材シート１１と裏面側太陽電池封止材シート１２、受光面側太陽電池封止材シート１１と表面側透明保護部材１４、裏面側太陽電池封止材シート１２と裏面側保護部材１５とを接着する。
　太陽電池モジュールの製造に当たっては、樹脂シートを予め作っておき、樹脂シートが溶融する温度で圧着するという従来同様のラミネート方法によって、例えば、ラミネート温度が１４５～１７０℃、真空圧１０Ｔｏｒｒ以下で、０．５～１０分間真空下で加熱する。次いで、大気圧による加圧を２～３０分間程度行い、既に述べたような構成のモジュールを形成することができる。この場合、樹脂シートは特定の架橋剤を含有することで優れた架橋特性を有しており、モジュールの形成において二段階の接着工程を経る必要はなく、高温度で短時間に完結することができ、モジュールの生産性を格段に改良することができる。また、オーブン等を用いた二段階の接着工程を経ることも可能であり、二段階の接着工程を経る場合は、例えば、１２０～１７０℃の範囲で１～１２０分加熱し、モジュールを生産することも可能である。 <Method for manufacturing solar cell module>
Although the manufacturing method of the solar cell module in this embodiment is not specifically limited, For example, the following method is mentioned.
First, a plurality of solar cell elements 13 that are electrically connected using the interconnector 16 are sandwiched between a pair of light receiving surface side solar cell sealing material sheets 11 and a back surface side solar cell sealing material sheet 12, and these light receiving surface sides are further sandwiched between them. A laminated body is produced by sandwiching the solar cell encapsulant sheet 11 and the back side solar cell encapsulant sheet 12 between the front side transparent protective member 14 and the back side protective member 15. Next, the laminate is heated to receive the light-receiving surface side solar cell sealing material sheet 11 and the back surface side solar cell sealing material sheet 12, the light receiving surface side solar cell sealing material sheet 11 and the front surface side transparent protective member 14, and the back surface side. The solar cell sealing material sheet 12 and the back surface side protection member 15 are bonded.
In the production of the solar cell module, a resin sheet is prepared in advance, and is subjected to pressure bonding at a temperature at which the resin sheet melts. For example, the lamination temperature is 145 to 170 ° C., and the vacuum pressure is 10 Torr or less. Heat for 5-10 minutes under vacuum. Next, pressurization by atmospheric pressure is performed for about 2 to 30 minutes, and a module having the configuration as described above can be formed. In this case, the resin sheet has excellent cross-linking properties by containing a specific cross-linking agent, and it is not necessary to go through a two-step bonding process in forming the module, and can be completed in a short time at a high temperature. This can greatly improve module productivity. It is also possible to go through a two-step bonding process using an oven or the like. In the case of going through a two-step bonding process, for example, the module is produced by heating at 120 to 170 ° C. for 1 to 120 minutes. It is also possible.
　以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above can also be employ | adopted.
　以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
（実施例１）
１．樹脂シートの製造
　実施例１～６および比較例１～６について、次のように樹脂組成物を作製した。まず、エチレン・酢酸ビニル共重合体（ＥＶＡ）、架橋剤、架橋助剤、シランカップリング剤、光安定化剤、紫外線吸収剤および耐熱安定剤を表１に示す処方で配合して樹脂組成物を得た。 Example 1
1. Production of Resin Sheet For Examples 1 to 6 and Comparative Examples 1 to 6, resin compositions were prepared as follows. First, an ethylene / vinyl acetate copolymer (EVA), a crosslinking agent, a crosslinking aid, a silane coupling agent, a light stabilizer, an ultraviolet absorber, and a heat stabilizer are blended in the formulation shown in Table 1 to form a resin composition. Got.
　なお、表１中における各成分の配合割合の単位は質量部である。また、表１中における各成分の詳細は下記のとおりである。
・ＥＶＡ１：エチレン・酢酸ビニル共重合体（酢酸ビニル含有率２８質量％、ＭＦＲ：１５ｇ／１０分）
・ＥＶＡ２：エチレン・酢酸ビニル共重合体（酢酸ビニル含有率２８質量％、ＭＦＲ：３０ｇ／１０分）
・架橋剤：ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネート
・架橋助剤：トリアリルイソシアヌレート
・シランカップリング剤：γ－メタクリロキシプロピルトリメトキシシラン
・光安定化剤：ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート
・紫外線吸収剤：２－ヒドロキシ－４－ノルマル－オクチルオキシベンゾフェノン
・耐熱安定剤：オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート In addition, the unit of the mixture ratio of each component in Table 1 is a mass part. Moreover, the detail of each component in Table 1 is as follows.
EVA1: Ethylene / vinyl acetate copolymer (vinyl acetate content 28% by mass, MFR: 15 g / 10 min)
EVA2: ethylene-vinyl acetate copolymer (vinyl acetate content 28 mass%, MFR: 30 g / 10 min)
Crosslinking agent: t-butylperoxy-2-ethylhexyl carbonate Crosslinking aid: triallyl isocyanurate Silane coupling agent: γ-methacryloxypropyltrimethoxysilane Light stabilizer: bis (2,2,6 , 6-tetramethyl-4-piperidyl) sebacate / UV absorber: 2-hydroxy-4-normal-octyloxybenzophenone / heat stabilizer: octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate
＜耐スコーチ性評価＞
　単軸押出成形機（スクリュー径３０ｍｍφ）にて、ダイス温度１０５℃の条件下で上記樹脂組成物をシート状に溶融押出した。このときのシート厚みは０．４５ｍｍであった。押出されたシート表面を目視で確認し、評価結果を以下の通りに分類した。
　ゲル無し：○
　ゲル有り：× <Scorch resistance evaluation>
The resin composition was melt-extruded into a sheet form under the condition of a die temperature of 105 ° C. using a single screw extruder (screw diameter: 30 mmφ). The sheet thickness at this time was 0.45 mm. The extruded sheet surface was visually confirmed, and the evaluation results were classified as follows.
No gel: ○
With gel: ×
＜ヘイズ評価＞
　以下の方法に従い、耐スコーチ性評価で得られた樹脂シートとガラス板との積層体を作製した。
　幅１２０ｍｍ×長さ７５ｍｍサイズにカットした旭硝子ファブリテック社製の３．２ｍｍ厚みの青板フロートガラス２枚の間に、幅１２０ｍｍ×長さ７５ｍｍにカットした０．４５ｍｍ厚の樹脂シートを４枚積層した。真空ラミネーター（ＮＰＣ社製：ＬＭ－１１０ｘ１６０－Ｓ）を用いて熱板温度１３０℃で、真空時間３分、加圧時間３０分にてラミネートした。
　得られた積層体を１００℃に設定したオーブン（タバイエスペック社製：ＰＨＨ－４０１）に投入した。１５分後にオーブンの電源を切り、一晩放置して徐冷状態にした。
　徐冷した積層体のヘイズを、日本電色工業社製ＮＤＨ５０００を用いて測定し、評価結果を以下の通りに分類した。
　≦０．８％：○
　０．８％＜：× <Haze evaluation>
According to the following method, the laminated body of the resin sheet and glass plate obtained by scorch-proof evaluation was produced.
4 sheets of 0.45mm thick resin sheet cut to width 120mm x length 75mm between 2 sheets of 3.2mm thick blue plate float glass made by Asahi Glass Fabrictech Co., Ltd. cut to 120mm width x 75mm length Laminated. Lamination was performed using a vacuum laminator (manufactured by NPC: LM-110 × 160-S) at a hot plate temperature of 130 ° C., a vacuum time of 3 minutes, and a pressurization time of 30 minutes.
The obtained laminate was put into an oven set at 100 ° C. (manufactured by Tabai Espec: PHH-401). After 15 minutes, the oven was turned off and left overnight to cool slowly.
The haze of the slowly cooled laminate was measured using NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd., and the evaluation results were classified as follows.
≦ 0.8%: ○
0.8% <: ×
＜気泡発生確認評価＞
以下の方法に従い、耐スコーチ性評価で得られた樹脂シートとガラス板との積層体を作製した。
　幅１２０ｍｍ×長さ７５ｍｍサイズにカットした旭硝子ファブリテック社製の３．２ｍｍ厚みの青板フロートガラス２枚の間に、幅１２０ｍｍ×長さ７５ｍｍにカットした０．４５ｍｍ厚の樹脂シートを１枚積層した。真空ラミネーター（ＮＰＣ社製：ＬＭ－１１０ｘ１６０－Ｓ）を用いて熱板温度１５０℃で、真空時間３分、加圧時間１０分にてラミネートした。
　得られた積層体を目視で確認し、評価結果を以下の通りに分類した。
　気泡未発生：○
　気泡発生：× <Bubble generation confirmation evaluation>
According to the following method, the laminated body of the resin sheet and glass plate obtained by scorch-proof evaluation was produced.
One 0.45 mm thick resin sheet cut to 120 mm width x 75 mm length between two 3.2 mm thick blue plate float glass made by Asahi Glass Fabrictech Co., Ltd. cut to 120 mm width x 75 mm length Laminated. Lamination was performed using a vacuum laminator (manufactured by NPC: LM-110 × 160-S) at a hot plate temperature of 150 ° C., a vacuum time of 3 minutes, and a pressurization time of 10 minutes.
The obtained laminate was visually confirmed, and the evaluation results were classified as follows.
No bubble generation: ○
Bubble generation: ×
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～６の樹脂シートは透明性と気泡防止性に優れるとともにゲルの発生も抑制されていた。 The resin sheets of Examples 1 to 6 were excellent in transparency and bubble prevention properties, and the generation of gel was suppressed.
　この出願は、２０１６年２月２９日に出願された日本出願特願２０１６－０３７８９５号を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application claims priority based on Japanese Patent Application No. 2016-037895 filed on February 29, 2016, the entire disclosure of which is incorporated herein.

Claims (11)

  1. 　合わせガラス用中間膜または太陽電池封止材に用いられる樹脂シートであって、
    　エチレン・酢酸ビニル共重合体と、
    　架橋剤であるカーボネート系有機過酸化物と、
    　架橋助剤であるシアヌレート化合物と、
    を含み、
    　当該樹脂シート中の前記カーボネート系有機過酸化物の含有量が、前記エチレン・酢酸ビニル共重合体１００質量部に対して、１．０質量部以上１．５質量部以下であり、
    　当該樹脂シート中の前記シアヌレート化合物の含有量が、前記エチレン・酢酸ビニル共重合体１００質量部に対して、１．２質量部以上１．５質量部以下である樹脂シート。     A resin sheet used for an interlayer film for laminated glass or a solar cell sealing material,
    An ethylene / vinyl acetate copolymer;
    A carbonate-based organic peroxide as a crosslinking agent;
    A cyanurate compound which is a crosslinking aid;
    Including
    The content of the carbonate organic peroxide in the resin sheet is 1.0 part by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer,
    The resin sheet whose content of the said cyanurate compound in the said resin sheet is 1.2 mass parts or more and 1.5 mass parts or less with respect to 100 mass parts of said ethylene-vinyl acetate copolymers.
  2. 　請求項１に記載の樹脂シートにおいて、
    　前記カーボネート系有機過酸化物が、ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネートを含む樹脂シート。     In the resin sheet according to claim 1,
    A resin sheet in which the carbonate-based organic peroxide contains t-butylperoxy-2-ethylhexyl carbonate.
  3. 　請求項１または２に記載の樹脂シートにおいて、
    　前記シアヌレート化合物がトリアリルシアヌレートおよびトリアリルイソシアヌレートから選択される少なくとも一種を含む樹脂シート。     In the resin sheet according to claim 1 or 2,
    A resin sheet containing at least one selected from the group consisting of triallyl cyanurate and triallyl isocyanurate.
  4. 　請求項１乃至３いずれか一項に記載の樹脂シートにおいて、
    　ＡＳＴＭ　Ｄ１２３８に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定される前記エチレン・酢酸ビニル共重合体のＭＦＲが１０ｇ／１０分以上５０ｇ／１０分以下である樹脂シート。     In the resin sheet as described in any one of Claims 1 thru | or 3,
    A resin sheet according to ASTM D1238, wherein the MFR of the ethylene-vinyl acetate copolymer is 10 g / 10 min or more and 50 g / 10 min or less measured under conditions of 190 ° C. and 2.16 kg load.
  5. 　請求項１乃至４いずれか一項に記載の樹脂シートにおいて、
    　前記エチレン・酢酸ビニル共重合体中の酢酸ビニル単位の含有量が２５質量％以上３５質量％以下である樹脂シート。     In the resin sheet as described in any one of Claims 1 thru | or 4,
    The resin sheet whose content of the vinyl acetate unit in the said ethylene-vinyl acetate copolymer is 25 to 35 mass%.
  6. 　請求項１乃至５いずれか一項に記載の樹脂シートにおいて、
    　当該樹脂シート中の前記カーボネート系有機過酸化物の含有量に対する前記シアヌレート化合物の含有量の質量比が０．９以上１．５以下である樹脂シート。     In the resin sheet as described in any one of Claims 1 thru | or 5,
    The resin sheet whose mass ratio of content of the said cyanurate compound with respect to content of the said carbonate type organic peroxide in the said resin sheet is 0.9-1.5.
  7. 　請求項１乃至６いずれか一項に記載の樹脂シートにおいて、
    　当該樹脂シート中の前記カーボネート系有機過酸化物および前記シアヌレート化合物の合計含有量が、前記エチレン・酢酸ビニル共重合体１００質量部に対して、２．３質量部以上２．８質量部以下である樹脂シート。     In the resin sheet as described in any one of Claims 1 thru | or 6,
    The total content of the carbonate organic peroxide and the cyanurate compound in the resin sheet is 2.3 parts by mass or more and 2.8 parts by mass or less with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer. A resin sheet.
  8. 　請求項１乃至７いずれか一項に記載の樹脂シートにおいて、
    　前記エチレン・酢酸ビニル共重合体の含有量が、当該樹脂シートに含まれる樹脂成分の全体を１００質量％としたとき、８０質量％以上である樹脂シート。     In the resin sheet according to any one of claims 1 to 7,
    The resin sheet whose content of the said ethylene-vinyl acetate copolymer is 80 mass% or more when the whole resin component contained in the said resin sheet is 100 mass%.
  9. 　請求項１乃至８いずれか一項に記載の樹脂シートを含むガラス用中間膜と、
    　前記合わせガラス用中間膜の両面に設けられた透明基板と、
    を備える合わせガラス。     An interlayer film for glass comprising the resin sheet according to any one of claims 1 to 8,
    Transparent substrates provided on both sides of the interlayer film for laminated glass,
    Laminated glass with.
  10. 　請求項９に記載の合わせガラスにおいて、
    　建築物に使用される合わせガラス。     In the laminated glass according to claim 9,
    Laminated glass used in buildings.
  11. 　表面側透明保護部材と、
    　裏面側保護部材と、
    　太陽電池素子と、
    　請求項１乃至８いずれか一項に記載の樹脂シートの架橋体であり、かつ、前記太陽電池素子を前記表面側透明保護部材と前記裏面側保護部材との間に封止する封止層と、
    を備えた太陽電池モジュール。     A surface-side transparent protective member;
    A back side protection member;
    A solar cell element;
    A sealing layer that is a crosslinked body of the resin sheet according to any one of claims 1 to 8, and that seals the solar cell element between the front surface side transparent protective member and the rear surface side protective member. ,
    Solar cell module with
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CN111801303B (en) * 2018-02-14 2022-11-08 三井—陶氏聚合化学株式会社 Resin composition for laminated glass interlayer or solar cell sealing material, laminated glass interlayer, laminated glass, solar cell sealing material, and solar cell module
JP7254226B2 (en) 2018-02-14 2023-04-07 三井・ダウポリケミカル株式会社 LAMINATED GLASS INTERMEDIATE FILM OR RESIN COMPOSITION FOR SOLAR CELL ENCLOSURE MATERIAL, LAMINATED GLASS INTERMEDIATE FILM, LAMINATED GLASS, SOLAR CELL ENCLOSURE MATERIAL AND SOLAR CELL MODULE
JP7254226B6 (en) 2018-02-14 2023-04-21 三井・ダウポリケミカル株式会社 LAMINATED GLASS INTERMEDIATE FILM OR RESIN COMPOSITION FOR SOLAR CELL ENCLOSURE MATERIAL, LAMINATED GLASS INTERMEDIATE FILM, LAMINATED GLASS, SOLAR CELL ENCLOSURE MATERIAL AND SOLAR CELL MODULE

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