WO2012111660A1 - Solar cell substrate, and solar cell element - Google Patents
Solar cell substrate, and solar cell element Download PDFInfo
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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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- solar cell
- repeating unit
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- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
The present invention addresses the problem of providing a solar cell substrate exhibiting superior steam barrier properties. The present invention relates to a solar cell substrate formed from a liquid crystal polyester having a repeating unit represented by formula (1), a repeating unit represented by formula (2), and a repeating unit represented by formula (3); wherein the ratio of the content of the repeating units containing a 2, 6-naphthylene group to the total amount of all of the repeating units is at least 40 mol%. (1) - O - Ar1 - CO - (2) - CO - Ar2 - CO - (3) - O - Ar3 - O - (Ar1 represents a 2, 6-naphthylene group, a 1, 4-phenylene group, or a 4, 4'-biphenylene group. Ar2 and Ar3 independently represent a 2, 6-naphthylene group, a 1, 4-phenylene group, a 1, 3-phenylene group, or a 4, 4'-biphenylene group.)
Description
本発明は、液晶ポリエステルから構成される太陽電池用基板に関する。また、本発明は、この太陽電池用基板を用いてなる太陽電池素子に関する。
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 | substrate for solar cells.
図１は、太陽電池素子の例を模式的に示す断面図である。この例では、太陽電池用基板１の上に、裏面電極層２、光電変換層３及び表面電極層４がこの順に配置されることにより、太陽電池素子５が構成されている。また、光電変換層３は、ｐ型半導体層３ａ、ｉ型半導体層３ｂ及びｎ型半導体層３ｃから構成されている。そして、太陽電池素子５は、通常、複数個連結されて、図２に示すように、封止層７により封止され、その表側（受光面側）に表面保護シート６が配置され、その裏側（受光面とは反対の面側）にバックシート８が配置され、表面保護シート６及びバックシート８の周縁部がフレーム９で固定されることにより、太陽電池モジュール１０が構成されている。
FIG. 1 is a cross-sectional view schematically showing an example of a solar cell element. In this example, 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. Then, 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.
太陽電池用基板には、電極層や光電変換層の腐食等の劣化を防止すべく、水蒸気バリア性が求められる。そこで、太陽電池用基板の材料として、水蒸気バリア性に優れる太陽電池基板を与えることから、液晶ポリエステルが検討されている。例えば、特許文献１には、太陽電池用基板の材料として、ｐ－ヒドロキシ安息香酸に由来する繰返し単位を６０モル％、テレフタル酸に由来する繰返し単位を１５モル％、イソフタル酸に由来する繰返し単位を５モル％、及び４，４－ジヒドロキシビフェニルに由来する繰返し単位を２０モル％有する液晶ポリエステルを用いることが、具体的に開示されている。また、特許文献２には、太陽電池用基板の材料として、所定の液晶ポリエステルの商品（住友化学（株）の「スミカスーパーＥ６０００」やポリプラスチック（株）の「ベクトラＡ９５０」）を用いることが、具体的に開示されている。
The substrate for the solar cell is required to have a water vapor barrier property in order to prevent the electrode layer and the photoelectric conversion layer from being deteriorated such as corrosion. Therefore, liquid crystal polyester has been studied as a material for a solar cell substrate, because it provides a solar cell substrate having excellent water vapor barrier properties. For example, 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. It is specifically disclosed to use a liquid crystal polyester having 5 mol% of styrene and 20 mol% of repeating units derived from 4,4-dihydroxybiphenyl. 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.
本発明の目的は、液晶ポリエステルから構成され、さらに水蒸気バリア性に優れる太陽電池用基板を提供することにある。
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.
前記目的を達成するため、本発明は、下記式（１）で表される繰返し単位と、下記式（２）で表される繰返し単位と、下記式（３）で表される繰返し単位とを有し、２，６－ナフチレン基を含む繰返し単位の含有量が、全繰返し単位の合計量に対して、４０モル％以上である液晶ポリエステルから構成される太陽電池用基板を提供する。
In order to achieve the object, 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.
－Ｏ－Ａｒ1－ＣＯ－ （１）
－ＣＯ－Ａｒ2－ＣＯ－ （２）
－Ｏ－Ａｒ3－Ｏ－ （３）
（Ａｒ1は、２，６－ナフチレン基、１，４－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ2及びＡｒ3は、それぞれ独立に、２，６－ナフチレン基、１，４－フェニレン基、１，３－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ1、Ａｒ2又はＡｒ3で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。） —O—Ar 1 —CO— (1)
—CO—Ar 2 —CO— (2)
—O—Ar 3 —O— (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 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.)
－ＣＯ－Ａｒ2－ＣＯ－ （２）
－Ｏ－Ａｒ3－Ｏ－ （３）
（Ａｒ1は、２，６－ナフチレン基、１，４－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ2及びＡｒ3は、それぞれ独立に、２，６－ナフチレン基、１，４－フェニレン基、１，３－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ1、Ａｒ2又はＡｒ3で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。） —O—Ar 1 —CO— (1)
—CO—Ar 2 —CO— (2)
—O—Ar 3 —O— (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 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.)
また、本発明は、液晶ポリエステルから構成され、温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が０．００５ｇ／ｍ2・２４ｈ以下である太陽電池用基板を提供する。
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%.
さらに、本発明は、厚さ５０μｍのフィルムにしたときの温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が０．００５ｇ／ｍ2・２４ｈ以下である液晶ポリエステルから構成される太陽電池用基板を提供する。
Furthermore, 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 μm is formed. A battery substrate is provided.
加えて、本発明は、前記いずれかの太陽電池用基板上に、裏面電極層、光電変換層及び表面電極層がこの順に設けられてなる太陽電池素子を提供する。
In addition, 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.
本発明の太陽電池用基板は、水蒸気バリア性に優れており、これを用いることにより、電極層や光電変換層の腐食等の劣化が効果的に防止された太陽電池素子を得ることができる。
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.
本発明の太陽電池用基板を構成する液晶ポリエステルは、溶融時に光学異方性を示すポリエステルであり、好適には、下記式（１）で表される繰返し単位（以下、繰返し単位（１）ということがある）と、下記式（２）で表される繰返し単位（以下、繰返し単位（２）ということがある）と、下記式（３）で表される繰返し単位（以下、繰返し単位（３）ということがある）とを有するものである。
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)). 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)). )).
－Ｏ－Ａｒ1－ＣＯ－ （１）
－ＣＯ－Ａｒ2－ＣＯ－ （２）
－Ｏ－Ａｒ3－Ｏ－ （３）
（Ａｒ1は、２，６－ナフチレン基、１，４－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ2及びＡｒ3は、それぞれ独立に、２，６－ナフチレン基、１，４－フェニレン基、１，３－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ1、Ａｒ2又はＡｒ3で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、炭素数１～１０のアルキル基又は炭素数６～２０のアリール基で置換されていてもよい。） —O—Ar 1 —CO— (1)
—CO—Ar 2 —CO— (2)
—O—Ar 3 —O— (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.)
－ＣＯ－Ａｒ2－ＣＯ－ （２）
－Ｏ－Ａｒ3－Ｏ－ （３）
（Ａｒ1は、２，６－ナフチレン基、１，４－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ2及びＡｒ3は、それぞれ独立に、２，６－ナフチレン基、１，４－フェニレン基、１，３－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ1、Ａｒ2又はＡｒ3で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、炭素数１～１０のアルキル基又は炭素数６～２０のアリール基で置換されていてもよい。） —O—Ar 1 —CO— (1)
—CO—Ar 2 —CO— (2)
—O—Ar 3 —O— (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.)
前記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。前記アルキル基の例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ヘキシル基、２－エチルヘキシル基、ｎ－オクチル基及びｎ－デシル基が挙げられ、その炭素数は、通常１～１０である。前記アリール基の例としては、フェニル基、ｏ－トリル基、ｍ－トリル基、ｐ－トリル基、１－ナフチル基及び２－ナフチル基が挙げられ、その炭素数は、通常６～２０である。前記水素原子がこれらの基で置換されている場合、その数は、Ａｒ1、Ａｒ2又はＡｒ3で表される前記基毎に、それぞれ独立に、通常２個以下であり、好ましくは１個以下である。
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Examples of the alkyl group 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. Examples of the aryl group 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. . When 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.
繰返し単位（１）は、所定の芳香族ヒドロキシカルボン酸に由来する繰返し単位である。繰返し単位（１）としては、Ａｒ1が２，６－ナフチレン基であるもの、すなわち６－ヒドロキシ－２－ナフトエ酸に由来する繰返し単位が好ましい。
The repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid. As 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.
繰返し単位（２）は、所定の芳香族ジカルボン酸に由来する繰返し単位である。繰返し単位（２）としては、Ａｒ2が２，６－ナフチレン基であるもの、すなわち２，６－ナフタレンジカルボン酸に由来する繰返し単位、及びＡｒ2が１，４－フェニレン基であるもの、すなわちテレフタル酸に由来する繰返し単位が好ましい。
The repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid. As the repeating unit (2), 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.
繰返し単位（３）は、所定の芳香族ジオールに由来する繰返し単位である。繰返し単位（３）としては、Ａｒ3が１，４－フェニレン基であるもの、すなわちヒドロキノンに由来する繰返し単位、及びＡｒ3が４，４’－ビフェニリレン基であるもの、すなわち４，４’－ジヒドロキシビフェニルに由来する繰返し単位が好ましい。
The repeating unit (3) is a repeating unit derived from a predetermined aromatic diol. As the repeating unit (3), 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.
液晶ポリエステル中、２，６－ナフチレン基を含む繰返し単位の含有量、すなわち、Ａｒ1が２，６－ナフチレン基である繰返し単位（１）、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）、及びＡｒ3が２，６－ナフチレン基である繰返し単位（３）の合計含有量は、全繰返し単位の合計量（液晶ポリエステルを構成する各繰返し単位の質量を各繰返し単位の式量で割ることにより、各繰返し単位の物質量相当量（モル）を求め、それらを合計した値）に対して、４０モル％以上である。かかる所定の繰返し単位組成を有する液晶ポリエステルをフィルム化することにより、水蒸気バリア性に優れる液晶ポリエステルフィルムを得ることができる。この２，６－ナフチレン基の含有量は、好ましくは５０モル％以上、より好ましくは６０モル％以上、さらに好ましくは７０モル％以上である。
Content of 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. 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.
また、液晶ポリエステル中、繰返し単位（１）の含有量は、全繰返し単位の合計量に対して、好ましくは３０～８０モル％、より好ましくは４０～７０モル％、さらに好ましくは４５～６５モル％であり、繰返し単位（２）の含有量は、全繰返し単位の合計量に対して、好ましくは１０～３５モル％、より好ましくは１５～３０モル％、さらに好ましくは１７．５～２７．５モル％であり、繰返し単位（３）の含有量は、全繰返し単位の合計量に対して、好ましくは１０～３５モル％、より好ましくは１５～３０モル％、さらに好ましくは１７．５～２７．５モル％である。このような所定の繰返し単位組成を有する液晶ポリエステルは、耐熱性と成形性とのバランスに優れている。なお、繰返し単位（２）の含有量と繰返し単位（３）の含有量とは、実質的に等しいことが好ましい。また、液晶ポリエステルは、必要に応じて繰返し単位（１）～（３）以外の繰返し単位を有していてもよいが、その含有量は、全繰返し単位の合計量に対して、通常１０モル％以下、好ましくは５モル％以下である。
In the liquid crystal polyester, 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. In addition, it is preferable that content of a repeating unit (2) and content of a repeating unit (3) are substantially equal. 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.
耐熱性や溶融張力が高い液晶ポリエステルの典型的な例は、全繰返し単位の合計量に対して、Ａｒ1が２，６－ナフチレン基である繰返し単位（１）、すなわち６－ヒドロキシ－２－ナフトエ酸に由来する繰返し単位を、好ましくは４０～７４．８モル％、より好ましくは４０～６４．５モル％、さらに好ましくは５０～５８モル％有し、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）、すなわち２，６－ナフタレンジカルボン酸に由来する繰返し単位を、好ましくは１２．５～３０モル％、より好ましくは１７．５～３０モル％、さらに好ましくは２０～２５モル％有し、Ａｒ2が１，４－フェニレン基である繰返し単位（２）、すなわちテレフタル酸に由来する繰返し単位を、好ましくは０．２～１５モル％、より好ましくは０．５～１２モル％、さらに好ましくは２～１０モル％有し、Ａｒ3が１，４－フェニレン基である繰返し単位（３）、すなわちヒドロキノンに由来する繰返し単位を、好ましくは１２．５～３０モル％、より好ましくは１７．５～３０モル％、さらに好ましくは２０～２５モル％有し、かつ、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）の含有量が、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）及びＡｒ2が１，４－フェニレン基である繰返し単位（２）の合計含有量に対して、好ましくは０．５モル倍以上、より好ましくは０．６モル倍以上のものである。
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%. a mole%, 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.
液晶ポリエステルは、繰返し単位（１）を与えるモノマー、すなわち所定の芳香族ヒドロキシカルボン酸と、繰返し単位（２）を与えるモノマー、すなわち所定の芳香族ジカルボン酸と、繰返し単位（３）を与えるモノマー、すなわち所定の芳香族ジオールとを、２，６－ナフチレン基を有するモノマーの合計量、すなわち６－ヒドロキシ－２－ナフトエ酸、２，６－ナフタレンジカルボン酸及び２，６－ナフタレンジオールの合計量が、全モノマーの合計量に対して、４０モル％以上になるようにして、重合（重縮合）させることにより、製造することができる。その際、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸及び芳香族ジオールは、それぞれ独立に、その一部又は全部に代えて、その重合可能な誘導体が用いられてもよい。芳香族ヒドロキシカルボン酸及び芳香族ジカルボン酸のようなカルボキシル基を有する化合物の重合可能な誘導体の例としては、カルボキシル基をアルコキシカルボニル基又はアリールオキシカルボニル基に変換してなるもの、カルボキシル基をハロホルミル基に変換してなるもの、カルボキシル基をアシルオキシカルボニル基に変換してなるものが挙げられる。芳香族ヒドロキシカルボン酸及び芳香族ジオールのようなヒドロキシル基を有する化合物の重合可能な誘導体の例としては、ヒドロキシル基をアシル化してアシルオキシル基に変換してなるものが挙げられる。
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. In that case, 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. Examples of 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. And a group formed by converting a carboxyl group into an acyloxycarbonyl group. Examples of 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.
また、液晶ポリエステルは、モノマーを溶融重合させ、得られた重合物（プレポリマー）を固相重合させることにより、製造することが好ましい。これにより、耐熱性や溶融張力が高い液晶ポリエステルを操作性良く製造することができる。溶融重合は、触媒の存在下に行ってもよく、この触媒の例としては、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、酢酸カリウム、三酸化アンチモン等の金属化合物や、Ｎ，Ｎ－ジメチルアミノピリジン、Ｎ－メチルイミダゾール等の含窒素複素環式化合物が挙げられ、含窒素複素環式化合物が好ましく用いられる。こうして得られる前記所定の繰り返し単位組成を有する液晶ポリエステルは、水蒸気バリア性に優れており、本発明の太陽電池用基板の材料として好適に用いられる。
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. Examples of 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.
液晶ポリエステルは、その流動開始温度が、好ましくは２８０℃以上、より好ましくは２９０℃以上、さらに好ましくは２９５℃以上であり、また、通常３８０℃以下、好ましくは３５０℃以下である。流動開始温度が高いほど、耐熱性や溶融張力が向上し易いが、あまり高いと、溶融させるために高温を要し、成形時に熱劣化し易くなる。
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. As 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.
なお、流動開始温度は、フロー温度又は流動温度とも呼ばれ、内径１ｍｍ、長さ１０ｍｍのノズルを持つ毛細管レオメーターを用い、９．８ＭＰａ（１００ｋｇ／ｃｍ2）の荷重下において、４℃／分の昇温速度で液晶ポリエステルの加熱溶融体をノズルから押し出すときに、溶融粘度が４８００Ｐａ・ｓ（４８，０００ポイズ）を示す温度であり、液晶ポリエステルの分子量の目安となるものである（小出直之編、「液晶ポリマー－合成・成形・応用－」、株式会社シーエムシー、１９８７年６月５日、ｐ．９５参照）。
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).
本発明における液晶ポリエステルは、好適には、厚さ５０μｍのフィルムにしたときの温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が、好ましくは０．０５ｇ／ｍ2・２４ｈ以下、より好ましくは０．０１ｇ／ｍ2・２４ｈ以下、さらに好ましくは０．００５ｇ／ｍ2・２４ｈ以下である。
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 μm, 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.
液晶ポリエステルには、必要に応じて他の成分を配合して、組成物としてもよい。他の成分の例としては、充填材、液晶ポリエステル以外の熱可塑性樹脂及び添加剤が挙げられる。組成物全体に占める液晶ポリエステルの割合は、好ましくは８０質量％以上であり、より好ましくは９０質量％以上である。
The liquid crystal polyester may be blended with other components as necessary to form a composition. Examples of 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.
充填材の例としては、ミルドガラスファイバー、チョップドガラスファイバー等のガラス繊維、チタン酸カリウムウイスカー、アルミナウイスカ、ホウ酸アルミニウムウイスカ、炭化けい素ウイスカ、窒化けい素ウイスカ等の金属又は非金属系ウイスカ類、ガラスビーズ、中空ガラス球、ガラス粉末、マイカ、タルク、クレー、シリカ、アルミナ、チタン酸カリウム、ウォラスナイト、炭酸カルシウム（重質、軽質、膠質等）、炭酸マグネシウム、塩基性炭酸マグネシウム、硫酸ソーダ、硫酸カルシウム、硫酸バリウム、亜硫酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、けい酸カルシウム、けい砂、けい石、石英、酸化チタン、酸化亜鉛、酸化鉄グラファイト、モリブデン、アスベスト、シリカアルミナ繊維、アルミナ繊維、石膏繊維、炭素繊維、カーボンブラック、ホワイトカーボン、けいそう土、ベントナイト、セリサイト、シラス及び黒鉛が挙げられ、必要に応じてそれらの２種以上を用いることもできる。中でも、ガラス繊維、マイカ、タルク及び炭素繊維が好ましく用いられる。
Examples of 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 beads, hollow glass spheres, glass powder, mica, talc, clay, silica, alumina, potassium titanate, wollastonite, calcium carbonate (heavy, light, colloidal, etc.), magnesium carbonate, basic magnesium carbonate, sodium sulfate , Calcium sulfate, barium sulfate, calcium sulfite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium silicate, silica sand, silica, quartz, titanium oxide, zinc oxide, iron oxide graphite, molybdenum, asbestos, silica alumina Wei, alumina fibers, gypsum fibers, carbon fibers, carbon black, white carbon, diatomaceous earth, bentonite, sericite, Shirasu and graphite are mentioned, it is also possible to use two or more of them, if necessary. Among these, glass fiber, mica, talc and carbon fiber are preferably used.
充填材は、必要に応じて、表面処理されたものであってもよく、この表面処理剤の例としては、シラン系カップリング剤、チタネート系カップリング剤、ボラン系カップリング剤等の反応性カップリング剤、及び高級脂肪酸、高級脂肪酸エステル、高級脂肪酸金属塩、フルオロカーボン系界面活性剤等の潤滑剤が挙げられる。
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 include coupling agents and lubricants such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants.
液晶ポリエステル以外の熱可塑性樹脂の例としては、ポリカーボネート、ポリアミド、ポリサルフォン、ポリフェニレンスルフィド、ポリフェニレンエーテル、ポリエーテルケトン及びポリエーテルイミド樹脂が挙げられる。
Examples of thermoplastic resins other than liquid crystal polyester include polycarbonate, polyamide, polysulfone, polyphenylene sulfide, polyphenylene ether, polyether ketone, and polyetherimide resin.
添加剤の例としては、フッ素樹脂、金属石鹸類等の離型改良剤、核剤、酸化防止剤、安定剤、可塑剤、滑剤、着色防止剤、着色剤、紫外線吸収剤、帯電防止剤、潤滑剤及び難燃剤が挙げられる。
Examples of 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.
こうして得られる液晶ポリエステル又はその組成物をフィルム化することにより、本発明の太陽電池用基板となる液晶ポリエステルフィルムを得ることができる。フィルム化の方法としては、例えば、押出成形法、プレス成形法、溶液流延法及び射出成形法が挙げられ、押出成形法が好ましい。押出成形法としては、例えば、Ｔダイ法やインフレーション法が挙げられ、Ｔダイ法において、一軸延伸してもよいし、二軸延伸してもよい。
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. Examples of 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. Examples of 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.
一軸延伸フィルムの延伸倍率（ドラフト比）は、通常１．１～４０、好ましくは１０～４０、より好ましくは１５～３５である。二軸フィルムのＭＤ方向（押出方向）の延伸倍率は、通常１．２～４０倍であり、二軸フィルムのＴＤ方向（押出方向に垂直な方向）の延伸倍率は、通常１．２～２０倍である。インフレーションフィルムのＭＤ方向の延伸倍率（ドローダウン比＝バブル引取速度／樹脂吐出速度）は、通常１．５～５０、好ましくは５～３０であり、インフレーションフィルムのＴＤの延伸倍率（ブロー比＝バブル径／環状スリット径）は、通常１．５～１０、好ましくは２～５である。
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 stretch ratio in the MD direction of the inflation film (drawdown ratio = bubble take-off speed / resin discharge speed) is usually 1.5 to 50, preferably 5 to 30, and the stretch ratio of TD of the inflation film (blow ratio = bubble) Diameter / annular slit diameter) is usually 1.5 to 10, preferably 2 to 5.
液晶ポリエステルフィルムの厚さは、好ましくは５～１００μｍであり、より好ましくは１０～７５μｍであり、さらに好ましくは１５～７５μｍである。あまり薄いと、強度が不十分になり、あまり厚いと、フレキシブル性が不十分になる。
The thickness of the liquid crystal polyester film is preferably 5 to 100 μm, more preferably 10 to 75 μm, and further preferably 15 to 75 μm. If it is too thin, the strength will be insufficient, and if it is too thick, the flexibility will be insufficient.
こうして得られる液晶ポリエステルフィルムは、水蒸気バリア性に優れており、本発明の太陽電池用基板として用いられる。この液晶ポリエステルフィルムは、温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が、好ましくは０．０５ｇ／ｍ2・２４ｈ以下、より好ましくは０．０１ｇ／ｍ2・２４ｈ以下、さらに好ましくは０．００５ｇ／ｍ2・２４ｈ以下である。
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.
なお、液晶ポリエステルフィルムを複数枚積層したり、液晶ポリエステルフィルムに熱可塑性樹脂フィルム等の他のフィルムを積層したりして得られる積層フィルムも、本発明の太陽電池用基板として用いられる。また、液晶ポリエステルフィルム又は前記積層フィルムに、さらに水蒸気バリア性を高めるべく、水蒸気バリア層を設けたり、他の機能層を設けたりして得られる積層フィルムも、本発明の太陽電池用基板として用いられる。
In addition, 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. In addition, 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.
水蒸気バリア層は、液晶ポリエステルフィルムの少なくとも一方の面上に設けられる。液晶ポリエステルフィルムの片面上に設ける場合、液晶ポリエステルフィルムの裏面（電極層が設けられる面とは反対の面）上に設けることが好ましい。
The water vapor barrier layer is provided on at least one surface of the liquid crystal polyester film. When providing on the single side | 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.
水蒸気バリア層を構成する物質としては、アルミニウム、ケイ素、チタン、クロム、鉄、コバルト、ニッケル、銅、亜鉛、銀及び金からなる群から選ばれる少なくとも１種の元素の単体、酸化物、窒化物及び酸窒化物が好ましく、必要に応じてそれらの２種以上を用いてもよい。
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.
水蒸気バリア層の形成方法としては、例えば、蒸着法、スパッタリング法、イオンプレーティング法等のＰＶＤ法、プラズマＣＶＤ法、熱ＣＶＤ法、レーザーＣＶＤ法等のＣＶＤ法、及びゾル－ゲル法、めっき法、塗布法等のウェット法が挙げられる。また、別途調製乃至入手した箔を、液晶ポリエステルフィルムに貼合してもよい。
As 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.
こうして得られる太陽電池用基板は、水蒸気バリア性に優れており、これを用いることにより、電極層や光電変換層の腐食等の劣化が効果的に防止された太陽電池素子を得ることができる。
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.
太陽電池素子は、典型的には、図１に示す如く、太陽電池基板１上に、裏面電極層２、光電変換層３及び表面電極層４をこの順に設けることにより得られる。
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.
裏面電極層２の材料は、光線反射率が高い導電体であることが好ましく、その例としては、銀、アルミニウム、銅、金、プラチナ、ニッケル、錫、鉄等の金属；ステンレス、アルミニウム合金等の合金；及びＩＴＯ、酸化アルミニウム、酸化錫等の金属酸化物が挙げられる。裏面電極層２の形成方法の例としては、真空蒸着法、スパッタリング法、ＣＶＤ法、電解めっき法及び無電解めっき法が挙げられる。
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.
光電変換層３の材料は、シリコンであることが好ましく、光電変換層３は、アモルファスシリコン層であってもよいし、微結晶シリコン層であってもよい。また、光電変換層３が図１に示す如きｎｉｐ型構造のものである場合、ｐ型半導体層３ａに含まれる不純物は、ホウ素であることが好ましく、ｎ型半導体層３ｃに含まれる不純物は、リンや窒素であることが好ましい。光電変換層３の形成は、容量結合型プラズマＣＶＤ法や誘導結合型プラズマＣＶＤ法の如きＣＶＤ法で行うことが好ましい。
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. When the photoelectric conversion layer 3 has a nip type structure as shown in FIG. 1, the impurity contained in the p-type semiconductor layer 3a is preferably boron, and 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.
表面電極層４の材料は、透明性が高い導電体であることが好ましく、その例としては、酸化錫、ＩＴＯ、ＦＴＯ及び酸化亜鉛が挙げられる。表面電極層４の形成方法の例としては、真空蒸着法、スパッタリング法及びＣＶＤ法が挙げられる。
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.
こうして得られる太陽電池素子５は、例えば、図２に示す如く、その複数個を連結して、封止層７により封止し、その表側（受光面側）に表面保護シート６を配置し、その裏側にバックシート８を配置し、表面保護シート６及びバックシート８の周縁部をフレーム９に固定することにより、太陽電池モジュールを構成することができる。また、本発明の太陽電池用基板は、集積型構造の太陽電池モジュールの基板として用いることもできる。
For example, as shown in FIG. 2, 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.
〔流動開始温度の測定〕
フローテスター（（株）島津製作所の「ＣＦＴ－５００型」）を用いて、試料約２ｇを、内径１ｍｍ、長さ１０ｍｍのダイスを取り付けた毛細管型レオメーターに充填し、９．８ＭＰａ（１００ｋｇｆ／ｃｍ2）の荷重下において、昇温速度４℃／分で試料を溶融させながら押し出し、溶融粘度が４８００Ｐａ・ｓ（４８０００ポイズ）を示す温度を測定した。 [Measurement of flow start temperature]
Using a flow tester (“CFT-500 type” manufactured by Shimadzu Corp.), about 2 g of the sample was filled into a capillary rheometer equipped with a die having an inner diameter of 1 mm and a length of 10 mm, and 9.8 MPa (100 kgf / The sample was extruded while melting at a temperature rising rate of 4 ° C./min under a load of cm 2 ), and a temperature at which the melt viscosity was 4800 Pa · s (48000 poise) was measured.
フローテスター（（株）島津製作所の「ＣＦＴ－５００型」）を用いて、試料約２ｇを、内径１ｍｍ、長さ１０ｍｍのダイスを取り付けた毛細管型レオメーターに充填し、９．８ＭＰａ（１００ｋｇｆ／ｃｍ2）の荷重下において、昇温速度４℃／分で試料を溶融させながら押し出し、溶融粘度が４８００Ｐａ・ｓ（４８０００ポイズ）を示す温度を測定した。 [Measurement of flow start temperature]
Using a flow tester (“CFT-500 type” manufactured by Shimadzu Corp.), about 2 g of the sample was filled into a capillary rheometer equipped with a die having an inner diameter of 1 mm and a length of 10 mm, and 9.8 MPa (100 kgf / The sample was extruded while melting at a temperature rising rate of 4 ° C./min under a load of cm 2 ), and a temperature at which the melt viscosity was 4800 Pa · s (48000 poise) was measured.
〔水蒸気バリア性の評価〕
ＪＩＳ Ｋ７１２９ Ｃ法に準拠して、ガス透過率・透湿度測定装置（ＧＴＲテック（株）の「ＧＴＲ－３０Ｘ」）により、温度４０℃、相対湿度９０％の条件で、水蒸気透過度を測定した。 [Evaluation of water vapor barrier properties]
In accordance with JIS K7129 C method, the water vapor transmission rate was measured at a temperature of 40 ° C. and a relative humidity of 90% with a gas permeability / moisture permeability measuring device (“GTR-30X” from GTR Tech Co., Ltd.). .
ＪＩＳ Ｋ７１２９ Ｃ法に準拠して、ガス透過率・透湿度測定装置（ＧＴＲテック（株）の「ＧＴＲ－３０Ｘ」）により、温度４０℃、相対湿度９０％の条件で、水蒸気透過度を測定した。 [Evaluation of water vapor barrier properties]
In accordance with JIS K7129 C method, the water vapor transmission rate was measured at a temperature of 40 ° C. and a relative humidity of 90% with a gas permeability / moisture permeability measuring device (“GTR-30X” from GTR Tech Co., Ltd.). .
〔ＩＴＯ膜の表面抵抗率の測定〕
ＩＴＯ膜の表面抵抗率（シート抵抗）は、４探針法抵抗測定装置（三菱化学製ロレスタＡＰ）により測定した。 [Measurement of surface resistivity of ITO film]
The surface resistivity (sheet resistance) of the ITO film was measured with a four-probe resistance measuring device (Loresta AP manufactured by Mitsubishi Chemical).
ＩＴＯ膜の表面抵抗率（シート抵抗）は、４探針法抵抗測定装置（三菱化学製ロレスタＡＰ）により測定した。 [Measurement of surface resistivity of ITO film]
The surface resistivity (sheet resistance) of the ITO film was measured with a four-probe resistance measuring device (Loresta AP manufactured by Mitsubishi Chemical).
製造例１
攪拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１０３４．９９ｇ（５．５モル）、２，６－ナフタレンジカルボン酸３７８．３３ｇ（１．７５モル）、テレフタル酸８３．０７ｇ（０．５モル）、ヒドロキノン２７２．５２ｇ（２．４７５モル：２，６－ナフタレンジカルボン酸及びテレフタル酸の合計量に対して０．２２５モル過剰）、無水酢酸１２２６．８７ｇ（１２モル）、及び触媒として１－メチルイミダゾール０．１７ｇを入れ、反応器内のガスを窒素ガスで置換した後、窒素ガス気流下、攪拌しながら、室温から１４５℃まで１５分かけて昇温し、１４５℃で１時間還流させた。次いで、副生酢酸及び未反応の無水酢酸を留去しながら、１４５℃から３１０℃まで３時間３０分かけて昇温し、３１０℃で３時間保持した後、内容物を取り出し、室温まで冷却した。得られた固形物を、粉砕機で粒径約０．１～１ｍｍに粉砕後、窒素雰囲気下、室温から２５０℃まで１時間かけて昇温し、２５０℃から３１０℃まで１０時間かけて昇温し、３１０℃で５時間保持することにより、固相重合を行った。固相重合後、冷却して、粉末状の液晶ポリエステルを得た。この液晶ポリエステルは、全繰り返し単位の合計量に対して、Ａｒ1が２，６－ナフチレン基である繰返し単位（１）を５５モル％、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）を１７．５モル％、Ａｒ2が１，４－フェニレン基である繰返し単位（２）を５モル％、及びＡｒ3が１，４－フェニレン基である繰返し単位（３）を２２．５％有し、その流動開始温度は３３３℃であった。 Production Example 1
In a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 103.499 g (5.5 mol) of 6-hydroxy-2-naphthoic acid and 2,6-naphthalenedicarboxylic acid 378 were added. 0.33 g (1.75 mol), 83.07 g (0.5 mol) of terephthalic acid, 272.52 g of hydroquinone (2.475 mol: 0.225 based on the total amount of 2,6-naphthalenedicarboxylic acid and terephthalic acid) Molar excess), 1226.87 g (12 moles) of acetic anhydride, and 0.17 g of 1-methylimidazole as a catalyst, and after replacing the gas in the reactor with nitrogen gas, stirring at room temperature under a nitrogen gas stream To 145 ° C. over 15 minutes and refluxed at 145 ° C. for 1 hour. Next, while distilling off by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 145 ° C. to 310 ° C. over 3 hours and 30 minutes, held at 310 ° C. for 3 hours, then the contents were taken out and cooled to room temperature did. The obtained solid is pulverized to a particle size of about 0.1 to 1 mm with a pulverizer, then heated from room temperature to 250 ° C. over 1 hour in a nitrogen atmosphere, and then increased from 250 ° C. to 310 ° C. over 10 hours. Solid state polymerization was performed by warming and holding at 310 ° C. for 5 hours. After solid state polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester. In this liquid crystalline polyester, 55 mol% of the repeating unit (1) in which Ar 1 is a 2,6-naphthylene group and Ar 2 is a 2,6-naphthylene group in terms of the total amount of all repeating units ( 2) 17.5 mol%, Ar 2 is 1,4-phenylene group repeating unit (2) 5 mol%, and Ar 3 is 1,4-phenylene group repeating unit (3) 22. 5%, and the flow start temperature was 333 ° C.
攪拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１０３４．９９ｇ（５．５モル）、２，６－ナフタレンジカルボン酸３７８．３３ｇ（１．７５モル）、テレフタル酸８３．０７ｇ（０．５モル）、ヒドロキノン２７２．５２ｇ（２．４７５モル：２，６－ナフタレンジカルボン酸及びテレフタル酸の合計量に対して０．２２５モル過剰）、無水酢酸１２２６．８７ｇ（１２モル）、及び触媒として１－メチルイミダゾール０．１７ｇを入れ、反応器内のガスを窒素ガスで置換した後、窒素ガス気流下、攪拌しながら、室温から１４５℃まで１５分かけて昇温し、１４５℃で１時間還流させた。次いで、副生酢酸及び未反応の無水酢酸を留去しながら、１４５℃から３１０℃まで３時間３０分かけて昇温し、３１０℃で３時間保持した後、内容物を取り出し、室温まで冷却した。得られた固形物を、粉砕機で粒径約０．１～１ｍｍに粉砕後、窒素雰囲気下、室温から２５０℃まで１時間かけて昇温し、２５０℃から３１０℃まで１０時間かけて昇温し、３１０℃で５時間保持することにより、固相重合を行った。固相重合後、冷却して、粉末状の液晶ポリエステルを得た。この液晶ポリエステルは、全繰り返し単位の合計量に対して、Ａｒ1が２，６－ナフチレン基である繰返し単位（１）を５５モル％、Ａｒ2が２，６－ナフチレン基である繰返し単位（２）を１７．５モル％、Ａｒ2が１，４－フェニレン基である繰返し単位（２）を５モル％、及びＡｒ3が１，４－フェニレン基である繰返し単位（３）を２２．５％有し、その流動開始温度は３３３℃であった。 Production Example 1
In a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 103.499 g (5.5 mol) of 6-hydroxy-2-naphthoic acid and 2,6-naphthalenedicarboxylic acid 378 were added. 0.33 g (1.75 mol), 83.07 g (0.5 mol) of terephthalic acid, 272.52 g of hydroquinone (2.475 mol: 0.225 based on the total amount of 2,6-naphthalenedicarboxylic acid and terephthalic acid) Molar excess), 1226.87 g (12 moles) of acetic anhydride, and 0.17 g of 1-methylimidazole as a catalyst, and after replacing the gas in the reactor with nitrogen gas, stirring at room temperature under a nitrogen gas stream To 145 ° C. over 15 minutes and refluxed at 145 ° C. for 1 hour. Next, while distilling off by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 145 ° C. to 310 ° C. over 3 hours and 30 minutes, held at 310 ° C. for 3 hours, then the contents were taken out and cooled to room temperature did. The obtained solid is pulverized to a particle size of about 0.1 to 1 mm with a pulverizer, then heated from room temperature to 250 ° C. over 1 hour in a nitrogen atmosphere, and then increased from 250 ° C. to 310 ° C. over 10 hours. Solid state polymerization was performed by warming and holding at 310 ° C. for 5 hours. After solid state polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester. In this liquid crystalline polyester, 55 mol% of the repeating unit (1) in which Ar 1 is a 2,6-naphthylene group and Ar 2 is a 2,6-naphthylene group in terms of the total amount of all repeating units ( 2) 17.5 mol%, Ar 2 is 1,4-phenylene group repeating unit (2) 5 mol%, and Ar 3 is 1,4-phenylene group repeating unit (3) 22. 5%, and the flow start temperature was 333 ° C.
製造例２
製造例１と同様の反応器に、ｐ－ヒドロキシ安息香酸９１１ｇ（６．６モル）、テレフタル酸２７４ｇ（１．６５モル）、イソフタル酸９１ｇ（０．５５モル）、４，４’－ジヒドロキシビフェニル４０９ｇ（２．２モル）、無水酢酸１２３５ｇ（１２．１モル）、及び触媒として１－メチルイミダゾール０．１７ｇを入れ、反応器内のガスを窒素ガスで置換した後、窒素ガス気流下、攪拌しながら、室温から１５０℃まで１５分かけて昇温し、１５０℃で１時間還流させた。次いで、１－メチルイミダゾール１．７ｇを添加した後、副生酢酸及び未反応の無水酢酸を留去しながら、１５０℃から３２０℃まで２時間５０分かけて昇温し、トルクの上昇が認められた時点で、内容物を取り出し、室温まで冷却した。得られた固形物を、粉砕機で粒径約０．１～１ｍｍに粉砕後、窒素雰囲気下、室温から２５０℃まで１時間かけて昇温し、２５０℃から２８５℃まで５時間かけて昇温し、２８５℃で３時間保持することにより、固相重合を行った。固相重合後、冷却して、粉末状の液晶ポリエステルを得た。この液晶ポリエステルは、Ａｒ1が１，４－フェニレン基である繰返し単位（１）を６０モル％、Ａｒ2が１，４－フェニレン基である繰返し単位（２）を１５モル％、Ａｒ2が１，３－フェニレン基である繰返し単位（２）を５モル％、及びＡｒ3が４，４’－ビフェニリレン基である繰返し単位（３）を２０％有し、その流動開始温度は３２７℃であった。 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. Next, after adding 1.7 g of 1-methylimidazole, the temperature was raised from 150 ° C. to 320 ° C. over 2 hours and 50 minutes while distilling off by-product acetic acid and unreacted acetic anhydride, and an increase in torque was observed. At that time, the contents were removed and cooled to room temperature. The obtained solid is pulverized to a particle size of about 0.1 to 1 mm with a pulverizer, then heated from room temperature to 250 ° C. over 1 hour in a nitrogen atmosphere, and then increased from 250 ° C. to 285 ° C. over 5 hours. Solid state polymerization was performed by warming and holding at 285 ° C. for 3 hours. After solid state polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester. In 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.
製造例１と同様の反応器に、ｐ－ヒドロキシ安息香酸９１１ｇ（６．６モル）、テレフタル酸２７４ｇ（１．６５モル）、イソフタル酸９１ｇ（０．５５モル）、４，４’－ジヒドロキシビフェニル４０９ｇ（２．２モル）、無水酢酸１２３５ｇ（１２．１モル）、及び触媒として１－メチルイミダゾール０．１７ｇを入れ、反応器内のガスを窒素ガスで置換した後、窒素ガス気流下、攪拌しながら、室温から１５０℃まで１５分かけて昇温し、１５０℃で１時間還流させた。次いで、１－メチルイミダゾール１．７ｇを添加した後、副生酢酸及び未反応の無水酢酸を留去しながら、１５０℃から３２０℃まで２時間５０分かけて昇温し、トルクの上昇が認められた時点で、内容物を取り出し、室温まで冷却した。得られた固形物を、粉砕機で粒径約０．１～１ｍｍに粉砕後、窒素雰囲気下、室温から２５０℃まで１時間かけて昇温し、２５０℃から２８５℃まで５時間かけて昇温し、２８５℃で３時間保持することにより、固相重合を行った。固相重合後、冷却して、粉末状の液晶ポリエステルを得た。この液晶ポリエステルは、Ａｒ1が１，４－フェニレン基である繰返し単位（１）を６０モル％、Ａｒ2が１，４－フェニレン基である繰返し単位（２）を１５モル％、Ａｒ2が１，３－フェニレン基である繰返し単位（２）を５モル％、及びＡｒ3が４，４’－ビフェニリレン基である繰返し単位（３）を２０％有し、その流動開始温度は３２７℃であった。 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. Next, after adding 1.7 g of 1-methylimidazole, the temperature was raised from 150 ° C. to 320 ° C. over 2 hours and 50 minutes while distilling off by-product acetic acid and unreacted acetic anhydride, and an increase in torque was observed. At that time, the contents were removed and cooled to room temperature. The obtained solid is pulverized to a particle size of about 0.1 to 1 mm with a pulverizer, then heated from room temperature to 250 ° C. over 1 hour in a nitrogen atmosphere, and then increased from 250 ° C. to 285 ° C. over 5 hours. Solid state polymerization was performed by warming and holding at 285 ° C. for 3 hours. After solid state polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester. In 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.
実施例１
製造例１で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ２５μｍの液晶ポリエステルフィルムを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．０１１ｇ／ｍ2・２４ｈであり、太陽電池用基板として、水蒸気バリア性に優れている。 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 μm. 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.
製造例１で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ２５μｍの液晶ポリエステルフィルムを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．０１１ｇ／ｍ2・２４ｈであり、太陽電池用基板として、水蒸気バリア性に優れている。 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 μm. 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.
実施例２
製造例１で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ５０μｍの液晶ポリエステルを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．００３ｇ／ｍ2・２４ｈであり、太陽電池用基板として、水蒸気バリア性に優れている。 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 μm. 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.
製造例１で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ５０μｍの液晶ポリエステルを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．００３ｇ／ｍ2・２４ｈであり、太陽電池用基板として、水蒸気バリア性に優れている。 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 μm. 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.
実施例３
実施例２で得られた積層フィルムについてイオンプレーティング法によりガスバリア層を形成した反対面にＩＴＯ(酸化インジュウムスズ)を用いて基板温度１８０℃にて厚さ２００ｎｍ透明電極(ＩＴＯ膜)を形成した。この積層フィルム上に形成した透明電極のシート抵抗を測定したところ９．１Ω／□であった。 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 9.1Ω / □.
実施例２で得られた積層フィルムについてイオンプレーティング法によりガスバリア層を形成した反対面にＩＴＯ(酸化インジュウムスズ)を用いて基板温度１８０℃にて厚さ２００ｎｍ透明電極(ＩＴＯ膜)を形成した。この積層フィルム上に形成した透明電極のシート抵抗を測定したところ９．１Ω／□であった。 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 9.1Ω / □.
比較例１
製造例２で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ２５μｍの液晶ポリエステルフィルムを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．３４３ｇ／ｍ2・２４ｈであり、太陽電池用基板として、水蒸気バリア性が不十分である。 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 μm. 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.
製造例２で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ２５μｍの液晶ポリエステルフィルムを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．３４３ｇ／ｍ2・２４ｈであり、太陽電池用基板として、水蒸気バリア性が不十分である。 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 μm. 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.
比較例２
製造例２で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ５０μｍの液晶ポリエステルフィルムを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．０８０ｇ／ｍ2・２４ｈであり、太陽電池用基板として、水蒸気バリア性が不十分である。 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 μm. 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.
製造例２で得られた液晶ポリエステルを、二軸押出機（（株）池貝の「ＰＣＭ－３０」）で造粒し、ペレット状にした後、一軸押出機（スクリュー径５０ｍｍ）に供給して溶融させ、Ｔダイ（リップ長さ３００ｍｍ、リップクリアランス１ｍｍ、ダイ温度３５０℃）からフィルム状に押し出して冷却し、厚さ５０μｍの液晶ポリエステルフィルムを得た。この液晶ポリエステルフィルムの水蒸気透過度は、０．０８０ｇ／ｍ2・２４ｈであり、太陽電池用基板として、水蒸気バリア性が不十分である。 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 μm. 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.
比較例３
比較例２で得られた積層フィルムについてイオンプレーティング法によりガスバリア層を形成した反対面にＩＴＯ(酸化インジュウムスズ)を用いて基板温度１８０℃にて厚さ２００ｎｍ透明電極を形成した。この積層フィルム上に形成した透明電極のシート抵抗を測定したところ１２．３Ω／□であった。 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 12.3Ω / □.
比較例２で得られた積層フィルムについてイオンプレーティング法によりガスバリア層を形成した反対面にＩＴＯ(酸化インジュウムスズ)を用いて基板温度１８０℃にて厚さ２００ｎｍ透明電極を形成した。この積層フィルム上に形成した透明電極のシート抵抗を測定したところ１２．３Ω／□であった。 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 12.3Ω / □.
１・・・太陽電池用基板、２・・・裏面電極層、３・・・光電変換層、
３ａ・・・ｐ型半導体層、３ｂ・・・ｉ型半導体層、３ｃ・・・ｎ型半導体層、
４・・・表面電極層、５・・・太陽電池素子、
６・・・表面保護シート、７・・・封止層、８・・・バックシート、
９・・・フレーム、１０・・・太陽電池モジュール。 DESCRIPTION OF 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.
３ａ・・・ｐ型半導体層、３ｂ・・・ｉ型半導体層、３ｃ・・・ｎ型半導体層、
４・・・表面電極層、５・・・太陽電池素子、
６・・・表面保護シート、７・・・封止層、８・・・バックシート、
９・・・フレーム、１０・・・太陽電池モジュール。 DESCRIPTION OF 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.
Claims (6)
- 下記式（１）で表される繰返し単位と、下記式（２）で表される繰返し単位と、下記式（３）で表される繰返し単位とを有し、２，６－ナフチレン基を含む繰返し単位の含有量が、全繰返し単位の合計量に対して、４０モル％以上である液晶ポリエステルから構成される太陽電池用基板。
－Ｏ－Ａｒ1－ＣＯ－ （１）
－ＣＯ－Ａｒ2－ＣＯ－ （２）
－Ｏ－Ａｒ3－Ｏ－ （３）
（Ａｒ1は、２，６－ナフチレン基、１，４－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ2及びＡｒ3は、それぞれ独立に、２，６－ナフチレン基、１，４－フェニレン基、１，３－フェニレン基又は４，４’－ビフェニリレン基を表す。Ａｒ1、Ａｒ2又はＡｒ3で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。） It has 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), and includes a 2,6-naphthylene group. A solar cell substrate comprising a liquid crystal polyester having a repeating unit content of 40 mol% or more based on the total amount of all repeating units.
—O—Ar 1 —CO— (1)
—CO—Ar 2 —CO— (2)
—O—Ar 3 —O— (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 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.) - 温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が０．０５ｇ／ｍ2・２４ｈ以下である請求項１に記載の太陽電池用基板。 The substrate for solar cells according to claim 1, wherein the water vapor permeability measured at a temperature of 40 ° C and a relative humidity of 90% is 0.05 g / m 2 · 24 h or less.
- 温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が０．００５ｇ／ｍ2・２４ｈ以下である液晶ポリエステルから構成される太陽電池用基板。 A substrate for a solar cell comprising 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%.
- 厚さ５０μｍのフィルムにしたときの温度４０℃及び相対湿度９０％にて測定される水蒸気透過度が０．００５ｇ／ｍ2・２４ｈ以下である液晶ポリエステルから構成される太陽電池用基板。 A solar cell substrate comprising a liquid crystalline 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 μm is formed.
- 前記液晶ポリエステルから構成される層の少なくとも一方の面上に、水蒸気バリア層が設けられてなる請求項１～４のいずれかに記載の太陽電池用基板。 The solar cell substrate according to any one of claims 1 to 4, wherein a water vapor barrier layer is provided on at least one surface of the layer composed of the liquid crystalline polyester.
- 請求項１～４のいずれかに記載の太陽電池用基板上に、裏面電極層、光電変換層及び表面電極層がこの順に設けられてなる太陽電池素子。 A solar cell element comprising a back electrode layer, a photoelectric conversion layer, and a front electrode layer provided in this order on the solar cell substrate according to any one of claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-030910 | 2011-02-16 | ||
| JP2011030910 | 2011-02-16 |
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| WO2012111660A1 true WO2012111660A1 (en) | 2012-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2012/053385 WO2012111660A1 (en) | 2011-02-16 | 2012-02-14 | Solar cell substrate, and solar cell element |
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|---|---|
| JP (1) | JP2012186453A (en) |
| TW (1) | TW201245323A (en) |
| WO (1) | WO2012111660A1 (en) |
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| TWI740515B (en) | 2019-12-23 | 2021-09-21 | 長春人造樹脂廠股份有限公司 | Liquid crystal polymer film and laminate comprising the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004140143A (en) * | 2002-10-17 | 2004-05-13 | National Institute Of Advanced Industrial & Technology | Substrate for solar cell and solar cell |
| JP2007154169A (en) * | 2005-11-08 | 2007-06-21 | Sumitomo Chemical Co Ltd | Liquid crystal polyester resin composition and molded product for electronic part |
| JP2010135782A (en) * | 2008-11-10 | 2010-06-17 | Sumitomo Chemical Co Ltd | Solar cell |
| JP2010141156A (en) * | 2008-12-12 | 2010-06-24 | Sekisui Chem Co Ltd | Solar battery module |
| WO2011021543A1 (en) * | 2009-08-17 | 2011-02-24 | 住友化学株式会社 | Back sheet for solar cell, and solar cell module |
-
2012
- 2012-02-09 JP JP2012026032A patent/JP2012186453A/en active Pending
- 2012-02-14 WO PCT/JP2012/053385 patent/WO2012111660A1/en active Application Filing
- 2012-02-14 TW TW101104722A patent/TW201245323A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004140143A (en) * | 2002-10-17 | 2004-05-13 | National Institute Of Advanced Industrial & Technology | Substrate for solar cell and solar cell |
| JP2007154169A (en) * | 2005-11-08 | 2007-06-21 | Sumitomo Chemical Co Ltd | Liquid crystal polyester resin composition and molded product for electronic part |
| JP2010135782A (en) * | 2008-11-10 | 2010-06-17 | Sumitomo Chemical Co Ltd | Solar cell |
| JP2010141156A (en) * | 2008-12-12 | 2010-06-24 | Sekisui Chem Co Ltd | Solar battery module |
| WO2011021543A1 (en) * | 2009-08-17 | 2011-02-24 | 住友化学株式会社 | Back sheet for solar cell, and solar cell module |
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| TW201245323A (en) | 2012-11-16 |
| JP2012186453A (en) | 2012-09-27 |
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