WO2009154252A1 - フッ素樹脂フィルムの改質方法 - Google Patents
フッ素樹脂フィルムの改質方法 Download PDFInfo
- Publication number
- WO2009154252A1 WO2009154252A1 PCT/JP2009/061111 JP2009061111W WO2009154252A1 WO 2009154252 A1 WO2009154252 A1 WO 2009154252A1 JP 2009061111 W JP2009061111 W JP 2009061111W WO 2009154252 A1 WO2009154252 A1 WO 2009154252A1
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- WO
- WIPO (PCT)
- Prior art keywords
- fluororesin film
- gas
- film
- group
- modifying
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 17
- 239000011737 fluorine Substances 0.000 title claims abstract description 17
- 239000011347 resin Substances 0.000 title claims abstract description 15
- 229920005989 resin Polymers 0.000 title claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 87
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 18
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 13
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 16
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- -1 polychlorotrifluoroethylene Polymers 0.000 claims description 8
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 7
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 7
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920001780 ECTFE Polymers 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920005615 natural polymer Polymers 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- SYNPRNNJJLRHTI-UHFFFAOYSA-N 2-(hydroxymethyl)butane-1,4-diol Chemical compound OCCC(CO)CO SYNPRNNJJLRHTI-UHFFFAOYSA-N 0.000 description 2
- NJNWCIAPVGRBHO-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-[(oxo-$l^{5}-phosphanylidyne)methyl]azanium Chemical group OCC[N+](C)(C)C#P=O NJNWCIAPVGRBHO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000002346 iodo group Chemical group I* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- BEEJMIJJLULTNC-VIFPVBQESA-N CCC[C@H](C)CCCC[IH]N Chemical compound CCC[C@H](C)CCCC[IH]N BEEJMIJJLULTNC-VIFPVBQESA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- TWMKXPBVMFGBRH-UHFFFAOYSA-N methanol;terephthalic acid Chemical compound OC.OC.OC(=O)C1=CC=C(C(O)=O)C=C1 TWMKXPBVMFGBRH-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
Definitions
- the present invention relates to a method for modifying a fluororesin film that imparts hydrophilicity to the surface of the fluororesin film.
- a fluororesin film such as a polyvinyl fluoride (PVF) film, an aluminum foil laminate, polyethylene terephthalate (PET) subjected to aluminum vapor deposition or Si vapor deposition for improving weather resistance and gas barrier properties.
- PVF polyvinyl fluoride
- PET polyethylene terephthalate
- Si Si vapor deposition for improving weather resistance and gas barrier properties.
- a fluororesin film is excellent from the viewpoint of long-term durability. Therefore, the demand as a back sheet material is increasing.
- a material made of a fluororesin having a C—F bond has a problem in that its surface energy is small and water and oil repellency are exhibited, so that adhesion is low.
- Examples of techniques for improving the adhesiveness of such a fluororesin film include plasma discharge treatment, corona discharge treatment, and flame treatment. These surface modification technologies improve the adhesion by introducing hydrophilic functional groups (eg, —COOH group, —OH group, SO 3 H group, SO 2 F X group, etc.) on the resin surface. is doing.
- hydrophilic functional groups eg, —COOH group, —OH group, SO 3 H group, SO 2 F X group, etc.
- the processing method requires a large-scale apparatus and increases the manufacturing cost. Further, there is a problem that the deterioration with time after the surface modification is severe and the adhesion performance cannot be maintained for a long time.
- Patent Document 1 a synthetic or natural polymer material having a specific gravity of 1.6 or less and containing no ether bond, carbonate bond, amide bond, or urethane bond is selected.
- a surface modification method is described in which a mixed gas composed of a fluorine gas and one kind of gas containing an oxygen element is brought into contact with a natural polymer material, thereby imparting hydrophilicity.
- the contact angle with respect to water on the surface of a synthetic polymer or natural polymer material is reduced by 10 degrees or more by the surface modification method.
- the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a method for modifying a fluororesin film that is simple in a short time and is less likely to cause hydrophilic deterioration with time. Moreover, it is providing the solar cell backsheet provided with the fluororesin film obtained by the modification
- the inventors of the present application have examined a method for modifying a fluororesin film and a back sheet for a solar cell in order to solve the conventional problems. As a result, the inventors have found that the object can be achieved by adopting the following configuration, and have completed the present invention.
- the method for modifying a fluororesin film according to the present invention includes a gas containing fluorine atoms and at least one of a gas containing oxygen atoms or an inert gas. It is characterized in that hydrophilicity is imparted to the surface of the fluororesin film by bringing the processing gas contained therein into contact.
- the manufacturing cost is suppressed by bringing the fluorine resin film surface into contact with a treatment gas containing a gas containing fluorine atoms and at least one of a gas containing oxygen atoms or an inert gas.
- a treatment gas containing a gas containing fluorine atoms and at least one of a gas containing oxygen atoms or an inert gas can be easily performed in a short time.
- the hydrophilicity-dependent fluororesin film can also reduce the hydrophilic deterioration with time by the said method.
- the fluororesin film is made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene ( PCTFE), ethylene-chlorotrifluoroethylene copolymer (ETFFE), or ethylene-tetrafluoroethylene copolymer (ETFE).
- PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
- PVDF polyvinylidene fluoride
- PVF polyvinyl fluoride
- PCTFE polychlorotrifluoroethylene
- ETFFE ethylene-chlorotrifluoroethylene copolymer
- ETFE ethylene-tetrafluoroethylene copolymer
- the fluororesin film preferably contains an additive that is reactive with the processing gas.
- hydrophilicity on the surface of the fluororesin film is promoted by adding an additive that is reactive to the processing gas in the fluororesin film. Thereby, it becomes possible to perform a hydrophilic treatment more effectively.
- the content of the additive is preferably in the range of 0.1 to 90% by weight with respect to the total weight of the fluororesin film.
- the solar cell backsheet according to the present invention has a structure in which the fluororesin film described above is bonded to both surfaces of a base film via an adhesive in order to solve the above-described problems.
- the fluororesin film described above is imparted with hydrophilicity, it has excellent adhesive adhesion. Therefore, the said fluororesin film can be bonded together on both surfaces of a base film, and this laminated body can be used as a back sheet for solar cells. Further, the hydrophilicity imparted by the treatment can maintain its performance over a long period of time, so that it is excellent in terms of process management, and the reliability of the product can be improved.
- the present invention has the following effects by the means described above. That is, according to the present invention, the manufacturing cost is reduced by bringing the fluorine resin film surface into contact with a treatment gas containing a gas containing fluorine atoms and at least one of a gas containing oxygen atoms or an inert gas. Since the hydrophilic treatment can be easily performed in a short time while suppressing, the production efficiency can be improved. Moreover, the fluororesin film obtained by the said method can be applied suitably for the back seat
- the method for modifying a fluororesin film according to the present embodiment includes a fluororesin film that has a relatively low critical surface tension and is difficult to wet, and includes a gas containing fluorine atoms, a gas containing oxygen atoms, or an inert gas. Hydrophilization is performed by contacting a processing gas containing either of them.
- a fluororesin having a critical surface tension of 18 mN / m or more, preferably 20 mN / m or more, before the hydrophilic treatment is preferable to use. If the critical surface tension before treatment is less than 18 mN / m, there is a disadvantage that sufficient hydrophilicity cannot be imparted.
- the hydrophilization of the fluororesin film is preferably performed so that the critical surface tension of the surface is 25 mN / m or more, preferably 30 mN / m or more, more preferably 35 mN / m or more. If the critical surface tension is less than 25 mN / m, the hydrophilicity becomes insufficient and the adhesiveness with the adhesive is lowered, which is not preferable.
- the fluororesin film may be a single layer or a laminated structure in which at least two films are laminated. Further, the thickness of the fluororesin film (total thickness in the case of a laminated structure) is not particularly limited, and is preferably in the range of 10 to 100 ⁇ m, for example. Furthermore, the planar shape of the fluororesin film is not particularly limited, and can be set as necessary.
- the constituent material of the fluororesin film should have at least one of a nitrogen-containing group, a silicon-containing group, an oxygen-containing group, a phosphorus-containing group, a sulfur-containing group, a hydrocarbon group, and a halogen-containing group in its molecular structure.
- a nitrogen-containing group include an amide group and an amino group.
- the silicon-containing group include a trialkylsilyl group, a silyl ether group, a —Si (CH 3 ) 2 O— group, and the like.
- the oxygen-containing group include an ester group, a carbonate group, and an ether group.
- the phosphorus-containing group include a phosphorylcholine group.
- Examples of the sulfur-containing group include a sulfo group and a sulfonyl group.
- Examples of the hydrocarbon group include a methyl group, a methylene group, and a phenyl group.
- As the halogen-containing group for example, —CHX— group, —CHX 2 group, —CX 2 — group, —CX 3 group (X is at least selected from the group consisting of F atom, Cl atom, Br atom and I atom) Any one kind.) Etc. are mentioned.
- tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer PFA
- PVDF polyvinylidene fluoride
- PVF polyvinyl fluoride
- PCTFE polychlorotrifluoroethylene
- EDFFE ethylene copolymer
- ETFE ethylene-tetrafluoroethylene copolymer
- the constituent materials of the film on the front surface side and the film on the back surface side may be the same or different from each other.
- the degree of hydrophilicity can be made different between the film on the front surface and the film on the back surface, even if the hydrophilic treatment is performed under the same conditions.
- an additive exhibiting reactivity with the processing gas is added to the fluororesin film.
- the hydrophilization can be further promoted with respect to the hydrophilization treatment by the processing gas.
- the composition ratio of the additives on the front side film and the back side film may be the same or different from each other.
- the composition ratio of the additives it is possible to vary the value of the critical surface tension between the film on the front surface side and the film on the back surface side, despite the hydrophilic treatment under the same processing conditions. That is, the hydrophilicity can be further improved on the side of the film where the amount of the additive is larger even under the same processing conditions.
- the additives are classified into organic additives and inorganic additives.
- a resin component other than the polymer compound exemplified as the constituent material of the fluororesin film and having a functional group reactive to the processing gas in the molecular structure is preferable.
- the gas containing fluorine atoms reacts with the reactive functional group, so that the fluorination treatment can be promoted.
- the hydrophilicity can be further improved.
- Examples of functional groups that are reactive with the processing gas include nitrogen-containing groups, silicon-containing groups, oxygen-containing groups, phosphorus-containing groups, sulfur-containing groups, hydrocarbon groups, and halogen-containing groups.
- Examples of the nitrogen-containing group include an amide group and an amino group.
- Examples of the silicon-containing group include a trialkylsilyl group, a silyl ether group, and a —Si (CH 3 ) 2 O— group.
- Examples of the oxygen-containing group include an ester group, a carbonate group, and an ether group.
- Examples of the phosphorus-containing group include a phosphorylcholine group.
- Examples of the sulfur-containing group include a sulfo group and a sulfonyl group.
- hydrocarbon group examples include a methyl group, a methylene group, and a phenyl group.
- halogen-containing group for example, —CHX— group, —CHX 2 group, —CX 2 — group, —CX 3 group (X is at least selected from the group consisting of F atom, Cl atom, Br atom and I atom) Any one kind.) Etc. are mentioned.
- the resin component is, for example, polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexane dimethanol terephthalate (PCT), polycarbonate. (PC), polyolefin and the like.
- PMMA polymethyl methacrylate
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- PCT polycyclohexane dimethanol terephthalate
- PC polycarbonate.
- PC polyolefin and the like.
- the inorganic additive is not particularly limited, and examples thereof include white pigments such as titanium oxide and calcium carbonate, and black pigments such as carbon black. These inorganic additives may be used alone or in combination of two or more. Furthermore, you may use together an organic additive and an inorganic additive.
- the addition amount of the additive is not particularly limited, and is preferably in the range of 0.1 to 90% by weight, and preferably in the range of 0.1 to 80% by weight with respect to the total weight of the fluororesin film. Is more preferable.
- the addition amount is less than 0.1% by weight, for example, sufficient hydrophilicity may not be obtained even when a hydrophilic treatment is performed.
- the addition amount exceeds 90% by weight, there is a disadvantage that the performance of the fluororesin itself cannot be maintained.
- the processing gas is not particularly limited as long as it contains a gas containing fluorine atoms and at least one of a gas containing oxygen atoms or an inert gas.
- the gas containing fluorine atoms is not particularly limited.
- the method for modifying a fluororesin film of the present invention can perform the gas containing fluorine atoms in a concentration range of 0.001 to 99% by volume with respect to the total volume of the processing gas.
- the concentration of the gas containing fluorine atoms is large, the fluororesin film that is the object to be processed may be damaged. Therefore, it is preferable that the gas has a low concentration, specifically, for example, 0.001 to 50% by volume, and more preferably 0.001 to 10% by volume.
- oxygen (O 2) gas and sulfur dioxide gas (SO 2) include carbonyl fluoride (COF 2), and the like. These gases may be used alone or in combination of two or more.
- the gas containing oxygen atoms can be performed in a concentration range of 0.001 to 99% by volume with respect to the total volume of the processing gas.
- the gas has a low concentration from the viewpoint of processing cost, and specifically, it is, for example, 0.01 to 50% by volume, more preferably 0.1 to 20% by volume.
- the processing gas may be mixed with an inert gas such as dry air, nitrogen, argon, helium, neon, krypton, or xenon for dilution.
- an inert gas such as dry air, nitrogen, argon, helium, neon, krypton, or xenon for dilution.
- the method for modifying a fluororesin film of the present invention can be performed using, for example, the reaction apparatus shown in FIG. First, a reaction container 4 for hydrophilizing the fluororesin film is prepared, and the fluororesin film 5 is placed in the reaction container 4. It does not specifically limit as the reaction container 4, For example, things made from stainless steel, aluminum, or nickel can be used.
- the valve of the vacuum line 7 is opened and evacuated, and after reaching a predetermined pressure (for example, 10 Pa), the valve of the vacuum line 7 is closed.
- a predetermined pressure for example, 10 Pa
- the valves of the first supply line 1 for supplying a gas containing fluorine atoms, the second supply line 2 for supplying a gas containing oxygen atoms, and the third supply line 3 for supplying an inert gas are provided.
- the stopper is appropriately opened as necessary, and a processing gas adjusted to a predetermined concentration is introduced into the reaction vessel 4.
- the critical surface tension of the fluororesin film 5 after the hydrophilic treatment can be controlled by appropriately setting the concentration of the processing gas, the processing time, the processing temperature, and the gas flow rate as necessary.
- the reaction may be performed while continuously supplying the processing gas under normal pressure, increased pressure, or reduced pressure, or may be performed under atmospheric pressure, under pressure, or under reduced pressure.
- the concentration of the gas containing fluorine atoms in the processing gas can be adjusted by the amount of gas supplied from each of the first supply line 1 to the third supply line 3.
- the treatment time of the hydrophilization treatment is not particularly limited, but the reaction between the fluororesin and the treatment gas occurs explosively in the initial reaction. Therefore, the effect of hydrophilization can be obtained by a relatively short treatment. Specifically, for example, it is in the range of 1 second to 600 minutes, preferably 1 second to 100 minutes, more preferably 1 second to 30 minutes. If the treatment time is less than 1 second, sufficient hydrophilicity may not be imparted to the fluororesin film 5 in some cases.
- the treatment temperature of the hydrophilization treatment is not particularly limited, but is within the range of ⁇ 50 ° C. to 150 ° C. in consideration of the heat resistant temperature of the fluororesin film 5 (heat resistant temperature when an additive is added). It is preferably 0 ° C. to 100 ° C. If the treatment temperature is less than ⁇ 50 ° C., sufficient hydrophilicity may not be imparted to the fluororesin film 5 in some cases. On the other hand, when the treatment temperature exceeds 150 ° C., the fluororesin film 5 may be thermally deformed, and the yield may be reduced.
- the gas flow rate of the processing gas flowing inside the reaction vessel 4 is not particularly limited, but if the gas flow rate is fast, the reaction may occur explosively. For this reason, it is important to appropriately set the concentration and flow rate of the fluorinated gas at the initial stage of the reaction. That is, the concentration and flow rate may be appropriately increased or decreased depending on the progress of the reaction. Further, the gas flow rate may be appropriately set according to the size of the reaction vessel 4 and the shape of the fluororesin film 5.
- the valve of the third supply line 3 is opened to introduce an inert gas, and the treatment gas in the reaction vessel 4 is replaced with an inert gas at a predetermined flow rate.
- the valve of the exhaust line 6 is also opened. Thereafter, the valves of the third supply line 3 and the exhaust line 6 are closed and the valve of the vacuum line 7 is opened, and the reaction vessel 4 is evacuated to a predetermined pressure (for example, 10 Pa) or less.
- valve of the vacuum line 7 is closed, the valve of the third supply line 3 is opened, and the inert gas is introduced to atmospheric pressure.
- the valve of the exhaust line 6 is opened, and the hydrofluorinated fluororesin film 5 is taken out.
- the hydrophilized fluororesin film taken out from the reaction vessel 4 can be washed with a washing liquid such as water or alcohol. Thereby, unreacted F 2 adsorbed on the surface of the fluororesin film and HF generated by the reaction can be removed, and a hydrophilic surface excellent in stability can be formed.
- the fluororesin film obtained by the hydrophilic treatment as described above can be suitably applied to, for example, a solar cell backsheet.
- a solar cell backsheet for example, an embodiment as shown in FIG. 2 is possible. That is, the fluororesin film 8 according to the present invention is bonded to both surfaces of the base film 9 via an adhesive.
- the adhesiveness with the adhesive is good, and therefore peeling due to deterioration with time can be prevented. Since the laminated film thus produced has a gas barrier property against water vapor, oxygen gas, etc., it is possible to produce a solar cell backsheet having excellent reliability.
- the adhesive is not particularly limited, and for example, a urethane adhesive, an epoxy adhesive, or the like can be used. It is also possible to use a pressure sensitive adhesive (adhesive).
- the pressure sensitive adhesive is not particularly limited, and for example, an acrylic pressure sensitive adhesive, a rubber pressure sensitive adhesive, a urethane pressure sensitive adhesive or the like can be used.
- Example 1 First, as shown in FIG. 1, a PVDF film (manufactured by Nichias Co., Ltd., trade name: Naflon; thickness 2 mm) was introduced into the reaction vessel 4 as the fluororesin film 5. Next, the valve of the vacuum line 7 was opened and the pressure was reduced until the inside of the reaction vessel 4 became 10 Pa or less.
- a PVDF film manufactured by Nichias Co., Ltd., trade name: Naflon; thickness 2 mm
- the valve of the vacuum line 7 is closed, and the valves of the first supply line 1 for supplying the gas containing fluorine atoms and the second supply line 2 for supplying the gas containing oxygen atoms are opened at the same time.
- Oxygen gas / nitrogen gas 5: 95: 0 (volume ratio)
- a processing gas adjusted to a total flow rate of 1.0 L / min was introduced into the reaction vessel 4 to atmospheric pressure.
- the valves of the first supply line 1 and the second supply line 2 were closed at the same time, the inside of the reaction vessel was sealed, and kept for 5 minutes.
- the temperature in the reaction vessel 4 was maintained at 30 ° C.
- the valves of the third supply line 3 and the exhaust line 6 for supplying an inert gas are opened, and a mixed gas of fluorine gas / oxygen gas / nitrogen gas in the reaction vessel 4 at a flow rate of 10 L / min. was replaced with nitrogen gas. Thereafter, the valves of the third supply line 3 and the exhaust line 6 were closed, the valve of the vacuum line 7 was opened, and the pressure in the reaction vessel was reduced to 10 Pa or less.
- valve of the vacuum line 7 was closed, the valve of the third supply line 3 was opened, and nitrogen gas was introduced into the reaction vessel 4 at a flow rate of 1.0 L / min to atmospheric pressure.
- the valve of the exhaust line 6 was opened, and the PVDF film after the hydrophilic treatment was taken out.
- the PVDF film taken out was washed with stirring at room temperature by UPW (ultra pure water) for 1 hour. After cleaning, the surface UPW was blown with nitrogen gas, and then dried under reduced pressure at room temperature to 10 Pa or less.
- the contact angle ( ⁇ ) of the dried PVDF film was measured using a Drop Master 300 manufactured by Kyowa Interface Science Co., Ltd.
- Example 2 In this example, a hydrophilization treatment was performed in the same manner as in Example 1 except that a PVF film (manufactured by DuPont, trade name: Tedlar) was used as the fluororesin film. was calculated.
- a PVF film manufactured by DuPont, trade name: Tedlar
- Example 3 In this example, a hydrophilization treatment was performed in the same manner as in Example 1 except that a PFA film (company name: Nichias Co., Ltd., trade name: Naflon) was used as the fluororesin film. The critical surface tension was calculated.
- a PFA film company name: Nichias Co., Ltd., trade name: Naflon
- Example 4 In this example, a hydrophilization treatment was performed in the same manner as in Example 1 except that a PCTFE film (Company name: Yodogawa Hutech Co., Ltd., trade name: Yodoflon) was used as the fluororesin film. Thereafter, the critical surface tension was calculated.
- a PCTFE film Company name: Yodogawa Hutech Co., Ltd., trade name: Yodoflon
- Example 5 In this example, a hydrophilization treatment was performed in the same manner as in Example 1 except that an ETFE film (company name: Yodogawa Hutec Co., Ltd., trade name: Yodoflon) was used as the fluororesin film. Thereafter, the critical surface tension was calculated.
- an ETFE film company name: Yodogawa Hutec Co., Ltd., trade name: Yodoflon
- the critical surface tension was calculated.
- the processing gas is supplied into the reaction vessel 4 by closing the valves of the vacuum line 7 and the valves of the first supply line 1 for supplying gas containing fluorine atoms and the third supply line 3 for supplying nitrogen gas.
- the plug was opened and the second supply line 2 for supplying a gas containing oxygen atoms was closed.
- Example 9 In this example, a hydrophilization treatment was performed in the same manner as in Example 8 except that a PVF film (manufactured by DuPont, trade name: Tedlar) was used as the fluororesin film. was calculated.
- a PVF film manufactured by DuPont, trade name: Tedlar
- Example 10 In this example, the hydrophilization treatment was performed in the same manner as in Example 1 except that the treatment time was 0.5 minutes and the temperature inside the reaction vessel 4 was changed to 100 ° C. The tension was calculated.
- Example 11 In this example, a hydrophilization treatment was performed in the same manner as in Example 10 except that a PVF film (manufactured by DuPont, trade name: Tedlar) was used as the fluororesin film. was calculated.
- a PVF film manufactured by DuPont, trade name: Tedlar
- the processing gas is supplied into the reaction vessel 4 by closing the valve of the vacuum line 7, the first supply line 1 for supplying a gas containing fluorine atoms, the second supply line 2 for supplying oxygen gas, and nitrogen gas.
- the valve of the 3rd supply line 3 which supplies was opened at the same time.
- Example 13 In this example, a hydrophilization treatment was performed in the same manner as in Example 12 except that a PVF film (manufactured by DuPont, trade name: Tedlar) was used as the fluororesin film. was calculated.
- a PVF film manufactured by DuPont, trade name: Tedlar
- Example 14 In this example, the hydrophilization treatment was performed in the same manner as in Example 2 except that a PVF film containing 30% by weight of PMMA was added to the total weight of the fluororesin film. Thereafter, the critical surface tension was calculated.
- Example 15 In this example, a PVDF film added with PMMA (polymethyl methacrylate) having a content of 30% by weight based on the total weight of the fluororesin film was used. Further, the treatment time was 5 minutes, and the temperature inside the reaction vessel 4 was changed to 30 ° C. Otherwise, the hydrophilic treatment was performed in the same manner as in Example 12, and then the critical surface tension was calculated.
- PMMA polymethyl methacrylate
- Example 16 In this example, the hydrophilization treatment was performed in the same manner as in Example 15 except that a PVDF film containing 90% by weight of PMMA was added to the total weight of the fluororesin film. Thereafter, the critical surface tension was calculated.
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Abstract
Description
即ち、本発明によれば、フッ素樹脂フィルム表面に、フッ素原子を含むガスと、酸素原子を含むガス又は不活性ガスの少なくとも何れか一方とを含有する処理ガスを接触させることにより、製造コストを抑制しつつ、短時間で簡易に親水化処理を行うことができるので、製造効率の向上が図れる。また、当該方法により得られたフッ素樹脂フィルムは、例えば、太陽電池用のバックシートに好適に適用することができる。
次に、必要に応じて、フッ素原子を含むガスを供給する第1供給ライン1、酸素原子を含むガスを供給する第2供給ライン2、不活性ガスを供給する第3供給ライン3の弁を適宜必要に応じて開栓し、所定濃度に調整した処理ガスを反応容器4に導入する。
先ず、図1に示すように、フッ素樹脂フィルム5としてPVDFフィルム(ニチアス(株)製、商品名;ナフロン;厚み2mm)を反応容器4に導入した。次に、真空ライン7の弁を開栓して、反応容器4内が10Pa以下になるまで減圧にした。
本実施例に於いては、フッ素樹脂フィルムとして、PVFフィルム(デュポン社製、商品名;テドラー)を用いたこと以外は、実施例1と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、フッ素樹脂フィルムとして、PFAフィルム(会社名;ニチアス(株)、商品名;ナフロン)を用いたこと以外は、実施例1と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、フッ素樹脂フィルムとして、PCTFEフィルム(会社名;淀川ヒューテック(株)、商品名;ヨドフロン)を用いたこと以外は、実施例1と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、フッ素樹脂フィルムとして、ETFEフィルム(会社名;淀川ヒューテック(株)、商品名;ヨドフロン)を用いたこと以外は、実施例1と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、処理ガスとして、フッ素ガス/二酸化硫黄ガス/窒素ガス=5:95:0(体積比)にした以外は、実施例1と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、処理ガスとして、フッ素ガス/フッ化カルボニルガス/窒素ガス=5:95:0(体積比)にした以外は、実施例1と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、処理ガスとして、フッ素ガス/窒素ガス=0.001:99.999(体積比)を用いたこと以外は、実施例1と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。尚、反応容器4内部への処理ガスの供給は、真空ライン7の弁を閉栓し、フッ素原子を含むガスを供給する第1供給ライン1及び窒素ガスを供給する第3供給ライン3の弁を同時に開栓し、更に、酸素原子を含むガスを供給する第2供給ライン2を閉栓して行った。
本実施例に於いては、フッ素樹脂フィルムとして、PVFフィルム(デュポン社製、商品名;テドラー)を用いたこと以外は、実施例8と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、処理時間を0.5分間とし、反応容器4内部の温度を100℃に変更したこと以外は、実施例1と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、フッ素樹脂フィルムとして、PVFフィルム(デュポン社製、商品名;テドラー)を用いたこと以外は、実施例10と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、処理ガスとしてフッ素ガス/酸素ガス/窒素ガス=0.5:20:79.5(体積比)を用い、処理時間を1分間、反応容器4内部の温度を50℃に変更したこと以外は、実施例1と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。尚、反応容器4内部への処理ガスの供給は、真空ライン7の弁を閉栓し、フッ素原子を含むガスを供給する第1供給ライン1、酸素ガスを供給する第2供給ライン2及び窒素ガスを供給する第3供給ライン3の弁を同時に開栓して行った。
本実施例に於いては、フッ素樹脂フィルムとして、PVFフィルム(デュポン社製、商品名;テドラー)を用いたこと以外は、実施例12と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、フッ素樹脂フィルムとして、その全重量に対し含有量が30重量%のPMMAを添加したPVFフィルムを用いたこと以外は、実施例2と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
本実施例に於いては、フッ素樹脂フィルムとして、その全重量に対し含有量が30重量%のPMMA(ポリメタクリル酸メチル)を添加したPVDFフィルムを用いた。また、処理時間を5分間とし、反応容器4内部の温度を30℃に変更した。それ以外は、実施例12と同様にして親水化処理を行い、その後、臨界表面張力の算出を行った。
2 第2供給ライン
3 第3供給ライン
4 反応容器
5 フッ素樹脂フィルム
6 排気ライン
7 真空ライン
8 フッ素樹脂フィルム
9 基材フィルム
Claims (5)
- フッ素樹脂フィルムに、フッ素原子を含むガスと、酸素原子を含むガス又は不活性ガスの少なくとも何れか一方とを含有する処理ガスを接触させることにより、当該フッ素樹脂フィルムの表面に親水性を付与するフッ素樹脂フィルムの改質方法。
- 前記フッ素樹脂フィルムが、テトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体(PFA)、ポリフッ化ビニリデン(PVDF)、ポリフッ化ビニル(PVF)、ポリクロロトリフルオロエチレン(PCTFE)、エチレン-クロロトリフルオロエチレン共重合体(ETCFE)、又はエチレン-テトラフルオロエチレン共重合体(ETFE)からなる請求項1に記載のフッ素樹脂フィルムの改質方法。
- 前記フッ素樹脂フィルム中には、前記処理ガスに対し反応性を示す添加剤が含まれている請求項1又は2に記載のフッ素樹脂フィルムの改質方法。
- 前記添加剤の含有量は、フッ素樹脂フィルムの全重量に対し0.1~90重量%の範囲内である請求項3に記載のフッ素樹脂フィルムの改質方法。
- 請求項1~4の何れか1項に記載のフッ素樹脂フィルムを、基材フィルムの両面に接着剤を介して貼り合わせた構造の太陽電池用バックシート。
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EP09766700.0A EP2292682B1 (en) | 2008-06-19 | 2009-06-18 | Method for modifying fluorine resin film |
US12/992,961 US11548993B2 (en) | 2008-06-19 | 2009-06-18 | Method for modifying fluoring resin film |
CN2009801229091A CN102066470B (zh) | 2008-06-19 | 2009-06-18 | 氟树脂膜的改性方法 |
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EP (1) | EP2292682B1 (ja) |
JP (1) | JP5582729B2 (ja) |
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WO2010140603A1 (ja) * | 2009-06-04 | 2010-12-09 | ステラケミファ株式会社 | 積層フィルムの製造方法 |
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JP5934978B2 (ja) * | 2012-04-23 | 2016-06-15 | パナソニックIpマネジメント株式会社 | 太陽電池モジュール |
KR101604283B1 (ko) * | 2014-12-08 | 2016-03-17 | 엘에스산전 주식회사 | 태양전지 모듈 |
CN107540777B (zh) * | 2016-06-23 | 2020-06-09 | 浙江省化工研究院有限公司 | 一种改性聚三氟氯乙烯树脂、其制备方法及应用 |
KR102515102B1 (ko) | 2017-10-24 | 2023-03-27 | 삼성에스디아이 주식회사 | 이차 전지용 외장재 및 이를 포함하는 이차 전지 |
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EP2292682A1 (en) | 2011-03-09 |
EP2292682A4 (en) | 2013-04-03 |
JP2010024446A (ja) | 2010-02-04 |
JP5582729B2 (ja) | 2014-09-03 |
CN102066470A (zh) | 2011-05-18 |
US11548993B2 (en) | 2023-01-10 |
EP2292682B1 (en) | 2017-09-13 |
US20110086230A1 (en) | 2011-04-14 |
CN102066470B (zh) | 2013-12-04 |
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