WO2014007253A1 - Composition de résine thermoplastique, corps moulé en résine thermoplastique, corps moulé en résine thermoplastique multicouche, et module de cellule solaire - Google Patents

Composition de résine thermoplastique, corps moulé en résine thermoplastique, corps moulé en résine thermoplastique multicouche, et module de cellule solaire Download PDF

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Publication number
WO2014007253A1
WO2014007253A1 PCT/JP2013/068151 JP2013068151W WO2014007253A1 WO 2014007253 A1 WO2014007253 A1 WO 2014007253A1 JP 2013068151 W JP2013068151 W JP 2013068151W WO 2014007253 A1 WO2014007253 A1 WO 2014007253A1
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Prior art keywords
thermoplastic resin
flaky glass
meth
molded body
resin molded
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PCT/JP2013/068151
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English (en)
Japanese (ja)
Inventor
慶之 岡本
洋 新納
林　健太郎
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三菱レイヨン株式会社
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Priority to JP2013531806A priority Critical patent/JPWO2014007253A1/ja
Publication of WO2014007253A1 publication Critical patent/WO2014007253A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • 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 thermoplastic resin composition, a thermoplastic resin molded body, a thermoplastic resin laminated molded body, and a solar cell module.
  • This application claims priority based on Japanese Patent Application No. 2012-152115 for which it applied to Japan on July 6, 2012, and uses the content here.
  • a glass material has been used for a top sheet member of a solar cell module.
  • the glass topsheet member has good dimensional stability and flame retardancy, but it is necessary to use chemically tempered glass to reduce the thickness for weight reduction, which is large like a solar cell module.
  • the cost is high.
  • replacement with a resin material has been studied in order to reduce the weight of the solar cell module.
  • a resin material having good translucency is required in order to improve the photoelectric conversion efficiency of the solar cell.
  • Patent Document 1 proposes a sheet in which glass having a refractive index difference of 0.01 to 0.04 with a transparent resin is dispersed in a transparent resin as a glass substitute resin sheet.
  • the glass used is fibrous and has a small fiber diameter, multiple scattering is likely to occur in the resulting molded body, and the translucency may be reduced.
  • flaky glass discloses that the flaky glass is dispersed in an amount of 0.1 to 20% by weight in a thermoplastic resin. There has been proposed a molded body obtained by the above process.
  • the present invention has been made in view of the above circumstances, and is a heat capable of providing a top sheet member for a solar cell module that is excellent in translucency and that suppresses a decrease in the maximum output of the solar cell module even after a thermal cycle test. It is an object of the present invention to provide a thermoplastic resin composition, a thermoplastic resin molded body and a thermoplastic resin laminate molded body that can be used as a top sheet member for a solar cell module, and a solar cell module having the above performance.
  • thermoplastic resin composition comprising a thermoplastic resin (A) and flaky glass (B),
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin composition is 30 to 80,
  • the content of the flaky glass (B) in the thermoplastic resin composition is 25 to 70 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A).
  • thermoplastic resin composition in which a difference between a refractive index of the thermoplastic resin (A) and a refractive index of the flaky glass (B) in the thermoplastic resin composition is 0 or more and 0.05 or less.
  • thermoplastic resin molded article containing the thermoplastic resin (A) and the flaky glass (B),
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin molded body is 25 to 70
  • the content of the flaky glass (B) in the thermoplastic resin molded body is 25 to 70 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A).
  • the difference between the refractive index of the thermoplastic resin (A) in the thermoplastic resin molded body and the refractive index of the flaky glass (B) is from 0 to 0.05
  • a thermoplastic resin molded article having a total light transmittance of 86% to 93% in the thermoplastic resin molded article is from 0 to 0.05
  • the melt flow rate of the thermoplastic resin (A) in the thermoplastic resin molded body is 5 g / 10 min or more and 20 g / 10 min or less, according to any one of the above [5] to [7] Thermoplastic resin molding.
  • thermoplastic resin molded article according to any one of [5] to [8], wherein the thermoplastic resin (A) is a (meth) acrylic resin or a polycarbonate resin.
  • thermoplastic resin laminated molded article in which a (meth) acrylic polymer protective layer is laminated on the thermoplastic resin molded article according to any one of [5] to [9].
  • the thermoplastic resin laminate molded article according to [10] comprising at least one component selected from the group consisting of products.
  • thermoplastic resin molded article according to any one of [6] to [9] or the thermoplastic resin laminate molded article according to [10] or [11] .
  • thermoplastic resin molded body or the thermoplastic resin laminated molded body is a sheet having a thickness of 1 to 3 mm.
  • thermoplastic resin molded article that is excellent in translucency and reduced in deformation due to temperature change.
  • thermoplastic resin molded body as a top sheet member for a solar cell module, it is possible to provide a lightweight solar cell module in which a decrease in maximum output is suppressed.
  • thermoplastic resin (A) is one of the components of the thermoplastic resin composition which is one embodiment of the present invention.
  • the melt flow rate (hereinafter sometimes referred to as MFR) of the thermoplastic resin (A) is preferably 5 g / 10 minutes or more and 20 g / 10 minutes or less.
  • the MFR of the thermoplastic resin is more preferably 8 g / 10 minutes or more and 17 g / 10 minutes or less, and further preferably 12 g / 10 minutes or more and 15 g / 10 minutes or less.
  • the “melt flow rate” of the thermoplastic resin (A) here means the fluidity of the molten plastic. The measurement of the melt flow rate of the thermoplastic resin (A) is performed under the conditions of a temperature of 230 degrees and a load of 37.3 N in accordance with JIS K7210.
  • the mass average molecular weight (Mw) measured by GPC is preferably 50,000 to 200,000.
  • Mw of the thermoplastic resin (A) is 50,000 or more, it is preferable in terms of improving the strength and durability of the thermoplastic resin molded article, and when the Mw of the thermoplastic resin (A) is 200,000 or less, This is preferable in terms of improving processability such as fluidity of the thermoplastic resin composition at the time of molding when obtaining a plastic resin molded body.
  • the lower limit value of Mw of the thermoplastic resin (A) is more preferably 60,000 or more.
  • the upper limit value of Mw of the thermoplastic resin (A) is more preferably 150,000 or less.
  • the Mw of the thermoplastic resin (A) is more preferably 60,000 or more and 150,000 or less.
  • the lower limit value of Mw of the thermoplastic resin (A) is more preferably 70,000 or more.
  • the upper limit value of Mw of the thermoplastic resin (A) is more preferably 100,000 or less. That is, the Mw of the thermoplastic resin (A) is more preferably 70,000 or more and 100,000 or less.
  • thermoplastic resin (A) examples include (meth) acrylic resins and polycarbonate resins.
  • a (meth) acrylic resin is used as the thermoplastic resin (A)
  • the weather resistance of the thermoplastic resin molded article of the present invention described later can be improved.
  • polycarbonate resin as a thermoplastic resin (A)
  • the impact resistance of a thermoplastic resin molding can be improved.
  • (meth) acrylic resin a polymer containing a (meth) acrylic acid ester unit, and (meth), since the difference in refractive index from the glass flake (B) described later can be easily adjusted to 0.05 or less.
  • MS resin which is a copolymer of acrylic ester and styrene is preferable, and a polymer containing (meth) acrylic ester units is more preferable. These can be used alone or in combination of two or more.
  • “(meth) acrylic resin” means one or both of “acrylic resin” and “methacrylic resin”
  • (meth) acrylic acid” means “acrylic acid”. And “methacrylic acid” or both.
  • Examples of the (meth) acrylic acid ester that is a raw material for a polymer containing a (meth) acrylic acid ester unit include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, Iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and (meth ) 2-hydroxyethyl acrylate. These can be used alone or in combination of two or more.
  • the polymer containing a (meth) acrylic acid ester unit can contain other monomer units other than the (meth) acrylic acid ester unit as needed.
  • examples of other monomers that are raw materials for constituting other monomer units include vinyl esters such as vinyl acetate; aromatic vinyls such as styrene, p-methylstyrene, ⁇ -methylstyrene, and vinylnaphthalene.
  • Monomers; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; ⁇ , ⁇ -unsaturated carboxylic acids such as (meth) acrylic acid and crotonic acid; and maleimides such as N-ethylmaleimide and N-cyclohexylmaleimide Compounds and the like. These can be used alone or in combination of two or more.
  • a polymer containing a (meth) acrylic acid ester unit As a polymer containing a (meth) acrylic acid ester unit, a polymer containing a (meth) acrylic acid ester unit has good light transmittance, heat resistance, mechanical properties and moldability. ) 80-100% by mass of methyl (meth) acrylate unit and 0-20% by mass of other monomer units based on the total mass of the polymer containing acrylate units, and A polymer having 50 to 100% by mass of methyl methacrylate units with respect to the total mass of methyl (meth) acrylate units is preferred.
  • the polycarbonate resin is not particularly limited, and examples thereof include “Iupilon” (registered trademark) manufactured by Mitsubishi Engineering Plastics Co., Ltd. and “SD Polyca” (registered trademark) manufactured by Sumika Stylon Co., Ltd.
  • flaky glass is one of the components of the thermoplastic resin composition that is one embodiment of the present invention.
  • flaky glass means flat glass having a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less and an aspect ratio of 30 or more and 200 or less. Examples of the shape of the flaky glass include polygons and circles, and are not particularly limited.
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin composition is 30 to 80.
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin composition is 30 or more, the aspect ratio of the flaky glass (B) in the thermoplastic resin molding can be 25 or more, and the thermoplastic resin The translucency of the molded product is improved.
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin composition is 80 or less, the aspect ratio of the flaky glass (B) in the thermoplastic resin molded body can be 75 or less, The impact resistance of the plastic resin molding is improved.
  • the lower limit of the aspect ratio of the flaky glass (B) in the thermoplastic resin composition is preferably 35 or more, and more preferably 45 or more.
  • the upper limit of the aspect ratio of the flaky glass (B) in the thermoplastic resin composition is preferably 75 or less, more preferably 70 or less, and even more preferably 65 or less. That is, the aspect ratio of the flaky glass (B) in the thermoplastic resin composition is preferably 35 or more and 75 or less, more preferably 45 or more and 75 or less, still more preferably 45 or more and 70 or less, and more preferably 45 or more and 65 or less.
  • the following are particularly preferred:
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin composition which is one embodiment of the present invention is the average particle diameter of the flaky glass (B) by the thickness value of the flaky glass (B). It is the value obtained by dividing.
  • the “thickness” of the flaky glass (B) here can be measured with an electron microscope or the like. Specifically, the “thickness of the flaky glass (B) in the thermoplastic resin composition” is obtained by measuring the cross-section or surface of the raw flaky glass (B) alone or the thermoplastic resin composition with an electron microscope. It can be observed from the surface direction of the flaky glass (B) and measured using a scale bar of an electron microscope.
  • the average particle size of the flaky glass (B) in the thermoplastic resin composition is preferably 30 to 600 ⁇ m.
  • the average particle size of the flaky glass (B) in the thermoplastic resin composition is preferably 30 to 600 ⁇ m.
  • the average particle size of the flaky glass (B) in the thermoplastic resin composition is preferable in terms of improving the translucency of the thermoplastic resin molded article.
  • the average particle diameter of the flaky glass (B) in the thermoplastic resin composition before molding exceeds 600 ⁇ m, it is preferable in that the flaky glass (B) is broken during the molding process and the average particle diameter becomes 600 ⁇ m or less.
  • the average particle diameter of the flaky glass (B) in the thermoplastic resin composition is preferably 600 ⁇ m or less from the viewpoint of workability when obtaining a thermoplastic resin composition or a thermoplastic resin molded article.
  • the lower limit of the average particle size of the flaky glass (B) in the thermoplastic resin composition is more preferably 80 ⁇ m or more, and even more preferably 200 ⁇ m or more.
  • the upper limit of the average particle size of the flaky glass (B) in the thermoplastic resin composition is more preferably 500 ⁇ m or less, and even more preferably 400 ⁇ m or less.
  • the average particle size of the flaky glass (B) in the thermoplastic resin composition is more preferably 80 ⁇ m or more and 500 ⁇ m or less, and further preferably 200 ⁇ m or more and 400 ⁇ m or less.
  • the “average particle diameter of the flaky glass (B) in the thermoplastic resin composition” which is one embodiment of the present invention, is obtained by ashing the thermoplastic resin composition using an electric muffle furnace. After obtaining (B), using a particle size distribution measuring device (LA-950V2 (trade name) manufactured by HORIBA, Ltd.), laser light having a wavelength of 650 ⁇ m is applied to the flaky glass (B) flowing in water. This is a value obtained by irradiating and analyzing the average particle size from the scattering pattern.
  • the glass constituting the flaky glass (B) include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, quartz, low dielectric constant glass, and high dielectric constant glass. Is mentioned.
  • the thermoplastic resin composition according to one embodiment of the present invention contains 25 to 70 parts by mass of flaky glass (B) with respect to 100 parts by mass of the thermoplastic resin (A).
  • the thermal linear expansion coefficient of the thermoplastic resin molded article obtained by molding the thermoplastic resin composition is set to the glass level ( That is, it can be close to 7-9 ppm / K), and the decrease in the maximum output of the solar cell module after the thermal cycle test can be suppressed.
  • the lower limit of the content of the flaky glass (B) with respect to 100 parts by mass of the thermoplastic resin (A) is preferably 30 parts by mass or more.
  • 60 mass parts or less is preferable and, as for the upper limit of content of flake shaped glass (B) with respect to 100 mass parts of thermoplastic resins (A), 50 mass parts or less are more preferable.
  • the content of the flaky glass (B) with respect to 100 parts by mass of the thermoplastic resin (A) is preferably 30 parts by mass or more and 60 parts by mass or less, more preferably 30 parts by mass or more and 50 parts by mass. The following is more preferable.
  • the difference between the refractive index of the thermoplastic resin (A) and the refractive index of the flaky glass (B) in the thermoplastic resin composition is 0 or more and 0.05 or less.
  • the difference between the refractive index of the thermoplastic resin (A) in the thermoplastic resin composition and the refractive index of the flaky glass (B) in the thermoplastic resin composition is preferably 0 or more and 0.04 or less, more preferably 0 or more and 0.03 or less. .
  • the “refractive index of the thermoplastic resin (A) in the thermoplastic resin composition” herein refers to the refractive index of the thermoplastic resin (A) used as a raw material. means.
  • the refractive index of the thermoplastic resin (A) in the thermoplastic resin composition is the Abbe refractometer (NAR-2: manufactured by Atago Co., Ltd.) in accordance with JIS K 7142 using the thermoplastic resin (A) used as a raw material. Etc. can be measured.
  • the “refractive index of the flaky glass (B) in the thermoplastic resin composition” herein refers to the refractive index of the flaky glass (B) used as a raw material. Means rate.
  • the refractive index of the flaky glass (B) in the thermoplastic resin composition is determined by immersing the flaky glass (B) used as a raw material in a refractive index standard solution having various refractive indexes, and observing the flaky glass (B ) And the refractive index standard solution can be measured as the refractive index of the glass flake (B).
  • thermoplastic resin composition in the present invention, known stabilizers and additives may be added to the thermoplastic resin composition as necessary.
  • thermoplastic resin composition examples include powder and pellets.
  • pellet used herein means a granular form having a longest length of 1 mm or more and 10 mm or less and having a polyhedron, a cylinder, a sphere, or other shapes.
  • the longest length is preferably 1 to 5 mm, more preferably 1 to 3 mm, from the viewpoint of handleability and ease of molding.
  • the “powder” here means a powdery solid substance having a particle size of 1 mm or less.
  • the powder preferably has a particle size of 200 ⁇ m or more and 1 mm or less from the viewpoint of handleability and ease of molding.
  • the thermoplastic resin composition may be, for example, a powder obtained by mixing a thermoplastic resin (A) and flaky glass (B), and a pellet obtained by melt-kneading the thermoplastic resin (A) and flaky glass (B). It is good.
  • thermoplastic resin composition can be obtained, for example, as follows. A raw material partial polymer containing a monomer for obtaining a (meth) acrylic resin, or a (meth) acrylic resin dissolved in a raw material containing a monomer for obtaining another (meth) acrylic resin A syrup-like product (hereinafter sometimes referred to as “syrup”) is obtained. Next, the flaky glass (B) is dispersed therein, and then the syrup is polymerized. As a result, a thermoplastic resin composition can be obtained.
  • thermoplastic resin (A) and the flaky glass (B) examples include premixers such as a ribbon blender, a tumbler, a nauter mixer, a Henschel mixer, a super mixer, and a planetary mixer.
  • apparatus for melting and kneading the thermoplastic resin (A) and the flaky glass (B) include, for example, melt kneading apparatuses such as a Banbury mixer, a kneader, a roll, a kneader ruder, a single screw extruder, a twin screw extruder, and the like. Can be mentioned.
  • the temperature at the time of mixing or melt-kneading the thermoplastic resin (A) and the flaky glass (B) is preferably 250 degrees or more and 280 degrees or less.
  • a method for supplying various raw materials to the melt-kneading apparatus a method in which the respective components are mixed and supplied in advance is preferable, but it is also possible to supply each component independently to the melt-kneading apparatus.
  • thermoplastic resin molded product means a product obtained by molding a thermoplastic resin composition into a desired shape, for example, a molding method such as injection molding, extrusion molding or compression molding. Can be molded by.
  • the thermoplastic resin molded body according to one embodiment of the present invention contains 25 to 70 parts by mass of flaky glass (B) with respect to 100 parts by mass of the thermoplastic resin (A).
  • the coefficient of thermal expansion of the thermoplastic resin molded body is made of glass. (That is, 7 to 9 ppm / K), and a decrease in the maximum output of the solar cell module after the thermal cycle test can be suppressed.
  • the content of the flaky glass (B) is 70 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A), thereby obtaining a thermoplastic resin molded body. Good processability during molding.
  • the lower limit of the content of the flaky glass (B) with respect to 100 parts by mass of the thermoplastic resin (A) in the thermoplastic resin molded body is preferably 30 parts by mass or more.
  • 60 mass parts or less is preferable and, as for the upper limit of content of flake shaped glass (B) with respect to 100 mass parts of thermoplastic resins (A) in a thermoplastic resin molding, 50 mass parts or more are more preferable.
  • the content of the flaky glass (B) with respect to 100 parts by mass of the thermoplastic resin (A) in the thermoplastic resin molded body is preferably 30 parts by mass or more and 60 parts by mass or less, more preferably 30 parts by mass or more and 50 parts by mass. The following is more preferable.
  • the difference between the refractive index of the thermoplastic resin (A) and the refractive index of the flaky glass (B) in the thermoplastic resin molding is 0 or more and 0.05 or less.
  • the difference between the refractive index of the thermoplastic resin (A) and the refractive index of the flaky glass (B) is preferably from 0 to 0.04, more preferably from 0 to 0.03.
  • the “refractive index of the thermoplastic resin (A) in the thermoplastic resin molded product” herein has the same meaning as the “refractive index of the thermoplastic resin (A) in the thermoplastic resin composition”. Means the refractive index measured using the thermoplastic resin (A). Further, the “refractive index of the flaky glass (B) in the thermoplastic resin molded product” herein has the same meaning as the “refractive index of the flaky glass (B) in the thermoplastic resin composition”. Means the refractive index measured using the flaky glass (B).
  • the total light transmittance of the thermoplastic resin molded body is 86% or more and 93% or less.
  • the total light transmittance of the resin molded product can be 86% or more and 93% or less.
  • the “total light transmittance of the thermoplastic resin molding” as used herein means the ratio of the total transmitted light beam to the parallel incident light beam of the test piece.
  • the total light transmittance of the thermoplastic resin molded body is measured with a haze meter (HM-150 (trade name) manufactured by Murakami Color Research Laboratory Co., Ltd.) according to JIS K 6361-1. I can do it.
  • the melt flow rate (MFR) of the thermoplastic resin (A) in the thermoplastic resin molded body is preferably 5 g / 10 min or more and 20 g / 10 min or less.
  • the MFR of the thermoplastic resin in the thermoplastic resin molded body is more preferably 8 g / 10 min or more and 17 g / 10 min or less, and further preferably 12 g / 10 min or more and 15 g / 10 min or less.
  • the “melt flow rate” of the thermoplastic resin (A) in the thermoplastic resin molded product means the fluidity of the molten plastic.
  • the measurement of the melt flow rate of the thermoplastic resin (A) in the thermoplastic resin molding is performed under the conditions of a temperature of 230 degrees and a load of 37.3 N in accordance with JIS K7210.
  • the flaky glass (B) in the thermoplastic resin molded product is flaky (flaky).
  • the “flaky glass” in the flaky glass (B) in the thermoplastic resin molded body means a flat glass having a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less and an aspect ratio of 30 or more and 200 or less. . Examples of the shape include a polygon and a circle, and are not particularly limited.
  • the form of the flaky glass (B) in the thermoplastic resin molded body is the same as the form of the flaky glass (B) in the thermoplastic resin composition, or molding conditions for obtaining the thermoplastic resin molded body, etc.
  • the average particle size and aspect ratio of the flaky glass (B) may be smaller than the average particle size and aspect ratio of the flaky glass (B) in the thermoplastic resin composition.
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin molded product is 25 to 70.
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin molded body is 25 or more.
  • the translucency of the thermoplastic resin molded body is improved.
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin molded body is 70 or less, the surface smoothness of the thermoplastic resin molded body is improved.
  • the lower limit of the aspect ratio of the flaky glass (B) in the thermoplastic resin molding is preferably 30 or more, and more preferably 35 or more.
  • the upper limit of the aspect ratio of the flaky glass (B) in the thermoplastic resin molded body is preferably 65 or less. That is, the aspect ratio of the flaky glass (B) in the thermoplastic resin molded body is preferably 30 or more and 65 or less, and more preferably 35 or more and 65 or less.
  • the aspect ratio of the flaky glass (B) in the thermoplastic resin molded product is the thickness of the flaky glass (B) using the value of the average particle diameter of the flaky glass (B) in the thermoplastic resin molded product as a raw material. It is a value obtained by dividing by the value. "The thickness of the flaky glass (B) used as a raw material" can be measured by the same method as described above.
  • the thermoplastic resin molded body preferably has a thermal linear expansion coefficient at 50 ° C. of 8 ppm / K or more and 40 ppm / K or less, and 8 ppm / K. As mentioned above, it is more preferable that it is 37 ppm / K or less.
  • the average particle size of the flaky glass (B) in the thermoplastic resin molding is preferably 25 to 500 ⁇ m.
  • the average particle size of the flaky glass (B) in the thermoplastic resin molded body is preferably 25 to 500 ⁇ m.
  • the lower limit value of the average particle diameter of the flaky glass (B) in the thermoplastic resin molded body is more preferably 60 ⁇ m or more, and further preferably 150 ⁇ m or more.
  • the upper limit of the average particle size of the flaky glass (B) in the thermoplastic resin molded body is more preferably 400 ⁇ m or less, and further preferably 300 ⁇ m or less. That is, the average particle size of the flaky glass (B) in the thermoplastic resin molded body is more preferably 60 ⁇ m or more and 400 ⁇ m or less, and further preferably 150 ⁇ m or more and 300 ⁇ m or less.
  • the flaky glass (B) was obtained by ashing the thermoplastic resin molded body using an electric muffle furnace.
  • flaky glass (B) flowing in water is irradiated with a laser beam having a wavelength of 650 ⁇ m, and its scattering pattern. To the value obtained by analyzing the average particle diameter.
  • the shape of the thermoplastic resin molded body is preferably, for example, a sheet having a thickness of 1 to 3 mm.
  • the thermoplastic resin molded article has good rigidity, and the obtained solar cell module is preferable in that the maximum output can be maintained even after the thermal cycle test.
  • the lower limit value of the sheet thickness is more preferably 1.5 mm or more.
  • the upper limit value of the sheet thickness is more preferably 2.5 mm or less. That is, the thickness of the sheet is more preferably 1.5 mm or more and 2.5 mm or less.
  • the “sheet thickness” means a thickness in a cross section cut perpendicularly to the width direction of the sheet at the center in the sheet length direction.
  • thermoplastic resin molded body examples include a method obtained by molding a thermoplastic resin composition by a molding method such as injection molding, extrusion molding, or compression molding. Among these molding methods, extrusion molding is preferred because it can be uniformly molded into a desired shape. In order to obtain a plate-shaped or film-shaped molded body by extrusion molding, the molten resin extruded using an extruder such as a T-die can be taken out while being cooled by a cooling roll.
  • a molding method such as injection molding, extrusion molding, or compression molding.
  • extrusion molding is preferred because it can be uniformly molded into a desired shape.
  • the molten resin extruded using an extruder such as a T-die can be taken out while being cooled by a cooling roll.
  • the surface of the molded body in order to obtain a thermoplastic resin molded body having a surface excellent in smoothness, the surface of the molded body can be hot-pressed as necessary.
  • the heat pressing method include a continuous press method such as a batch press method using a high-pressure press, a roll press method, and a belt press method.
  • the temperature at the time of hot pressing include heating at 200 to 300 ° C.
  • An example of the press pressure is a press at 3 to 15 MPa.
  • thermoplastic resin laminate molding The thermoplastic resin laminate molded body is obtained by laminating a (meth) acrylic polymer protective layer on a thermoplastic resin molded body.
  • laminate includes the case where a (meth) acrylic polymer protective layer is “coated” on a thermoplastic resin molded body.
  • the (meth) acrylic polymer protective layer include functional layers having various functions such as weather resistance, impact resistance, scratch resistance, high hardness, and flexibility.
  • the (meth) acrylic polymer protective layer is a protective layer formed from a (meth) acrylic polymer.
  • the “(meth) acrylic polymer” here means a polymer obtained by polymerizing (meth) acrylic acid.
  • examples of the (meth) acrylic polymer include a (meth) acrylic film and a cured product of a (meth) acrylic coating composition containing a monomer having at least two (meth) acryloyloxy groups in the molecule. It is done.
  • the (meth) acrylic film is preferably a film having a thickness of 50 to 200 ⁇ m constituted by polymerization of (meth) acrylic acid.
  • (meth) acrylic acid for example, “Acryprene HBS006” (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd. ).
  • a cured product of a (meth) acrylic coating composition containing a monomer having at least two (meth) acryloyloxy groups in the molecule is a monomer having at least two (meth) acryloyloxy groups in the molecule
  • a coating composition containing a polymer of (meth) acrylic acid containing styrene is cured. Specific examples thereof include cured products of various (meth) acrylic coating compositions for forming various functional layers such as a hard coat layer.
  • the thermoplastic resin laminated molded body is preferably a sheet having a thickness of 1 to 3 mm.
  • the thermoplastic resin laminate molded article has good rigidity, and the obtained solar cell module is preferable in that the maximum output can be maintained even after the thermal cycle test.
  • the lower limit value of the sheet thickness is more preferably 1.5 mm or more.
  • the upper limit value of the sheet thickness is more preferably 2.5 mm or less.
  • the thickness of the sheet is more preferably 1.5 mm or more and 2.5 mm or less.
  • the “thickness of the sheet of the thermoplastic resin laminate molded product” as used herein refers to the thickness of a section cut perpendicularly to the width direction of the sheet at the center in the length direction of the sheet of the thermoplastic resin laminate molded product. Means.
  • Examples of a method for obtaining a thermoplastic resin laminated molded body include a hot press method and a coating method.
  • Examples of the temperature at the time of hot pressing include heating at 200 to 250 ° C.
  • An example of the press pressure is a press at 5 to 20 MPa.
  • As a coating method methods such as bar coating, gravure coating, and spin coating can be used.
  • the solar cell module which is one embodiment of the present invention is obtained using a thermoplastic resin molded body or a thermoplastic resin laminated molded body.
  • a solar cell module which is one embodiment of the present invention for example, a front protective member (a thermoplastic resin molded body or a thermoplastic resin laminated molded body of the present invention), a back surface protective member, a quadruple solar cell, a sealing material
  • the solar cell module comprised by the layer and electrode material is mentioned.
  • a front surface protection member (a thermoplastic resin molded body or a thermoplastic resin laminate molded body of the present invention) is provided on the light receiving surface side (front surface side) on which solar rays of the solar cell module are incident, and the solar cell module
  • a back surface protection member is provided on the surface (back surface side) facing the light receiving surface side.
  • a sealing material layer is formed between the front surface protection member (the thermoplastic resin molded body or the thermoplastic resin laminated molded body of the present invention) and the back surface protection member.
  • Quadruple solar cells and electrode materials are embedded in the sealing material layer, and the electrode material extending from the quadruple solar cells is in a state that can be connected to the outside of the solar cell module. In the quadruple solar cells, four solar cells are connected in series in two rows and two columns with an electrode material.
  • examples of the back surface protection member include a sheet in which a polyethylene terephthalate (PET) sheet is laminated on one or both sides of a resin sheet mainly composed of polyvinyl fluoride. .
  • PET polyethylene terephthalate
  • the solar battery cell in the solar battery module according to one embodiment of the present invention is not particularly limited as long as it is a solar battery cell that can generate power using the photovoltaic effect of a semiconductor, and a known solar battery cell is used. Can do.
  • a crystalline silicon cell is preferable from the viewpoint of a balance between power generation performance and cost.
  • insulating transparent resin As a sealing material in the solar cell module which is one embodiment of this invention, insulating transparent resin is mentioned, for example.
  • the insulating transparent resin include, for example, thermoplastic resins such as ethylene-vinyl acetate copolymer, polyvinyl butyral, ionomer resin, and low density polyethylene; and urethane curable resins, epoxy curable resins, ( Known curable resins such as a (meth) acrylate-based curable resin may be used.
  • part means “part by mass”.
  • thermoplastic resin (A) (a) Refractive index Pellets of thermoplastic resin (A) were molded at 220 ° C. and 10 MPa for 3 minutes using a 100TON heating molding machine (manufactured by Shoji Iron Works Co., Ltd.). It pressed and produced the test piece of thickness 2mm * length 20mm * width 8mm. Next, based on JIS K 7142, the refractive index of the test piece was measured with the D line of sodium using an Abbe refractometer (DR-A1 (trade name) manufactured by Atago Co., Ltd.).
  • DR-A1 Abbe refractometer
  • thermoplastic resin composition Average particle diameter and aspect ratio of flaky glass (B) 50 mg of thermoplastic resin composition was placed in an electric muffle furnace (manufactured by Advantech Toyo Co., Ltd., model “FUW-230PA”). )) And ashed at 400 ° C. for 1.5 hours or longer to obtain flaky glass (B). Next, 10 mg of flaky glass (B) was dispersed in 5 ml of water, the particle size was measured using a particle size distribution analyzer (LA-910 (trade name) manufactured by Horiba, Ltd.), and the mass average was obtained. The average particle size was taken. The aspect ratio of the flaky glass (B) was determined by repeating the average particle diameter with the thickness value (ie, 5 ⁇ m) described in the flaky glass (B) catalog.
  • thermoplastic resin molding (a) Total light transmittance A 5 cm square test piece was cut out from the thermoplastic resin molding, and a haze meter (Murakami Color Technology Research Co., Ltd.) based on JIS K 6361-1. The total light transmittance of the test piece was measured with a D65 light source using HM-150 (trade name) manufactured by Tokosho.
  • (D) Thermal linear expansion coefficient A test piece having a length of 15 mm and a width of 5 mm was cut out from a thermoplastic resin molded article, and JIS K 7197 was measured using a thermomechanical analyzer (TMA) (TMA8310 (trade name) manufactured by Rigaku Corporation). Based on the temperature increase rate of 5 ° C./minute, the coefficient of thermal expansion was measured in the range of 30 to 100 ° C. In the present invention, the value at 50 ° C. is defined as the thermal linear expansion coefficient.
  • melt flow rate The fluidity was evaluated by measuring the melt flow rate (MFR) according to JIS K7210 using pellets of thermoplastic resin. MFR was measured under the conditions of temperature: 230 ° C. and load: 37.3N.
  • (meth) acrylic coating composition (1) As a raw material for forming a (meth) acrylic polymer protective layer, 50 parts of phenoxyethyl acrylate (Biscoat # 192 manufactured by Osaka Organic Chemical Industry Co., Ltd.), 50 parts of bisphenol A-diepoxy diacrylate (manufactured by Kyoeisha Oil Chemical Co., Ltd., trade name: Epoxy ester 3000A), and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Geigy) (Product name: Darocur 1173) 1.5 parts were mixed to obtain a (meth) acrylic coating composition (1) containing a monomer having at least two (meth) acryloyloxy groups in the molecule.
  • thermoplastic resin (A) 100 parts of (meth) acrylic resin (trade name: Acrypet VH001, manufactured by Mitsubishi Rayon Co., Ltd.) as the thermoplastic resin (A) is C glass, a refractive index of 1.52, an average particle size of 667 ⁇ m, and an aspect ratio of 133 33 parts of flaky glass (B) (manufactured by Nippon Sheet Glass Co., Ltd., trade name “RCF-600”, thickness 5 ⁇ m) was added to obtain a dry blend. Next, the dry blend is melt-kneaded at 250 ° C.
  • thermoplastic resin composition was obtained.
  • the evaluation results of the obtained thermoplastic resin composition are shown in Table 1.
  • the thermoplastic resin composition was extruded into a sheet having a thickness of 2 mm and a width of 35 cm at 250 ° C. using a single-screw extruder (manufactured by Nakamura Industries Co., Ltd.).
  • the obtained sheet-like material is cut into a length of 50 cm, and the surface is smoothed under conditions of 220 ° C. and 10 MPa using a 100 TON heating molding machine (manufactured by Shoji Tekko Co., Ltd.), and a thermoplastic resin molding is performed.
  • Table 1 shows the evaluation results of the obtained thermoplastic resin molded article.
  • thermoplastic resin molded body cut to a width of 34.3 cm and a length of 37.3 cm, Sealing material (34.3cm x length 37.3cm x thickness 0.45mm) (ethylene-vinyl acetate copolymer manufactured by CI Kasei Co., Ltd., trade name “CIKcap”) 5 inches in which 4 cells are connected in series Solar cell (Asden Co., Ltd., polycrystalline silicon solar cell), width 34.3 cm ⁇ length 37.3 cm ⁇ thickness 0.45 mm sealing material (Ci Kasei Co., Ltd.
  • ethylene-vinyl acetate) Copolymer trade name “CIKcap”
  • back surface protective member having a width of 34.3 cm ⁇ length of 37.3 cm ⁇ thickness of 0.3 mm (a PET film laminate manufactured by MPackaging Co., Ltd., trade name “PTD250”)
  • the laminated body that is sequentially laminated is sandwiched between 500 mm square release films (trade name “HGS-P610”, manufactured by Nissan Sangyo Co., Ltd.) and a vacuum laminator (trade name, manufactured by NPC Corporation). LM-50X50-S ").
  • the inside of a vacuum laminator was 90 mmHg, the said laminated body was vacuum-bonded on condition of 135 degreeC for 15 minutes, and 101.3 kPa, and the solar cell module laminated body was obtained.
  • the two release films were peeled from the solar cell module laminate to obtain a solar cell module.
  • the evaluation results of the obtained solar cell module are shown in Table 1.
  • thermoplastic resin composition A thermoplastic resin composition, a thermoplastic resin molded article, and a solar cell module were obtained in the same manner as in Example 1 except that the content of the flaky glass (B) was changed as shown in Table 1. The evaluation results are shown in Table 1.
  • Comparative Example 1 when a TC50 test was performed on the solar cell module, power was not generated due to the disconnection of the wiring, and it was impossible to measure the maximum output value.
  • Example 4 A thermoplastic resin composition and a thermoplastic resin in the same manner as in Example 1 except that (meth) acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrypet TF8 001) is used as the thermoplastic resin (A). A molded body and a solar cell module were obtained. The evaluation results are shown in Table 1.
  • thermoplastic resin composition and the thermoplastic resin molding were the same as in Example 1 except that (meth) acrylic resin (Mitsubishi Rayon Co., Ltd., trade name: Acrypet MF001) was used as the thermoplastic resin (A).
  • the evaluation results are shown in Table 1.
  • thermoplastic resin composition (Example 6) Polycarbonate resin (Mitsubishi Engineer Plastic Co., Ltd., trade name: Iupilon S2000) as the thermoplastic resin (A) and E glass REF-600 (Nippon Sheet Glass Co., Ltd., trade name, refraction) as the flaky glass (B)
  • a thermoplastic resin composition, a thermoplastic resin molded article, and a solar cell module were obtained in the same manner as in Example 1 except that the ratio 1.56, the average particle diameter 600 ⁇ m, the thickness 5 ⁇ m, and the aspect ratio 120) were used.
  • the evaluation results are shown in Table 1.
  • Example 7 A 125- ⁇ m thick (meth) acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acryprene HBS006) is pasted as a (meth) acrylic polymer protective layer on the thermoplastic resin molded body obtained in Example 6. In addition, a thermoplastic resin laminate molded body was obtained. As an adhesive material for bonding, an optical material adhesive film PD-S1 (trade name, manufactured by Panac Co., Ltd.) was used. Table 1 shows the evaluation results of the obtained thermoplastic resin laminate molded body.
  • Example 8 On the thermoplastic resin molding obtained in Example 6, the (meth) acrylic coating composition (1) was applied as a (meth) acrylic polymer protective layer, and then cured by ultraviolet rays to give a thickness of 5 ⁇ m ( A thermoplastic resin laminate molded body on which a cured film of the (meth) acrylic coating composition (1) (hereinafter sometimes referred to as “film (1)”) was laminated was obtained.
  • Table 1 shows the evaluation results of the obtained thermoplastic resin laminate molded body.
  • Comparative Example 2 Example except that C glass RCF-160 (manufactured by Nippon Sheet Glass Co., Ltd., trade name, refractive index 1.52, average particle size 160 ⁇ m, thickness 5 ⁇ m, aspect ratio 32) is used as the glass flake (B).
  • C glass RCF-160 manufactured by Nippon Sheet Glass Co., Ltd., trade name, refractive index 1.52, average particle size 160 ⁇ m, thickness 5 ⁇ m, aspect ratio 32
  • Example 3 Example except that C glass RCF-015 (product name, refractive index 1.52, average particle size 26 ⁇ m, thickness 5 ⁇ m, aspect ratio 5) is used as glass flake (B).
  • C glass RCF-015 product name, refractive index 1.52, average particle size 26 ⁇ m, thickness 5 ⁇ m, aspect ratio 5
  • B glass flake
  • Example 4 Example 1 except that E glass REF-600 (manufactured by Nippon Sheet Glass Co., Ltd., trade name, refractive index 1.56, average particle size 600 ⁇ m, thickness 5 ⁇ m, aspect ratio 120) was used as the glass flake (B).
  • E glass REF-600 manufactured by Nippon Sheet Glass Co., Ltd., trade name, refractive index 1.56, average particle size 600 ⁇ m, thickness 5 ⁇ m, aspect ratio 120
  • a thermoplastic resin composition, a thermoplastic resin molded article, and a solar cell module were obtained. The evaluation results are shown in Table 1.
  • thermoplastic resin (A) 100 parts of Acrysilap SY-116 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), which is a raw material for the (meth) acrylic resin, and an RCF of C glass as the flaky glass (B) -600N (manufactured by Nippon Sheet Glass Co., Ltd., trade name, thickness 5 ⁇ m, refractive index 1.52, average particle diameter 437 ⁇ m, aspect ratio 87) 33 parts, and t-hexylperoxypivalate as a polymerization initiator (Japan) 0.2 part of oil and fat Co., Ltd.
  • thermoplastic resin molded body was obtained as a thermoplastic resin (A). Table 1 shows the evaluation results of the obtained thermoplastic resin laminate molded body.
  • thermoplastic resin molded articles are excellent in transparency and have little deformation due to temperature change, so that the maximum output of the solar cell module can be obtained even after the TC test. There was no decline.
  • Comparative Example 1 since the content of the flaky glass (B) is less than the lower limit value, the reduction of the thermal expansion coefficient is not sufficient, and deformation of the thermoplastic resin molded body during the TC50 test is prevented. I could't.
  • Comparative Example 4 the total light transmittance was lowered because the difference between the refractive index of the thermoplastic resin (A) and the refractive index of the flaky glass (B) was not less than the upper limit.
  • Comparative Example 5 the Charpy impact strength decreased because the aspect ratio of the flaky glass (B) was not less than the upper limit.
  • thermoplastic resin (A) 100 parts of Acrypet VH001 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), which is a thermoplastic resin (A), is flaky glass having a refractive index of 1.52, an average particle size of 437 ⁇ m, and an aspect ratio of 87, which is C glass.
  • B) 82 parts (made by Nippon Sheet Glass Co., Ltd., trade name “RCF-600”, thickness 5 ⁇ m) were added and dry blended. Next, the above dry blend was melt-kneaded at 250 ° C. using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd., 58 mm ⁇ twin screw extruder) to try to produce a strand. However, since the content of the flaky glass (B) exceeded the upper limit value and a continuous strand of the thermoplastic resin composition could not be obtained, the thermoplastic resin molded product was not evaluated.
  • the present invention can provide a thermoplastic resin molded article that is excellent in translucency and reduced in deformation due to temperature change, and uses this thermoplastic resin molded article as a top sheet member for a solar cell module. As a result, a decrease in the maximum output is suppressed, and a lightweight solar cell module can be provided, which is extremely useful industrially.

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Abstract

La présente invention concerne une composition de résine thermoplastique contenant (A) une résine thermoplastique et (B) des paillettes de verre. Les paillettes de verre (B) de la composition de résine thermoplastique ont un rapport de forme de 30 à 80, et la teneur en paillettes de verre (B) dans la composition de résine thermoplastique est de 25 à 70 parties en masse par rapport aux 100 parties en masse de la résine thermoplastique (A). La différence entre l'indice de réfraction de la résine thermoplastique (A) et l'indice de réfraction des paillettes de verre (B) dans la composition de résine thermoplastique va de 0 à 0,05 (inclus).
PCT/JP2013/068151 2012-07-06 2013-07-02 Composition de résine thermoplastique, corps moulé en résine thermoplastique, corps moulé en résine thermoplastique multicouche, et module de cellule solaire WO2014007253A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007077385A (ja) * 2005-08-19 2007-03-29 Asahi Kasei Chemicals Corp 高剛性加飾押出シート
JP2008074927A (ja) * 2006-09-20 2008-04-03 Sumitomo Metal Mining Co Ltd 成形体及びその製造方法
JP2011151391A (ja) * 2009-12-25 2011-08-04 Mitsubishi Rayon Co Ltd 太陽電池モジュール
WO2012093717A1 (fr) * 2011-01-07 2012-07-12 三菱レイヨン株式会社 Composition de résine acrylique thermoplastique contenant du verre et article moulé à partir de celle-ci
JP2012246473A (ja) * 2011-05-02 2012-12-13 Mitsubishi Rayon Co Ltd 成型体及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007077385A (ja) * 2005-08-19 2007-03-29 Asahi Kasei Chemicals Corp 高剛性加飾押出シート
JP2008074927A (ja) * 2006-09-20 2008-04-03 Sumitomo Metal Mining Co Ltd 成形体及びその製造方法
JP2011151391A (ja) * 2009-12-25 2011-08-04 Mitsubishi Rayon Co Ltd 太陽電池モジュール
WO2012093717A1 (fr) * 2011-01-07 2012-07-12 三菱レイヨン株式会社 Composition de résine acrylique thermoplastique contenant du verre et article moulé à partir de celle-ci
JP2012246473A (ja) * 2011-05-02 2012-12-13 Mitsubishi Rayon Co Ltd 成型体及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ACRYPETTM NO GRADE *

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