WO2012111660A1 - Substrat de cellule solaire, et élément de cellule solaire - Google Patents

Substrat de cellule solaire, et élément de cellule solaire Download PDF

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WO2012111660A1
WO2012111660A1 PCT/JP2012/053385 JP2012053385W WO2012111660A1 WO 2012111660 A1 WO2012111660 A1 WO 2012111660A1 JP 2012053385 W JP2012053385 W JP 2012053385W WO 2012111660 A1 WO2012111660 A1 WO 2012111660A1
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group
solar cell
repeating unit
liquid crystal
mol
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PCT/JP2012/053385
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Japanese (ja)
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細田　朋也
光男 前田
岡本　敏
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • H01L31/049—Protective back sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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 solar cell substrate composed of liquid crystal polyester. Moreover, this invention relates to the solar cell element which uses this board
  • FIG. 1 is a cross-sectional view schematically showing an example of a solar cell element.
  • the solar cell element 5 is configured by arranging the back electrode layer 2, the photoelectric conversion layer 3, and the front electrode layer 4 in this order on the solar cell substrate 1.
  • the photoelectric conversion layer 3 includes a p-type semiconductor layer 3a, an i-type semiconductor layer 3b, and an n-type semiconductor layer 3c.
  • a plurality of solar cell elements 5 are usually connected and sealed with a sealing layer 7 as shown in FIG. 2, and a surface protective sheet 6 is disposed on the front side (light receiving surface side), and the back side thereof.
  • the back sheet 8 is disposed (on the side opposite to the light receiving surface), and the peripheral portion of the surface protection sheet 6 and the back sheet 8 is fixed by the frame 9, thereby forming the solar cell module 10.
  • Patent Document 1 discloses that as a material for a substrate for a solar cell, a repeating unit derived from p-hydroxybenzoic acid is 60 mol%, a repeating unit derived from terephthalic acid is 15 mol%, and a repeating unit derived from isophthalic acid.
  • Patent Document 2 uses a predetermined liquid crystal polyester product (“SUMICA SUPER E6000” manufactured by Sumitomo Chemical Co., Ltd. or “Vectra A950” manufactured by Polyplastics Co., Ltd.) as a material for a solar cell substrate. , Specifically disclosed.
  • An object of the present invention is to provide a substrate for a solar cell that is made of liquid crystal polyester and further has an excellent water vapor barrier property.
  • the present invention comprises a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3).
  • the present invention provides a solar cell substrate comprising a liquid crystalline polyester having a repeating unit containing 2,6-naphthylene groups and having a content of 40 mol% or more based on the total amount of all repeating units.
  • Ar 1 represents a 2,6-naphthylene group, a 1,4-phenylene group or a 4,4′-biphenylylene group.
  • Ar 2 and Ar 3 are each independently a 2,6-naphthylene group, 1,4 Represents a -phenylene group, a 1,3-phenylene group or a 4,4′-biphenylylene group, wherein the hydrogen atoms in the group represented by Ar 1 , Ar 2 or Ar 3 are each independently a halogen atom or an alkyl group; Alternatively, it may be substituted with an aryl group.
  • the present invention also provides a solar cell substrate that is made of liquid crystal polyester and has a water vapor transmission rate of 0.005 g / m 2 ⁇ 24 h or less measured at a temperature of 40 ° C. and a relative humidity of 90%.
  • the present invention relates to a sun composed of a liquid crystal polyester having a water vapor transmission rate of 0.005 g / m 2 ⁇ 24 h or less measured at a temperature of 40 ° C. and a relative humidity of 90% when a film having a thickness of 50 ⁇ m is formed.
  • a battery substrate is provided.
  • the present invention provides a solar cell element in which a back electrode layer, a photoelectric conversion layer, and a front electrode layer are provided in this order on any of the solar cell substrates.
  • the solar cell substrate of the present invention is excellent in water vapor barrier properties, and by using this, it is possible to obtain a solar cell element in which deterioration such as corrosion of the electrode layer and the photoelectric conversion layer is effectively prevented.
  • the liquid crystalline polyester constituting the solar cell substrate of the present invention is a polyester that exhibits optical anisotropy when melted, and is preferably a repeating unit represented by the following formula (1) (hereinafter referred to as repeating unit (1)).
  • repeating unit (1) A repeating unit represented by the following formula (2) (hereinafter sometimes referred to as repeating unit (2)) and a repeating unit represented by the following formula (3) (hereinafter referred to as repeating unit (3)). )).
  • Ar 1 represents a 2,6-naphthylene group, a 1,4-phenylene group or a 4,4′-biphenylylene group.
  • Ar 2 and Ar 3 are each independently a 2,6-naphthylene group, 1,4 -Represents a phenylene group, a 1,3-phenylene group or a 4,4′-biphenylylene group, wherein the hydrogen atom in the group represented by Ar 1 , Ar 2 or Ar 3 is independently a halogen atom or a carbon number (It may be substituted with an alkyl group of 1 to 10 or an aryl group of 6 to 20 carbon atoms.)
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, Examples thereof include an n-octyl group and an n-decyl group, and the carbon number thereof is usually 1 to 10.
  • aryl group examples include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group, and the number of carbon atoms is usually 6-20.
  • the hydrogen atom is substituted with these groups, the number is usually 2 or less for each group represented by Ar 1 , Ar 2 or Ar 3 , and preferably 1 It is as follows.
  • the repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid.
  • the repeating unit (1) those in which Ar 1 is a 2,6-naphthylene group, that is, a repeating unit derived from 6-hydroxy-2-naphthoic acid is preferable.
  • the repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid.
  • Ar 2 is a 2,6-naphthylene group, that is, a repeating unit derived from 2,6-naphthalenedicarboxylic acid, and Ar 2 is a 1,4-phenylene group, Repeating units derived from terephthalic acid are preferred.
  • the repeating unit (3) is a repeating unit derived from a predetermined aromatic diol.
  • Ar 3 is a 1,4-phenylene group, that is, a repeating unit derived from hydroquinone, and Ar 3 is a 4,4′-biphenylylene group, that is, 4,4′-. Repeating units derived from dihydroxybiphenyl are preferred.
  • repeating unit containing 2,6-naphthylene group in liquid crystal polyester that is, repeating unit (1) in which Ar 1 is 2,6-naphthylene group, repeating unit in which Ar 2 is 2,6-naphthylene group (2) and the total content of the repeating unit (3) in which Ar 3 is a 2,6-naphthylene group is the total amount of all repeating units (the mass of each repeating unit constituting the liquid crystal polyester is expressed by the formula of each repeating unit) By dividing by the amount, the substance amount equivalent amount (mole) of each repeating unit is obtained, and the sum thereof is 40 mol% or more.
  • a liquid crystal polyester film having excellent water vapor barrier properties By forming a liquid crystal polyester having such a predetermined repeating unit composition into a film, a liquid crystal polyester film having excellent water vapor barrier properties can be obtained.
  • the content of 2,6-naphthylene groups is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 70 mol% or more.
  • the content of the repeating unit (1) is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, still more preferably 45 to 65 mol, based on the total amount of all repeating units.
  • the content of the repeating unit (2) is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, still more preferably 17.5 to 27.27%, based on the total amount of all repeating units.
  • the content of the repeating unit (3) is preferably from 10 to 35 mol%, more preferably from 15 to 30 mol%, still more preferably from 17.5 to mol based on the total amount of all repeating units. 27.5 mol%.
  • the liquid crystal polyester having such a predetermined repeating unit composition has an excellent balance between heat resistance and moldability.
  • the liquid crystalline polyester may have a repeating unit other than the repeating units (1) to (3) as necessary, but the content thereof is usually 10 moles relative to the total amount of all the repeating units. % Or less, preferably 5 mol% or less.
  • a typical example of a liquid crystalline polyester having high heat resistance and high melt tension is a repeating unit (1) in which Ar 1 is a 2,6-naphthylene group, that is, 6-hydroxy-2- with respect to the total amount of all repeating units.
  • the repeating unit derived from naphthoic acid is preferably 40 to 74.8 mol%, more preferably 40 to 64.5 mol%, still more preferably 50 to 58 mol%, and Ar 2 is a 2,6-naphthylene group.
  • the repeating unit (2) that is, the repeating unit derived from 2,6-naphthalenedicarboxylic acid is preferably 12.5 to 30 mol%, more preferably 17.5 to 30 mol%, and still more preferably 20 to 25 mol%.
  • repeating units Ar 2 is 1,4-phenylene group (2), i.e., repeating units derived from terephthalic acid, preferably 0.2 to 15 mol%, more preferably 0. To 12 mol%, more preferably having 2 to 10 mol%, the repeating units Ar 3 is 1,4-phenylene group (3), i.e., a repeating unit derived from hydroquinone, preferably 12.5 to 30 mol %, more preferably 17.5 to 30 mol%, more preferably having 20-25 mol%, and the content of the repeating unit (2) Ar 2 is 2,6-naphthylene group, Ar 2 is The total content of the repeating unit (2) which is a 2,6-naphthylene group and the repeating unit (2) wherein Ar 2 is a 1,4-phenylene group is preferably 0.5 mol times or more, more preferably It is 0.6 mol times or more.
  • the liquid crystalline polyester is a monomer that gives a repeating unit (1), that is, a predetermined aromatic hydroxycarboxylic acid, a monomer that gives a repeating unit (2), that is, a monomer that gives a predetermined aromatic dicarboxylic acid, and a repeating unit (3), That is, a predetermined aromatic diol is added to a total amount of monomers having 2,6-naphthylene groups, that is, a total amount of 6-hydroxy-2-naphthoic acid, 2,6-naphthalenedicarboxylic acid and 2,6-naphthalenediol.
  • the polymer can be produced by polymerization (polycondensation) so as to be 40 mol% or more based on the total amount of all monomers.
  • the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, and the aromatic diol may be independently replaced by a part or all of the polymerizable derivatives thereof.
  • polymerizable derivatives of a compound having a carboxyl group such as an aromatic hydroxycarboxylic acid and an aromatic dicarboxylic acid include those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group, and a carboxyl group as a haloformyl.
  • a group formed by converting a carboxyl group into an acyloxycarbonyl group a group formed by converting a carboxyl group into an acyloxycarbonyl group.
  • polymerizable derivatives of hydroxyl group-containing compounds such as aromatic hydroxycarboxylic acids and aromatic diols include those obtained by acylating a hydroxyl group and converting it to an acyloxyl group.
  • the liquid crystalline polyester is preferably produced by melt polymerizing monomers and solid-phase polymerizing the obtained polymer (prepolymer). Thereby, liquid crystalline polyester with high heat resistance and high melt tension can be manufactured with good operability.
  • Melt polymerization may be carried out in the presence of a catalyst.
  • this catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, Nitrogen-containing heterocyclic compounds such as N, N-dimethylaminopyridine and N-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.
  • the liquid crystal polyester having the predetermined repeating unit composition thus obtained is excellent in water vapor barrier properties and is suitably used as a material for the solar cell substrate of the present invention.
  • the liquid crystal polyester has a flow start temperature of preferably 280 ° C. or higher, more preferably 290 ° C. or higher, further preferably 295 ° C. or higher, and is usually 380 ° C. or lower, preferably 350 ° C. or lower.
  • a flow start temperature preferably 280 ° C. or higher, more preferably 290 ° C. or higher, further preferably 295 ° C. or higher, and is usually 380 ° C. or lower, preferably 350 ° C. or lower.
  • the flow start temperature is higher, the heat resistance and melt tension are more likely to be improved. However, if the flow start temperature is too high, a high temperature is required for melting, and thermal deterioration tends to occur during molding.
  • the flow start temperature is also called flow temperature or flow temperature, and is 4 ° C./min under a load of 9.8 MPa (100 kg / cm 2 ) using a capillary rheometer having a nozzle with an inner diameter of 1 mm and a length of 10 mm.
  • This is a temperature at which the melt viscosity shows 4800 Pa ⁇ s (48,000 poise) when the heated melt of the liquid crystal polyester is extruded from the nozzle at a temperature rising rate of 5 ° C., which is a measure of the molecular weight of the liquid crystal polyester (See Naoyuki, “Liquid Crystal Polymers—Synthesis / Molding / Applications”, CMC Corporation, June 5, 1987, p. 95).
  • the liquid crystal polyester in the present invention preferably has a water vapor transmission rate measured at a temperature of 40 ° C. and a relative humidity of 90% when formed into a film having a thickness of 50 ⁇ m, preferably 0.05 g / m 2 ⁇ 24 h or less, More preferably, it is 0.01 g / m ⁇ 2 > * 24h or less, More preferably, it is 0.005 g / m ⁇ 2 > * 24h or less.
  • the liquid crystal polyester may be blended with other components as necessary to form a composition.
  • other components include fillers, thermoplastic resins other than liquid crystal polyesters, and additives.
  • the ratio of the liquid crystal polyester in the entire composition is preferably 80% by mass or more, and more preferably 90% by mass or more.
  • fillers include glass fibers such as milled glass fibers and chopped glass fibers, potassium titanate whiskers, alumina whiskers, aluminum borate whiskers, silicon carbide whiskers, silicon nitride whiskers, and other metal or non-metallic whiskers.
  • glass fiber, mica, talc and carbon fiber are preferably used.
  • the filler may be surface-treated as necessary, and examples of the surface treatment agent include reactivity such as a silane coupling agent, a titanate coupling agent, and a borane coupling agent.
  • examples of the surface treatment agent include reactivity such as a silane coupling agent, a titanate coupling agent, and a borane coupling agent.
  • Examples include coupling agents and lubricants such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants.
  • thermoplastic resins other than liquid crystal polyester include polycarbonate, polyamide, polysulfone, polyphenylene sulfide, polyphenylene ether, polyether ketone, and polyetherimide resin.
  • additives include mold release improvers such as fluororesins and metal soaps, nucleating agents, antioxidants, stabilizers, plasticizers, lubricants, anti-coloring agents, coloring agents, ultraviolet absorbers, antistatic agents, Examples include lubricants and flame retardants.
  • a liquid crystal polyester film to be the solar cell substrate of the present invention By forming the liquid crystal polyester thus obtained or a composition thereof into a film, a liquid crystal polyester film to be the solar cell substrate of the present invention can be obtained.
  • the film forming method include an extrusion molding method, a press molding method, a solution casting method, and an injection molding method, and the extrusion molding method is preferable.
  • the extrusion molding method include a T-die method and an inflation method. In the T-die method, uniaxial stretching or biaxial stretching may be performed.
  • the draw ratio (draft ratio) of the uniaxially stretched film is usually 1.1 to 40, preferably 10 to 40, more preferably 15 to 35.
  • the stretch ratio in the MD direction (extrusion direction) of the biaxial film is usually 1.2 to 40 times, and the stretch ratio in the TD direction (direction perpendicular to the extrusion direction) of the biaxial film is usually 1.2 to 20 times. Is double.
  • the thickness of the liquid crystal polyester film is preferably 5 to 100 ⁇ m, more preferably 10 to 75 ⁇ m, and further preferably 15 to 75 ⁇ m. If it is too thin, the strength will be insufficient, and if it is too thick, the flexibility will be insufficient.
  • the liquid crystal polyester film thus obtained has excellent water vapor barrier properties and is used as the substrate for solar cells of the present invention.
  • the liquid crystal polyester film water vapor transmission rate being measured at a temperature 40 ° C. and a relative humidity of 90%, preferably from 0.05g / m 2 ⁇ 24h or less, more preferably 0.01g / m 2 ⁇ 24h or less, further Preferably, it is 0.005 g / m 2 ⁇ 24 h or less.
  • a laminated film obtained by laminating a plurality of liquid crystal polyester films or laminating other films such as a thermoplastic resin film on the liquid crystal polyester film is also used as the solar cell substrate of the present invention.
  • a laminated film obtained by providing a water vapor barrier layer or other functional layer on the liquid crystal polyester film or the laminated film to further improve the water vapor barrier property is also used as the solar cell substrate of the present invention. It is done.
  • the water vapor barrier layer is provided on at least one surface of the liquid crystal polyester film.
  • surface of a liquid crystal polyester film providing on the back surface (surface opposite to the surface in which an electrode layer is provided) of a liquid crystal polyester film is preferable.
  • Substances constituting the water vapor barrier layer include at least one element selected from the group consisting of aluminum, silicon, titanium, chromium, iron, cobalt, nickel, copper, zinc, silver and gold, an oxide, and a nitride And oxynitrides are preferable, and two or more of them may be used as necessary.
  • a method for forming the water vapor barrier layer for example, a vapor deposition method, a sputtering method, a PVD method such as an ion plating method, a CVD method such as a plasma CVD method, a thermal CVD method, a laser CVD method, a sol-gel method, a plating method, etc. And wet methods such as a coating method. Further, a foil prepared or obtained separately may be bonded to the liquid crystal polyester film.
  • the solar cell substrate thus obtained is excellent in water vapor barrier properties, and by using this, a solar cell element in which deterioration such as corrosion of the electrode layer and the photoelectric conversion layer is effectively prevented can be obtained.
  • a solar cell element is typically obtained by providing a back electrode layer 2, a photoelectric conversion layer 3, and a surface electrode layer 4 in this order on a solar cell substrate 1 as shown in FIG.
  • the material of the back electrode layer 2 is preferably a conductor having high light reflectivity. Examples thereof include metals such as silver, aluminum, copper, gold, platinum, nickel, tin, and iron; stainless steel, aluminum alloy, and the like. And metal oxides such as ITO, aluminum oxide, and tin oxide. Examples of the method for forming the back electrode layer 2 include a vacuum deposition method, a sputtering method, a CVD method, an electrolytic plating method, and an electroless plating method.
  • the material of the photoelectric conversion layer 3 is preferably silicon, and the photoelectric conversion layer 3 may be an amorphous silicon layer or a microcrystalline silicon layer.
  • the impurity contained in the p-type semiconductor layer 3a is preferably boron
  • the impurity contained in the n-type semiconductor layer 3c is It is preferably phosphorus or nitrogen.
  • the photoelectric conversion layer 3 is preferably formed by a CVD method such as a capacitively coupled plasma CVD method or an inductively coupled plasma CVD method.
  • the material of the surface electrode layer 4 is preferably a highly transparent conductor, and examples thereof include tin oxide, ITO, FTO, and zinc oxide.
  • Examples of the method for forming the surface electrode layer 4 include a vacuum deposition method, a sputtering method, and a CVD method.
  • the solar cell element 5 obtained in this way is connected in a plural number and sealed with a sealing layer 7, and a surface protection sheet 6 is arranged on the front side (light receiving surface side),
  • a solar cell module can be configured by disposing the back sheet 8 on the back side and fixing the peripheral portions of the surface protective sheet 6 and the back sheet 8 to the frame 9.
  • the solar cell substrate of the present invention can also be used as a substrate for a solar cell module having an integrated structure.
  • Production Example 2 In the same reactor as in Production Example 1, 911 g (6.6 mol) of p-hydroxybenzoic acid, 274 g (1.65 mol) of terephthalic acid, 91 g (0.55 mol) of isophthalic acid, 4,4′-dihydroxybiphenyl 409 g (2.2 mol), 1235 g of acetic anhydride (12.1 mol), and 0.17 g of 1-methylimidazole as a catalyst were added, and the gas in the reactor was replaced with nitrogen gas, followed by stirring under a nitrogen gas stream While raising the temperature from room temperature to 150 ° C. over 15 minutes, the mixture was refluxed at 150 ° C. for 1 hour.
  • the mixture was cooled to obtain a powdery liquid crystal polyester.
  • this liquid crystal polyester 60 mol% of the repeating unit (1) in which Ar 1 is a 1,4-phenylene group, 15 mol% of the repeating unit (2) in which Ar 2 is a 1,4-phenylene group, and Ar 2 is 5% by mole of the repeating unit (2) which is a 1,3-phenylene group and 20% of the repeating unit (3) whose Ar 3 is a 4,4′-biphenylylene group, and its flow initiation temperature is 327 ° C. there were.
  • Example 1 The liquid crystalline polyester obtained in Production Example 1 was granulated with a twin-screw extruder ("PCM-30" by Ikekai Co., Ltd.), pelletized, and then supplied to a single-screw extruder (screw diameter 50 mm). It was melted, extruded from a T die (lip length: 300 mm, lip clearance: 1 mm, die temperature: 350 ° C.) and cooled to obtain a liquid crystal polyester film having a thickness of 25 ⁇ m.
  • the liquid crystal polyester film has a water vapor permeability of 0.011 g / m 2 ⁇ 24 h, and is excellent in water vapor barrier properties as a solar cell substrate.
  • Example 2 The liquid crystalline polyester obtained in Production Example 1 was granulated with a twin-screw extruder ("PCM-30" by Ikekai Co., Ltd.), pelletized, and then supplied to a single-screw extruder (screw diameter 50 mm). It was melted, extruded from a T-die (lip length 300 mm, lip clearance 1 mm, die temperature 350 ° C.) into a film and cooled to obtain a liquid crystal polyester having a thickness of 50 ⁇ m.
  • the liquid crystal polyester film has a water vapor permeability of 0.003 g / m 2 ⁇ 24 h, and is excellent in water vapor barrier properties as a solar cell substrate.
  • Example 3 A 200 nm thick transparent electrode (ITO film) was formed at a substrate temperature of 180 ° C. using ITO (Indium Tin Oxide) on the opposite surface of the laminated film obtained in Example 2 on which the gas barrier layer was formed by ion plating. The sheet resistance of the transparent electrode formed on this laminated film was measured and found to be 9.1 ⁇ / ⁇ .
  • ITO Indium Tin Oxide
  • Comparative Example 1 The liquid crystalline polyester obtained in Production Example 2 was granulated with a twin-screw extruder ("PCM-30" from Ikekai Co., Ltd.), pelletized, and then supplied to a single-screw extruder (screw diameter 50 mm). It was melted, extruded from a T die (lip length: 300 mm, lip clearance: 1 mm, die temperature: 350 ° C.) and cooled to obtain a liquid crystal polyester film having a thickness of 25 ⁇ m.
  • the water vapor permeability of the liquid crystal polyester film is 0.343 g / m 2 ⁇ 24 h, and the water vapor barrier property is insufficient as a substrate for a solar cell.
  • Comparative Example 2 The liquid crystalline polyester obtained in Production Example 2 was granulated with a twin-screw extruder ("PCM-30" from Ikekai Co., Ltd.), pelletized, and then supplied to a single-screw extruder (screw diameter 50 mm). It was melted and extruded from a T die (lip length 300 mm, lip clearance 1 mm, die temperature 350 ° C.) into a film and cooled to obtain a liquid crystal polyester film having a thickness of 50 ⁇ m.
  • the water vapor permeability of this liquid crystal polyester film is 0.080 g / m 2 ⁇ 24 h, and the water vapor barrier property is insufficient as a substrate for a solar cell.
  • Comparative Example 3 About the laminated film obtained in Comparative Example 2, a transparent electrode having a thickness of 200 nm was formed on the opposite surface of the gas barrier layer formed by ion plating method using ITO (Indium Tin Oxide) at a substrate temperature of 180 ° C. When the sheet resistance of the transparent electrode formed on this laminated film was measured, it was 12.3 ⁇ / ⁇ .
  • ITO Indium Tin Oxide
  • SYMBOLS 1 Substrate for solar cells, 2 ... Back electrode layer, 3 ... Photoelectric conversion layer, 3a ... p-type semiconductor layer, 3b ... i-type semiconductor layer, 3c ... n-type semiconductor layer, 4 ... surface electrode layer, 5 ... solar cell element, 6 ... surface protective sheet, 7 ... sealing layer, 8 ... backsheet, 9 ... frame, 10 ... solar cell module.

Abstract

La présente invention concerne le problème consistant à fournir un substrat de cellule solaire présentant des propriétés de barrière à la vapeur supérieures. L'invention concerne un substrat de cellule solaire formé à partir d'un polyester à cristaux liquides présentant un motif répétitif représenté par la formule (1), un motif répétitif représenté par la formule (2), et un motif répétitif représenté la formule (3), le rapport de la teneur des motifs répétitifs contenant un groupe 2, 6-naphthylène en fonction de la quantité totale de tous les motifs répétitifs étant d'au moins 40% molaire. (1) - O - Ar1 - CO - (2) - CO - Ar2 - CO - (3) - O - Ar3 - O -, Ar1 représentant un groupe 2, 6-naphthylène, un groupe 1, 4-phénylène, ou un groupe 4, 4'-biphénylène. Ar2 et Ar3 représentent indépendamment un groupe 2, 6-naphthylène, un groupe 1, 4-phénylène, un groupe 1, 3-phénylène, ou un groupe 4, 4'-biphénylène.)
PCT/JP2012/053385 2011-02-16 2012-02-14 Substrat de cellule solaire, et élément de cellule solaire WO2012111660A1 (fr)

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TWI740515B (zh) 2019-12-23 2021-09-21 長春人造樹脂廠股份有限公司 液晶高分子膜及包含其之積層板

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004140143A (ja) * 2002-10-17 2004-05-13 National Institute Of Advanced Industrial & Technology 太陽電池用基板および太陽電池
JP2007154169A (ja) * 2005-11-08 2007-06-21 Sumitomo Chemical Co Ltd 液晶ポリエステル樹脂組成物及び電子部品用成形品
JP2010135782A (ja) * 2008-11-10 2010-06-17 Sumitomo Chemical Co Ltd 太陽電池
JP2010141156A (ja) * 2008-12-12 2010-06-24 Sekisui Chem Co Ltd 太陽電池モジュール
WO2011021543A1 (fr) * 2009-08-17 2011-02-24 住友化学株式会社 Plaque arrière pour cellule solaire et module à cellule solaire

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004140143A (ja) * 2002-10-17 2004-05-13 National Institute Of Advanced Industrial & Technology 太陽電池用基板および太陽電池
JP2007154169A (ja) * 2005-11-08 2007-06-21 Sumitomo Chemical Co Ltd 液晶ポリエステル樹脂組成物及び電子部品用成形品
JP2010135782A (ja) * 2008-11-10 2010-06-17 Sumitomo Chemical Co Ltd 太陽電池
JP2010141156A (ja) * 2008-12-12 2010-06-24 Sekisui Chem Co Ltd 太陽電池モジュール
WO2011021543A1 (fr) * 2009-08-17 2011-02-24 住友化学株式会社 Plaque arrière pour cellule solaire et module à cellule solaire

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