JP4959911B2 - Fluororesin film and laminate containing layer of the film - Google Patents
Fluororesin film and laminate containing layer of the film Download PDFInfo
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- JP4959911B2 JP4959911B2 JP2003270030A JP2003270030A JP4959911B2 JP 4959911 B2 JP4959911 B2 JP 4959911B2 JP 2003270030 A JP2003270030 A JP 2003270030A JP 2003270030 A JP2003270030 A JP 2003270030A JP 4959911 B2 JP4959911 B2 JP 4959911B2
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- 229920001577 copolymer Polymers 0.000 claims description 53
- 229910052731 fluorine Inorganic materials 0.000 claims description 49
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 47
- 239000011737 fluorine Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000000155 melt Substances 0.000 claims description 20
- 239000000057 synthetic resin Substances 0.000 claims description 17
- 229920003002 synthetic resin Polymers 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 13
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229920002313 fluoropolymer Polymers 0.000 claims description 6
- 239000004811 fluoropolymer Substances 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000011147 inorganic material Substances 0.000 claims description 6
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 239000007769 metal material Substances 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 4
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 4
- 229940018557 citraconic acid Drugs 0.000 claims description 4
- 238000010411 cooking Methods 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000013361 beverage Nutrition 0.000 claims description 3
- 239000008280 blood Substances 0.000 claims description 3
- 210000004369 blood Anatomy 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
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- 238000004806 packaging method and process Methods 0.000 claims description 2
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- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 19
- -1 perfluoro Chemical group 0.000 description 15
- 229910000831 Steel Inorganic materials 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229920001038 ethylene copolymer Polymers 0.000 description 7
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- XJSRKJAHJGCPGC-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XJSRKJAHJGCPGC-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- UJIGKESMIPTWJH-UHFFFAOYSA-N 1,3-dichloro-1,1,2,2,3-pentafluoropropane Chemical compound FC(Cl)C(F)(F)C(F)(F)Cl UJIGKESMIPTWJH-UHFFFAOYSA-N 0.000 description 1
- RFJVDJWCXSPUBY-UHFFFAOYSA-N 2-(difluoromethylidene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane Chemical compound FC(F)=C1OC(F)(F)C(F)(C(F)(F)F)O1 RFJVDJWCXSPUBY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、溶融成形性フッ素樹脂のフィルム及び積層体に関する。 The present invention relates to a film and a laminate of a melt moldable fluororesin.
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、テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体、エチレン/テトラフルオロエチレン共重合体(以下、ETFEという。)等のフッ素樹脂は、優れた耐熱性、耐候性、耐薬品性、電気絶縁性等の特性に優れることから、種々の分野で用いられている。 Fluororesin such as tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer (hereinafter referred to as ETFE) has excellent heat resistance. It is used in various fields because of its excellent properties such as weather resistance, chemical resistance and electrical insulation.
しかし、これらのフッ素樹脂は他材料との接着性が充分でなく、広範な用途へ適用性を向上するために、接着性を改良する種々の方法が開発されてきた。 However, these fluororesins do not have sufficient adhesion to other materials, and various methods for improving adhesion have been developed in order to improve applicability to a wide range of applications.
例えば、フッ素樹脂の表面にナトリウムエッチング処理(例えば、特許文献1を参照。)やコロナ放電処理(例えば、特許文献2を参照。)等を行った後に、接着剤を用いて他材料と接着させる方法、基材の表面をサンドブラスト処理した後にフッ素樹脂を融着させる方法等が挙げられる。しかし、これらの方法は工程が煩雑で生産性が低く、また、接着力が一定でない場合があった。 For example, after performing a sodium etching process (for example, refer patent document 1), a corona discharge process (for example, refer patent document 2), etc. to the surface of a fluororesin, it is made to adhere | attach with another material using an adhesive agent. Examples thereof include a method and a method of fusing a fluororesin after sandblasting the surface of the substrate. However, these methods have complicated processes and low productivity, and the adhesive force may not be constant.
一方、官能基を有する含フッ素共重合体を用いて、フッ素樹脂と他材料とを接着する方法が提案されている。特許文献3には、ETFEに無水マレイン酸をグラフト重合させて接着性ETFEを得る方法が開示されている。この方法ではグラフト重合工程が必要であり、生産性が低い。特許文献4には、無水マレイン酸とフッ素モノマーとを共重合し、接着性の含フッ素共重合体の製造方法が開示されている。この製造方法は、トリフルオロ酢酸と液体状態又は超臨界状態の二酸化炭素やヘキサフルオロプロピレン等とを溶媒として用いる等、高価な溶媒を使用する特殊な方法であった。 On the other hand, a method of bonding a fluororesin and another material using a fluorine-containing copolymer having a functional group has been proposed. Patent Document 3 discloses a method for obtaining adhesive ETFE by graft polymerization of maleic anhydride to ETFE. This method requires a graft polymerization step and has low productivity. Patent Document 4 discloses a method for producing an adhesive fluorine-containing copolymer by copolymerizing maleic anhydride and a fluorine monomer. This production method is a special method using an expensive solvent, such as using trifluoroacetic acid and liquid or supercritical carbon dioxide, hexafluoropropylene, or the like as a solvent.
本発明の目的は、生産性に優れ、接着性、耐熱性、耐薬品性、耐候性に優れる含フッ素共重合体のフィルム及び積層体を提供することにある。 An object of the present invention is to provide a film and a laminate of a fluorinated copolymer which are excellent in productivity and excellent in adhesion, heat resistance, chemical resistance and weather resistance.
本発明は、テトラフルオロエチレン及び/又はクロロトリフルオロエチレンに基づく重合単位(a)、フッ素モノマー(ただし、テトラフルオロエチレン及びクロロトリフルオロエチレンを除く。)に基づく重合単位(b)、及びイタコン酸、無水イタコン酸、シトラコン酸及び無水シトラコン酸からなる群から選ばれる1種以上に基づく重合単位(c)を含有し、((a)+(b)+(c))に対して(a)が50〜99.8モル%、(b)が0.1〜49.99モル%、(c)が0.01〜5モル%であり、容量流速が0.1〜1000mm3/秒である含フッ素共重合体(A)を含む溶融成形性フッ素樹脂を成形してなるフッ素樹脂フィルムを提供する。 The present invention relates to a polymerized unit (a) based on tetrafluoroethylene and / or chlorotrifluoroethylene, a polymerized unit (b) based on a fluorine monomer (excluding tetrafluoroethylene and chlorotrifluoroethylene), and itaconic acid. A polymerized unit (c) based on one or more selected from the group consisting of itaconic anhydride, citraconic acid and citraconic anhydride, and (a) for ((a) + (b) + (c)) Is 50 to 99.8 mol%, (b) is 0.1 to 49.99 mol%, (c) is 0.01 to 5 mol%, and the volume flow rate is 0.1 to 1000 mm 3 / sec. Provided is a fluororesin film formed by molding a melt-formable fluororesin containing a fluorocopolymer (A).
また、本発明は、前記フッ素樹脂フィルムの層を含有する積層体を提供する。 Moreover, this invention provides the laminated body containing the layer of the said fluororesin film.
本発明の含フッ素共重合体(A)を含む溶融成形性フッ素樹脂のフィルムは、薬品性、衛生性、非粘着性、防汚性、汚れ除去性、耐候性、防錆性、撥水性、撥油性、耐水性、耐着氷雪性に優れ、表面の摩擦係数が低く、誘電率が低い。本発明のフッ素樹脂フィルムは、合成樹脂、金属材料、無機材料、木材との接着性に優れる。 The film of the melt-formable fluororesin containing the fluorine-containing copolymer (A) of the present invention has chemical properties, hygiene, non-adhesiveness, antifouling properties, stain removal properties, weather resistance, rust resistance, water repellency, Excellent oil repellency, water resistance and icing and snow resistance, low surface friction coefficient and low dielectric constant. The fluororesin film of the present invention is excellent in adhesiveness with synthetic resins, metal materials, inorganic materials, and wood.
本発明における含フッ素共重合体(A)は、テトラフルオロエチレン(以下、TFEという。)及び/又はクロロトリフルオロエチレン(以下、CTFEという。)に基づく重合単位(a)、フッ素モノマー(ただし、TFE及びCTFEを除く。)に基づく重合単位(b)、及びイタコン酸(以下、IACという。)、無水イタコン酸(以下、IAHという。)、シトラコン酸(以下、CACという。)及び無水シトラコン酸(以下、CAHという。)からなる群から選ばれる1種以上に基づく重合単位(c)を含有する。 The fluorine-containing copolymer (A) in the present invention is a polymerized unit (a) based on tetrafluoroethylene (hereinafter referred to as TFE) and / or chlorotrifluoroethylene (hereinafter referred to as CTFE), a fluorine monomer (however, Polymerized units (b) based on TFE and CTFE), itaconic acid (hereinafter referred to as IAC), itaconic anhydride (hereinafter referred to as IAH), citraconic acid (hereinafter referred to as CAC) and citraconic anhydride. (Hereinafter referred to as CAH) containing polymerized units (c) based on one or more selected from the group consisting of.
本発明の含フッ素共重合体(A)において、((a)+(b)+(c))に対して(a)が50〜99.8モル%、(b)が0.1〜49.99モル%、(c)が0.01〜5モル%である。ここで、((a)+(b)+(c))は、(a)と(b)と(c)との合計を表す。 In the fluorine-containing copolymer (A) of the present invention, (a) is 50 to 99.8 mol% and (b) is 0.1 to 49 with respect to ((a) + (b) + (c)). .99 mol% and (c) is 0.01 to 5 mol%. Here, ((a) + (b) + (c)) represents the sum of (a), (b), and (c).
好ましくは、(a)が50〜99.5モル%、(b)が0.2〜49.9モル%、(c)が0.01〜3モル%であり、より好ましくは(a)が50〜99モル%、(b)が0.3〜49.9モル%、(c)が0.03〜1モル%である。(a)、(b)及び(c)のモル%がこの範囲にあると、含フッ素共重合体(A)は、耐熱性、耐薬品性に優れる。さらに、(b)のモル%がこの範囲にあると、含フッ素共重合体(A)は、成形性に優れ、耐ストレスクラック性等の機械物性に優れる。(c)のモル%がこの範囲にあると、含フッ素共重合体(A)は、他材料との接着性に優れる。 Preferably, (a) is 50 to 99.5 mol%, (b) is 0.2 to 49.9 mol%, (c) is 0.01 to 3 mol%, more preferably (a) is 50 to 99 mol%, (b) is 0.3 to 49.9 mol%, and (c) is 0.03 to 1 mol%. When the mol% of (a), (b) and (c) is within this range, the fluorinated copolymer (A) is excellent in heat resistance and chemical resistance. Furthermore, when the mol% of (b) is in this range, the fluorinated copolymer (A) is excellent in moldability and mechanical properties such as stress crack resistance. When the mol% of (c) is within this range, the fluorine-containing copolymer (A) is excellent in adhesiveness with other materials.
(b)におけるフッ素モノマーとしては、フッ化ビニル、フッ化ビニリデン(以下、VDFという。)、トリフルオロエチレン、ヘキサフルオロプロピレン(以下、HFPという。)、CF2=CFOR1(ここで、R1は炭素数1から10のエーテル性酸素原子を含んでもよいペルフルオロアルキル基。)、CF2=CFOR2SO2X1(R2は炭素数1から10のエーテル性酸素原子を含んでもよいペルフルオロアルキレン基、X1はハロゲン原子又は水酸基。)、CF2=CFOR3CO2X2(ここで、R3は炭素数1から10のエーテル性酸素原子を含んでもよいペルフルオロアルキレン基、X2は水素原子又は炭素数3以下のアルキル基。)、CF2=CF(CF2)pOCF=CF2(ここで、Pは1又は2。)、CH2=CX3(CF2)qX4(ここで、X3は水素原子又はフッ素原子、qは2〜10の整数、X4は水素原子又はフッ素原子。)及びペルフルオロ(2−メチレン−4−メチル−1,3−ジオキソラン)等が挙げられる。 As the fluorine monomer in (b), vinyl fluoride, vinylidene fluoride (hereinafter referred to as VDF), trifluoroethylene, hexafluoropropylene (hereinafter referred to as HFP), CF 2 = CFOR 1 (here, R 1 Is a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms.), CF 2 = CFOR 2 SO 2 X 1 (R 2 is a perfluoroalkylene which may contain an etheric oxygen atom having 1 to 10 carbon atoms) Group, X 1 is a halogen atom or a hydroxyl group.), CF 2 = CFOR 3 CO 2 X 2 (wherein R 3 is a perfluoroalkylene group which may contain an etheric oxygen atom having 1 to 10 carbon atoms, X 2 is hydrogen) atom or alkyl group having 3 or less carbon atoms.), CF 2 = CF ( CF 2) p OCF = CF 2 ( wherein, P is Or 2.), CH 2 = CX 3 (CF 2) q X 4 ( wherein, X 3 represents a hydrogen atom or a fluorine atom, q is an integer of 2 to 10, X 4 is a hydrogen atom or a fluorine atom.) And perfluoro (2-methylene-4-methyl-1,3-dioxolane) and the like.
好ましくは、VDF、HFP、CF2=CFOR1及びCH2=CX3(CF2)qX4であり、より好ましくは、CF2=CFOR1及びCH2=CX3(CF2)qX4である。
CF2=CFOR1としては、CF2=CFOCF2CF3、CF2=CFOCF2CF2CF3、CF2=CFOCF2CF2CF2CF3、CF2=CFO(CF2)8F等が挙げられる。好ましくは、CF2=CFOCF2CF2CF3である。
CH2=CX3(CF2)qX4としては、CH2=CH(CF2)2F、CH2=CH(CF2)3F、CH2=CH(CF2)4F、CH2=CF(CF2)3H、CH2=CF(CF2)4H等が挙げられる。好ましくは、CH2=CH(CF2)4F及びCH2=CH(CF2)2Fである。
Preferably, VDF, HFP, CF 2 = CFOR 1 and CH 2 = CX 3 (CF 2 ) q X 4 , more preferably CF 2 = CFOR 1 and CH 2 = CX 3 (CF 2 ) q X 4. It is.
Examples of CF 2 = CFOR 1 include CF 2 = CFOCF 2 CF 3 , CF 2 = CFOCF 2 CF 2 CF 3 , CF 2 = CFOCF 2 CF 2 CF 2 CF 3 , CF 2 = CFO (CF 2 ) 8 F, and the like. It is done. Preferably, a CF 2 = CFOCF 2 CF 2 CF 3.
As CH 2 = CX 3 (CF 2 ) q X 4 , CH 2 = CH (CF 2 ) 2 F, CH 2 = CH (CF 2 ) 3 F, CH 2 = CH (CF 2 ) 4 F, CH 2 ═CF (CF 2 ) 3 H, CH 2 ═CF (CF 2 ) 4 H, and the like. Preferably, CH 2 ═CH (CF 2 ) 4 F and CH 2 ═CH (CF 2 ) 2 F.
(c)は、IAC、IAH、CAC及びCAHからなる群から選ばれる1種以上の重合単位である。より好ましくは、(c)はIAH及びCAHに基づく重合単位である。以下、IAC、IAH、CAC及びCAHを合わせて酸モノマーという。
含フッ素共重合体(A)の製造時に酸モノマーを用いると特開平11−193312に記載の無水マレイン酸を用いた場合に必要となる特殊な重合方法を用いることなく、酸モノマーに基づく重合単位を有する含フッ素共重合体(A)を容易に製造できるので好ましい。
(C) is at least one polymer unit selected from the group consisting of IAC, IAH, CAC and CAH. More preferably, (c) is a polymerized unit based on IAH and CAH. Hereinafter, IAC, IAH, CAC and CAH are collectively referred to as an acid monomer.
When an acid monomer is used in the production of the fluorinated copolymer (A), a polymer unit based on the acid monomer is used without using a special polymerization method required when maleic anhydride described in JP-A-11-19312 is used. Since the fluorine-containing copolymer (A) which has this can be manufactured easily, it is preferable.
本発明における含フッ素共重合体(A)は、(a)、(b)、(c)に加えて、さらに非フッ素含有モノマーに基づく重合単位(d)を含有し、(d)の含有量が((a)+(b)+(c))/(d)のモル比が100/5〜100/100である含フッ素共重合体であることも好ましい。(d)がこれより少ない場合は重合時に(d)の含有量を制御することが難しく、これより多い場合はフィルムの耐熱性、耐薬品性が充分でない。 The fluorine-containing copolymer (A) in the present invention contains, in addition to (a), (b), (c), a polymer unit (d) based on a non-fluorine-containing monomer, and the content of (d) Is preferably a fluorine-containing copolymer having a molar ratio of ((a) + (b) + (c)) / (d) of 100/5 to 100/100. When (d) is less than this, it is difficult to control the content of (d) during polymerization, and when it is more than this, the heat resistance and chemical resistance of the film are insufficient.
非フッ素含有モノマーとしては、エチレン、プロピレン等の炭素数3以下のオレフィン、酢酸ビニル等のビニルエステル、エチルビニルエーテル、シクロヘキシルビニルエーテル等のビニルエーテル等が挙げられる。エチレン、プロピレン及び酢酸ビニルが好ましく、エチレンがより好ましい。 Examples of the non-fluorine-containing monomer include olefins having 3 or less carbon atoms such as ethylene and propylene, vinyl esters such as vinyl acetate, vinyl ethers such as ethyl vinyl ether and cyclohexyl vinyl ether, and the like. Ethylene, propylene and vinyl acetate are preferred, and ethylene is more preferred.
本発明における含フッ素共重合体(A)の最も好ましい具体例としては、TFE/CF2=CFOCF2CF2CF3/IAH共重合体、TFE/CF2=CFOCF2CF2CF3/CAH共重合体、TFE/HFP/IAH共重合体、TFE/HFP/CAH共重合体、TFE/VDF/IAH共重合体、TFE/VDF/CAH共重合体、TFE/CH2=CH(CF2)4F/IAH/エチレン共重合体、TFE/CH2=CH(CF2)4F/CAH/エチレン共重合体、TFE/CH2=CH(CF2)2F/IAH/エチレン共重合体、TFE/CH2=CH(CF2)2F/CAH/エチレン共重合体、CTFE/CH2=CH(CF2)4F/IAH/エチレン共重合体、CTFE/CH2=CH(CF2)4F/CAH/エチレン共重合体、CTFE/CH2=CH(CF2)2F/IAH/エチレン共重合体、CTFE/CH2=CH(CF2)2F/CAH/エチレン共重合体等が挙げられる。 As the most preferred specific examples of the fluorine-containing copolymer (A) in the present invention, TFE / CF 2 = CFOCF 2 CF 2 CF 3 / IAH copolymer, TFE / CF 2 = CFOCF 2 CF 2 CF 3 / CAH co Polymer, TFE / HFP / IAH copolymer, TFE / HFP / CAH copolymer, TFE / VDF / IAH copolymer, TFE / VDF / CAH copolymer, TFE / CH 2 = CH (CF 2 ) 4 F / IAH / ethylene copolymer, TFE / CH 2 ═CH (CF 2 ) 4 F / CAH / ethylene copolymer, TFE / CH 2 ═CH (CF 2 ) 2 F / IAH / ethylene copolymer, TFE / CH 2 = CH (CF 2 ) 2 F / CAH / ethylene copolymer, CTFE / CH 2 = CH ( CF 2) 4 F / IAH / ethylene copolymer, CTFE / CH 2 = CH (CF 2 ) 4 F / CAH / ethylene copolymer, CTFE / CH 2 = CH (CF 2 ) 2 F / IAH / ethylene copolymer, CTFE / CH 2 = CH (CF 2 ) 2 F / Examples include CAH / ethylene copolymers.
本発明における含フッ素共重合体(A)は、溶融成形性のフッ素樹脂であり、成形方法に適した成形温度を有することが好ましい。このため、(a)、(b)、(c)及び必要に応じて(d)の含有量を上記範囲内で適宜調節し、含フッ素共重合体(A)の融点を最適化することが好ましい。 The fluorinated copolymer (A) in the present invention is a melt moldable fluororesin, and preferably has a molding temperature suitable for the molding method. For this reason, the content of (a), (b), (c) and, if necessary, the content of (d) can be appropriately adjusted within the above range to optimize the melting point of the fluorinated copolymer (A). preferable.
本発明における含フッ素共重合体(A)の容量流速(以下、Q値という。)は、0.1〜1000mm3/秒である。Q値は、含フッ素共重合体(A)の溶融流動性を表す指標であり、分子量の目安となる。Q値が大きいと分子量が低く、小さいと分子量が高いことを示す。本発明におけるQ値は、島津製作所製フローテスタを用いて、樹脂の融点より50℃高い温度において、荷重7kg下に直径2.1mm、長さ8mmのオリフィス中に押出すときの含フッ素共重合体(A)の押出し速度である。Q値が小さすぎると溶融流動性が低下し均一で表面が平滑なフィルムが得られず、大きすぎると含フッ素共重合体(A)の機械的強度が低下する。本発明における含フッ素共重合体(A)のQ値は1〜500mm3/秒が好ましく、2〜200mm3/秒がより好ましい。本発明における含フッ素共重合体(A)の融点は120〜310℃が好ましく、150〜300℃がより好ましく、180〜300℃が最も好ましい。 The volume flow rate (hereinafter referred to as Q value) of the fluorinated copolymer (A) in the present invention is 0.1 to 1000 mm 3 / sec. The Q value is an index representing the melt fluidity of the fluorinated copolymer (A) and is a measure of the molecular weight. A large Q value indicates a low molecular weight, and a small Q value indicates a high molecular weight. The Q value in the present invention is a fluorine-containing copolymer weight when extruded into an orifice having a diameter of 2.1 mm and a length of 8 mm under a load of 7 kg at a temperature 50 ° C. higher than the melting point of the resin using a flow tester manufactured by Shimadzu Corporation. This is the extrusion speed of the combined (A). If the Q value is too small, a melt fluidity is lowered and a uniform and smooth film cannot be obtained. If it is too large, the mechanical strength of the fluorinated copolymer (A) is lowered. Q value of the fluorocopolymer (A) in the present invention is preferably from 1 to 500 mm 3 / sec, 2~200mm 3 / sec is more preferable. 120-310 degreeC is preferable, as for melting | fusing point of the fluorine-containing copolymer (A) in this invention, 150-300 degreeC is more preferable, and 180-300 degreeC is the most preferable.
本発明における溶融成形性フッ素樹脂は、実質的に上記含フッ素共重合体(A)のみからなっていてもよく、上記含フッ素共重合体(A)と他の成分からなる溶融成形性の組成物であってもよい。他の成分としては、上記含フッ素共重合体(A)以外の溶融成形性フッ素樹脂、フッ素樹脂以外の溶融成形性合成樹脂、樹脂以外の添加剤などがある。上記含フッ素共重合体(A)以外の溶融成形性フッ素樹脂としては、重合単位(c)を含有しない以外は上記含フッ素共重合体(A)と同じ組成の含フッ素重合体(以下、含フッ素重合体(B)という)が好ましい。フッ素樹脂以外の溶融成形性合成樹脂としては耐熱性高分子が好ましく、樹脂以外の添加剤としては粉末状充填剤、強化線維、安定剤などがある。特に、ポリイミド、PPS等の耐熱性高分子、酸化チタン等の顔料やカーボンブラック等の導電性粉末等の充填剤、カーボン繊維、銅粉、酸化銅、ヨウ化銅等の銅系熱安定剤等が好ましい。 The melt-formable fluororesin in the present invention may consist essentially of only the above-mentioned fluorine-containing copolymer (A), and a melt-formable composition comprising the above-mentioned fluorine-containing copolymer (A) and other components. It may be a thing. Examples of other components include a melt moldable fluororesin other than the above-mentioned fluorine-containing copolymer (A), a melt moldable synthetic resin other than a fluororesin, and an additive other than a resin. As the melt-formable fluororesin other than the above-mentioned fluorocopolymer (A), a fluoropolymer having the same composition as the above-mentioned fluorocopolymer (A) except that it does not contain a polymer unit (c) A fluoropolymer (B) is preferred. As the melt-moldable synthetic resin other than the fluororesin, a heat-resistant polymer is preferable, and as the additive other than the resin, there are a powder filler, a reinforcing fiber, a stabilizer and the like. In particular, heat-resistant polymers such as polyimide and PPS, pigments such as titanium oxide, fillers such as conductive powder such as carbon black, copper-based heat stabilizers such as carbon fiber, copper powder, copper oxide, and copper iodide Is preferred.
本発明のフッ素樹脂フィルムは、含フッ素共重合体(A)を含む溶融成形性フッ素樹脂を成形してなるフッ素樹脂フィルムである。溶融成形性フッ素樹脂が実質的に前記含フッ素共重合体(A)のみからなる場合、そのフッ素樹脂フィルムの成形方法としては、溶融押出法が好ましい。成形温度は、溶融成形性フッ素樹脂の融点及び分解温度により適宜調節される。スクリュー温度は100〜400℃が好ましく、Tダイ温度は150℃〜400℃が好ましい。スクリュー回転数は特に限定されないが、10〜200回転/分が好ましい。押出機内の溶融成形性フッ素樹脂の滞留時間は1〜20分が好ましい。 The fluororesin film of the present invention is a fluororesin film formed by molding a melt-formable fluororesin containing the fluorocopolymer (A). When the melt-formable fluororesin consists essentially of the fluorine-containing copolymer (A), a melt extrusion method is preferred as a method for forming the fluororesin film. The molding temperature is appropriately adjusted depending on the melting point and decomposition temperature of the melt-moldable fluororesin. The screw temperature is preferably 100 to 400 ° C, and the T die temperature is preferably 150 to 400 ° C. The screw rotation speed is not particularly limited, but is preferably 10 to 200 rotations / minute. The residence time of the melt-formable fluororesin in the extruder is preferably 1 to 20 minutes.
本発明のフッ素樹脂フィルムが前記含フッ素共重合体(A)と前記含フッ素重合体(B)とを含む溶融成形性フッ素樹脂からなるフィルムの場合、フィルムの耐薬品性がさらに向上する。含フッ素重合体(B)の含有量は含フッ素共重合体(A)の100質量部に対して10〜5000質量部が好ましく、50〜3000質量部がより好ましく、100〜1000質量部が最も好ましい。含フッ素重合体(B)の含有量が少なすぎると耐薬品性の向上の効果が充分でなく、多すぎると他材料との接着性が充分でない。本発明のフッ素樹脂フィルムが上記含フッ素共重合体(A)と他の成分からなる溶融成形性の組成物である場合、フッ素樹脂以外の溶融成形性合成樹脂や樹脂以外の添加剤の含有量は、含フッ素共重合体(A)の100質量部に対して0.1〜50質量部が好ましい。含フッ素共重合体(A)以外の成分を含む上記溶融成形性フッ素樹脂の成形条件は、前記含フッ素共重合体(A)の成形条件に準じて設定することが好ましい。 In the case where the fluororesin film of the present invention is a film made of a melt-formable fluororesin containing the fluorocopolymer (A) and the fluoropolymer (B), the chemical resistance of the film is further improved. The content of the fluoropolymer (B) is preferably 10 to 5000 parts by mass, more preferably 50 to 3000 parts by mass, and most preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the fluorocopolymer (A). preferable. If the content of the fluoropolymer (B) is too small, the effect of improving the chemical resistance is not sufficient, and if it is too large, the adhesion to other materials is not sufficient. When the fluororesin film of the present invention is a melt moldable composition comprising the above-mentioned fluorocopolymer (A) and other components, the content of melt moldable synthetic resins other than fluororesins and additives other than resins Is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the fluorinated copolymer (A). The molding conditions for the melt-formable fluororesin containing components other than the fluorinated copolymer (A) are preferably set according to the molding conditions for the fluorinated copolymer (A).
本発明の積層体は、上記フッ素樹脂フィルムの層を含有する積層体である。該積層体は、含フッ素共重合体(A)を含む溶融成形性フッ素樹脂(以下、溶融成形性フッ素樹脂(A)という。)と含フッ素共重合体(A)以外の溶融成形性合成樹脂(以下、溶融成形性合成樹脂(C)という。)とを共押出し成形してなる積層体、又は溶融成形性フッ素樹脂(A)を基材の表面に押出しラミネートしてなる積層体が好ましい。 The laminated body of this invention is a laminated body containing the layer of the said fluororesin film. The laminate is a melt-formable fluororesin other than the melt-formable fluororesin (hereinafter referred to as melt-formable fluororesin (A)) containing the fluorocopolymer (A) and the fluorocopolymer (A). A laminate obtained by coextrusion molding (hereinafter referred to as melt moldable synthetic resin (C)) or a laminate obtained by extruding and laminating a melt moldable fluororesin (A) on the surface of the substrate is preferred.
溶融成形性フッ素樹脂(A)と溶融成形性合成樹脂(C)とを共押出し成形する方法において、溶融成形性フッ素樹脂(A)と溶融成形性合成樹脂(C)とは、2機以上の押出機の吐出口から吐出され、溶融状態で接触しつつダイを通り積層体に成形される。共押出し温度は、溶融成形性フッ素樹脂(A)及び溶融成形性合成樹脂(C)の融点及び分解温度により適宜調節される。スクリュー温度は100〜400℃が好ましく、ダイ温度は150℃〜400℃が好ましい。スクリュー回転数は特に限定されないが10〜200回転/分が好ましい。得られる積層体は、通常フィルム状又は板状であることが好ましい。 In the method of coextrusion molding of the melt moldable fluororesin (A) and the melt moldable synthetic resin (C), the melt moldable fluororesin (A) and the melt moldable synthetic resin (C) include two or more machines. It is discharged from the discharge port of the extruder and is formed into a laminate through the die while contacting in a molten state. The coextrusion temperature is appropriately adjusted depending on the melting point and decomposition temperature of the melt moldable fluororesin (A) and the melt moldable synthetic resin (C). The screw temperature is preferably 100 to 400 ° C, and the die temperature is preferably 150 to 400 ° C. The screw rotation speed is not particularly limited, but is preferably 10 to 200 rotations / minute. It is preferable that the obtained laminate is usually a film or a plate.
溶融成形性合成樹脂(C)としては、非フッ素系の溶融成形性合成樹脂や含フッ素共重合体(A)以外のフッ素系の溶融成形性合成樹脂が挙げられる。具体例としては、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)、ポリカーボネート(PC)、ポリエチレンナフタレート(PEN)、ポリブチレンナフタレート(PBN)等のポリエステル;ポリエチレン(PE)、ポリプロピレン(PP)等のポリオレフィン;ポリフッ化ビニリデン(PVDF)、ポリクロロトリフルオロエチレン(PCTFE)、エチレン/テトラフルオロエチレン共重合体(ETFE)、エチレン/クロロトリフルオロエチレン共重合体(ECTFE)、テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体(FEP)、テトラフルオロエチレン/ヘキサフルオロプロピレン/ビニリデンフルオライド共重合体(THV)、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)等のフッ素樹脂;ポリアミド6、ポリアミド66、ポリアミド46、ポリアミド11、ポリアミド12、ポリアミドMXD6(半芳香族系ポリアミド)等のポリアミド;ポリ(エチレン/酢酸ビニル)、ポリ(酢酸ビニル)、ポリビニルアルコール(PVA)、ポリ(エチレン/ビニルアルコール)、ポリスチレン、ポリ塩化ビニリデン、ポリアクリロニトリル、ポリオキシメチレン、ポリフェニレンスルフィド、ポリフェニレンエーテル、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリスルホン、ポリアリレート等が挙げられる。 Examples of the melt moldable synthetic resin (C) include non-fluorine-based melt moldable synthetic resins and fluorine-based melt moldable synthetic resins other than the fluorine-containing copolymer (A). Specific examples include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate (PC), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN); polyethylene (PE), polypropylene (PP) Polyolefins such as polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexa Fluoropropylene copolymer (FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), tetrafluoroethylene / perfluoro (al Fluorine resin such as polyamide (polyvinyl ether) copolymer (PFA); polyamide such as polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide MXD6 (semi-aromatic polyamide); poly (ethylene / vinyl acetate), Poly (vinyl acetate), polyvinyl alcohol (PVA), poly (ethylene / vinyl alcohol), polystyrene, polyvinylidene chloride, polyacrylonitrile, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, polyimide, polyamideimide, polyetherimide, polysulfone, Examples include polyarylate.
溶融成形性フッ素樹脂(A)を基材の表面に押出しラミネートする方法において、押出され溶融状態の溶融成形性フッ素樹脂(A)のフィルムが基材と接触することによりフィルムと基材が強固に接着する。押出し温度は溶融成形性フッ素樹脂(A)の融点及び分解温度により適宜調節される。スクリュー温度は100〜400℃が好ましく、Tダイ温度は150℃〜400℃が好ましい。スクリュー回転数は特に限定されないが10〜200回転/分が好ましい。溶融成形性フッ素樹脂(A)の押出機内の滞留時間は1〜20分が好ましい。 In the method of extruding and laminating a melt-formable fluororesin (A) onto the surface of a substrate, the film and the substrate are strengthened by contacting the extruded melt-formable fluororesin (A) film with the substrate. Glue. The extrusion temperature is appropriately adjusted depending on the melting point and decomposition temperature of the melt-formable fluororesin (A). The screw temperature is preferably 100 to 400 ° C, and the T die temperature is preferably 150 to 400 ° C. The screw rotation speed is not particularly limited, but is preferably 10 to 200 rotations / minute. The residence time in the extruder of the melt moldable fluororesin (A) is preferably 1 to 20 minutes.
押出しラミネートに用いられる基材の材料としては、前記溶融成形性合成樹脂(C)に加えて、鉄、ステンレス鋼、アルミニウム等の金属材料、ガラス、セラミックス等無機材料、ポリテトラフルオロエチレン、木材等が挙げられる。基材の形状としては、フィルムに加えて、板、シート、織物、不織布等の形状が使用できる。得られる積層体は、積層フィルムに加えて、板、シート、織物、不織布等の基材との積層体である。 In addition to the melt-moldable synthetic resin (C), the base material used for extrusion lamination includes metal materials such as iron, stainless steel, and aluminum, inorganic materials such as glass and ceramics, polytetrafluoroethylene, and wood. Is mentioned. As the shape of the substrate, in addition to the film, shapes such as a plate, a sheet, a woven fabric and a non-woven fabric can be used. The obtained laminated body is a laminated body with base materials, such as a board, a sheet | seat, a textile fabric, and a nonwoven fabric, in addition to a laminated film.
本発明の積層体は、また、あらかじめ製造された本発明のフッ素樹脂フィルムを基材に積層して得られる積層体であってもよい。この場合の積層方法としては、加熱した基材の表面にフッ素樹脂フィルムを接触させ、フッ素樹脂フィルムを基材に融着させる方法が好ましい。基材の加熱温度は溶融成形性フッ素樹脂(A)の融点以上、分解温度以下の範囲に調節するが、通常150℃〜400℃が好ましい。また、基材と接触させる前にフィルム表面をコロナ放電処理等の方法で表面処理すると、接着性がされに向上するので好ましい。基材としては鉄、ステンレス鋼、アルミニウム等の金属材料、ガラス、セラミックス等の無機材料、ポリイミド等の耐熱性高分子等が挙げられる。この場合には、種々の形状の基材を用いることができる。 The laminate of the present invention may also be a laminate obtained by laminating a pre-manufactured fluororesin film of the present invention on a substrate. As a laminating method in this case, a method in which a fluororesin film is brought into contact with the surface of the heated substrate and the fluororesin film is fused to the substrate is preferable. Although the heating temperature of a base material is adjusted to the range more than melting | fusing point of a melt moldable fluororesin (A) and below decomposition temperature, 150 to 400 degreeC is preferable normally. Moreover, it is preferable to surface-treat the film surface by a method such as corona discharge treatment before bringing it into contact with the base material, since the adhesiveness is further improved. Examples of the substrate include metal materials such as iron, stainless steel, and aluminum, inorganic materials such as glass and ceramics, and heat-resistant polymers such as polyimide. In this case, various shapes of base materials can be used.
以下に実施例を挙げて本発明を詳細に説明するが、本発明はこれらに限定されない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
[合成例1]
内容積が94リットルの撹拌機付き重合槽を脱気し、1−ヒドロトリデカフルオロヘキサンの71.3kg、1,3−ジクロロ−1,1,2,2,3−ペンタフルオロプロパン(旭硝子社製、AK225cb、以下、AK225cbという。)の20.4kg、CH2=CH(CF2)2Fの562g、IAHの4.45gを仕込み、重合槽内を66℃に昇温し、TFE/Eのモル比で89/11のガスで1.5MPa/Gまで昇圧した。重合開始剤としてtert−ブチルペルオキシピバレートの0.7%濃度の1−ヒドロトリデカフルオロヘキサン溶液の1Lを仕込み、重合を開始させた。重合中圧力が一定になるようにTFE/Eの60/40モル比のモノマー混合ガスを連続的に仕込んだ。また、重合中に仕込むTFEとEの合計モル数に対して3.3モル%に相当する量のCH2=CH(CF2)2Fと0.5モル%に相当する量のIAHを連続的に仕込んだ。重合開始9.9時間後、モノマー混合ガスの7.28kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに常圧までパージした。
[Synthesis Example 1]
A polymerization tank equipped with a stirrer with an internal volume of 94 liters was degassed and 71.3 kg of 1-hydrotridecafluorohexane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane (Asahi Glass Co., Ltd.) Made of AK225cb, hereinafter referred to as AK225cb), 562 g of CH 2 ═CH (CF 2 ) 2 F, and 4.45 g of IAH were charged, and the temperature inside the polymerization tank was raised to 66 ° C., and TFE / E The pressure was increased to 1.5 MPa / G with a gas having a molar ratio of 89/11. As a polymerization initiator, 1 L of a 1% -hydrotridecafluorohexane solution of 0.7% concentration of tert-butylperoxypivalate was charged to initiate polymerization. A monomer mixed gas of 60/40 molar ratio of TFE / E was continuously charged so that the pressure was constant during the polymerization. Further, CH 2 ═CH (CF 2 ) 2 F in an amount corresponding to 3.3 mol% and IAH in an amount corresponding to 0.5 mol% are continuously added to the total number of moles of TFE and E charged during the polymerization. I was charged. 9.9 hours after the start of polymerization, when 7.28 kg of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.
得られたスラリ状の含フッ素共重合体(A)1を、水の77kgを仕込んだ200Lの造粒槽に投入し、撹拌下105℃まで昇温して溶媒を留出除去しながら造粒した。得られた造粒物を150℃で15時間乾燥することにより、6.9kgの含フッ素共重合体(A)1の造粒物1が得られた。 The obtained slurry-like fluorine-containing copolymer (A) 1 is put into a 200 L granulation tank charged with 77 kg of water, and heated to 105 ° C. with stirring to granulate while distilling and removing the solvent. did. The obtained granulated product was dried at 150 ° C. for 15 hours to obtain 6.9 kg of the granulated product 1 of the fluorinated copolymer (A) 1.
溶融NMR分析、フッ素含有量分析及び赤外吸収スペクトル分析の結果から、テトラフルオロエチレンに基づく重合単位/CH2=CH(CF2)2Fに基づく重合単位/無水イタコン酸に基づく重合単位/エチレンに基づく重合単位が96.2/3.3/0.5/64.2(モル比)であった。含フッ素共重合体(A)1のQ値は28mm3/秒、融点は240℃であった。 From the results of melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis, polymerized units based on tetrafluoroethylene / polymerized units based on CH 2 ═CH (CF 2 ) 2 F / polymerized units based on itaconic anhydride / ethylene The polymerization unit based on the formula was 96.2 / 3.3 / 0.5 / 64.2 (molar ratio). The fluorine-containing copolymer (A) 1 had a Q value of 28 mm 3 / sec and a melting point of 240 ° C.
[実施例1]
含フッ素共重合体(A)1の造粒物1をスクリュー径30mmの1軸押出機を用いてバレル温度280℃、ダイ温度300℃で押出したペレット1を作成した。このペレット1をスクリュー径30mmの1軸押出機を用いて、Tダイ温度300℃で成形して、ロールに巻き取り、厚さ50μm、幅15cmのフッ素樹脂フィルム1を得た。フッ素樹脂フィルム1の引張破断強度は45MPa、引張破断伸度は350%であった。
[Example 1]
A pellet 1 was prepared by extruding the granulated product 1 of the fluorinated copolymer (A) 1 at a barrel temperature of 280 ° C. and a die temperature of 300 ° C. using a single screw extruder having a screw diameter of 30 mm. This pellet 1 was molded at a T-die temperature of 300 ° C. using a single screw extruder having a screw diameter of 30 mm, and wound around a roll to obtain a fluororesin film 1 having a thickness of 50 μm and a width of 15 cm. The fluororesin film 1 had a tensile strength at break of 45 MPa and a tensile elongation at break of 350%.
[実施例2]
下層を成形するシリンダにポリカーボネートのペレットを供給し、上層を成形するシリンダにペレット1を供給し、それぞれシリンダの輸送ゾーンに移送させた。ポリカーボネートのペレット、ペレット1の輸送ゾーンにおける加熱温度をそれぞれ240℃、270℃とした。共ダイの温度を270℃として2層共押出しを行い、2層積層フィルムを得た。積層フィルムの厚さは100μm、幅は15cmであった。含フッ素共重合体(A)1の層の厚さは50μm、ポリカーボネート層の厚さは200μmであり、両層の剥離強度は50N/cmであり、強固に接着していた。得られた積層フィルムは、外装材、内装材、屋根材、膜構造物用フィルム等に用いられる。
[Example 2]
Polycarbonate pellets were supplied to the cylinder forming the lower layer, pellets 1 were supplied to the cylinder forming the upper layer, and each was transferred to the transport zone of the cylinder. The heating temperature in the transport zone for the pellets of polycarbonate and pellets 1 was 240 ° C. and 270 ° C., respectively. Two-layer coextrusion was carried out at a temperature of the common die of 270 ° C. to obtain a two-layer laminated film. The laminated film had a thickness of 100 μm and a width of 15 cm. The thickness of the fluorine-containing copolymer (A) 1 was 50 μm, the thickness of the polycarbonate layer was 200 μm, the peel strength of both layers was 50 N / cm, and they were firmly bonded. The obtained laminated film is used for exterior materials, interior materials, roofing materials, films for membrane structures, and the like.
[実施例3]
実施例1のフッ素樹脂フィルム1を、300℃に加熱した厚さ0.2mm、幅15cmの鋼板に接触させて融着させ、フッ素樹脂フィルム1と鋼板との積層体を得た。鋼板とフッ素樹脂フィルム1は強固に接着していて剥離強度は55N/cmであった。この積層体を1N塩酸に浸し、100℃で1週間保持した。浸漬後、フッ素樹脂フィルムの外観に変化なかった。フッ素樹脂フィルムと鋼板との剥離強度は45N/cmであり、強固に接着していた。浸漬後、フッ素樹脂フィルムを融着しなかった側の鋼板表面は腐食が激しかったが、フッ素樹脂フィルムを融着した側の鋼板表面はほとんど腐食がなかった。このように鋼板にフッ素樹脂フィルム1をラミネートした積層板は、耐腐食性に優れることから、調理用器具の保護版、飲料用の缶材料、加湿器の蒸気出口部位等に用いられる。
[Example 3]
The fluororesin film 1 of Example 1 was brought into contact with and fused to a steel sheet having a thickness of 0.2 mm and a width of 15 cm heated to 300 ° C. to obtain a laminate of the fluororesin film 1 and the steel sheet. The steel plate and the fluororesin film 1 were firmly bonded, and the peel strength was 55 N / cm. This laminate was immersed in 1N hydrochloric acid and held at 100 ° C. for 1 week. After immersion, the appearance of the fluororesin film did not change. The peel strength between the fluororesin film and the steel plate was 45 N / cm and was firmly bonded. After immersion, the steel plate surface on the side where the fluororesin film was not fused was severely corroded, but the steel plate surface on the side where the fluororesin film was fused was hardly corroded. Thus, since the laminated board which laminated the fluororesin film 1 on the steel plate is excellent in corrosion resistance, it is used for the protection plate of cooking utensils, the can material for drinks, the steam outlet part of the humidifier, and the like.
[実施例4]
実施例1のペレット1をスクリュー径30mmの1軸押出機を用いて、Tダイ温度310℃で押出し成形し、厚さ30μm、幅13cmのフッ素樹脂フィルム2とし、フッ素樹脂フィルム2が溶融状態の時に幅20cmの鋼板の表面に接触させる押出しラミネーションを行った。鋼板とフッ素樹脂フィルム2とは強固に接着し、その剥離強度は45N/cmであった。鋼板にフッ素樹脂フィルム2を押出しラミネーションしてなる積層体は、調理器具の保護版、飲料用の缶材料、加湿器の蒸気出口部位等に用いられる。
[Example 4]
The pellet 1 of Example 1 was extruded using a single screw extruder with a screw diameter of 30 mm at a T die temperature of 310 ° C. to obtain a fluororesin film 2 having a thickness of 30 μm and a width of 13 cm, and the fluororesin film 2 was in a molten state. Extrusion lamination was sometimes performed to contact the surface of a 20 cm wide steel plate. The steel plate and the fluororesin film 2 were firmly bonded, and the peel strength was 45 N / cm. A laminate formed by extruding and laminating the fluororesin film 2 on a steel plate is used for a protective plate for cooking utensils, a can material for beverages, a steam outlet portion of a humidifier, and the like.
本発明のフッ素樹脂フィルム及び積層体の用途としては、ステンレス鋼シートとの積層体からなる飲料用缶材料、調理器具表面保護板、内外装用の化粧板保護フィルム、加湿器の蒸気出口部品被覆フィルム、ポリカーボネート等との積層板からなる外装材及び屋根材、ウレタン樹脂又はガラスクロス等との積層体からなるベルト、アラミド織布等との積層体からなる気球材料、ポリアミド、エチレン酢酸ビニル樹脂、ゴム等との積層体からなる膜構造物用フィルム、アルミシートとの積層体からなる太陽電池用表面材料、アルミ箔等との積層体からなるヒートシール包装材料、食品及び医療品包装用多層フィルム、ホワイトボード用多層フィルム、高速道路防音壁用保護フィルム、ポリエチレンテレフタレート等との積層体からなる離型フィルム、シャワー遮蔽カーテン用積層フィルム、輸液バック及び血液バック用積層フィルム、壁紙用積層フィルム、耐熱パウチ用フィルム、合わせガラス中間膜、農業ハウス用フィルム、接着用フィルム、ゴム栓用耐薬品性被覆フィルム、低誘電率のフレキシブルプリント基板用フィルム、太陽電池用保護フィルム等が挙げられる。 Applications of the fluororesin film and laminate of the present invention include beverage can materials comprising laminates with stainless steel sheets, cooking utensil surface protective plates, decorative plate protective films for interior and exterior, and steam outlet component coating films for humidifiers , Exterior materials and roof materials made of laminates with polycarbonate, etc., belts made of laminates with urethane resin or glass cloth, balloon materials made of laminates with aramid woven fabric, polyamide, ethylene vinyl acetate resin, rubber Film for film structure comprising a laminate with the like, surface material for solar cells comprising a laminate with aluminum sheet, heat seal packaging material comprising a laminate with aluminum foil, multilayer film for food and medical product packaging, A mold release film consisting of a laminate of whiteboard multilayer film, highway soundproof wall protection film, polyethylene terephthalate, etc. Film, laminated film for shower shielding curtain, laminated film for infusion bag and blood bag, laminated film for wallpaper, film for heat-resistant pouch, interlayer film for laminated glass, film for agricultural house, film for adhesive, chemical resistant coating film for rubber stopper And a film for a flexible printed circuit board having a low dielectric constant, a protective film for a solar cell, and the like.
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JP2006297843A (en) * | 2005-04-25 | 2006-11-02 | Asahi Glass Co Ltd | Fluororesin laminate |
JP5057201B2 (en) * | 2005-08-26 | 2012-10-24 | 旭硝子株式会社 | Fluoropolymer molded body having a functional surface |
US20100036073A1 (en) * | 2008-08-08 | 2010-02-11 | E. I. Du Pont De Nemours And Company | Non-Melt-Flowable Perfluoropolymer Comprising Repeating Units Arising From Tetrafluoroethylene and a Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond |
JP2011011456A (en) * | 2009-07-02 | 2011-01-20 | Toyobo Co Ltd | Multilayered fluoroplastic film, and multilayered fluoroplastic substrate |
JP5610018B2 (en) * | 2013-03-28 | 2014-10-22 | 東洋紡株式会社 | Multilayer fluoropolymer substrate |
WO2015002251A1 (en) * | 2013-07-04 | 2015-01-08 | 旭硝子株式会社 | Insulating tape for covering, and method for producing structure |
JP2015034278A (en) * | 2013-07-12 | 2015-02-19 | 旭硝子株式会社 | Fluororesin composition, molten and kneaded material, electric cable, manufacturing method of molten and kneaded material, and manufacturing method of covering material for electric cable |
TWI691576B (en) * | 2013-11-29 | 2020-04-21 | 日商Agc股份有限公司 | Then the film and flexible metal laminate |
JP6753415B2 (en) * | 2015-11-13 | 2020-09-09 | Agc株式会社 | Copolymer and composition containing it |
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