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WO2013015259A1 - Feuille stratifiée et son procédé de production - Google Patents

Feuille stratifiée et son procédé de production Download PDF

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Publication number
WO2013015259A1
WO2013015259A1 PCT/JP2012/068651 JP2012068651W WO2013015259A1 WO 2013015259 A1 WO2013015259 A1 WO 2013015259A1 JP 2012068651 W JP2012068651 W JP 2012068651W WO 2013015259 A1 WO2013015259 A1 WO 2013015259A1
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Prior art keywords
layer
mass
laminated sheet
resin
less
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Ceased
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PCT/JP2012/068651
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English (en)
Japanese (ja)
Inventor
塩見篤史
青山滋
巽規行
高橋弘造
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Toray Industries Inc
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Toray Industries Inc
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Publication of WO2013015259A1 publication Critical patent/WO2013015259A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/85—Protective back sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/544—Torsion strength; Torsion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • 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 laminated sheet capable of achieving both flame retardancy and curl characteristics.
  • the present invention relates to a laminated sheet that can be suitably used as a back sheet for a solar cell, and a method for producing the laminated sheet.
  • a solar cell is composed of a power generation element sealed with a transparent sealing material such as ethylene-vinyl acetate copolymer (EVA), and a transparent substrate such as glass and a resin sheet called a back sheet bonded together.
  • EVA ethylene-vinyl acetate copolymer
  • the Sunlight is introduced into the solar cell through the transparent substrate. Sunlight introduced into the solar cell is absorbed by the power generation element, and the absorbed light energy is converted into electrical energy. The converted electric energy is taken out by a lead wire connected to the power generation element and used for various electric devices.
  • the structure which provides gas barrier property and an electrical property by pasting together various raw materials to the biaxially-stretched polyethylene terephthalate (PET) which is a cheap and high-performance with the back laminate has been examined.
  • the olefin resin is a material generally used as a back sheet because it has good adhesion to the sealing material.
  • Patent Document 1 A configuration in which olefins are laminated on both sides of the polycarbonate (Patent Document 1), and a configuration in which a polycarbonate layer is laminated on a cyclic olefin-based resin ( Patent Document 2) has been proposed.
  • the sheet in which the olefin resin is laminated on both surface layers of the polycarbonate resin has a drawback that the flame retardance is low because the layers made of the olefin resin are provided on both surface layers of the sheet.
  • the whole laminated sheet from the asymmetry of the layer which consists of cyclic olefin-type resin and the layer which consists of polycarbonate-type resin When curled, when used as a solar cell backsheet, there were problems such as causing a positional deviation from the sealing material.
  • the present invention provides a solar cell backsheet that achieves both flame retardancy and curl characteristics.
  • the present invention has the following configuration. That is, a laminated sheet having a layer (P1 layer) having a polycarbonate-based resin as a main component (P1 layer), an adhesive layer (P2 layer), and a layer (P3 layer) having a polyolefin-based resin as a main component,
  • P1 layer has a thickness of T1
  • P2 layer has a thickness of T2
  • P3 layer has a thickness of T3 and satisfies the following formulas (1) and (2) Sheet.
  • a laminated sheet that is superior in flame retardancy and curl characteristics as compared with conventional laminated sheets of olefin resin and polycarbonate resin.
  • Such a laminated sheet can be suitably used for a solar cell backsheet, and a high-performance solar cell can be provided by using the backsheet.
  • the present invention has a layer (P1 layer) mainly composed of polycarbonate-based resin, an adhesive layer (P2 layer), and a layer (P3 layer) mainly composed of polyolefin-based resin.
  • P1 layer mainly composed of polycarbonate-based resin
  • P2 layer an adhesive layer
  • P3 layer a layer mainly composed of polyolefin-based resin.
  • the main component is contained exceeding 50 mass%.
  • the polycarbonate resin which is the main component of the P1 layer, is a polymer obtained by reacting a dihydroxydiaryl compound with a carbonate such as phosgene or diphenyl carbonate.
  • dihydroxydiaryl compounds used in polycarbonate resins include 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy Phenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl) -3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis ( 4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis
  • a compound having 3 or more phenolic hydroxyl groups may be used for the polycarbonate resin in the present invention.
  • examples thereof include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl)- Heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis [4,4- (4,4 And '-dihydroxydiphenyl) -cyclohexyl] -propane.
  • the polycarbonate-based resin which is the main component of the P1 layer is a polycarbonate whose main component is 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) as a dihydroxydiaryl compound. It is preferable to use a resin based on heat resistance and heat and humidity resistance.
  • the main component referred to here is bisphenol A of 80 mol% or more, more preferably 90 mol% or more, and more preferably 95 mol% or more of all dihydroxydiaryl compounds used in the polycarbonate resin. (In the present specification, the same applies to the main component in the case of other structures).
  • the polycarbonate-based resin that is the main component of the P1 layer is that 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) as a dihydroxydiaryl compound can further improve heat resistance and moist heat resistance. And more preferable.
  • the P1 layer preferably does not contain a polyolefin-based resin or is less than 3% by mass.
  • the P1 layer polycarbonate resin preferably has a number average molecular weight (Mn) of 10,000 or more and 50,000 or less. More preferably, it is 12000 or more and 40000 or less, More preferably, it is 15000 or more and 30000 or less.
  • the higher the glass transition temperature (Tg) of the P1 layer polycarbonate-based resin the higher the moisture and heat resistance and the heat resistance. It is preferable from the viewpoint of form retention in the sealing step of the laminated sheet in the step of sealing together.
  • the Tg was measured by heating the resin from 25 ° C. to 300 ° C. (1st RUN) at a rate of temperature increase of 20 ° C./min.
  • the differential scanning calorimetry chart of 2ndRUN obtained by rapidly cooling to room temperature or below and then raising the temperature from room temperature to 300 ° C. at a rate of temperature increase of 20 ° C./min.
  • the glass transition temperature Tg is preferably 125 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 135 ° C. or higher, and particularly preferably 140 ° C. or higher.
  • the P1 layer constituting the laminated sheet of the present invention contains inorganic particles in a range of 3% by mass to less than 50% by mass. More preferably, they are 5 mass% or more and 30 mass% or less, More preferably, they are 10 mass% or more and 20 mass% or less.
  • the inorganic particles are used for imparting a necessary function to the sheet depending on the purpose. When it is contained in an amount of 50% by mass or more, handling properties may be deteriorated.
  • examples of inorganic particles that can be suitably used in the present invention include inorganic particles having ultraviolet absorbing ability, particles having a large refractive index difference from polycarbonate resins, conductive particles, pigments, and the like.
  • a particle means a thing with 5 nm or more as a primary particle size by the diameter of the projected equivalent conversion circle
  • the particle size means a primary particle size
  • the particle means a primary particle.
  • the inorganic particles in the present invention for example, gold, silver, copper, platinum, palladium, rhenium, vanadium, osmium, cobalt, iron, zinc, ruthenium, praseodymium, chromium, nickel, aluminum, tin, Metals such as zinc, titanium, tantalum, zirconium, antimony, indium, yttrium, lanthanum, zinc oxide, titanium oxide, cesium oxide, antimony oxide, tin oxide, indium tin oxide, yttrium oxide, lanthanum oxide, zirconium oxide, oxide Metal oxides such as aluminum and silicon oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, metal fluorides such as cryolite, metal phosphates such as calcium phosphate, carbonates such as calcium carbonate, barium sulfate, etc. Sulfate , Talc, kaolin and the like.
  • titanium oxide is preferably used as the inorganic particles in that high reflection characteristics can be imparted, and rutile titanium oxide is more preferably used in terms of higher ultraviolet resistance.
  • the method of causing the polycarbonate resin constituting the P1 layer to contain inorganic particles is preferably a method in which the polycarbonate resin and the inorganic particles are melt-kneaded in advance using a vented biaxial kneading extruder or a tandem extruder.
  • a high-concentration master pellet having a higher inorganic particle content than the amount of inorganic particles contained in the P1 layer is prepared, mixed with a polycarbonate resin, and diluted to obtain a predetermined P1 layer inorganic particle content. Is preferable from the viewpoint of heat and moisture resistance.
  • the P1 layer constituting the laminated sheet of the present invention contains organic particles in the range of 0.1% by mass or more and 20% by mass or less.
  • the organic particles include silicone compounds, crosslinked particles such as crosslinked styrene, crosslinked acryl, and crosslinked melamine, and carbon compounds such as carbon, fullerene, carbon fiber, and carbon nanotube.
  • the ultraviolet absorbing ability of the particles can be utilized for a long time.
  • the effect of the present invention that suppresses the change in color tone can be remarkably exhibited, and the sheet can also have a design property.
  • It is preferably 0.5% by mass or more from the viewpoint of design properties, and is preferably 12% by mass or less from the viewpoint of suppressing thickening during melt extrusion caused by organic particles. More preferably, it is 1 mass% or more and 8 mass% or less.
  • the P1 layer and the P3 layer of the laminated sheet of the present invention may have other additives (for example, a heat stabilizer, an ultraviolet absorber, a weather stabilizer, an organic lubricant, as long as the effects of the present invention are not impaired). Pigments, dyes, fillers, antistatic agents, nucleating agents, etc.
  • the inorganic particles referred to in the present invention may not be implied by the additives herein.
  • an ultraviolet absorber is selected as an additive, it is possible to further improve the ultraviolet resistance of the laminated sheet of the present invention.
  • a benzotriazole type ultraviolet ray it is preferable to contain an absorbent.
  • an antistatic agent or the like an improvement in withstand voltage can be expected.
  • P1 layer in this invention is provided in the surface layer from a flame-retardant viewpoint.
  • an adhesive layer is provided between the P1 layer and the P3 layer.
  • the resin used for the P2 layer is preferably one that adheres to both the P1 and P3 layers.
  • low crystalline soft polymers such as acid-modified polyolefins and unsaturated polyolefins, ethylene-acrylic acid ester-maleic anhydride ternary Examples thereof include acrylic adhesives such as copolymers and ethylene vinyl acetate copolymers.
  • the acid-modified polyolefin examples include “Admer” manufactured by Mitsui Chemicals, Inc. and “Modic” manufactured by Mitsubishi Chemical Corporation as commercially available products.
  • the P2 layer contains a polyolefin-based elastomer in a proportion of 5% by mass or more and 50% by mass or less with respect to the P2 layer from the viewpoint that the interlayer adhesion after the wet heat treatment can be improved.
  • the interlayer adhesion after the wet heat treatment is the delamination strength after the treatment at 120 ° C. and 100% RH for 48 hours, and the details are as described in “Characteristic Evaluation Method F. Item” in the Examples.
  • the polyolefin-based elastomer may be contained according to the required interlayer adhesion, but is preferably 10% by mass or more for improving interlayer adhesion, and is preferably 30% by mass or less from the viewpoint of cost.
  • the polyolefin-based elastomer generally refers to a copolymer obtained by copolymerizing other ⁇ -olefin with polypropylene or polyethylene. Examples of the ⁇ -olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and the like.
  • the polyolefin-based elastomer may be a commercially available product, for example, “Thermo Run”, “Zeras” manufactured by Mitsubishi Chemical Corporation, “Excellen”, “Tough Selenium”, “Esplen”, “Hibler” manufactured by Kuraray, Preferred examples include “Septon”, “Notio” manufactured by Mitsui Chemicals, Inc., “ENGAGE” manufactured by Dow Chemical Co., Ltd., and the like.
  • the P2 layer contains the modified styrene thermoplastic elastomer in a proportion of 3% by mass or more and 15% by mass or less with respect to the P2 layer, so that the interlayer adhesion after treatment at 120 ° C. and 100% RH for 48 hours can be improved.
  • the fall of the delamination strength by wet heat processing can be suppressed.
  • the degree to which the decrease in delamination strength due to wet heat treatment is suppressed is determined by the degree of delamination strength after wet heat treatment relative to the initial delamination strength between the P1 and P2 layers and between the P2 and P3 layers.
  • the ratio is determined based on the ratio of decrease, and details are as described in “Characteristic Evaluation Method J. Section” in the Examples. In order to improve interlayer adhesion, it is preferably 5% by mass or more, and preferably 12% by mass or less from the viewpoint of cost.
  • modified styrene thermoplastic elastomer examples include a modified styrene-ethylene-butylene-styrene block copolymer.
  • the modified styrene thermoplastic elastomer may be a commercially available product, for example, “Tuftec” M1913 manufactured by Asahi Kasei Chemicals Corporation.
  • the P3 layer in the present invention is mainly composed of a polyolefin resin.
  • the polyolefin resin in the present invention include polyethylene, polypropylene, polybutene, polymethylpentene, polycycloolefin, polyhexene, polyoctene, polydecene, and polydodecene.
  • polyethylene and polypropylene are preferable because they are easy to process and relatively inexpensive.
  • These polyolefin resins may be mixed and copolymerized with other olefin components. For example, when an ethylene-propylene copolymer or an ethylene-propylene-butene copolymer is used, the crystallinity of the resin can be lowered.
  • the polyolefin resin which comprises P3 layer contains 70 mass% or more of propylene components.
  • the polyolefin resin constituting the P3 layer when a mixture of a plurality of polyolefin resins is used as the polyolefin resin constituting the P3 layer, it is preferable to contain a polyethylene resin as a constituent component in the range of 5% by mass to 30% by mass. Since the polyethylene resin does not contain tertiary carbon, it is less likely to be oxidized than polypropylene resin, and has high durability against deterioration due to oxidation.
  • the component mentioned here is mixed in the P3 layer and is distinguished from the copolymerized component. If the content is less than 5% by mass, the improvement effect is low.
  • mixing of incompatible olefins such as polypropylene and polyethylene may reduce brittleness due to poor dispersion.
  • a compatibilizer for the P3 layer is preferable to include a compatibilizer for the P3 layer.
  • a compatibilizing agent for example, in a combination of polypropylene and polyethylene, an ethylene-ethylene / butylene / ethylene copolymer is preferably used as a compatibilizing agent, and “Dynalon” 6200P manufactured by JSR Corporation is an example of a commercially available product.
  • the compatibilizing agent is preferably contained in the range of 0.1% by mass to 10% by mass. If it is 0.1% by mass or less, the compatibility effect is low, and if it is 10% by mass or more, the adhesion with the sealant may be lowered.
  • polyolefin elastomer may be used as the polyolefin resin that can be used when a mixture of a plurality of polyolefin resins is used.
  • Polyolefin elastomers are those obtained by copolymerizing polypropylene and polyethylene with other ⁇ -olefins.
  • Preferred ⁇ -olefins are 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- Examples include octene, 1-nonene, 1-decene, 1-dodecene and 4-methyl-1-pentene.
  • polyolefin-based elastomers are preferably contained in a proportion of 5% by mass or more and 50% by mass or less with respect to the P3 layer.
  • a polyolefin-based elastomer in addition to the improvement in interlayer adhesion after treatment at 120 ° C. and 100% RH for 48 hours, the rigidity of the P3 layer is reduced, so that the curling of the laminated sheet is improved, which is preferable.
  • P3 layer contains polyolefin-type elastomer, it is preferable also from a viewpoint which can suppress the fall of the delamination strength by wet heat processing.
  • it is 10 mass% or more and 30 mass% or less.
  • the polyolefin-based elastomer may be a commercially available product, for example, “Thermo Run”, “Zeras” manufactured by Mitsubishi Chemical Corporation, “Excellen”, “Tough Selenium”, “Esplen”, “Hibler” manufactured by Kuraray, Preferred examples include “Septon”, “Notio” manufactured by Mitsui Chemicals, Inc., “ENGAGE” manufactured by Dow Chemical Co., Ltd., and the like.
  • the crystal melting energy of the P3 layer is preferably 80 J / g or less. Setting the crystal melting energy within this range is preferable from the viewpoint of reducing curling and improving the adhesion to the sealing material. More preferably, it is 70 J / g or less, More preferably, it is 60 J / g or less.
  • the crystal melting energy refers to the differential scanning calorimeter “Robot DSC-RDC220” manufactured by Seiko Denshi Kogyo Co., Ltd. according to JIS-K7122 (1987 version), and the disk session “SSC / 5200” for data analysis. This is a value obtained from the second run measured using, and the details are as described in “Characteristic Evaluation Method C. Item” in the Examples.
  • the crystal melting energy can be adjusted by copolymerizing other olefin components in the olefin molecular chain or by the stereoregularity of the olefin crystal form.
  • the stereoregularity can be adjusted by a catalyst during polymerization.
  • the copolymer component ⁇ -olefin is preferable as described above, and ethylene-propylene copolymer and ethylene-propylene-butene copolymer are particularly preferable.
  • the stereoregularity of the olefin is preferably atactic.
  • the lower limit of the crystal melting energy is not particularly limited, but most of them are 10 J / g or more when a polyolefin resin is the main component.
  • the melting endothermic peak temperature of the P3 layer in the present invention is preferably 100 ° C. or higher and 150 ° C. or lower. If it is less than 100 ° C, the heat resistance may be inferior. On the other hand, if it exceeds 150 ° C., the adhesiveness to the sealing material may be lowered.
  • the P3 layer has a phase separation structure and exhibits a melting endothermic peak temperature
  • all of them are preferably 100 ° C. or higher and 150 ° C. or lower.
  • the crystal melting energy is The sum of the peaks is preferably 80 J / g or less.
  • the melt flow rate (MFR) (230 ° C.) of the polyolefin resin is preferably from 0.5 to 30. If it is less than 0.5 or more than 30, the fluidity is low, and stacking unevenness or flow marks may occur.
  • the polycarbonate resin is contained in the range of 5% by mass to 25% by mass with respect to the P3 layer.
  • the polycarbonate-based resin within this range, it is possible to minimize a decrease in gas barrier properties and improve flame retardancy and curl characteristics. If it is less than 5% by mass, the effect of improving the flame retardancy is low, and if it exceeds 25% by mass, the gas barrier property and the adhesion to the sealing material may be inferior.
  • the gas barrier property refers to the water vapor permeability obtained by measuring according to the method prescribed in Appendix B of “Water vapor permeability test method for plastic films and sheets (instrument measurement method)” JIS-K7129 (1992 edition).
  • the details are as described in “Characteristic Evaluation Method I. Item” in the Examples.
  • the flame retardancy is a burning rate of the sheet when the sheet is ignited, and details are as described in “Characteristic Evaluation Method G. Item” in the Examples.
  • In view of the adhesion to the sealing material it is preferably 15% by mass or less.
  • the P3 layer constituting the laminated sheet of the present invention preferably contains inorganic particles in the range of 1% by mass to 30% by mass with respect to the P3 layer. More preferably, they are 2 mass% or more and 20 mass% or less, More preferably, they are 3 mass% or more and 10 mass% or less.
  • the inorganic particles are used for imparting a necessary function to the film according to the purpose.
  • inorganic oxides having ultraviolet absorbing ability use metal oxides such as titanium oxide, zinc oxide, and cerium oxide, they are resistant to ultraviolet rays caused by the particles.
  • titanium oxide is preferably used as the inorganic particles in that high reflection characteristics can be imparted
  • rutile titanium oxide is more preferably used in terms of higher ultraviolet resistance.
  • the P3 layer constituting the laminated sheet of the present invention contains organic particles in the range of 0.1% by mass to 20% by mass with respect to the P3 layer. 0.5 mass% or more is preferable from a viewpoint of concealability and design property, and 12 mass% or less is preferable from a viewpoint of the thickening suppression at the time of the melt extrusion resulting from an organic particle. More preferably, it is 1 mass% or more and 8 mass% or less.
  • the organic particles include silicone compounds, crosslinked particles such as crosslinked styrene, crosslinked acryl, and crosslinked melamine, and carbon compounds such as carbon, fullerene, carbon fiber, and carbon nanotube. Further, when carbon is used as the organic particles in the P3 layer, it is particularly preferable because design properties and ultraviolet resistance can be simultaneously imparted.
  • the expressions (1) and (2) when the thickness of the P1 layer is T1, the thickness of the P2 layer is T2, and the thickness of the P3 layer is T3, the expressions (1) and (2) must be satisfied.
  • T2 ⁇ 12 ⁇ m (2) By satisfying the expressions (1) and (2) at the same time, curling of the entire sheet can be suppressed.
  • curl is a total value of the height at which the four corners of the sheet float from the plane when the laminated sheet having a thickness of 27 ⁇ m or more is cut into a 100 mm square and the cut sheet is placed on a flat surface in an unweighted state.
  • the details are as described in “Characteristic Evaluation Method D. Item” in the Examples.
  • T1 / T3 is preferably 15 or less. More preferably, it is 10 or less, More preferably, it is 5 or less, Most preferably, it is 2 or less.
  • T1 / T3 is less than 0.5, the lamination ratio of polyolefin is too large, and the curl becomes large regardless of the thickness of T2.
  • T1 / T3 is preferably 0.6 or more, and most preferably 0.7 or more.
  • curling occurs when T2 is less than 12 ⁇ m. Curling can be reduced by satisfying this range. Furthermore, satisfying the formula (2) also has an effect of improving interlayer adhesion after treatment at 120 ° C. and 100% RH for 48 hours, and further has an effect of suppressing a decrease in delamination strength due to wet heat treatment.
  • the degree to which the decrease in the delamination strength due to the wet heat treatment is suppressed is determined by the delamination strength after the wet heat treatment relative to the initial delamination strength between the P1 layer and the P2 layer and between the P2 layer and the P3 layer. Judgment is made based on the ratio of the degree of decrease, and details are as described in “Characteristic Evaluation Method J. Section” in the Examples.
  • the upper limit of the thickness T2 of the P2 layer is not particularly limited, but is preferably 100 ⁇ m or less for reasons such as production speed. Furthermore, if considering the curling characteristics, delamination strength, production speed, etc., the thickness of the P2 layer is preferably 5% or more and 20% or less, and 15 ⁇ m or more and 60 ⁇ m or less with respect to the total thickness of the laminated sheet. Is preferred. More preferably, it is 20 ⁇ m or more and 40 ⁇ m or less.
  • the delamination strength refers to the strength when peeling with the T-type measured according to JIS-K6854-3 (1999 edition). In view of use outdoors such as a solar cell backsheet, the initial delamination strength and the delamination strength after 120 ° C.
  • RH 48 hr wet heat treatment are both preferably 3 N / 15 mm or more. More preferably, both are 5 N / 15 mm or more, More preferably, both are 8 N / 15 mm or more, Most preferably, both are 10 N / 15 mm or more.
  • the initial delamination strength is determined by the interaction between the release interface resins in addition to the thickness of T2, and the resin may be selected according to the required peel strength.
  • the main component of the P1 layer is polycarbonate. Therefore, the resin constituting the P2 layer should have a high acid value, or a polar functional group should be introduced into the resin. Etc. are effective.
  • the delamination strength after the wet heat treatment at 120 ° C. and 100% RH for 48 hours can suppress a decrease from the initial delamination strength by including the polyolefin elastomer in the P2 layer and the P3 layer in addition to the thickness of T2.
  • the total thickness of the laminated sheet of the present invention is preferably 27 ⁇ m or more and 600 ⁇ m or less, more preferably 30 ⁇ m or more and 450 ⁇ m or less, and most preferably 40 ⁇ m or more and 400 ⁇ m or less.
  • thickness is suitably adjusted within the said range according to the withstand voltage requested
  • the thickness of the laminated sheet of the present invention is less than 27 ⁇ m, the flatness of the sheet may be reduced, or the P2 layer may be too thin, and the effect of improving characteristics due to the inclusion of particles may be reduced. In this case, for example, when used as a solar cell backsheet, the overall thickness of the solar cell may become too thick.
  • the thickness T1 of the P1 layer in the laminated sheet of the present invention is preferably 5 ⁇ m or more and 200 ⁇ m or less, and when used for a solar cell backsheet, it may be determined by a required withstand voltage. Preferably they are 30 micrometers or more and 190 micrometers or less, More preferably, they are 50 micrometers or more and 180 micrometers or less. If it is less than 5 ⁇ m, there is no self-supporting property, and if it exceeds 200 ⁇ m, the overall thickness of the solar battery cell may be too thick.
  • the thickness T3 of the P3 layer in the laminated sheet of the present invention is preferably 10 ⁇ m or more and 400 ⁇ m or less, and when used for a solar cell backsheet, it may be determined by the required water vapor permeability and withstand voltage. Preferably they are 10 micrometers or more and 250 micrometers or less, More preferably, they are 30 micrometers or more and 200 micrometers or less. When the thickness is less than 10 ⁇ m, the adhesiveness with the sealing material is deteriorated, the water vapor permeability is deteriorated, and when the thickness is more than 400 ⁇ m, the entire thickness of the solar battery cell may be too thick.
  • the laminated structure of the laminated sheet in the present invention is at least P1 layer / P2 layer / P3 layer, and the P3 layer is provided on any one of the surface layers.
  • the adhesion to the sealing material is improved.
  • P3 layer is provided in both surface layers, although it is excellent in adhesiveness, since a polyolefin resin is made into a main structural component, a flame retardance is hard to be acquired.
  • P1 layer is provided in both surface layers, although it is excellent in a flame retardance, sufficient adhesiveness with a sealing material cannot be obtained.
  • each of the P1 layer, the P2 layer, and the P3 layer may have a laminated structure, and may have a multilayer structure according to a required function.
  • the laminated sheet of the present invention can be laminated with other films and the like.
  • the P3 layer may have a laminated structure provided on any one of the surface layers.
  • other films include polyester layers for increasing mechanical strength, antistatic layers, adhesion layers with other materials, UV resistant layers for further improving UV resistance, and flame resistance for imparting flame resistance
  • a layer, a hard coat layer for improving impact resistance and scratch resistance, and the like can be arbitrarily selected and used depending on applications.
  • the adhesion to other sheet materials and a sealing material for example, ethylene vinyl acetate
  • an ultraviolet resistant layer, a flame retardant layer, a conductive layer for improving a voltage at which a partial discharge phenomenon, which is an index of insulation, is generated can be used.
  • the laminated sheet of the present invention preferably has a ⁇ b of 10 or less when the P1 layer is used as the incident surface from the viewpoint of ultraviolet resistance.
  • ⁇ b is a value calculated using K0 as the b value measured with the laminated sheet P1 layer before the ultraviolet treatment as the incident surface, and K as the b value measured with the laminated sheet P1 layer after the ultraviolet treatment as the incident surface, Details are as described in “Characteristic Evaluation Method H. Item” in the Examples.
  • Preferably it is 6 or less. More preferably, it is 3 or less.
  • a preferable method is to add 10% by mass or more of inorganic particles to the P1 layer, and ⁇ b can be reduced according to the content of inorganic particles.
  • the laminated sheet of the present invention preferably has a water vapor permeability of 0.0001 g / m 2 ⁇ day to 10 g / m 2 ⁇ day. More preferably, it is 0.0001 g / m 2 ⁇ day or more and 5 g / m 2 ⁇ day or less, and most preferably 0.0001 g / m 2 ⁇ day or more and 3 g / m 2 ⁇ day or less. By setting it as this range, deterioration inside the solar cell due to permeation of gas from the back sheet to the sealing material can be prevented.
  • the water vapor transmission rate is a value obtained by measurement according to the method prescribed in Appendix B of “Test method for water vapor transmission rate of plastic film and sheet (instrument measurement method)” JIS-K7129 (1992). Is as described in “Characteristic Evaluation Method I. Item” in the Examples.
  • the water vapor transmission rate can be adjusted by the total thickness of the P2 layer thickness T2 and the P3 layer thickness T3, and the water vapor transmission rate decreases as the total thickness increases.
  • the manufacturing method of the lamination sheet of the present invention As a method of laminating the P1, P2, and P3 layers in the laminated sheet of the present invention, for example, the P1 layer raw material, the P2 layer raw material, and the P3 layer raw material are respectively charged into three extruders and melted. Co-extrusion onto a cast drum cooled from the die and processing it into a sheet (co-extrusion method), and the raw material of the coating layer is put into an extruder and melt extruded and laminated while extruding from the die.
  • melt laminating method each film is prepared separately, heat-pressed by a heated group of rolls (heat laminating method), method of bonding via an adhesive (adhesion method), and other solvents
  • a method (coating method) of applying and drying the dissolved material, a method combining these, and the like can be used.
  • the coextrusion method is preferred in that the production process is short and the adhesion between the layers is good.
  • the manufacturing method by a coextrusion method is explained in full detail.
  • a composition for P1 layer having a polycarbonate resin as a main constituent, a composition for P2 layer, and a P3 layer having a polyolefin resin as a main constituent are fed to separate extruders and melted respectively.
  • the composition for the P1 layer is 240 ° C. or more and 300 ° C. or less under a nitrogen stream, and the composition for the P2 layer and It is preferable that the composition for the P3 layer is supplied to each of three extruders heated to 180 ° C. or higher and 280 ° C.
  • the P1 layer, the P2 layer, and the P3 layer are joined and laminated in this order, and extruded from the T-die into a sheet shape to form a laminated sheet.
  • the P1 layer, the P2 layer, and the P3 layer are joined and laminated using a multi-manifold die, a feed block, a static mixer, pinol, or the like, and co-extruded from the die.
  • a multi-manifold is preferable from the viewpoint of suppressing lamination unevenness.
  • the laminate sheet of the present invention can be obtained by extruding the laminate sheet discharged from the die by the above method onto a cooling body such as a casting drum and cooling and solidifying it.
  • a composition obtained by mixing a resin obtained by processing the laminated sheet of the present invention into chips or flakes in a range of 5% by mass or more and 50% by mass or less with respect to the composition for P3 layer and a composition for P3 layer It is also possible to do.
  • a known method may be used as a method of processing into a chip shape or flake shape, but it is preferable to form a flake shape without melting and heating as much as possible from the viewpoint of suppressing a decrease in molecular weight and oxidation deterioration.
  • the cooling temperature at the first stage is 50 ° C. or higher, “the glass transition temperature of the polycarbonate resin—10 ° C.”
  • the casting is performed by a calendar method.
  • the drum roll temperature in contact with the P3 layer is set to 15 ° C. or less, the volume shrinkage at the time of olefin cooling solidification is suppressed and the curling of the sheet is reduced. This is preferable.
  • winding a laminated sheet in a roll shape it is preferable from the viewpoint of reducing the curl of the sheet when the P3 layer is wound around the outer surface.
  • the laminated sheet of the present invention obtained by the above-described method may be subjected to processing such as heat treatment or aging as necessary within the range where the effects of the present invention are not impaired.
  • the upper limit of the heat treatment temperature is not more than “glass transition temperature ⁇ 10 ° C.”, more preferably “glass transition temperature ⁇ 30 ° C.” or less, more preferably “less than“ glass transition temperature ”of the resin constituting the P1 layer, from the planarity of the sheet.
  • the glass transition temperature is ⁇ 50 ° C. or lower.
  • the heat treatment time is preferably 5 seconds or more and 30 minutes or less. By heat-treating, the thermal dimensional stability of the laminated sheet of the present invention can be improved.
  • corona treatment or plasma treatment may be performed.
  • the solar cell of the present invention is characterized by using the laminated sheet of the present invention as a back sheet.
  • the laminated sheet of the present invention By using the laminated sheet of the present invention, it becomes possible to increase the durability or to make it thinner as compared to conventional solar cells.
  • An example of the configuration is shown in FIG.
  • a power generating element connected with a lead wire for taking out electricity (not shown in FIG. 1) is sealed with a transparent sealing material 2 such as EVA resin, a transparent substrate 4 such as glass, and the laminate of the present invention.
  • seat is bonded and comprised as the solar cell backsheet 1, it is not limited to this, It can use for arbitrary structures.
  • unit of this invention was shown in FIG. 1, it is also possible to use the composite sheet of the lamination sheet of this invention and another film according to the other required required characteristic.
  • a method of laminating with other films, etc. for example, a method of co-extrusion and processing into a sheet (co-extrusion method), a coating layer raw material is put into an extruder into a sheet made of a single film Then, melt extrusion and laminating while extruding from the die (melt laminating method), making each film separately, thermocompression bonding with heated rolls etc. (thermal laminating method), pasting through adhesive A method of bonding (adhesion method), a method of applying and drying a solution dissolved in a solvent (coating method), a method of combining these, and the like can be used.
  • the above-described solar cell backsheet 1 is installed on the back surface of the sealing material 2 in which the power generating element is sealed.
  • the P3 layer is disposed so as to be positioned on the sealing material 2 side. This is preferable in that the adhesion to the stopper can be further increased.
  • the power generating element 3 converts light energy of sunlight into electric energy, and is based on crystalline silicon, polycrystalline silicon, microcrystalline silicon, amorphous silicon, copper indium selenide, compound semiconductor, dye enhancement Arbitrary elements such as a sensitive system can be used in series or in parallel according to the desired voltage or current depending on the purpose. Since the transparent substrate 4 having translucency is located on the outermost surface layer of the solar cell, a transparent material having high weather resistance, high contamination resistance, and high mechanical strength characteristics in addition to high transmittance is used. In the solar cell of the present invention, the transparent substrate 4 having translucency can be made of any material as long as it satisfies the above characteristics.
  • Examples thereof include glass, tetrafluoroethylene-ethylene copolymer (ETFE), polyfluoride.
  • glass it is more preferable to use a tempered glass.
  • when using the resin-made translucent base material what extended
  • the sealing material 2 for sealing the power generating element covers the surface of the power generating element with resin and fixes it, protects the power generating element from the external environment, and has a light-transmitting base material for the purpose of electrical insulation.
  • a material having high transparency, high weather resistance, high adhesion, and high heat resistance is used to adhere to the backsheet and the power generation element. Examples thereof include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) resin, ethylene-methacrylic acid copolymer (EMAA), Ionomer resins, polyvinyl butyral resins, and mixtures thereof are preferably used.
  • the solar cell backsheet used in the laminated sheet of the present invention into the solar cell system, it is possible to obtain a highly durable and / or thin solar cell system compared to conventional solar cells. It becomes.
  • the solar cell of the present invention can be suitably used for various applications without being limited to outdoor use and indoor use such as a solar power generation system and a power source for small electronic components.
  • the observation location is determined randomly, the vertical direction of the image is parallel to the thickness direction of the laminated sheet, and the horizontal direction of the image is parallel to the surface direction of the laminated sheet.
  • observation is performed by shifting the observation position in the thickness direction, and an image that can confirm the entire thickness is prepared by combining a plurality of images.
  • A3 The layer thickness T1 of the P1 layer, the layer thickness T2 of the P2 layer, and the thickness T3 of the P3 layer in the image obtained in (A2) were determined.
  • T1 was divided by T3, and the lamination ratio T1 / T3 was calculated.
  • Inorganic particle content Wa1, Wa2, organic particle content Wa3, Wa4 Each of the P1 layer and the P3 layer is scraped or peeled off from the laminated sheet to separate the P1 layer and the P3 layer. About them, the inorganic particle content rate Wa1 of the P1 layer and the inorganic particle content rate Wa2 of the P3 layer are as follows. The organic particle content Wa3 of the P1 layer and the organic particle content Wa4 of the P3 layer were determined. The mass wa1 ′′ (g) of the material cut out from the P1 layer and the mass wa3 ′′ (g) of the material cut out from the P3 layer were measured.
  • FIG. 2A is a peak top showing the melting point Tm
  • FIG. 2B is a peak top showing the melting point Tm
  • E. Adhesiveness to sealing material Using the strength when peeled at 180 ° measured according to JIS-K6854-2 (1994 edition), the adhesiveness of the sealing material was evaluated from the peel strength between the EVA sheet and the P3 layer. did.
  • the test specimen is a 500 ⁇ m-thick EVA sheet manufactured by Sanvic Co., Ltd., and a laminated sheet of Examples and Comparative Examples subjected to corona treatment on a semi-tempered glass having a thickness of 3 mm, and a commercially available glass laminator is used. After depressurization, a product subjected to press treatment at 143 ° C. under a load of 29.4 N / cm 2 for 15 minutes was used.
  • the width of the test piece for the peel strength test was 10 mm, two test pieces were prepared, and each test piece was measured at three locations with different locations, and the average value of the obtained measured values was taken as the peel strength value.
  • the adhesiveness of the sealing material was determined as follows.
  • peel strength is 50 N / 10 mm or more: S
  • peel strength is 40 N / 10 mm or more and less than 50 N / 10 mm: A
  • peel strength is 30N / 10mm or more and less than 40N / 10mm: B
  • the peel strength is 20 N / 10 mm or more and less than 30 N / 10 mm:
  • C When peel strength is less than 20 N / 10 mm: D S to C are good, and S is the best among them.
  • Interlayer adhesion after wet heat treatment Adhesion was evaluated from the delamination strength after wet heat treatment.
  • the delamination strength the strength at the time of peeling with a T-type measured according to JIS-K6854-3 (1994 edition) was used.
  • the interlayer may be an interlayer capable of interfacial separation such as between the P1 layer and the P2 layer and between the P2 layer and the P3 layer.
  • the width of the test piece for the peel strength test is 15 mm, and two test pieces are prepared. The test piece is changed in place and measured at three points, and the average value of the obtained measured values is the delamination strength after the wet heat treatment. As described below, the interlayer adhesion after the wet heat treatment was determined.
  • peel strength is 10N / 15mm or more: S When the peel strength is 6 N / 15 mm or more and less than 10 N / 15 mm: A When peel strength is 3N / 15mm or more and less than 6N / 15mm: B When peel strength is 1N / 15mm or more and less than 3N / 15mm: C When peel strength is less than 1 N / 15 mm: D S to C are good, and S is the best among them.
  • the sheet was cut into a size of 13 mm x 125 mm, and the first marked line was drawn at 25.4 mm from the cut end in the longitudinal direction, and the second marked line was drawn at 101.6 mm.
  • the obtained burning rate was determined as follows.
  • the ultraviolet ray treatment is performed using a xenon weather meter SC750 manufactured by Suga Test Instruments Co., Ltd., at a temperature of 65 ° C., a relative humidity of 50% RH, and an intensity of 150 mW / cm 2 (light source: xenon lamp).
  • the P1 layer side was irradiated for 1000 hours.
  • the interlayer may be an interlayer capable of interfacial separation such as between the P1 layer and the P2 layer and between the P2 layer and the P3 layer.
  • the width of the test piece for the peel strength test was 15 mm, two test pieces were prepared, and each test piece was measured at three locations by changing the location. The average value of the obtained measured values was taken as the delamination strength. Further, as a wet heat treatment condition, a pressure cooker manufactured by Tabai Espec Co., Ltd. was used for 48 hours under the conditions of a temperature of 120 ° C. and 100% RH. From the value calculated from the equation (6), the degree of suppression of decrease in delamination strength due to wet heat treatment was determined as follows.
  • delamination strength reduction ratio after wet heat treatment When the delamination strength reduction ratio after wet heat treatment is 1.0 or more: S When delamination strength reduction ratio after wet heat treatment is 0.7 or more and less than 1.0: A When the delamination strength reduction ratio after wet heat treatment is 0.5 or more and less than 0.7: B When the delamination strength reduction ratio after wet heat treatment is 0.3 or more and less than 0.5: C When the delamination strength reduction ratio after wet heat treatment is less than 0.3: D S to B are good, and S is the best among them.
  • PC1 "Taflon” A2200 manufactured by Idemitsu Kosan Co., Ltd. Used in Examples 1-35, 37-80 and Comparative Examples 1-4.
  • PC2 "Taflon” A1700 manufactured by Idemitsu Kosan Co., Ltd. Used in Example 36 and Examples 81-101.
  • Adhesive Resin 1 “Modic” F534A manufactured by Mitsubishi Chemical Corporation, acid-modified polyolefin Used in Examples 1-36, 40-80, and Comparative Examples 1-4.
  • Adhesive resin 2 “Modic” F532 manufactured by Mitsubishi Chemical Corporation, acid-modified polyolefin Used in Example 37.
  • Adhesive Resin 3 “Modic” P553A manufactured by Mitsubishi Chemical Corporation, acid-modified polyolefin Used in Example 38.
  • Adhesive Resin 4 “Admer” SF731, manufactured by Mitsui Chemicals, Inc., acid-modified polyolefin Used in Example 39.
  • Adhesive resin 5 “Modic” F535 manufactured by Mitsubishi Chemical Corporation, acid-modified polyolefin Used in Examples 81 to 101.
  • LLCPE1 "Sumikasen L” GA401 manufactured by Sumitomo Chemical Co., Ltd. Used in Examples 1 to 7 and Examples 81 to 101.
  • PP1 Prime Polymer Co., Ltd. “Prime Polypro” E100GV Used in Examples 8-14.
  • PP2 Prime Polymer Co., Ltd. “Prime Polypro” F704NP manufactured by Prime Polymer Used in Examples 15-21 and Comparative Examples 1-4.
  • PP3 Prime Polymer Co., Ltd. “Prime Polypro” F744NP (ethylene content 4.2 mass%) Used in Examples 22-28.
  • EPBC1 "Noblen” FL6745A manufactured by Sumitomo Chemical Co., Ltd. Used in Examples 29-80.
  • EPC1 "Nobren” FL6412 manufactured by Sumitomo Chemical Co., Ltd. Used in Examples 81-101.
  • Inorganic particles Rutile type titanium dioxide was used as inorganic particles.
  • the following mastered resin was used so that it might become a mixing ratio of a table
  • (MB2) Resin obtained by mastering PC2 and titanium dioxide at a ratio of 50% by mass / 50% by mass Reference Example 2, Examples 6 to 39, 42, 43, 68 to 78, Used for P1 layer of 88-94 and Comparative Examples 1-4.
  • (MB5) Resin in which EPC1 and titanium dioxide were mastered at a ratio of 30% by mass / 70% by mass Reference Examples 1, 2, Examples 12, 13, 19, 20, 26, Used for P3 layer of 27, 81-94.
  • (MB6) Resin in which EPBC1 and titanium dioxide were mastered at a ratio of 30% by mass / 70% by mass Used for P3 layer of Examples 33, 34, 36 to 42, 44 to 62, 68 to 78.
  • Examples 1 to 101, Comparative Examples 1 and 2 Using the extruder 1, the extruder 2 and the extruder 3, the resin was put into each extruder at the resin mixing ratio shown in Table 1 for each layer and melted at the extrusion temperature shown in Table 1. Next, the layers melt-extruded from the extruder 1 are the P1 layer, the extruder 2 is the P2 layer, the extruder 3 is the P3 layer, and the layers are joined together in the order of P1 layer / P2 layer / P3 layer. The resin discharged from the die was cooled and solidified on the cast drum to obtain a laminated sheet. The P1 layer, P2 layer, and P3 layer had thicknesses and lamination ratios shown in Table 1.
  • the P1 layer PC and the resin mastered with PC were those dried at 110 ° C. for 6 hours.
  • the obtained laminated sheet was evaluated for flame retardancy, curl characteristics, and adhesion to a sealing material.
  • Table 1 it was found that the examples were laminated sheets excellent in flame retardancy and curl characteristics.
  • Examples 6 to 39, 42, 43, and 68 to 78 had excellent ultraviolet resistance because the P1 layer contained titanium dioxide as inorganic particles.
  • the P3 layer also contained titanium dioxide as inorganic particles, and thus was further excellent in UV resistance.
  • Examples 1 to 7 and 22 to 80 had excellent adhesion to the sealing material because the melting point of the P3 layer was about 130 ° C.
  • the P3 layer of Examples 14, 21, 28, 35, 50 to 55, 59, 63 to 72, 79, 80, and the P2 layer of Examples 56 to 62, 73 to 78 contained polyolefin elastomer. It was excellent in curling, adhesion to a sealing material, and suppression of a decrease in delamination strength after wet heat treatment. Furthermore, the polyolefin elastomer was contained in the P3 layer of Examples 14, 21, 28, 35, 50 to 55, 59, 63 to 72, 79, 80 and the P2 layer of Examples 56 to 62, 73 to 78. In addition, the degree of suppression of decrease in delamination strength was excellent.
  • Example 59 included polyolefin elastomer in both P2 and P3 layers, and Examples 62 and 78 included 50% by mass of polyolefin elastomer in P2 layer. Excellent suppression. Further, in Examples 14 and 21 to 80, since the crystal melting energy of the P3 layer was 80 J / g or less, the curl characteristics and the adhesion to the sealing material were excellent. Further, the P1 layer of Examples 40, 41, 44 to 67, 79, and 80 and the P3 layer of Examples 63 to 67 contained carbon black as organic particles, and thus were excellent in ultraviolet resistance and design. On the other hand, Comparative Example 1 was inferior in curl characteristics because the thickness of the P2 layer was less than 12 ⁇ m. Since Comparative Example 2 had T1 / T3 of less than 0.5, the curl characteristics were inferior.
  • P2 layers of Examples 84 to 87, 91 to 94, and 98 to 101 contained a modified styrene elastomer, they were excellent in the degree of suppressing the decrease in delamination strength.
  • Examples 85 to 87, 92 to 94, and 99 to 101 were more excellent in flame retardancy and curl characteristics because the P3 layer contained a polycarbonate resin. Moreover, since the loss generated during the production of the laminated sheet was reused, the yield was improved and the productivity was excellent.
  • the P1 layer PC used was dried at 110 ° C. for 6 hours.
  • the obtained laminated sheet was evaluated for flame retardancy and curl characteristics. As a result, as shown in Table 1, since the P3 layer was not provided on at least one surface layer, the adhesion with the sealing material was inferior.
  • the laminated sheet of the present invention can provide a laminated sheet having excellent compatibility between flame retardancy and curl characteristics as compared with conventional laminated sheets of polycarbonate resin and polyolefin resin.
  • Such laminated sheets are suitable for applications where importance is placed on wet heat resistance, resistance to ultraviolet rays, and light reflectivity, including back plates for solar cells, liquid crystal display reflectors, automotive materials, and building materials. Can be used.
  • a solar cell backsheet having high durability and a solar cell using the same can be provided.
  • Back sheet for solar cell 2 Sealing material 3: Power generation element 4: Transparent substrate 5: Surface on the sealing material 2 side of the back sheet for solar cell 6: Side opposite to the sealing material 2 of the back sheet for solar cell Surface a: melting endothermic peak temperature b: crystal melting energy

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Abstract

La présente invention se rapporte à une feuille stratifiée ayant des propriétés de gondolement et résistance à la flamme par rapport à une feuille stratifiée classique d'une résine de polycarbonate et d'une résine de polyoléfine. L'invention se rapporte également à une feuille de soutien à durabilité élevée destinée à une cellule solaire, réalisée par l'utilisation de la feuille stratifiée, et à une cellule solaire utilisant la feuille de soutien. La feuille stratifiée comprend une structure stratifiée ayant une couche (couche P1) dont le composant structural primaire est une résine de polycarbonate, une couche adhésive (couche P2) et une (couche P3) dont le composant structural primaire est une résine de polyoléfine, au moins une couche de surface étant la couche P3. La feuille stratifiée répond aux formules (1) et (2) où l'épaisseur de la couche P1 de la feuille stratifiée est T1, l'épaisseur de la couche P2 est T2 et l'épaisseur de la couche P3 est T3. T1/T3 > 0,5··· (1) T2 > 12 µm··· (2)
PCT/JP2012/068651 2011-07-26 2012-07-24 Feuille stratifiée et son procédé de production Ceased WO2013015259A1 (fr)

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WO2021181314A1 (fr) * 2020-03-12 2021-09-16 藤森工業株式会社 Composition de résine adhésive, article moulé en résine adhésive, stratifié de résine adhésive et élément d'étanchéité de boîtier
WO2021181315A1 (fr) * 2020-03-12 2021-09-16 藤森工業株式会社 Composition de résine adhésive, article moulé en résine adhésive, stratifié de résine adhésive et élément d'étanchéité de boîtier

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