CN113056507A - 金属板被覆用膜和树脂被覆金属板 - Google Patents
金属板被覆用膜和树脂被覆金属板 Download PDFInfo
- Publication number
- CN113056507A CN113056507A CN201980071195.XA CN201980071195A CN113056507A CN 113056507 A CN113056507 A CN 113056507A CN 201980071195 A CN201980071195 A CN 201980071195A CN 113056507 A CN113056507 A CN 113056507A
- Authority
- CN
- China
- Prior art keywords
- film
- metal plate
- coating
- range
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 119
- 239000002184 metal Substances 0.000 title claims abstract description 119
- 238000000576 coating method Methods 0.000 title claims abstract description 67
- 239000011248 coating agent Substances 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims description 55
- 239000011347 resin Substances 0.000 title claims description 55
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- 230000000930 thermomechanical effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 241000219000 Populus Species 0.000 abstract 1
- 238000000034 method Methods 0.000 description 37
- 238000003475 lamination Methods 0.000 description 30
- 230000037303 wrinkles Effects 0.000 description 30
- 230000000704 physical effect Effects 0.000 description 19
- 239000010410 layer Substances 0.000 description 17
- 238000005259 measurement Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 14
- 230000009477 glass transition Effects 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000009998 heat setting Methods 0.000 description 8
- 238000010030 laminating Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- YIFFAEJYCUTZAO-UHFFFAOYSA-N 2-(4-propylphenoxy)ethanol Chemical compound CCCC1=CC=C(OCCO)C=C1 YIFFAEJYCUTZAO-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
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Abstract
本发明的金属板被覆用膜的特征在于,长边方向的杨氏模量EMD与宽度方向的杨氏模量ETD的比(EMD/ETD)在1.1~4.0的范围内,利用热机械分析装置测定的200℃的热收缩率在长边方向和宽度方向均为20%以下。长边方向的杨氏模量EMD与宽度方向的杨氏模量ETD的和(EMD+ETD)优选在3000MPa~12000MPa的范围内。存在于最低温侧的熔化峰温度Tm1优选在210℃~280℃的范围内。
Description
技术领域
本发明涉及金属板被覆用膜和树脂被覆金属板。
背景技术
以往,在使用了非镀锡薄板(以下记载为TFS)、铝等金属容器的内表面和外表面,出于防腐蚀的目的,广泛进行了通过涂装来被覆表面。而且,这样的涂装使用了环氧系树脂、酚系树脂等各种热固化性树脂。然而,对于使用了热固化性树脂的被覆方法,涂料的干燥需要长时间,因此,不仅生产率降低,而且还存在消耗大量的能量,排出大量的溶剂这样的问题。因此,为了解决这些问题,提出了众多在金属板层叠热塑性树脂进行被覆的方法。作为在金属板层叠热塑性树脂的方法,有对实施了镀覆处理等各种表面处理的金属板进行加热,使热塑性树脂膜热压接于该金属板并进行层压的方法。
在使热塑性树脂膜热压接于已加热的金属板时,存在暴露于高温气氛下的热塑性树脂膜发生热收缩的问题。此外,有时因热塑性树脂膜的热收缩而产生皱褶或者在与金属板之间混入气泡。由于热塑性树脂膜的热收缩,不仅产品宽度变小,生产率差,而且混入气泡、皱褶这之类的缺陷,从而导致品质降低。
作为抑制金属板被覆用膜的热收缩的方法,在专利文献1中提出了采用使用担负耐热性的结晶化温度高的树脂的层、使用担负耐冲击性、耐变形性的高熔点树脂的层以及使用担负与金属的密合性的玻璃化转变温度低的树脂的层这3层构成的方法。另外,在专利文献2~4中还提出了通过规定层压辊的直径、橡胶衬里厚度的方法,对在层压辊附近行进的金属带喷吹气体的方法以及对层压部进行减压的方法之类的制造方法的设计来谋求抑制气泡的方法。
现有技术文献
专利文献
专利文献1:日本特开平7-290666号公报
专利文献2:日本特开平6-8335号公报
专利文献3:日本特开平7-214724号公报
专利文献4:日本特开平7-186353号公报
发明内容
然而,专利文献1中记载的方法设想了制罐时、制罐后的热处理时的耐热性,无法实现本发明所要求的高层压温度条件下的热收缩抑制。另外,专利文献2~4中记载的方法无法实质上抑制膜的热收缩,并且在本发明所要求的高层压温度条件下没有效果。
本发明是鉴于上述课题而作出的。其目的在于提供一种在热压接层压法中,特别是高温下的热收缩小,因此能够制造广泛的产品,且也能够抑制皱褶的产生、气泡的混入的金属板被覆用膜和树脂被覆金属板。
本发明的金属板被覆用膜的特征在于,长边方向的杨氏模量EMD与宽度方向的杨氏模量ETD的比(EMD/ETD)在1.1~4.0的范围内,利用热机械分析装置测定的200℃的热收缩率在长边方向和宽度方向均为20%以下。
本发明的金属板被覆用膜的特征在于,在上述发明中,长边方向的杨氏模量EMD与宽度方向的杨氏模量ETD的和(EMD+ETD)在3000MPa~12000MPa的范围内。
本发明的金属板被覆用膜的特征在于,在上述发明中,存在于最低温侧的熔化峰温度Tm1在210℃~280℃的范围内。
本发明的金属板被覆用膜的特征在于,在上述发明中,聚酯树脂在总成分中所占的比例为80质量%以上。
本发明的金属板被覆用膜的特征在于,在上述发明中,膜厚度在3.0μm~25μm的范围内。
本发明的金属板被覆用膜的特征在于,在上述发明中,用于容器的表面被覆。
本发明的树脂被覆金属板的特征在于,至少在单面具备本发明的金属板被覆用膜。
根据本发明的金属板被覆用膜和树脂被覆金属板,在热压接层压法中,特别是高温下的热收缩小,因此能够制造广泛的产品,且也能够抑制皱褶的产生、气泡的混入。
具体实施方式
以下,对本发明的金属板被覆用膜和树脂被覆金属板进行说明。
本发明的金属板被覆用膜的特征在于,长边方向的杨氏模量EMD与宽度方向的杨氏模量ETD的比(EMD/ETD)在1.1~4.0的范围内。这里所谓的长边方向是指膜被制膜时的膜的行进方向,例如如果为卷状的膜,则是指卷的卷绕方向。另外,与长边方向正交的方向相当于宽度方向。从与金属板的热压接时的宽度方向热收缩和气泡、皱褶的混入抑制的观点考虑,比(EMD/ETD)如果在1.2~3.5的范围内,则更优选。如果在1.3~3.0的范围内,则更进一步优选,如果在1.5~2.5的范围内,则进一步特别优选。
比(EMD/ETD)小于1.1时,有时在热压接时的高温下,膜容易在宽度方向收缩,产品宽度变窄。另外,有时因该膜收缩而在膜与金属板之间混入气泡、皱褶。特别是比(EMD/ETD)为1.0时,膜的取向意味着各向同性、或者为无取向,任一情况从与金属板的热压接时的宽度方向热收缩和气泡、皱褶的混入的观点考虑均不优选。即使取向为各向同性,宽度方向的残留应力也残留很多,特别是无法完全抑制高温时的宽度方向热收缩。另外,在无取向膜的情况下,由于没有弹力,因此,在即将热压接之前因热而软化的膜容易产生气泡。应予说明,如果如上所述在树脂被覆金属板内大量混入气泡、皱褶,则有时例如在深拉深成型成2片罐的罐体时成为缺陷,耐腐蚀性差。
另一方面,比(EMD/ETD)超过4.0时,有时长边方向的取向过强,在热压接时的高温下,膜容易在长边方向收缩,根据情况,膜发生断裂。另外,也有时宽度方向的弹性变得过弱,导致产生皱褶。此外,在用于容器的表面被覆的情况下,有时由于各向异性高而无法成型出均匀的容器,耐腐蚀性差。使比(EMD/ETD)在上述的范围内如后所述可通过将无拉伸膜在长边方向进行单轴拉伸的方法或对双轴拉伸膜进行再纵拉伸的方法来实现。
本发明的金属板被覆用膜的特征在于,利用热机械分析装置(TMA)测定的200℃的热收缩率在长边方向和宽度方向均为20%以下。对于利用TMA测定的200℃的热收缩率,从与金属板的热压接时的宽度方向热收缩和气泡、皱褶的混入抑制的观点考虑,如果长边方向和宽度方向均为15%以下,则更优选。如果为13%以下,则进一步优选,如果为11%以下,则特别优选。长边方向的200℃的热收缩率超过20%时,有时在热压接时的高温下,膜在长边方向过于收缩,容易产生皱褶,根据情况,膜发生断裂。另外,宽度方向的200℃的热收缩率超过20%时,有时在热压接时的高温下,膜容易在宽度方向收缩,产品宽度变窄。另外,有时因该膜收缩而在膜与金属板之间混入气泡、皱褶。应予说明,如果如上所述在树脂被覆金属板内大量混入气泡、皱褶,则有时例如在深拉深成型成2片罐的罐体时成为缺陷,耐腐蚀性差。
从热压接时的皱褶混入、膜断裂的观点考虑,如果利用TMA所测定的200℃的热收缩率在长边方向和宽度方向均为-20%以上,即200℃的热膨胀率(或者热伸长率)为20%以下,则优选。使利用TMA测定的200℃的热收缩率在长边方向和宽度方向均在上述的范围内如后所述可通过应用拉伸后的热处理、松弛而实现。
本发明的金属板被覆用膜中,长边方向的杨氏模量EMD与宽度方向的杨氏模量ETD的和(EMD+ETD)优选在3000MPa~12000MPa的范围内。从能够在树脂被覆金属板制造时不产生皱褶的地进行膜输送的观点以及制成容器的加工性的观点考虑,和(EMD+ETD)如果在3200MPa~10000MPa的范围内,则更优选。如果在3400MPa~9000MPa的范围内,则进一步优选,如果在3600MPa~8500MPa的范围内,则特别优选。
如果和(EMD+ETD)为3000MPa以上,则膜的弹性充分,在输送时、热压接时均能够平滑地保持膜。另一方面,如果和(EMD+ETD)为12000MPa以下,则加工成容器时的加工性优异。作为使和(EMD+ETD)为上述范围内的方法,有使后述的以聚酯树脂为主成分构成的膜,或者在后述的条件下将膜拉伸或热固定的方法。
本发明的金属板被覆用膜中,存在于最低温侧的熔化峰温度Tm1优选在210℃~280℃的范围内。这里所谓的存在于最低温侧的熔化峰是指在将具有不同熔化行为的树脂混合2种以上的情况下检测出的起因于各个树脂的熔化峰温度中存在于最低温侧的熔化峰。另外,在单独树脂的情况下或者即使混合多种树脂也仅能检测出1个熔化峰的情况下,是指该熔化峰。应予说明,有时熔化峰重合,低温侧的熔化峰作为高温侧的主峰的肩而存在,此时,将肩的温度作为存在于最低温侧的熔化峰温度。
从在与金属板的热压接时的高温下抑制利用膜的热收缩、因软化所致的气泡、皱褶的混入的观点考虑,存在于最低温侧的熔化峰温度Tm1如果在215℃~260℃的范围内,则更优选。如果在218℃~260℃的范围内,则进一步优选,如果在220℃~260℃的范围内,则特别优选。如果存在于最低温侧的熔化峰温度Tm1为210℃以上,则能够更容易地进行没有缺陷的热压接。另一方面,如果存在于最低温侧的熔化峰温度Tm1为280℃以下,则能够得到与金属板的更良好的密合性。
本发明的金属板被覆用膜优选以聚酯树脂为主成分。应予说明,“主成分”是指特定的成分在总成分中所占的比例为80质量%以上,更优选为85质量%以上,进一步优选为90质量%以上,特别优选为95质量%以上。作为聚酯树脂,优选为通过由以芳香族二羧酸或脂肪族二羧酸与二醇为主要的构成成分的单体的聚合而得到的树脂、或者它们的混合物。
这里,作为芳香族二羧酸,可例示对苯二甲酸、间苯二甲酸、邻苯二甲酸、萘二甲酸、二苯基二羧酸、二苯基醚二羧酸、二苯基砜二羧酸、二苯氧基乙烷二羧酸、5-磺基间苯二甲酸钠等。作为脂肪族二羧酸,可例示草酸、琥珀酸、己二酸、辛二酸、癸二酸、二聚酸、马来酸、富马酸、十二烷二酸、环己烷二羧酸以及它们的酯衍生物等。这些酸成分可以仅使用1种,也可以并用2种以上,此外,也可以将对羟基苯甲酸等羟基羧酸等共聚。
另外,作为二醇成分,可例示乙二醇、丙二醇、丁二醇、戊二醇、己二醇、新戊二醇、环己烷二甲醇、二乙二醇、三乙二醇、聚亚烷基二醇、2,2-双(4-羟基乙氧基苯基)丙烷、异山梨醇(1,4:3,6-二脱水葡萄糖醇、1,4:3,6-二脱水-D-山梨糖醇)、螺二醇、双酚A、双酚S等。其中,优选使用乙二醇、丁二醇。这些二醇成分可以仅使用1种,也可以并用2种以上。
作为本发明的金属板被覆用膜的聚酯树脂,从与金属板的密合性的观点考虑,优选使用上述聚酯中聚对苯二甲酸乙二醇酯和其共聚物、聚萘二甲酸乙二醇酯和其共聚物、聚对苯二甲酸丁二醇酯和其共聚物。另外,也可以优选使用它们的混合物。
本发明的金属板被覆用膜中,只要不阻碍本发明的效果,则可以共聚偏苯三酸、均苯三酸、三羟甲基丙烷等多官能化合物。此外,出于赋予功能性的目的,可以添加聚酯以外的树脂成分。作为上述树脂成分,可以使用聚乙烯、聚丙烯、聚(4-甲基1-戊烯)、聚羧酸等链状聚烯烃、降冰片烯类的开环易位聚合、加成聚合、与其它烯烃类的加成共聚物即脂环族聚烯烃、聚乳酸、聚琥珀酸丁酯等生物分解性聚合物、尼龙6、尼龙11、尼龙12、尼龙66等聚酰胺、芳族聚酰胺、聚甲基丙烯酸甲酯、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、聚乙烯醇缩丁醛、乙烯乙酸乙烯酯共聚物、聚缩醛、聚乙醇酸、聚苯乙烯、苯乙烯共聚物聚甲基丙烯酸甲酯、聚碳酸酯、聚醚砜、聚醚醚酮、改性聚苯醚、聚苯硫醚、聚醚酰亚胺、聚酰亚胺、聚芳酯、四氟乙烯树脂、三氟乙烯树脂、三氟氯乙烯树脂、四氟乙烯-六氟丙烯共聚物、聚偏氟乙烯等。应予说明,它们可以为共聚物,也可以为混合物。
从提高耐热性的方面出发,优选在构成本发明的金属板被覆用膜的树脂中在0.0001质量%~1.0质量%的范围内添加公知的抗氧化剂。进一步优选在0.001质量%~1.0质量%的范围内。作为抗氧化剂的种类,没有特别限定,例如可以使用分类为受阻酚系类、肼类、亚磷酸酯类等公知的抗氧化剂。
在构成本发明的金属板被覆用膜的树脂中,在不阻碍本发明的效果的范围内,除上述的抗氧化剂以外,还可以包含各种添加剂。例如可以使用增滑剂、结晶成核剂、热稳定剂、防带电剂、防粘连剂、填充剂、粘度调整剂、着色颜料等。
本发明的金属板被覆用膜中,膜厚度优选在3.0μm~25μm的范围内。从树脂被覆金属板制造时的膜输送性、热压接时的皱褶、气泡的混入抑制、以及膜熔融抑制的观点考虑,膜厚度如果在4.0μm~20μm的范围内,则更优选。如果在5.0μm~15μm的范围内,则进一步优选,如果在6.0μm~10μm的范围内,则特别优选。
如果膜厚度为3.0μm以上,则能够发挥更优异的膜输送性,可靠地被覆金属板。另外,作为容器使用时,可得到更良好的耐腐蚀性。另一方面,如果膜厚度为25μm以下,则能够更可靠地防止与金属板的热压接时的气泡的混入。另外,能够在不损害作为容器使用时的耐腐蚀性的情况下抑制作为树脂被覆金属板的成本上升。
本发明的金属板被覆用膜即使是同一树脂组合物的单层构成也可优选使用,但出于赋予功能性的目的,优选为层叠为2层以上的构成。作为层叠构成,例如可以层叠于金属板的表层为与金属板密合性高的组成,其相反侧的表层为耐划伤性优异的树脂组成,进而内层为赋予耐热性、耐腐蚀性的组成等。另外,仅使表层含有增滑剂,或者仅使内层含有颜料是以不阻碍本发明的效果的方式含有添加剂的优选的方法。作为层叠方向,不仅可以为上述的厚度方向的层叠,也可以在长边方向、宽度方向进行层叠,但从作为金属板被覆用膜的功能赋予的观点考虑,优选向厚度方向的层叠。作为层叠方法,例如使用进料块方式、多歧管方式的共挤出法或与其它膜贴合的方法、将熔融的树脂直接层叠在膜上的层压法均可。
接着,以下对本发明的金属板被覆用膜的制造方法进行说明,但未必限定于此。制造本发明的金属板被覆用膜时,首先,以颗粒等形态准备上述优选的聚酯树脂。颗粒根据需要在热风中或真空下干燥后与各种添加剂一起供给到挤出机。在挤出机内,加热熔融到熔点以上的树脂利用齿轮泵等将挤出量均匀化,介由过滤器等去除异物、改性的树脂等。制成层叠构成时,供给到与上述不同的挤出机,通过各自不同流路送入到层叠装置。作为层叠装置,可以使用进料块、多歧管模。
这些树脂在利用T型模头成型为片状后排出。然后,从T型模头排出的熔融片被挤出到流延鼓等冷却体上,然后进行冷却固化,以无拉伸膜的形式得到。此时,出于提高流延鼓等冷却体与熔融片的密合性的目的,优选使用线状、带状、针状或刀状等电极,通过静电力使其密合,进行骤冷固化。另外,也优选从狭缝状、点状、面状的装置吹出气体使其密合,进行骤冷固化的方法;利用夹辊使其密合,进行骤冷固化的方法;以及将它们组合的方法。
以这样的方式得到的无拉伸膜优选接着进行纵向拉伸而制成单轴拉伸膜。另外,也优选在纵向拉伸、横向拉伸和双轴拉伸后再次在纵向进行拉伸。
首先,对单轴拉伸膜的制造方法进行说明。得到的无拉伸膜向纵向拉伸。这里,向纵向拉伸是指用于对膜赋予长边方向的分子取向的拉伸。通常,利用辊的周速差来实施,其行进方向的拉伸可以以1个阶段进行,另外,也可以使用多根辊对以多个阶段地进行。作为拉伸的倍率,根据树脂的种类而不同,优选在2.0倍~6.0倍的范围内。更优选在2.5倍~5.5倍的范围内,进一步优选在3.0倍~5.0倍的范围内。
纵向拉伸倍率小于2.0倍时,有时产生拉伸不均,长边方向的厚度不均变大。另一方面,纵向拉伸倍率超过6.0倍时,有时过于赋予长边方向的取向,导致容易热收缩,或者宽度方向的弹性变弱,从而容易产生皱褶。另外,作为纵向拉伸温度,优选为构成膜的树脂的玻璃化转变温度~玻璃化转变温度+100℃。更优选为玻璃化转变温度+10℃~玻璃化转变温度+80℃的范围内,进一步优选为玻璃化转变温度+30℃~玻璃化转变温度+70℃的范围内。纵向拉伸温度过低时,有时膜在拉伸时发生断裂,或者过于赋予长边方向的取向,导致容易热收缩。另一方面,纵向拉伸温度变高时,存在拉伸膜热结晶化,膜在拉伸时发生断裂、或者相反地过于软化而粘合于辊的情况等。
向纵向拉伸的膜优选其后进行热固定。热固定优选一边在加热到高温的纵向拉伸机内的辊行进一边进行,作为热固定温度,优选为纵向拉伸温度~熔点-50℃。更优选在纵向拉伸温度以上、纵向拉伸温度+60℃以下且熔点-50℃以下的范围内,进一步优选在纵向拉伸温度+10℃以上、纵向拉伸温度+50℃以下且熔点-50℃以下的范围内。特别优选在纵向拉伸温度+20℃以上、纵向拉伸温度+40℃以下且熔点-50℃以下的范围内。该热固定对于减少单轴取向的膜的残留应力很重要,如果热固定温度过低,则有时得不到残留应力减少效果。另一方面,如果热固定温度过高,则也有时膜的收缩变大而向输送中的膜混入皱褶,或者根据情况发生膜破裂。
此外,热固定可以一边使膜在长边方向松弛一边进行,作为松弛率,优选在0.5%~10.0%的范围内。更优选在1.0%~8.0%的范围内,进一步优选在1.5%~6.0%的范围内。通过与热固定同时进行松弛,单轴取向的膜的残留应力进一步减少,因而优选。如果松弛率过低,则有时得不到残留应力减少效果。另一方面,如果松弛率过高,则有时膜不完全收缩而输送中的膜松动。被热固定的膜通过其后在冷却辊行进而被缓冷,得到单轴拉伸膜。
接着,对双轴拉伸后的再拉伸膜的制造方法进行说明。作为双轴拉伸的方法,可以使用在长边方向拉伸后在宽度方向拉伸,或者在宽度方向拉伸后在长边方向拉伸的逐次双轴拉伸法;或者在长边方向和宽度方向同时进行拉伸的同时双轴拉伸法等。在逐次双轴拉伸法的情况下,从品质的均匀化、设备省空间化的观点考虑,优选在长边方向拉伸后在宽度方向进行拉伸。这里,对在长边方向拉伸后在宽度方向进行拉伸的逐次双轴拉伸法进行描述。
首先,得到的无拉伸膜向纵向拉伸。这里,向纵向拉伸是指用于对膜赋予长边方向的分子取向的拉伸。通常利用辊的周速差实施,其行进方向的拉伸可以以1个阶段进行,另外,也可以使用多根辊对以多个阶段地进行。作为拉伸的倍率,根据树脂的种类而不同,优选在2.0倍~6.0倍的范围内。更优选在2.5倍~5.0倍的范围内,进一步优选在2.8倍~4.5倍的范围内。
纵向拉伸倍率小于2.0倍时,有时产生拉伸不均,长边方向的厚度不均变大。另一方面,纵向拉伸倍率超过6.0倍时,有时其后的宽度方向拉伸变得困难,膜发生断裂。另外,作为纵向拉伸温度,优选为构成膜的树脂的玻璃化转变温度~玻璃化转变温度+100℃。更优选为玻璃化转变温度+10℃~玻璃化转变温度+80℃的范围内,进一步优选为玻璃化转变温度+30℃~玻璃化转变温度+70℃的范围内。纵向拉伸温度过低时,有时膜在拉伸时发生断裂,或者过于赋予长边方向的取向,导致容易热收缩。另一方面,纵向拉伸温度过高时,存在无拉伸膜热结晶化,膜在拉伸时发生断裂,或者相反地过于软化而粘合于辊的情况等。
将被单轴拉伸的膜暂时缓冷,接着,把持膜端部而导入到拉幅式拉伸机。作为宽度方向拉伸倍率,优选为2.5倍~10.0倍的范围内,更优选为3.0倍~8.0倍的范围内,进一步优选在3.5倍~6.0倍的范围内。宽度方向的拉伸倍率小于2.5倍时,有时产生拉伸不均,宽度方向的厚度不均变大。另一方面,宽度方向拉伸倍率超过10.0倍时,有时其后的再拉伸变得困难,膜发生断裂。作为拉伸温度,优选为构成膜的树脂的玻璃化转变温度~玻璃化转变温度+100℃,更优选为玻璃化转变温度+30℃~玻璃化转变温度+100℃的范围内。进一步优选为玻璃化转变温度+35℃~玻璃化转变温度+90℃的范围内,特别优选为玻璃化转变温度+40℃~玻璃化转变温度+80℃的范围内。
宽度方向拉伸温度过低时,有时膜在拉伸时发生断裂,或者过于赋予宽度方向的取向,导致其后的再拉伸变得困难,膜发生断裂。另一方面,宽度方向拉伸温度过高时,有时相反地没有赋予取向,宽度方向的厚度不均变大。被宽度方向拉伸的膜优选其后暂时进行热固定。热固定优选在加热到高温的拉幅机内进行,作为热固定温度,优选为宽度方向拉伸温度~熔点-50℃。更优选为宽度方向拉伸温度以上、宽度方向拉伸温度+60℃以下且熔点-50℃以下的范围内,进一步优选为宽度方向拉伸温度+10℃以上、宽度方向拉伸温度+50℃以下且熔点-50℃以下的范围内。特别优选为宽度方向拉伸温度+20℃以上、宽度方向拉伸温度+40℃以下且熔点-50℃以下的范围内。
此外,热固定可以一边使膜在长边方向和/或宽度方向松弛一边进行。作为松弛率,优选在0.3%~5.0%的范围内,更优选在0.5%~4.0%以下的范围内,进一步优选在0.8%~3.0%的范围内。通过与热固定同时进行松弛,双轴取向的膜的残留应力进一步减少,因而优选。如果松弛率过低,则有时得不到残留应力减少效果。另一方面,如果松弛率过高,则有时膜不完全收缩而膜在拉幅内松动。被热固定的膜其后在拉幅内被缓冷,得到双轴拉伸膜。
得到的双轴拉伸膜可以直接再次导入到纵向拉伸机,也可以暂且利用卷绕机以卷的形式卷绕到芯上后,重新导入到纵向拉伸机。这里的再纵拉伸也利用辊的周速差实施,其行进方向的拉伸可以以1个阶段进行,另外,也可以使用多根辊对以多个阶段进行。作为再拉伸倍率,优选在1.2倍~2.8倍的范围内,更优选在1.4倍~2.6倍的范围内,进一步优选在1.6倍~2.4倍的范围内。
再拉伸倍率小于1.2倍时,有时产生拉伸不均,长边方向的厚度不均变大。另一方面,再拉伸倍率超过2.8倍时,有时过于赋予长边方向的取向,导致容易热收缩,或者膜发生断裂。另外,作为拉伸温度,更优选在80℃~150℃的范围内,进一步优选在90℃~140℃的范围内,特别优选在100℃~130℃的范围内。拉伸温度过低时,有时膜在拉伸时发生断裂,或者过于赋予长边方向的取向,导致容易热收缩。另一方面,拉伸温度过高时,有时相反地不赋予取向,长边方向的厚度不均变大。
被再拉伸的膜优选其后进行热固定。热固定优选一边在加热到高温的纵向拉伸机内的辊行进一边进行,作为热固定温度,优选为再拉伸温度~熔点-50℃。更优选在再拉伸温度以上、再拉伸温度+60℃以下且熔点-50℃的范围内,进一步优选在再拉伸温度+10℃以上、再拉伸温度+50℃以下且熔点-50℃的范围内。特别优选在再拉伸温度+20℃以上、再拉伸温度+40℃以下且熔点-50℃的范围内。该热固定对于减少在长边方向强取向的膜的残留应力很重要,如果热固定温度过低,则有时得不到残留应力减少效果。另一方面,如果热固定温度过高,则也有时膜的收缩变大而向输送中的膜混入皱褶,或者根据情况发生膜破裂。另外,有时膜的结晶化性变高,加工成容器时的加工性差,被覆于金属板的树脂膜被削掉,耐腐蚀性差。
此外,热固定可以一边使膜在长边方向松弛一边进行。作为松弛率,优选在0.5%~10.0%的范围内,更优选在1.0%~8.0%的范围内,进一步优选在1.5%~6.0%的范围内。通过与热固定同时进行松弛,在长边方向取向的膜的残留应力进一步减少,因而优选。如果松弛率过低,则有时得不到残留应力减少效果。另一方面,如果松弛率过高,则有时膜不完全收缩而输送中的膜松动。被热固定的膜其后通过在冷却辊行进被缓冷,得到再拉伸膜。
本发明的金属板被覆用膜能够抑制通过热压接层压法被覆金属板时的皱褶、气泡的混入,因此,能够适用于耐腐蚀性优异的容器。另外,本发明的金属板被覆用膜由于高温下的膜热收缩量少,因此通过被覆于金属板的至少单面,能够适用作树脂被覆金属板。
实施例
以下,利用实施例对本发明详细地进行说明。应予说明,特性通过以下所示的方法进行测定、评价。
(1)杨氏模量
使用株式会社INTESCO制精密万能材料试验机(210XL型),在23℃条件下测定。样品尺寸以测定方向(长边方向或宽度方向)为150mm、与测定方向呈直角的方向为10mm的方式切出。以原长50mm、拉伸速度300mm/分钟进行拉伸,依照JIS-K7127(1999)中规定的方法测定杨氏模量。应予说明,长边方向和宽度方向均分别反复进行5次上述测定。将长边方向的5次测定的平均值作为长边方向杨氏模量EMD,将宽度方向的5次测定的平均值作为宽度方向的杨氏模量ETD。
(2)200℃热收缩率
使用株式会社日立High-Tech Science制热机械分析装置(TMA7100C)进行测定。样品以测定方向(长边方向或宽度方向)的卡盘间为10mm、与测定方向呈直角的方向为4mm的方式切出并固定在卡盘间。测定模式为拉伸模式(测定载荷29.4mN),在流量100ml/分钟的氮气氛下以5℃/分钟从30℃升温到250℃。根据由测定得到的图表求出200℃时的TMA值(位移量)。应予说明,对于位移量,将收缩设为正的值,将膨胀或伸长设为负的值。将测定前的卡盘间设为L0,将200℃的位移量设为L1时,将按照以下所示的数式计算的值作为200℃热收缩率。
热收缩率(%)=(L1/L0)×100
(3)熔化峰温度Tm1
在铝制盘中采取本发明的膜5mg作为试样,使用TA仪器公司制差示扫描量热计(DSCQ100)进行测定。首先,在氮气氛下冷却到-50℃,然后以20℃/分钟升温到290℃。根据由测定得到的图表求出存在于最低温侧的熔化峰温度。应予说明,将上述测定反复进行3次,将其平均值作为本膜的存在于最低温侧的熔化峰温度Tm1。
(4)膜厚度
利用设置于株式会社Mitutoyo制Dial Gauge Stand 7001-10的同样为株式会社Mitutoyo制Dial Gauge S-10(带超硬球的测头)进行测定。测定改变场所进行10次,将其平均值作为膜厚度。
(5)基于热压接层压的树脂被覆金属板制作
作为金属板,使用以厚度0.22mm的T3CA作为原板的TFS(金属Cr层:120mg/m2、Cr氧化物层:以金属Cr换算计为10mg/m2)。利用热压接层压法(膜层压法)在金属板的两面被覆以下的实施例和比较例中制造的金属板被覆用膜。具体的层压条件为即将层压前的金属板温度250℃、层压辊温度60℃。应予说明,层压时的温度利用放射温度计测定层压前的温度(距夹持位置100mm的位置)。其后,通过从热压接经过1秒后进行水冷,从而得到在金属板的两面被覆有树脂被覆层的树脂被覆金属板。
(6)膜宽度变化
确认上述(5)中得到的树脂被覆金属板的膜宽度,算出相对于层压前的膜宽度的层压后的膜宽度变化收缩率,通过下述判断基准评价热压接层压性。
A(优秀):基于层压的宽度方向膜收缩率小于1.0%
B(良好):基于层压的宽度方向膜收缩率为1.0%以上且小于5.0%
C(不好):基于层压的宽度方向膜收缩率为5.0%以上
(7)气泡混入量
利用显微镜观察上述(5)中得到的树脂被覆金属板的表面,算出相对于500μm×500μm视场内的正常被覆部的气泡的面积比率,通过下述判断基准评价热压接层压性。
A(优秀):气泡混入面积率小于1.0%
B(良好):气泡混入面积率为1.0%以上且小于5.0%
C(不好):气泡混入面积率为5.0%以上
(8)皱褶混入条数
在得到的树脂被覆金属板200mm×200mm的范围内目视观察皱褶的混入状态,通过下述判断基准评价热压接层压性。
A(优秀):无皱褶混入
B(良好):混入1条皱褶
C(不好):混入2条以上皱褶
(9)金属罐耐腐蚀性
将上述(5)得到的树脂被覆金属板进行DRD(Draw&Redraw)成型,制作2片罐用罐体。使1重量%食盐水填充到罐容量的8成,将阴极浸入到食盐水内,将阳极设置于罐口部的金属露出的部位。对电极间施加6.2V的电压,测量通电4秒后的电流值。根据所测量的电流值,通过下述判断基准评价金属罐耐腐蚀性。
A(优秀):小于0.1mA
B(良好):0.1mA以上且小于5mA
C(不好):5mA以上
(实施例1)
作为膜的原料树脂,准备熔点为224℃的聚对苯二甲酸丁二醇酯(以下,记载为PBT)以及熔点为258℃的聚对苯二甲酸乙二醇酯(以下,记载为PET)的颗粒。分别在真空高温下使其充分干燥以便不含水分。其后,以PBT成为60质量%、PET成为40质量%的方式混合颗粒,制成其后与金属板热压接时的与金属板粘接的层(A层)用的树脂组合物A。此外,以PBT成为80质量%、PET成为20质量%的方式混合颗粒,制成其后与金属板热压接时的不与金属板粘接的层(B层),即表层侧用的树脂组合物B。将树脂组合物A、B分别投入到不同的2台单轴挤出机,在270℃下进行熔融混炼。接着,介由25μm截止的烧结过滤器进行异物除去后,利用将A层与B层的层叠比率设计成2:8的进料块使其合流,在厚度方向层叠2层。从T型模头排出所层叠的熔融树脂,在将表面温度控制为30℃的流延鼓上进行冷却固化,得到厚度18μm的无拉伸膜。接着使用已加热的陶瓷辊,以膜温度成为100℃的方式进行预热,在膜的长边方向进行3.0倍拉伸。其后,使用已加热的镜面HCr镀辊,在120℃进行热固定。应予说明,利用此时2根连续的镜面HCr镀辊间的速度差,在长边方向实施3.0%的松弛。最后缓冷到室温,将除去了端部的膜利用卷绕机卷绕,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例2)
使无拉伸膜的厚度为12μm,使长边方向的拉伸倍率为2.0倍,除此以外,与实施例1同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例3)
作为膜的原料树脂,准备熔点为258℃的PET的颗粒,在真空高温下使其充分干燥以便不含水分。将其投入到单轴挤出机,在280℃下进行熔融混练。接着,经由切成25μm的烧结过滤器,进行异物除去后,从T型模头排出,在对35℃控制表面温度的流延鼓上进行冷却固化,得到厚度150μm的无拉伸膜。接着,使用加热的陶瓷辊,以膜温度成为110℃的方式进行预热,在膜的长边方向进行3.5倍拉伸。其后,利用夹具在拉幅式拉伸机夹住并导入端部,在120℃下在宽度方向上以4.0倍拉伸。直接在140℃下进行热固定,并且在宽度方向实施1.5%的松弛。其后,缓慢冷却到室温,将除去了端部的膜导入到纵拉伸机。使用加热的陶瓷辊,以膜温度成为120℃的方式进行预热,在膜的长边方向进行2.0倍的再拉伸。其后,使用加热的镜面HCr电镀辊,在140℃进行热固定。应予说明,利用此时2根连续的镜面HCr电镀辊间的速度差,在长边方向上实施3.0%的松弛。最后缓慢冷却到室温,利用卷绕机卷绕除去了端部的膜,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例4)
使无拉伸膜的厚度为190μm,使长边方向的再拉伸倍率为2.8倍,除此以外,与实施例3同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例5)
使无拉伸膜的厚度为11.4μm,使长边方向的拉伸倍率为1.9倍,除此以外,与实施例1同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例6)
使向长边方向再拉伸后的热固定温度为160℃,除此以外,与实施例4同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例7)
作为膜的原料,准备熔点为258℃的PET以及熔点为208℃的间苯二甲酸共聚PET(以下,记载为CoPET)的颗粒。以A层侧为PET、B层侧为CoPET的方式层叠,使长边方向的拉伸温度为95℃,除此以外,与实施例1同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例8)
使无拉伸膜的厚度为15μm,除此以外,与实施例1同样地制作,得到厚度5.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例9)
使无拉伸膜的厚度为8.5μm,与实施例1同样地制作,得到厚度2.8μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例10)
使无拉伸膜的厚度为45μm,除此以外,与实施例1同样地制作,得到厚度15μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例11)
使无拉伸膜的厚度为80μm,除此以外,与实施例1同样地制作,得到厚度26μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例12)
使无拉伸膜的厚度为15μm,使长边方向的拉伸倍率为2.5倍,除此以外,与实施例1同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例13)
使无拉伸膜的厚度为24μm,使长边方向的拉伸倍率为4.0倍,除此以外,与实施例1同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例14)
使向长边方向再拉伸后的松弛率为0.5%,除此以外,与实施例3同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(实施例15)
使无拉伸膜的厚度为120μm,使长边方向的再拉伸倍率为1.2倍,除此以外,与实施例3同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(比较例1)
调节实施例1的从T型模头的树脂排出量,除此以外,通过同样的方法得到无拉伸膜,将除去了该无拉伸膜的端部的膜利用卷绕机进行卷绕,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(比较例2)
调节实施例3的从T型模头的树脂排出量,除此以外,通过同样的方法进行双轴拉伸,将在横向拉伸后除去了端部的膜利用卷绕机进行卷绕,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(比较例3)
在向长边方向再拉伸后不进行热固定和松弛,除此以外,与实施例3同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
(比较例4)
在长边方向的拉伸后不进行松弛,除此以外,与实施例1同样地制作,得到厚度6.0μm的金属板被覆用膜。将得到的膜的物性示于以下的表1。
〔评价〕
将实施例1~15和比较例1~4的热压接层压性的评价结果一并示于以下的表1。如表1所示,比较例1~4中,膜宽度变化、气泡混入以及皱褶混入中的至少一个为C评价(不好)。与此相对,实施例1~15中,膜宽度变化、气泡混入以及皱褶混入均为B(良好)评价以上。由此确认了根据本发明,在通过热压接层压法被覆于金属板时,特别是高温下的热收缩小,因此,能够制造广泛的产品,且也能够抑制皱褶的产生、气泡的混入。
[表1]
产业上的可利用性
根据本发明,能够提供在热压接层压法中,特别是高温下的热收缩小,因此能够制造广泛的产品,且也能够抑制皱褶的产生、气泡的混入的金属板被覆用膜和树脂被覆金属板。
Claims (7)
1.一种金属板被覆用膜,其特征在于,长边方向的杨氏模量EMD与宽度方向的杨氏模量ETD的比即EMD/ETD在1.1~4.0的范围内,利用热机械分析装置测定的200℃的热收缩率在长边方向和宽度方向均为20%以下。
2.根据权利要求1所述的金属板被覆用膜,其特征在于,长边方向的杨氏模量EMD与宽度方向的杨氏模量ETD的和即EMD+ETD在3000MPa~12000MPa的范围内。
3.根据权利要求1或2所述的金属板被覆用膜,其特征在于,存在于最低温侧的熔化峰温度Tm1在210℃~280℃的范围内。
4.根据权利要求1~3中任一项所述的金属板被覆用膜,其特征在于,聚酯树脂在总成分中所占的比例为80质量%以上。
5.根据权利要求1~4中任一项所述的金属板被覆用膜,其特征在于,膜厚度在3.0μm~25μm的范围内。
6.根据权利要求1~5中任一项所述的金属板被覆用膜,其特征在于,用于容器的表面被覆。
7.一种树脂被覆金属板,其特征在于,至少在单面具备权利要求1~6中任一项所述的金属板被覆用膜。
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