TWI649194B - Forming packaging material and forming case - Google Patents
Forming packaging material and forming case Download PDFInfo
- Publication number
- TWI649194B TWI649194B TW104112343A TW104112343A TWI649194B TW I649194 B TWI649194 B TW I649194B TW 104112343 A TW104112343 A TW 104112343A TW 104112343 A TW104112343 A TW 104112343A TW I649194 B TWI649194 B TW I649194B
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- packaging material
- molding
- heat
- mass
- Prior art date
Links
- 239000005022 packaging material Substances 0.000 title claims abstract description 79
- 238000000465 moulding Methods 0.000 claims abstract description 68
- 229920006015 heat resistant resin Polymers 0.000 claims abstract description 63
- 239000011888 foil Substances 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 239000012948 isocyanate Substances 0.000 claims abstract description 51
- -1 isocyanate compound Chemical class 0.000 claims abstract description 48
- 239000000853 adhesive Substances 0.000 claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 claims abstract description 44
- 239000000049 pigment Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 125000003118 aryl group Chemical group 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 229920001225 polyester resin Polymers 0.000 claims abstract description 28
- 239000004645 polyester resin Substances 0.000 claims abstract description 27
- 229920000728 polyester Polymers 0.000 claims abstract description 23
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 21
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 21
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 213
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- 238000004040 coloring Methods 0.000 claims description 28
- 239000012790 adhesive layer Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 24
- 229920005906 polyester polyol Polymers 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 20
- 238000000576 coating method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000006229 carbon black Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920006284 nylon film Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004925 Acrylic resin Chemical class 0.000 description 4
- 229920000178 Acrylic resin Chemical class 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 239000004952 Polyamide Substances 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Chemical class 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical class [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 238000005304 joining Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052755 nonmetal Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 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
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 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
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 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
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011548 physical evaluation Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000007493 shaping process Methods 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
- 239000001384 succinic acid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/14—Printing or colouring
- B32B38/145—Printing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
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- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
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- 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
- B32B2457/00—Electrical equipment
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- 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
- B32B2457/00—Electrical equipment
- B32B2457/10—Batteries
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- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Abstract
本發明提供一種成形用包裝材1，其構成係包含：作為外側層之耐熱性樹脂層2、作為內側層之熱可塑性樹脂層3、配設於此等兩層間之金屬箔層4、及配設於該金屬箔層與耐熱性樹脂層2之間之著色油墨層10，其特徵為：著色油墨層10，係由著色油墨組成物所成，該著色油墨組成物係包含：作為主劑之聚酯樹脂及作為硬化劑之多官能異氰酸酯化合物所成之二液硬化型聚酯聚氨酯樹脂接著劑、及含有無機顏料之著色顏料所成；聚酯樹脂之數目平均分子量(Mn)為8，000~25，000，質量平均分子量(Mw)為15，000~50，000，該等之比率(Mw/Mn)為1．3~2．5；多官能異氰酸酯化合物之50莫爾%以上為芳香族系多官能異氰酸酯化合物。本發明可提供於成形時及密封時，且即使在高溫多濕等之稍微嚴苛的環境下使用時，耐熱性樹脂層亦不會剝離之成形用包裝材。 The present invention provides a molding packaging material 1 which is composed of a heat-resistant resin layer 2 as an outer layer, a thermoplastic resin layer 3 as an inner layer, a metal foil layer 4 disposed between the two layers, and The colored ink layer 10 provided between the metal foil layer and the heat-resistant resin layer 2 is characterized in that the colored ink layer 10 is made of a colored ink composition, and the colored ink composition contains: A two-liquid curable polyester polyurethane resin adhesive made of a polyester resin and a polyfunctional isocyanate compound as a hardener, and a colored pigment containing an inorganic pigment; the number average molecular weight (Mn) of the polyester resin is 8,000 ~ 25,000, mass average molecular weight (Mw) is 15,000 ~ 50,000, the ratio of these (Mw / Mn) is 1.3 ~ 2.5; more than 50 mole% of polyfunctional isocyanate compound is aromatic A family of polyfunctional isocyanate compounds. The present invention can provide a packaging material for molding that does not peel off the heat-resistant resin layer even when used in a slightly severe environment such as high temperature and humidity during molding and sealing.
Description
本發明係關於例如可較佳地作為筆記型電腦用、行動電話用、車載用、固定型的蓄電池(鋰離子蓄電池)的外殼而使用；除此之外，亦可較佳地作為食品的包裝材、醫藥品的包裝材的成形用包裝材及成形外殼而使用者。 The present invention relates to, for example, a case for a notebook computer, a mobile phone, a vehicle, and a stationary battery (lithium-ion battery). The invention can also be used as a packaging for food. Materials, packaging materials for molding materials, packaging materials for pharmaceutical products, and molding cases for users.
鋰離子蓄電池等電池，為了統一裝設對象的電氣機器等機器的外觀與色彩，逐漸增加對著色的要求。例如，為了賦予穩重感、高級感，較多係將機器著色成黑色，此時電池亦往往著色成黑色。 In order to unify the appearance and color of electrical equipment such as lithium-ion batteries, the coloring requirements are gradually increasing. For example, in order to give a sense of stability and high-grade, the equipment is often colored black, and at this time the battery is often colored black.
此種的電池，係電池本體由包裝材(成形外殼)所包裝而成者，該包裝材一般係於金屬箔的兩面積層基材樹脂層所成的積層體。因此，欲將電池著色時，有以下手段：將電池之包裝材所使用的基材樹脂層著色、於基材樹脂層的下方設置著色印刷層、將基材樹脂層與金屬箔之間的接著劑層著色、若基材樹脂層係由複數層構成時則將此等層間的接著劑層著色等。 Such batteries are those in which the battery body is packed with a packaging material (molded case), and the packaging material is generally a laminated body formed of a two-layer metal substrate resin layer of a metal foil. Therefore, when the battery is to be colored, there are the following methods: coloring the base resin layer used for the battery packaging material, providing a colored printing layer under the base resin layer, and bonding the base resin layer to the metal foil. The agent layer is colored, and if the base resin layer is composed of a plurality of layers, the adhesive layer between these layers is colored.
以往，具有著色層之電池用包裝材，習知為：具有將基材層、接著劑層、金屬箔層、熱接著性樹脂層依序積層而成之構造，且係於基材 層、接著劑層、金屬箔層中之任一層含有珠光顏料或螢光顏料作為識別標示之構成者(參照專利文獻1)；具有將基材層、接著劑層、金屬箔層、熱接著性樹脂層依序積層而成之構造，且於基材層、接著劑層、金屬箔層中之任一層添加顏料作為識別標示而成者(參照專利文獻2)。 Conventionally, a battery packaging material having a colored layer is known to have a structure in which a base material layer, an adhesive layer, a metal foil layer, and a heat-adhesive resin layer are sequentially laminated, and is attached to the base material. Any one of the layer, the adhesive layer, and the metal foil layer includes a pearlescent pigment or a fluorescent pigment as an identification mark (see Patent Document 1); it has a base material layer, an adhesive layer, a metal foil layer, and thermal adhesiveness. A structure in which a resin layer is sequentially laminated, and a pigment is added to any one of a base material layer, an adhesive layer, and a metal foil layer as an identification mark (see Patent Document 2).
此外，為提升電池之放熱性，習知為在金屬箔層與外層薄膜間具備碳材料等之黑體材料層之電池用外裝材(參照專利文獻3)。 In addition, in order to improve the heat release property of a battery, it is known as a battery exterior material having a black body material layer such as a carbon material between a metal foil layer and an outer film (see Patent Document 3).
【專利文獻1】國際公開第2011/016506號公報 [Patent Document 1] International Publication No. 2011/016506
【專利文獻2】特開2011-054563號公報 [Patent Document 2] JP 2011-054563
【專利文獻3】特開2011-096552號公報 [Patent Document 3] JP 2011-096552
一般而言，將薄膜材、片材著色為黑色時，一般係以含碳黑等無機顏料的印刷油墨來設置印刷層。 Generally, when a film material or a sheet is colored black, a printing layer is generally provided with a printing ink containing an inorganic pigment such as carbon black.
然而，為了將電池著色為黑色，將含有碳黑作為顏料的黑色印刷層設置在構成電池包裝材的外側樹脂層的內面時，會產生下列問題。 However, in order to color the battery black, when the black printed layer containing carbon black as a pigment is provided on the inner surface of the outer resin layer constituting the battery packaging material, the following problems occur.
亦即，將上述黑色包裝材進行深引伸成形或鼓脹成形而成形為容器(外殼)形狀時，會產生外側樹脂層由包裝材之黑色印刷層剝離的問題。 In other words, when the black packaging material is formed into a container (housing) shape by deep drawing or inflation molding, a problem arises in that the outer resin layer is peeled from the black printing layer of the packaging material.
如此之外側樹脂層的剝離，會發生在對於封入電極或電解液後的黑色包裝材進行密封時，或亦會發生於黑色包裝材所包裝的電池在高溫多濕等的稍微嚴苛的環境下使用時。 In this way, the peeling of the outer resin layer may occur when the black packaging material sealed with the electrode or the electrolyte is sealed, or the battery packed by the black packaging material may be slightly harsh under high temperature and humidity. when using it.
並且，上述諸問題不限於使用碳黑的黑色包裝材，亦發生於使用其他無機顏料並以同樣方式著色成各種顏色的著色包裝材。 Furthermore, the above problems are not limited to black packaging materials using carbon black, but also occur in colored packaging materials that use other inorganic pigments and are colored in various colors in the same manner.
本發明係鑒於該技術背景而創作，目的在於提供一種成形用包裝材，其於成形時及密封時，且即使在高溫多濕等的稍微嚴苛的環境下使用時，耐熱性樹脂層亦不會剝離。 The present invention has been made in view of this technical background, and an object thereof is to provide a packaging material for molding, which has a heat-resistant resin layer even when used in a slightly severe environment such as high temperature and humidity during molding and sealing. Will peel off.
為達成前述目的，本發明提供以下之手段。 To achieve the foregoing object, the present invention provides the following means.
〔1〕一種成形用包裝材，其係包含：作為外側層之耐熱性樹脂層、作為內側層之熱可塑性樹脂層、配設於此等兩層間之金屬箔層、及配設於該金屬箔層與前述耐熱性樹脂層之間之著色油墨層，其特徵為：前述著色油墨層，係由著色油墨組成物所成，該著色油墨組成物係包含：作為主劑之聚酯樹脂及作為硬化劑之多官能異氰酸酯化合物所成之二液硬化型聚酯聚氨酯樹脂接著劑、及含有無機顏料之著色顏料；前述作為主劑之聚酯樹脂之數目平均分子量(Mn)為8000~25000，質量平均分子量(Mw)為15000~50000，該等之比率(Mw/Mn)為1．3~2．5； 前述作為硬化劑之多官能異氰酸酯化合物之50莫爾%以上為芳香族系多官能異氰酸酯化合物。 [1] A molding packaging material comprising a heat-resistant resin layer as an outer layer, a thermoplastic resin layer as an inner layer, a metal foil layer disposed between the two layers, and the metal foil The coloring ink layer between the layer and the heat-resistant resin layer is characterized in that the coloring ink layer is made of a coloring ink composition. The coloring ink composition includes a polyester resin as a main agent and a hardening agent. Two-liquid curable polyester polyurethane resin adhesive made of polyfunctional isocyanate compound of the agent, and coloring pigment containing inorganic pigment; the number average molecular weight (Mn) of the aforementioned polyester resin as the main agent is 8000 to 25,000, and the mass average The molecular weight (Mw) is 15,000 ~ 50,000, and the ratio of these (Mw / Mn) is 1.3 ~ 2.5; 50 mol% or more of the said polyfunctional isocyanate compound as a hardening | curing agent is an aromatic polyfunctional isocyanate compound.
〔2〕如前項1所記載之成形用包裝材，其中，前述著色油墨層中，相對於前述作為主劑之聚酯樹脂及前述著色顏料之合計質量，著色顏料之含有質量的比例為5質量%~60質量%。 [2] The packaging material for molding as described in the above item 1, wherein in the colored ink layer, the proportion of the contained mass of the colored pigment is 5 mass relative to the total mass of the polyester resin as the main agent and the colored pigment. % ~ 60% by mass.
〔3〕如前項1或2所記載之成形用包裝材，其中，前述著色顏料之50莫爾%以上係由前述無機顏料所構成。 [3] The packaging material for molding according to the above item 1 or 2, wherein 50% by mole or more of the colored pigment is composed of the inorganic pigment.
〔4〕如前項1~3中任一項所記載之成形用包裝材，其中，前述二液硬化型聚酯聚氨酯樹脂接著劑，其藉由前述主劑與前述硬化劑反應後之硬化膜的拉伸試驗(JIS K7162)獲得之楊氏模量為70MPa~400MPa。 [4] The packaging material for molding according to any one of the preceding paragraphs 1 to 3, wherein the two-liquid curable polyester polyurethane resin adhesive is formed by curing the cured film by reacting the main agent with the hardener. The Young's modulus obtained by a tensile test (JIS K7162) is 70 MPa to 400 MPa.
〔5〕如前項1~4中任一項所記載之成形用包裝材，其中，於前述金屬箔層之至少一面形成有化成皮膜者。 [5] The packaging material for molding according to any one of the preceding paragraphs 1 to 4, wherein a chemical conversion film is formed on at least one side of the metal foil layer.
〔6〕一種成形外殼，其特徵為其係對前項1~5中任一項所記載之成形用包裝材進行深引伸成形或鼓脹成形而成者。 [6] A molded case characterized by being formed by deep drawing or bulging the forming packaging material described in any one of the preceding paragraphs 1 to 5.
〔7〕如前項6所記載之成形外殼，其中，其係作為電池外殼使用者。 [7] The molded case as described in the foregoing paragraph 6, wherein it is used as a battery case user.
根據〔1〕的發明，由於在金屬箔層與耐熱性樹脂層之間設置有著色油墨層，因此可賦予成形用包裝材之外面側顏色。此外，由於著色油墨層係由著色油墨組成物所構成，而該著色油墨組成物係包含：作為 主劑之聚酯樹脂及作為硬化劑之多官能異氰酸酯化合物所成之二液硬化型聚酯聚氨酯樹脂接著劑、及含有無機顏料之著色顏料所成；且前述作為主劑之聚酯樹脂之數目平均分子量(Mn)為8000~25000，質量平均分子量(Mw)為15000~50000，該等之比率(Mw/Mn)為1．3~2．5；因此著色油墨層(著色油墨塗膜)可獲得適當的強度、延伸度、與優異之耐熱性。更進一步，因多官能異氰酸酯化合物之50莫爾%以上係由芳香族系多官能異氰酸酯化合物所構成，故可提升硬化後之接著強度。從而，在對此包裝材進行深引伸成形、鼓脹成形等的成形時，且在將包裝材密封以進行封裝時，耐熱性樹脂層不會由著色油墨層剝離。此外，即使在高溫多濕等的稍微嚴苛的環境下使用時，耐熱性樹脂層亦不會由著色油墨層剝離。 According to the invention of [1], since a colored ink layer is provided between the metal foil layer and the heat-resistant resin layer, it is possible to impart color to the outer surface side of the packaging material for molding. In addition, since the colored ink layer is composed of a colored ink composition, the colored ink composition includes: A two-liquid curable polyester polyurethane resin adhesive made of a polyester resin of a main agent and a polyfunctional isocyanate compound as a hardener, and a coloring pigment containing an inorganic pigment; and the number of the aforementioned polyester resins as a main agent The average molecular weight (Mn) is 8000 to 25,000, the mass average molecular weight (Mw) is 15,000 to 50,000, and the ratio (Mw / Mn) is 1.3 to 2.5; therefore, the colored ink layer (colored ink coating film) may be Obtain appropriate strength, elongation, and excellent heat resistance. Furthermore, since 50 mol% or more of the polyfunctional isocyanate compound is composed of an aromatic polyfunctional isocyanate compound, the bonding strength after curing can be improved. Therefore, the heat-resistant resin layer is not peeled from the colored ink layer when the packaging material is formed by deep-extrusion molding, inflation molding, or the like, and when the packaging material is sealed for packaging. Moreover, even when used in a slightly severe environment such as high temperature and humidity, the heat-resistant resin layer does not peel off from the colored ink layer.
根據〔2〕的發明，著色油墨層中，相對於聚酯聚氨酯樹脂接著劑與著色顏料之合計質量，著色顏料之含有比例為5質量%~60質量%，藉由在5質量%以上可得到充分隱蔽金屬箔層之效果，使金屬光澤無法直接以肉眼辨識，從而賦予穩重感、高級感，同時在60質量%以下，可充分確保著色油墨層對於耐熱性樹脂層之接著力。 According to the invention of [2], the content ratio of the coloring pigment in the colored ink layer is 5 mass% to 60 mass% based on the total mass of the polyester polyurethane resin adhesive and the coloring pigment. The effect of fully concealing the metal foil layer makes the metal luster impossible to be directly recognized by the naked eye, thereby giving a sense of stability and high quality, and at the same time 60% by mass or less, it can fully ensure the adhesion of the colored ink layer to the heat-resistant resin layer.
根據〔3〕的發明，由於前述著色顏料之50質量%以上係由無機顏料所構成，故可得到更充分之隱蔽金屬箔層之隱蔽力，藉此，可形成能賦予更加充分之穩重感、高級感的特定色調之著色油墨層。又，傳統上，一般為提升隱蔽力，而將著色顏料中之無機顏料之含有率設計在50質量%以上時，會產生該著色油墨層之密著力降低的問題，然而，本發明採用「作為主劑之聚酯樹脂之數目平均分子量(Mn)為8000~2 5000，質量平均分子量(Mw)為15000~50000，該等之比率(Mw/Mn)為1．3~2．5，且多官能異氰酸酯化合物之50莫爾%以上係由芳香族系多官能異氰酸酯化合物所構成」之限定構成，因此即使採用「著色顏料之50質量%以上為無機顏料所構成」之構成，仍可確保著色油墨層具有充分的密著力。 According to the invention of [3], since more than 50% by mass of the colored pigment is composed of an inorganic pigment, a more sufficient concealing power of the concealed metal foil layer can be obtained, whereby a more stable feeling can be formed, High-quality colored ink layer with specific hue. In addition, traditionally, in order to improve the hiding power, when the content of the inorganic pigment in the coloring pigment is designed to be 50% by mass or more, the problem of reducing the adhesion of the coloring ink layer occurs. However, the present invention uses The number average molecular weight (Mn) of the polyester resin of the main agent is 8000 ~ 2 5000, mass average molecular weight (Mw) is 15000 ~ 50,000, the ratio of these (Mw / Mn) is 1.3 ~ 2.5, and more than 50 mol% of the polyfunctional isocyanate compound is composed of aromatic polyfunctional isocyanate The "compound composition" has a limited composition. Therefore, even if the composition "50% by mass or more of the coloring pigment is composed of an inorganic pigment", it is possible to ensure sufficient adhesion of the coloring ink layer.
根據〔4〕的發明，可使上述效果(在成形時及密封時，又即使在高溫多濕等的稍微嚴苛的環境下使用時，耐熱性樹脂層亦不會由著色油墨層剝離之效果)特別的優異。 According to the invention of [4], the above-mentioned effect can be obtained (the effect that the heat-resistant resin layer does not peel off from the colored ink layer even when used in a slightly severe environment such as high temperature and humidity during molding and sealing. ) Is particularly excellent.
根據〔5〕的發明，因在金屬箔層之至少一面形成有化成皮膜，故可充分防止金屬箔的腐蝕，從而可提供高耐腐蝕性的成形用包裝材。 According to the invention of [5], since a chemical conversion film is formed on at least one side of the metal foil layer, corrosion of the metal foil can be sufficiently prevented, and a molding packaging material having high corrosion resistance can be provided.
根據〔6〕的發明，可提供不僅在密封時，且即使在高溫多濕等的稍微嚴苛的環境下使用時，耐熱性樹脂層亦不會由著色油墨層剝離的成形外殼。 According to the invention of [6], it is possible to provide a molded case in which the heat-resistant resin layer is not peeled off by the colored ink layer, not only during sealing, but also when used in a slightly severe environment such as high temperature and humidity.
根據〔7〕的發明，可提供不僅在密封時，且即使在高溫多濕等的稍微嚴苛的環境下使用時，耐熱性樹脂層亦不會由著色油墨層剝離的電池外殼。 According to the invention of [7], it is possible to provide a battery case in which the heat-resistant resin layer is not peeled from the colored ink layer, not only at the time of sealing but also when used in a slightly severe environment such as high temperature and humidity.
1‧‧‧成形用包裝材 1‧‧‧forming packaging materials
2‧‧‧耐熱性樹脂層(外側層) 2‧‧‧ heat-resistant resin layer (outer layer)
3‧‧‧熱可塑性樹脂層(內側層) 3‧‧‧ thermoplastic resin layer (inner layer)
4‧‧‧金屬箔層 4‧‧‧ metal foil layer
4a‧‧‧金屬箔層內側面 4a‧‧‧Inner side of metal foil layer
5‧‧‧第1接著劑層 5‧‧‧The first adhesive layer
6‧‧‧第2接著劑層 6‧‧‧The second adhesive layer
10‧‧‧著色油墨層 10‧‧‧Colored ink layer
20‧‧‧馬特塗層 20‧‧‧ Matt coating
【圖1】為表示本發明的成形用包裝材的一實施型態之斷面圖。 FIG. 1 is a cross-sectional view showing an embodiment of a molding packaging material according to the present invention.
【圖2】為表示本發明的成形用包裝材的另一實施型態之斷面圖。 Fig. 2 is a sectional view showing another embodiment of the packaging material for molding of the present invention.
【圖3】為二液硬化型聚酯聚氨酯樹脂接著劑的硬化膜之S-S曲線 圖。 [Figure 3] S-S curve of the cured film of the two-liquid curing type polyester polyurethane resin adhesive Illustration.
本發明之成形用包裝材1的一實施型態如圖1所示。此成形用包裝材1，係作為鋰離子蓄電池外殼用包裝材使用。亦即，前述成形用包裝材1，係被提供至深引伸成形等的成形而作為蓄電池外殼使用者。 An embodiment of the molding packaging material 1 of the present invention is shown in FIG. 1. This molding packaging material 1 is used as a packaging material for a lithium ion battery case. That is, the above-mentioned molding packaging material 1 is provided as a battery case user by molding such as deep-extrusion molding.
前述成形用包裝材1，係包含在金屬箔層4的上表面隔著第1接著劑層5與耐熱性樹脂層(外側層)2積層一體化，並同時在前述金屬箔層4的下表面隔著第2接著劑層6與熱可塑性樹脂層(內側層)3積層一體化而成之構成。此外，在前述金屬箔層4與前述耐熱性樹脂層2之間配置有著色油墨層10(參照圖1)。本實施型態，係在前述金屬箔層4的上表面隔著第1接著劑層5與前述著色油墨層10積層，並在該著色油墨層10的上表面與前述耐熱性樹脂層2積層(參照圖1)。此外，本實施型態中，在前述耐熱性樹脂層2之下表面係藉由印刷而積層有前述著色油墨層10。 The molding packaging material 1 is formed by laminating and integrating the heat-resistant resin layer (outer layer) 2 on the upper surface of the metal foil layer 4 with the first adhesive layer 5 interposed therebetween, and simultaneously on the lower surface of the metal foil layer 4. The second adhesive layer 6 and the thermoplastic resin layer (inner layer) 3 are laminated and integrated. A colored ink layer 10 is disposed between the metal foil layer 4 and the heat-resistant resin layer 2 (see FIG. 1). In this embodiment, the upper surface of the metal foil layer 4 is laminated with the colored ink layer 10 via the first adhesive layer 5 and the upper surface of the colored ink layer 10 is laminated with the heat-resistant resin layer 2 ( (See Figure 1). In addition, in the present embodiment, the colored ink layer 10 is laminated on the lower surface of the heat-resistant resin layer 2 by printing.
接著，對於本發明中各構成層進行詳細說明。 Next, each constituent layer in the present invention will be described in detail.
(耐熱性樹脂層) (Heat-resistant resin layer)
前述耐熱性樹脂層(外側層)2，雖無特別限定，但可列舉例如為，聚醯胺薄膜、聚酯薄膜等，使用此等的延伸薄膜為佳。其中，前述耐熱性樹脂層2，就成形性及強度觀點，以使用二軸延伸聚醯胺薄膜、二軸延伸聚對苯二甲酸丁二醇酯(PBT)膜、二軸延伸聚對苯二甲酸乙二醇酯(PET)膜、或二軸延伸聚萘二甲酸乙二醇酯(PEN)膜為特 佳。前述聚醯胺薄膜，雖無特別限定，但可列舉例如為，6-尼龍薄膜、6，6尼龍薄膜、MXD尼龍薄膜等。又，前述前述耐熱性樹脂層2，可由單層形成，亦或，可例如由PET膜/聚醯胺薄膜構成的複數層形成。 The heat-resistant resin layer (outer layer) 2 is not particularly limited, but examples thereof include a polyamide film, a polyester film, and the like, and it is preferable to use such a stretched film. Among them, the heat-resistant resin layer 2 uses a biaxially stretched polyfluorene film, a biaxially stretched polybutylene terephthalate (PBT) film, and a biaxially stretched polyterephthalate from the viewpoint of moldability and strength. Polyethylene formate (PET) film, or biaxially-stretched polyethylene naphthalate (PEN) film are special good. The polyamide film is not particularly limited, but examples thereof include 6-nylon film, 6,6 nylon film, and MXD nylon film. The heat-resistant resin layer 2 may be formed of a single layer, or may be formed of a plurality of layers made of, for example, a PET film / polyamine film.
前述耐熱性樹脂層2的厚度，以9μm~50μm為佳。使用聚酯薄膜時，厚度較佳為9μm~50μm，使用聚醯胺薄膜時，較佳厚度為10μm~50μm。藉由設定在上述較佳的下限值以上，可確保包裝材有充分之強度，並且藉由設定在上述較佳的上限值以下，可降低鼓脹成形時或深引伸成形時的應力而提升成形性。 The thickness of the heat-resistant resin layer 2 is preferably 9 μm to 50 μm. When a polyester film is used, the thickness is preferably 9 μm to 50 μm, and when a polyamide film is used, the thickness is preferably 10 μm to 50 μm. By setting above the above-mentioned preferred lower limit value, sufficient strength of the packaging material can be ensured, and by setting below the above-mentioned preferred upper limit value, the stress during inflation molding or deep extension molding can be reduced and improved Formability.
(熱可塑性樹脂層) (Thermoplastic resin layer)
前述熱可塑性樹脂層(內側層)3，係即使對於使用在鋰離子蓄電池等的腐蝕性高的電解液等，仍具備優異的耐藥品性，並同時擔負賦予包材熱密封性的作用者。 The above-mentioned thermoplastic resin layer (inner layer) 3 has excellent chemical resistance even when used in a highly corrosive electrolyte such as a lithium ion battery, and is also responsible for imparting heat-sealing properties to a packaging material.
前述熱可塑性樹脂層3，雖無特別限定，但較佳係熱可塑性樹脂未拉伸薄膜層。前述熱可塑性樹脂未拉伸薄膜層3，並無特別限定，以耐藥品性及熱密封性的觀點來看，由選自聚乙烯、聚丙烯、烯烴系共聚物、此等的酸改性物及離子聚合物所成群中至少1種之熱可塑性樹脂所組成的未拉伸薄膜所構成者為佳。 The thermoplastic resin layer 3 is not particularly limited, but is preferably a thermoplastic resin unstretched film layer. The thermoplastic resin unstretched film layer 3 is not particularly limited. From the viewpoint of chemical resistance and heat sealability, it is selected from the group consisting of polyethylene, polypropylene, olefin-based copolymers, and the like, and acid-modified products. An unstretched film composed of at least one type of thermoplastic resin in the group of ionic polymers is preferred.
前述熱可塑性樹脂層3的厚度，設定於20μm~80μm為佳。藉由設定在20μm以上，可充分地防止針孔的產生，藉由設定在80μm以下，可降低樹脂用量而達到成本的降低。其中，前述熱可塑性樹脂層3的厚度設定於30μm~50μm為特佳。又，前述熱可塑性樹脂層3，可為單層亦可為複數層。複數層構成之熱可塑性樹脂層3，可例示於嵌段 聚丙烯薄膜的兩面積層無規聚丙烯薄膜而成的三層薄膜等。 The thickness of the thermoplastic resin layer 3 is preferably set to 20 μm to 80 μm. By setting it to 20 μm or more, it is possible to sufficiently prevent the occurrence of pinholes. By setting it to 80 μm or less, the amount of resin used can be reduced and the cost can be reduced. The thickness of the thermoplastic resin layer 3 is particularly preferably set to 30 μm to 50 μm. The thermoplastic resin layer 3 may be a single layer or a plurality of layers. The thermoplastic resin layer 3 composed of a plurality of layers can be exemplified in the block Polypropylene film is a three-layer film made of two-layer random polypropylene film.
(金屬箔層) (Metal foil layer)
前述金屬箔層4，係擔負賦予成形用包裝材1阻止氧或水分侵入之氣體阻障性的作用者。前述金屬箔層4，並無特別限定，可列舉例如，鋁箔、銅箔、不銹鋼箔等，而一般係使用鋁箔。前述金屬箔層4的厚度，以20μm~100μm為佳。當厚度為20μm以上，於製造金屬箔時，可防止壓延時的針孔的產生，同時，當厚度為為100μm以下可降低鼓脹成形時或深引伸成形時的應力而提升成形性。 The metal foil layer 4 is responsible for imparting gas barrier properties to the packaging material 1 for molding to prevent oxygen or moisture from entering. The metal foil layer 4 is not particularly limited, and examples thereof include aluminum foil, copper foil, and stainless steel foil. Generally, aluminum foil is used. The thickness of the metal foil layer 4 is preferably 20 μm to 100 μm. When the thickness is 20 μm or more, pinholes can be prevented from being generated when the metal foil is manufactured. At the same time, when the thickness is 100 μm or less, the stress during bulging or deep drawing can be reduced to improve formability.
前述金屬箔層4，至少在內側的面4a(第2接著劑層6側之面)施有化成處理為佳(參照圖1、2)。實施如此之化成處理可充分防止內容物(電池的電解液、食品、醫藥品等)所致之金屬箔表面腐蝕。例如可藉由實施以下所述之處理以進行金屬箔之化成處理。亦即，例如可藉由在進行脫脂處理後之金屬箔的表面，塗布下述1)~3)中任一項後使其乾燥以實施化成處理。 It is preferable that the metal foil layer 4 is chemically treated at least on the inner surface 4a (the surface on the second adhesive layer 6 side) (see FIGS. 1 and 2). The chemical conversion treatment as described above can sufficiently prevent the surface of the metal foil from being corroded by the contents (the electrolyte of the battery, food, medicine, etc.). For example, a metal foil can be formed by performing the following processing. That is, for example, the surface of the metal foil after being subjected to the degreasing treatment may be coated with any one of the following 1) to 3) and then dried to perform a chemical conversion treatment.
1)含有選自磷酸、鉻酸、氟化物的金屬鹽及氟化物的非金屬鹽所成群中至少1種的化合物的混合物之水溶液 1) An aqueous solution containing a mixture of at least one compound selected from the group consisting of phosphoric acid, chromic acid, metal salts of fluoride, and non-metal salts of fluoride.
2)含有磷酸、丙烯酸系樹脂、殼聚醣衍生物樹脂(Chitosan derivative resins)及苯酚系樹脂所成群中至少1種的樹脂，及選自鉻酸及鉻(III)鹽所成群中至少1種的化合物的混合物之水溶液 2) A resin containing at least one of the group consisting of phosphoric acid, acrylic resin, Chitosan derivative resins, and phenol resin, and at least one member selected from the group consisting of chromic acid and chromium (III) salts An aqueous solution of a mixture of one compound
3)含有選自磷酸、丙烯酸系樹脂、殼聚醣衍生物樹脂、及苯酚系樹脂所成群中至少1種的樹脂、選自鉻酸及鉻(III)鹽所成群中至少1種的化合物、與選自氟化物的金屬鹽及氟化物的非金屬鹽所 成群中至少1種的化合物的混合物之水溶液。 3) A resin containing at least one member selected from the group consisting of phosphoric acid, an acrylic resin, a chitosan derivative resin, and a phenol-based resin, and at least one member selected from the group consisting of chromic acid and a chromium (III) salt. Compounds, and metal salts selected from fluorides and non-metal salts of fluorides An aqueous solution of a mixture of at least one compound in a group.
(著色油墨層) (Colored ink layer)
前述著色油墨層中10，係配置於前述金屬箔層4與前述耐熱性樹脂層2之間之層，在上述實施形態中，係擔負接合前述第1接著劑層5與前述耐熱性樹脂層2的接合作用，並賦予成形用包裝材1之外面側顏色(包含無彩色)之層。 The colored ink layer 10 is a layer disposed between the metal foil layer 4 and the heat-resistant resin layer 2. In the above embodiment, it is responsible for joining the first adhesive layer 5 and the heat-resistant resin layer 2 And a color (including achromatic color) layer on the outer surface side of the packaging material 1 for molding.
前述著色油墨層10，係由著色油墨組成物之硬化膜構成，該著色油墨組成物係包含：作為主劑之聚酯樹脂及作為硬化劑之多官能異氰酸酯化合物所成之二液硬化型聚酯聚氨酯樹脂接著劑(B)、及含有無機顏料之著色顏料(A)。 The colored ink layer 10 is composed of a hardened film of a colored ink composition. The colored ink composition includes a polyester resin as a main agent and a two-liquid curable polyester made of a polyfunctional isocyanate compound as a hardener. Polyurethane resin adhesive (B) and colored pigment (A) containing an inorganic pigment.
前述著色顏料(A)，係採用至少含有無機顏料之構成。前述著色顏料，除了前述無機顏料外，可列舉例如，偶氮系顏料、酞菁系顏料、縮合多環系顏料等。此外，前述無機顏料，並無特別限制，可列舉例如，碳黑、碳酸鈣、氧化鈦、氧化鋅、氧化鐵、氧化鋁粉等。其中，前述無機顏料係以使用碳黑為佳。前述無機顏料，使用平均粒徑為0．1μm~5μm者為佳。使用平均粒徑為0．5μm~2．5μm者為特佳。分散前述著色顏料時，使用顏料分散機使著色顏料分散為佳。分散前述著色顏料時，亦可使用界面活性劑等之顏料分散劑。 The coloring pigment (A) has a structure containing at least an inorganic pigment. Examples of the color pigments include, in addition to the inorganic pigments, azo-based pigments, phthalocyanine-based pigments, and condensed polycyclic-based pigments. The inorganic pigment is not particularly limited, and examples thereof include carbon black, calcium carbonate, titanium oxide, zinc oxide, iron oxide, and alumina powder. Among them, carbon black is preferably used as the inorganic pigment. The inorganic pigment is preferably one having an average particle diameter of 0.1 μm to 5 μm. It is particularly preferable to use an average particle diameter of 0.5 μm to 2.5 μm. When dispersing the color pigment, it is preferable to disperse the color pigment using a pigment disperser. When dispersing the color pigment, a pigment dispersant such as a surfactant may be used.
前述著色顏料(A)之50質量%以上由前述無機顏料所構成為佳。此時，可得到更充分之隱蔽金屬箔層4之隱蔽力，而能夠形成可賦予充分之穩重感、高級感之特定色調之著色油墨層10。其中，前述著色顏料(A)之60質量%以上由前述無機顏料所構成為更佳。 It is preferable that 50% by mass or more of the colored pigment (A) is composed of the inorganic pigment. At this time, a more sufficient concealing force of the concealed metal foil layer 4 can be obtained, and a colored ink layer 10 having a specific hue that can give a sufficient sense of stability and high-quality can be formed. Among them, it is more preferable that 60% by mass or more of the colored pigment (A) is composed of the inorganic pigment.
就前述二液硬化型聚酯聚氨酯樹脂接著劑(B)加以說明。前述作為主劑之聚酯樹脂，係以二羧酸及二醇作為原料而成的共聚物，較佳的材料及組成如以下所述。 The two-liquid curable polyester polyurethane resin adhesive (B) will be described. The polyester resin as the main agent is a copolymer obtained by using a dicarboxylic acid and a diol as raw materials. The preferred materials and compositions are as follows.
前述二羧酸，較佳係使用脂肪族二羧酸與芳香族二羧酸兩者。此外，脂肪族二羧酸的伸甲基鏈的伸甲基數的奇偶係影響樹脂的結晶性的因子，由於具有偶數的伸甲基的二羧酸可形成結晶性高的硬樹脂，因此使用具有偶數的伸甲基的脂肪族二羧酸較佳。伸甲基數為偶數的脂肪族二羧酸，係可例如為琥珀酸(伸甲基數2)、己二酸(伸甲基數4)、辛二酸(伸甲基數6)、癸二酸(伸甲基數8)等。前述芳香族二羧酸，係可例如為間苯二甲酸、對苯二甲酸、萘二羧酸、鄰苯二甲酸酐等。 The dicarboxylic acid is preferably both an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. In addition, the parity of the number of methylated chains of aliphatic dicarboxylic acids affects the crystallinity of the resin. Since dicarboxylic acids having an even number of methylenedicarboxylic acids can form hard resins with high crystallinity, they are used. An aliphatic dicarboxylic acid having an even number of methyl groups is preferred. The aliphatic dicarboxylic acid having an even number of methyl groups may be, for example, succinic acid (the number of methyl groups is 2), adipic acid (the number of methyl groups is 4), suberic acid (the number of methyl groups is 6), decyl Diacid (8 methyl groups) and the like. Examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and phthalic anhydride.
此外，相對於脂肪族二羧酸和芳香族二羧酸的合計量，其芳香族二羧酸的含有率為40莫爾%~80莫爾%的範圍，換言之，將脂肪族二羧酸的含有率保持為20莫爾%~60莫爾%的範圍，可生成接著強度高且成形性好的樹脂，從而可成形為成形性好且側壁高的外殼，且可形成能充分防止耐熱性樹脂層2由著色油墨層10剝離之成形用包裝材。芳香族二羧酸的含有率未滿40莫爾%時，會降低膜物性而易發生凝集剝離，從而容易發生耐熱性樹脂層2由著色油墨層10剝離，因此較不佳。另一方面，芳香族二羧酸的含有率超過80莫爾%時，有樹脂變硬而密著性能降低的傾向，因此亦較不佳。其中，相對於脂肪族二羧酸和芳香族二羧酸的合計量，芳香族二羧酸的含有率為50莫爾%~70莫爾%之範圍為特佳。 In addition, the content ratio of the aromatic dicarboxylic acid relative to the total amount of the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid is in the range of 40 mol% to 80 mol%. In other words, The content rate is maintained in the range of 20 mol% to 60 mol%, and a resin having high adhesion strength and good moldability can be formed, so that it can be molded into a shell with good moldability and high side walls, and a heat-resistant resin can be sufficiently prevented. The packaging material for molding in which the layer 2 is peeled from the colored ink layer 10. When the content of the aromatic dicarboxylic acid is less than 40 mol%, the physical properties of the film are lowered, and agglomeration and peeling are likely to occur, so that the heat-resistant resin layer 2 is likely to be peeled from the colored ink layer 10, which is not preferable. On the other hand, when the content rate of the aromatic dicarboxylic acid exceeds 80 mol%, the resin tends to be hard and the adhesion performance tends to be lowered, so it is also not preferable. Among them, the content of the aromatic dicarboxylic acid is particularly preferably in a range of 50 mol% to 70 mol% with respect to the total amount of the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid.
前述二醇，雖無特別限定，但可例如為，乙二醇、丙二醇、 1，3-丁二醇、1，4-丁二醇、二乙二醇、二丙二醇、新戊二醇、1，5-戊二醇、1，6-己二醇、辛二醇、1，4-環己二醇、2-丁基-2-乙基-1，3-丙二醇等。 The diol is not particularly limited, but may be, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, octanediol, 1 , 4-cyclohexanediol, 2-butyl-2-ethyl-1,3-propanediol and the like.
前述聚酯樹脂(主劑)的分子量，係將數目平均分子量(Mn)設定為8000~25000，將重量平均分子量(Mw)設定為15000~50000，且更進一步使該等的比率(Mw/Mn)為1．3~2．5者。數目平均分子量(Mn)為8000以上、重量平均分子量(Mw)為15000以上時可得適性的塗膜強度與耐熱性，數目平均分子量(Mn)為25000以下、重量平均分子量(Mw)為50000以下時可得不會過硬且適性的塗膜延伸度。此外，此等之比率(Mw/Mn)為1．3~2．5時可形成適性的分子量分布而能保持接著劑塗佈適性(分布廣)與性能(分布狹窄)平衡。前述聚酯樹脂之數目平均分子量(Mn)為10000~23000特佳，特佳之重量平均分子量(Mw)為20000~40000，特佳之(Mw/Mn)為1．5~2．3。 The molecular weight of the polyester resin (main agent) is a number average molecular weight (Mn) of 8000 to 25,000, a weight average molecular weight (Mw) of 15,000 to 50,000, and further such ratios (Mw / Mn ) Is from 1.3 to 2.5. When the number average molecular weight (Mn) is 8,000 or more and the weight average molecular weight (Mw) is 15,000 or more, suitable coating strength and heat resistance can be obtained. The number average molecular weight (Mn) is 25,000 or less and the weight average molecular weight (Mw) is 50,000 or less. In this case, an appropriate degree of elongation of the coating film that is not too hard is obtained. In addition, when these ratios (Mw / Mn) are 1.3 to 2.5, a suitable molecular weight distribution can be formed, and the adhesive coating suitability (wide distribution) and performance (narrow distribution) can be maintained in balance. The number average molecular weight (Mn) of the aforementioned polyester resin is particularly preferably 10,000 to 23,000, the weight average molecular weight (Mw) of the particularly good is 20,000 to 40,000, and the weight (Mw / Mn) of the especially good is 1.5 to 2.3.
前述聚酯樹脂(主劑)的分子量，可藉由多官能性之異氰酸酯進行鏈伸長而調整。亦即，若將主劑中的聚酯成分以NCO連結可生成末端為羥基的聚合物，可藉由調整異氰酸酯基與聚酯的羥基的當量比以調整聚酯樹脂(主劑)的分子量。本發明中，使用以該等的當量比(OH/NCO)為1．01~10之方式連結而成者為佳。又，其他的分子量調整方法，可列舉如調整二羧酸與二醇之共聚合反應的反應條件(調整二羧酸與二醇的摻合莫爾比)。 The molecular weight of the polyester resin (main agent) can be adjusted by chain extension of a polyfunctional isocyanate. That is, if the polyester component in the base agent is connected with NCO to produce a polymer having a hydroxyl group at the terminal, the molecular weight of the polyester resin (base agent) can be adjusted by adjusting the equivalent ratio of the isocyanate group to the hydroxyl group of the polyester. In the present invention, it is preferable to use a method in which the equivalent ratio (OH / NCO) is 1.01 to 10. In addition, other molecular weight adjustment methods include, for example, adjusting the reaction conditions of the copolymerization reaction of dicarboxylic acid and diol (adjusting the molar ratio of the dicarboxylic acid and diol).
亦可添加環氧系樹脂或丙烯酸系樹脂作為前述主劑之添加劑(著色油墨組成物之添加劑)。 An epoxy resin or an acrylic resin may be added as an additive (additive to the coloring ink composition) as the main agent.
又，前述聚酯樹脂(主劑)，採用作為較佳構成而列舉的限定構成中之任一種以上時，即使採用著色顏料之50質量%以上為無機顏料所構成之構成，仍可確保著色油墨層具有更充足的密著力的優點。前述聚酯樹脂(主劑)之較佳構成，在可得如此之效果的特點上，係特別重要之技術。 In addition, when the polyester resin (main agent) adopts any one or more of the limited structures listed as a preferable structure, the coloring ink can be ensured even if a structure composed of 50% by mass or more of the coloring pigment is an inorganic pigment. The layer has the advantage of more sufficient adhesion. The preferred composition of the aforementioned polyester resin (main agent) is a particularly important technique in that such effects can be obtained.
前述作為硬化劑的多官能異氰酸酯化合物，可使用芳香族系、脂肪族系、脂環族系的各種多官能異氰酸酯化合物。作為具體例，可列舉例如為，以脂肪族系的六亞甲基二異氰酸酯(HDI)、異佛爾酮二異氰酸酯(IPDI)、芳香族系的甲苯二異氰酸酯(TDI)、二苯基甲烷二異氰酸酯(MDI)等的二異氰酸酯的1種類或2種類以上做為基底而進行變性而成的多官能異氰酸酯變性體。作為變性手段，除了與水、甘油、三羥甲基丙烷等的多官能活性氫化合物的加成物以外，其他亦可列舉如利用異氰脲酸酯化、碳二醯亞胺化、聚合化等的多量化反應形成之多官能異氰酸酯變性體。可將此等的1種或2種以上混合使用。 As the polyfunctional isocyanate compound as the curing agent, various polyfunctional isocyanate compounds of an aromatic type, an aliphatic type, and an alicyclic type can be used. Specific examples include, for example, aliphatic hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), aromatic toluene diisocyanate (TDI), and diphenylmethane diisocyanate. A polyfunctional isocyanate modified product in which one or two or more types of diisocyanates such as isocyanate (MDI) are used as a substrate and denatured. Examples of the denaturation method include adducts with polyfunctional active hydrogen compounds such as water, glycerin, and trimethylolpropane, and other examples include isocyanuration, carbodiimidization, and polymerization. Multifunctional isocyanate denaturants formed by such multiple quantitative reactions. These may be used singly or in combination of two or more kinds.
前述作為硬化劑之多官能異氰酸酯化合物，其50莫爾%以上(50莫爾%以上100莫爾%以下)係由芳香族系多官能異氰酸酯化合物所構成。亦即，相對於多官能異氰酸酯化合物的全量100莫爾%，50莫爾%以上係由芳香族系多官能異氰酸酯化合物所構成。50莫爾%以上係由芳香族系多官能異氰酸酯化合物構成時，可增加硬化後之接著強度，故即使在進行更深之成型時，在成形時及密封時，且更進一步在高溫 多濕等的稍微嚴苛的環境下使用時，仍可充分防止耐熱性樹脂層著色層2由著色油墨層10剝離。其中，前述作為硬化劑之多官能異氰酸酯化合物，其70莫爾%以上由芳香族系多官能異氰酸酯化合物構成為佳，更進一步，其80莫爾%以上由芳香族系多官能異氰酸酯化合物構成為特佳。 The above-mentioned polyfunctional isocyanate compound as a curing agent has an amount of 50 mol% or more (50 mol% or more and 100 mol% or less) of an aromatic polyfunctional isocyanate compound. That is, 50 mol% or more of the total amount of the polyfunctional isocyanate compound is composed of an aromatic polyfunctional isocyanate compound. When 50 mol% or more is composed of an aromatic polyfunctional isocyanate compound, the adhesive strength after hardening can be increased, so even in deeper molding, during molding and sealing, and further at high temperatures When used in a slightly severe environment such as high humidity, the heat-resistant resin layer colored layer 2 can be sufficiently prevented from peeling off from the colored ink layer 10. Among them, the above-mentioned polyfunctional isocyanate compound as a curing agent is preferably composed of an aromatic polyfunctional isocyanate compound in an amount of 70 mol% or more, and furthermore, an aromatic polyfunctional isocyanate compound is used in an amount of 80 mol% or more. good.
又，前述多官能異氰酸酯化合物(硬化劑)，採用被列舉為較佳構成的限定構成中之任一種以上時，即使採用著色顏料之50質量%以上為無機顏料所構成之構成，亦有能確保著色油墨層具有更充足的密著力的優點。前述多官能異氰酸酯化合物(硬化劑)較佳的構成，在可得如此之效果的特點上，係特別重要之技術。 In addition, when the above-mentioned polyfunctional isocyanate compound (hardener) adopts any one or more of the limited structures listed as preferred structures, it is possible to ensure that even if a structure composed of 50% by mass or more of a colored pigment is an inorganic pigment, The colored ink layer has the advantage of more sufficient adhesion. The preferable constitution of the aforementioned polyfunctional isocyanate compound (hardener) is a particularly important technique in that such effects can be obtained.
前述二液硬化型聚酯聚氨酯樹脂接著劑中，主劑與硬化劑的摻合比例，以相對於多元醇羥基(OH)1莫爾異氰酸酯官能基(NCO)為2~25莫爾之比例摻合為佳。此等的莫爾比(NCO)/(OH)若未達2而異氰酸酯官能基(NCO)過少時，將無法充分進行硬化反應而無法得到適性的塗膜強度及耐熱性。另一方面，(NCO)/(OH)若超過25而異氰酸酯官能基(NCO)過多時，與多元醇以外的官能基反應太過，塗膜變得過硬而有無法得到適性的延伸之虞。多元醇羥基與異氰酸酯官能基的莫爾比(NCO)/(OH)為5~20為特佳。 In the aforementioned two-liquid curing type polyester polyurethane resin adhesive, the blending ratio of the main agent and the curing agent is blended in a ratio of 2 to 25 moles relative to the polyol hydroxyl (OH) 1 mole isocyanate functional group (NCO). Better together. When the Mohr ratio (NCO) / (OH) is less than 2, and the isocyanate functional group (NCO) is too small, the curing reaction cannot proceed sufficiently, and suitable coating film strength and heat resistance cannot be obtained. On the other hand, if (NCO) / (OH) exceeds 25 and there are too many isocyanate functional groups (NCO), the reaction with functional groups other than the polyol will be too much, and the coating film may become too hard and proper stretching may not be obtained. The molar ratio (NCO) / (OH) of the polyol hydroxyl group and the isocyanate functional group is particularly preferably 5-20.
前述二液硬化型聚酯聚氨酯樹脂接著劑，其反應後的硬化膜具有以下物性為佳。亦即，藉由前述主劑與前述硬化劑反應後之硬化膜之拉伸試驗(JIS K7162)獲得之楊氏模量為70MPa~400MPa為佳。楊氏模量為100MPa~300MPa為特佳。此外，前述硬化膜之斷裂強度為20MPa~70MPa，前述硬化膜之斷裂伸長 率為50%~400%為佳。斷裂強度30MPa~50MPa特佳，斷裂伸長率為100%~300%特佳。更進一步，二液硬化型聚酯聚氨酯樹脂接著劑之硬化膜的拉伸應力-歪斜曲線(S-S曲線)於斷裂前無顯示強度降低為佳。圖3係顯示S-S曲線的3種模式。相對於拉伸應力，模式A歪斜量較小而模式B歪斜量較大，但不論何者都伴隨拉伸應力增加而歪斜量增加，斷裂前亦無顯示強度降低。另一方面，模式C在歪斜量增加的過程，拉伸應力降低，於斷裂前顯示強度降低。本發明中，以二液硬化型接著劑的硬化膜的S-S曲線無強度降低為佳。更理想地，S-S曲線中無強度急遽變化的折點為更佳。 The two-liquid curable polyester polyurethane resin adhesive preferably has the following physical properties of the cured film after the reaction. That is, the Young's modulus obtained by a tensile test (JIS K7162) of the cured film after the reaction of the aforementioned main agent and the aforementioned curing agent is preferably 70 MPa to 400 MPa. The Young's modulus is particularly preferably 100 MPa to 300 MPa. In addition, the breaking strength of the hardened film is 20 MPa to 70 MPa, and the breaking elongation of the hardened film is The rate is preferably 50% ~ 400%. The breaking strength is particularly good at 30MPa ~ 50MPa, and the elongation at break is particularly good. Furthermore, it is preferable that the tensile stress-distortion curve (S-S curve) of the cured film of the two-liquid curable polyester polyurethane resin adhesive does not show a decrease in strength before breaking. Figure 3 shows three modes of the S-S curve. Compared with tensile stress, the amount of distortion in Mode A is small and the amount of distortion in Mode B is large, but the amount of distortion increases with the increase of tensile stress, and there is no reduction in display strength before fracture. On the other hand, in the process of increasing the amount of distortion in the mode C, the tensile stress decreases, and the strength decreases before the fracture. In the present invention, it is preferable that the strength of the S-S curve of the cured film using the two-liquid curing type adhesive does not decrease. More ideally, the inflection point in the S-S curve without sharp changes in intensity is better.
含有前述二液硬化型聚酯聚氨酯樹脂之接著劑，係將作為聚酯樹脂的原料的二羧酸及二醇進行縮合，主要係進一步利用多官能性的異氰酸酯將鍊伸長，並將溶劑及聚氨酯化反應催化劑、用以提升接著力的偶聯劑或環氧樹脂、消泡劑、勻染劑、紫外線吸收劑、抗氧化劑等的各種添加劑混合而成流動狀的聚酯樹脂溶液，對此摻合作為硬化劑的多官能異氰酸酯化合物或更進一步摻合溶劑，從而製備成低黏度流體狀物。 The adhesive containing the aforementioned two-liquid curable polyester-polyurethane resin condenses a dicarboxylic acid and a diol, which are raw materials of the polyester resin, and mainly uses a polyfunctional isocyanate to further extend the chain, and the solvent and polyurethane Chemical reaction catalyst, coupling agent or epoxy resin, antifoaming agent, leveling agent, ultraviolet absorber, antioxidant and other additives to improve the adhesive force are mixed to form a flowing polyester resin solution. A polyfunctional isocyanate compound that cooperates as a hardener or further blends a solvent to produce a low viscosity fluid.
前述著色油墨層10中，相對於前述聚酯樹脂(二液硬化型聚酯聚氨酯樹脂接著劑的主劑)與前述著色顏料的合計質量(當然，並不含溶劑)，著色顏料較佳的含有質量之比例設定為5質量%~60質量%為佳。在5質量%以上可得到充分的隱蔽金屬箔層4之效果，使金屬光澤無法直接用肉眼辨識，從而賦予充分之穩重感、高級感，同時成形時該成形部中亦不會產生局部的色彩不均。此外，在60質量%以下，著色油墨層10不會變硬變脆，從而可充分確保著色油墨層10對於耐熱性樹脂層2 之接著力，於成形時及密封時，且在高溫多濕等的稍微嚴苛的環境下使用時，亦可充分防止耐熱性樹脂層2由著色油墨層10剝離。其中，前述著色油墨層10中，相對於前述聚酯樹脂與前述著色顏料的合計質量，將著色顏料的含有質量之比例設定為15質量%~50質量%為特佳。 In the coloring ink layer 10, the coloring pigment preferably contains more than the total mass of the polyester resin (the main agent of the two-liquid curable polyester polyurethane resin adhesive) and the coloring pigment (of course, it does not include a solvent). The mass ratio is preferably set to 5 to 60% by mass. At 5% by mass or more, a sufficient effect of concealing the metal foil layer 4 can be obtained, so that the metallic luster cannot be directly recognized by the naked eye, thereby giving a sufficient sense of stability and high-quality, and at the same time, no local color is generated in the forming portion during forming Uneven. In addition, at 60% by mass or less, the colored ink layer 10 does not become hard and brittle, so that the colored ink layer 10 can sufficiently secure the heat-resistant resin layer 2. The adhesion force can also sufficiently prevent the heat-resistant resin layer 2 from peeling off from the colored ink layer 10 during molding and sealing, and when used in a slightly severe environment such as high temperature and humidity. Among them, in the colored ink layer 10, it is particularly preferable to set the content ratio of the colored pigment to 15 to 50% by mass relative to the total mass of the polyester resin and the colored pigment.
前述著色油墨層(硬化膜)10之厚度，設定在1μm~5μm為佳。 The thickness of the colored ink layer (cured film) 10 is preferably set to 1 μm to 5 μm.
(第1接著劑層) (1st adhesive layer)
前述第1接著劑層5，係擔負接合金屬箔層4與前述耐熱性樹脂層2(上述實施型態為著色油墨層10)之作用的層。前述第1接著劑層5，雖無特別限定，但可列舉例如：藉由2液硬化型接著劑所形成之接著劑層等。前述2液硬化型接著劑，可列舉例如，由選自於由聚氨酯系多元醇、聚酯系多元醇、聚醚系多元醇、及聚酯聚胺酯系多元醇所成群中之多元醇的1種或2種以上所構成之第1液、與由異氰酸酯所構成之第2液(硬化劑)構成之2液硬化型接著劑等。其中，使用由選自於聚酯系多元醇及聚酯聚氨酯系多元醇所成群中之多元醇的1種或2種以上所構成之第1液、與由異氰酸酯所構成之第2液(硬化劑)構成之2液硬化型接著劑為佳。前述第1接著劑層5，例如，可藉由凹版印刷法等方法，將前述2液硬化型接著劑等之接著劑塗佈於前述金屬箔層4之上表面或/及前述耐熱性樹脂層2之下表面(例如著色油墨層10之下表面)而形成。 The first adhesive layer 5 is a layer that is responsible for joining the metal foil layer 4 and the heat-resistant resin layer 2 (the colored ink layer 10 in the above embodiment). The first adhesive layer 5 is not particularly limited, but examples thereof include an adhesive layer formed by a two-liquid curing type adhesive. Examples of the two-liquid curing type adhesive include 1st polyols selected from the group consisting of polyurethane polyols, polyester polyols, polyether polyols, and polyester polyurethane polyols. A first liquid consisting of one or two or more types, a two-liquid curing type adhesive consisting of a second liquid (hardener) consisting of an isocyanate, and the like. Among them, a first liquid consisting of one or two or more polyols selected from the group consisting of polyester polyols and polyester polyurethane polyols, and a second liquid consisting of isocyanate ( A two-liquid curing type adhesive composed of a hardening agent) is preferred. The first adhesive layer 5 may be coated with an adhesive such as the two-liquid curing type adhesive on the upper surface of the metal foil layer 4 and / or the heat-resistant resin layer by a method such as a gravure printing method. 2 is formed on the lower surface (for example, the lower surface of the colored ink layer 10).
前述金屬箔層4與前述耐熱性樹脂層2的貼合方法，雖無特別限制，但較為推薦稱為乾式層壓的方法。具體的說，於金屬箔層4的上表面或耐熱性樹脂層2的下表面(上述實施型態中為著色油墨層10之下 表面)，或於此等之二側的面，塗布所調製的第1接著劑，使溶劑蒸發並形成乾燥被膜後，將金屬箔層4與耐熱性樹脂層2貼合。接著，根據第1接著劑的硬化條件使其硬化。藉此，將金屬箔層4與耐熱性樹脂層2隔著第1接著劑層5接合。又，第1接著劑的塗佈方法，可例示如凹版塗佈法、逆輥塗佈法、唇輥塗法等。 Although the method of bonding the metal foil layer 4 and the heat-resistant resin layer 2 is not particularly limited, a method called dry lamination is more recommended. Specifically, the upper surface of the metal foil layer 4 or the lower surface of the heat-resistant resin layer 2 (under the colored ink layer 10 in the above embodiment) Surface), or on the other two sides, the prepared first adhesive is applied to evaporate the solvent to form a dry film, and then the metal foil layer 4 and the heat-resistant resin layer 2 are bonded together. Then, the first adhesive is hardened according to the hardening conditions. Thereby, the metal foil layer 4 and the heat resistant resin layer 2 are joined via the first adhesive layer 5. Examples of the method for applying the first adhesive include a gravure coating method, a reverse roll coating method, and a lip roll coating method.
(第2接著劑層) (Second Adhesive Layer)
前述第2接著劑層6，雖無特別限定，但可列舉為例如，由聚氨酯系接著劑、丙烯酸系接著劑、環氧系接著劑、聚烯烴系接著劑、彈性體系接著劑、氟系接著劑、酸變性聚丙烯接著劑等所形成的接著劑層。其中，使用丙烯酸系接著劑、聚烯烴系接著劑為佳，此時，可提升成形用包裝材1的耐電解液性及水蒸氣阻障性。 Although the second adhesive layer 6 is not particularly limited, examples thereof include a polyurethane-based adhesive, an acrylic-based adhesive, an epoxy-based adhesive, a polyolefin-based adhesive, an elastic system adhesive, and a fluorine-based adhesive. An adhesive layer formed by an adhesive, an acid-denatured polypropylene adhesive, or the like. Among them, an acrylic adhesive and a polyolefin adhesive are preferably used. In this case, the electrolyte solution resistance and water vapor barrier properties of the packaging material 1 for molding can be improved.
前述金屬箔層4與前述熱可塑性樹脂層3的貼合方法，雖無特別限定，但例如可如同上述金屬箔層4與耐熱性樹脂層2的貼合，塗佈第2接著劑並乾燥後，將金屬箔層4與熱可塑性樹脂層3貼合的乾式層壓法。 Although the method of bonding the metal foil layer 4 and the thermoplastic resin layer 3 is not particularly limited, for example, the second adhesive may be applied and dried as in the case where the metal foil layer 4 and the heat-resistant resin layer 2 are bonded. A dry lamination method in which the metal foil layer 4 and the thermoplastic resin layer 3 are bonded together.
本發明的成形用包裝材1，並不限定為如圖1所示的積層構造，亦可追加更多層使包裝材的機能提升。圖2所示的成形用包裝材1，係在圖1所示構成之包裝材中，更於耐熱性樹脂層2的外面形成有馬特塗層20者。 The molding packaging material 1 of the present invention is not limited to a laminated structure as shown in FIG. 1, and more functions may be added to improve the function of the packaging material. The molding packaging material 1 shown in FIG. 2 is a packaging material having the structure shown in FIG. 1, and a Matt coating 20 is formed on the outer surface of the heat-resistant resin layer 2.
(馬特塗層) (Matt coating)
前述馬特塗層20，係賦予成形用包裝材1的表面良好的滑動性，從而提高成形性所設置之表面層。 The Matte coating layer 20 is a surface layer provided to give the surface of the molding packaging material 1 a good sliding property to improve the moldability.
前述馬特塗層20，係於耐熱性樹脂成分中分散含有無機微粒子的樹脂組成物所成的馬特塗層。其中，前述馬特塗層20，宜為由在二液硬化型之耐熱性樹脂中含有0．1質量%~1質量%之平均粒徑1μm~10μm之無機微粒子而成之樹脂組成物組成之構成。前述耐熱性樹脂，可列舉例如，丙烯酸系樹脂、環氧系樹脂、聚酯系樹脂、聚氨酯系樹脂、聚烯烴系樹脂、氟系樹脂、苯氧系樹脂等，而就耐熱性、耐藥品性的觀點，使用四氟乙烯或氟乙烯乙烯基醚(fluoroethylenevinylether)作為基底的氟系樹脂為佳。前述無機微粒子，雖無特別限定，但可列舉例如，二氧化矽、礬土、氧化鈣、碳酸鈣、硫酸鈣、矽酸鈣等，其中使用二氧化矽為佳。 The Matt coating 20 is a Matt coating formed by dispersing a resin composition containing inorganic fine particles in a heat-resistant resin component. Among them, the Matt coating 20 is preferably a resin composition made of inorganic fine particles having an average particle size of 1 to 10 μm in a two-liquid curing type heat-resistant resin. Make up. Examples of the heat-resistant resin include acrylic resin, epoxy-based resin, polyester-based resin, polyurethane-based resin, polyolefin-based resin, fluorine-based resin, and phenoxy-based resin. From the viewpoint, a fluororesin using tetrafluoroethylene or fluoroethylenevinylether as a substrate is preferred. The inorganic fine particles are not particularly limited, but examples thereof include silicon dioxide, alumina, calcium oxide, calcium carbonate, calcium sulfate, and calcium silicate. Among them, silicon dioxide is preferably used.
前述馬特塗層20的形成，可藉由將含有上述無機微粒子與耐熱性樹脂的馬特塗層組成物塗佈於前述耐熱性樹脂層2的表面並使其硬化以實施。 The Matt coating 20 can be formed by applying a Matt coating composition containing the inorganic fine particles and a heat-resistant resin to the surface of the heat-resistant resin layer 2 and curing it.
前述馬特塗層20的厚度(硬化後的厚度)係0．5~5μm為佳。設定為前述較佳下限值以上可充分得到提高滑動性的效果，同時設定為前述較佳上限值以下可抑制成本。其中，前述馬特塗層20的厚度(硬化後的厚度)，特佳係1~3μm。 The thickness (thickness after hardening) of the Matt coating 20 is preferably 0.5 to 5 μm. The effect of improving the sliding property can be sufficiently obtained by setting it to the above preferred lower limit value, and at the same time, the cost can be suppressed by setting it below the aforementioned preferred upper limit value. The thickness (thickness after hardening) of the Matt coating 20 is particularly preferably 1 to 3 μm.
前述馬特塗層20的表面的總值(gloss value)，基於JIS Z8741之60°反射角測定值，設定為1%~15%為佳。前述總值(gloss value)，係利用BYK社製的gloss測定器「micro-TRI-gloss-s」於60°反射角測定而得之值。 The gloss value of the surface of the Matte coating layer 20 is preferably 1% to 15% based on the 60 ° reflection angle measurement value of JIS Z8741. The aforementioned gloss value is a value obtained by measuring at a reflection angle of 60 ° using a gloss meter "micro-TRI-gloss-s" manufactured by BYK.
又，形成前述馬特塗層20的步驟之實施時期(實施順序)雖無特別限定，但接續在將耐熱性樹脂層2貼合於金屬箔層4(隔著第1 接著劑層5、著色油墨層10)的步驟後進行為佳。 In addition, although the implementation period (implementation order) of the step of forming the Matt coat layer 20 is not particularly limited, the heat-resistant resin layer 2 is bonded to the metal foil layer 4 (via the first It is preferable to carry out after the steps of the agent layer 5 and the colored ink layer 10).
上述實施型態中，雖採用在耐熱性樹脂層2之上表面積層有馬特塗層20的構成，但此馬特塗層20並非必須之構成層，亦可如圖1所示，採用不具有馬特塗層20之構成。 In the above embodiment, although the structure in which the Matte coating layer 20 is provided on the surface area layer above the heat-resistant resin layer 2 is adopted, the Matte coating layer 20 is not an essential constituent layer, and as shown in FIG. Structure of Matt coating 20.
此外，上述實施型態中，雖採用設置有第1接著劑層5與第2接著劑層6之構成，但此兩層5、6皆並非必須之構成層，亦可採用不設置此等之構成。 In addition, in the above-mentioned embodiment, although the configuration in which the first adhesive layer 5 and the second adhesive layer 6 are provided is adopted, neither of the two layers 5 and 6 is an indispensable constituent layer. Make up.
本發明之成形用包裝材1，並不限於以包含各層之貼合方法的上述例示之製造方法製造者，以其他製造方法製造者亦為本發明所包含。 The packaging material for molding 1 of the present invention is not limited to the manufacturer of the manufacturing method exemplified above including the bonding method of each layer, and manufacturers of other manufacturing methods are also included in the present invention.
可藉由將本發明之成形用包裝材1進行成形(深引伸成形、鼓脹成形等)以得到成形外殼(電池外殼等)。 The molded packaging material 1 of the present invention can be molded (deep drawing molding, inflation molding, etc.) to obtain a molded case (battery case, etc.).
此外，本發明之成形用包裝材1，雖然可適宜地作為鋰離子蓄電池外殼用包材使用，但並不特別限定為此用途。 In addition, although the molding packaging material 1 of the present invention can be suitably used as a packaging material for a lithium ion battery case, it is not particularly limited to this application.
接著，說明本發明的具體的實施例，但本發明並不特別限定於該等實施例。 Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.
<實施例1> <Example 1>
在厚度35μm的鋁箔(A8079鋁箔)4之兩面，塗佈由聚丙烯酸、三價鉻化合物、水、醇類所成的化成處理液，並在150℃進行乾燥，藉此製造在兩面形成有化成皮膜的鋁箔。此化成皮膜的鉻附著量，單面為為5mg/m2。 A 35 μm-thick aluminum foil (A8079 aluminum foil) 4 was coated with a chemical conversion treatment solution made of polyacrylic acid, a trivalent chromium compound, water, and alcohols, and dried at 150 ° C. to produce chemical compounds formed on both sides. Film of aluminum foil. The chromium adhesion amount of this chemical conversion film was 5 mg / m 2 on one side.
製得作為二液硬化型聚酯聚氨酯樹脂接著劑之主劑的聚酯樹脂(聚酯多元醇)。將新戊二醇30莫爾份、乙二醇30莫爾份、1，6-己二醇40莫爾份於80℃熔融後，一邊攪拌一邊將由脂肪族二羧酸的己二酸30莫爾份及芳香族二羧酸之間苯二甲酸70莫爾份構成之二羧酸混合物於210℃進行20小時之縮合反應，從而得到作為主劑的聚酯多元醇(聚酯樹脂)。此聚酯多元醇，數目平均分子量(Mn)為12000、重量平均分子量(Mw)為20500，此等的比率(Mw/Mn)為1．71。更進一步，對於前述獲得之聚酯多元醇40質量份加入乙酸乙酯60質量份，得到流動狀的聚酯多元醇樹脂溶液。此聚酯多元醇樹脂溶液中聚酯多元醇的羥值為2．2mgKOH/g(溶液值)。 A polyester resin (polyester polyol) was prepared as a main agent of the two-liquid curable polyester polyurethane resin adhesive. After 30 mol parts of neopentyl glycol, 30 mol parts of ethylene glycol, and 40 mol parts of 1,6-hexanediol were melted at 80 ° C., 30 mol of adipic acid from an aliphatic dicarboxylic acid was melted while stirring. A dicarboxylic acid mixture composed of 70 mol parts of phthalic acid between the molar fraction and the aromatic dicarboxylic acid was subjected to a condensation reaction at 210 ° C. for 20 hours, thereby obtaining a polyester polyol (polyester resin) as a main agent. The polyester polyol had a number average molecular weight (Mn) of 12,000, a weight average molecular weight (Mw) of 20,500, and the ratio (Mw / Mn) of the polyester polyol was 1.71. Furthermore, 60 parts by mass of ethyl acetate was added to 40 parts by mass of the polyester polyol obtained as described above to obtain a flowing polyester polyol resin solution. The hydroxyl value of the polyester polyol in the polyester polyol resin solution was 2.2 mgKOH / g (solution value).
接著，將平均粒徑1．0μm的碳黑13．3質量份、上述的聚酯多元醇樹脂溶液100質量份(聚酯多元醇40質量份)、與乙酸乙酯64．4質量份混合後，使用顏料分散機將碳黑顏料分散，藉此得到主劑油墨組成物。前述主劑油墨組成物中固體成分(聚酯多元醇及碳黑)之含有率為30質量%，固體成分中之著色顏料(碳黑)之含有率為25質量%。 Next, 13.3 parts by mass of carbon black having an average particle diameter of 1.0 μm, 100 parts by mass of the above-mentioned polyester polyol resin solution (40 parts by mass of polyester polyol), and 64.4 parts by mass of ethyl acetate were mixed. The carbon black pigment is dispersed using a pigment disperser to obtain a main agent ink composition. The content rate of the solid component (polyester polyol and carbon black) in the main agent ink composition was 30% by mass, and the content rate of the colored pigment (carbon black) in the solid content was 25% by mass.
相對於前述主劑油墨組成物100質量份，摻合作為硬化劑之甲苯二異氰酸酯(TDI)與三羥甲基丙烷所成的加合物(NCO%13．0%、固體成分75%；芳香族系多官能異氰酸酯化合物)7．1質量份，再摻合乙酸乙酯34．1質量份並予以攪拌，藉此得到著色油墨組成物。 The adduct (NCO% 13.0%, solid content 75%) of toluene diisocyanate (TDI) and trimethylolpropane blended as a hardener with respect to 100 parts by mass of the aforementioned main agent ink composition; aromatic Family-type polyfunctional isocyanate compound) 7.1 parts by mass, and 34.1 parts by mass of ethyl acetate were blended and stirred to obtain a colored ink composition.
前述著色油墨組成物中，異氰酸酯官能基(NCO)與聚酯 多元醇羥基(OH)的莫爾比(NCO)/(OH)為10。 In the aforementioned coloring ink composition, an isocyanate functional group (NCO) and a polyester The molar ratio (NCO) / (OH) of the polyol hydroxyl group (OH) was 10.
接著，於厚度15μm之二軸延伸尼龍薄膜(耐熱性樹脂層)2之一側的面上，塗布前述著色油墨組成物並將其乾燥，藉此形成著色油墨層10。此著色油墨層10乾燥後的厚度為3μm。 Next, the colored ink composition was coated on one side of one side of a biaxially stretched nylon film (heat-resistant resin layer) 2 having a thickness of 15 μm and dried to form a colored ink layer 10. The thickness of the colored ink layer 10 after drying was 3 μm.
接著，在前述於兩面形成有化成皮膜的鋁箔4的一側的面上，塗布二液硬化型聚酯聚氨酯樹脂接著劑並予以乾燥而形成第1接著劑層5，於該第1接著劑層5之表面貼合前述二軸延伸尼龍薄膜2之著色油墨層10側，並在鋁箔4的另一側的面上塗布聚丙烯酸接著劑並予以乾燥而形成第2接著劑層6，於第2接著劑層6之表面貼合厚度30μm之未延伸聚丙烯薄膜(熱可塑性樹脂層)3。將此積層體在40℃環境下放置5天，藉此得到圖1所示構成之成形用包裝材1。 Next, a two-liquid curable polyester polyurethane resin adhesive is applied to the surface of the one side of the aluminum foil 4 on which the chemical conversion film is formed on both sides, and dried to form a first adhesive layer 5. The surface of 5 is bonded to the side of the colored ink layer 10 of the biaxially stretched nylon film 2 described above, and a polyacrylic acid adhesive is coated on the other side of the aluminum foil 4 and dried to form a second adhesive layer 6. An unstretched polypropylene film (thermoplastic resin layer) 3 having a thickness of 30 μm was bonded to the surface of the adhesive layer 6. This laminated body was left to stand in a 40 ° C. environment for 5 days, thereby obtaining a molding packaging material 1 having a structure shown in FIG. 1.
<實施例2> <Example 2>
使用與實施例1相同之起始材料，並將二醇成分全量相對於二羧酸全量的摻合莫爾比調整成較實施例1為多，藉此獲得數目平均分子量(Mn)為8900、重量平均分子量(Mw)為15000、此等比率Mw/Mn為1．69之聚酯多元醇。 The same starting material as in Example 1 was used, and the blended mole ratio of the total amount of the diol component to the total amount of the dicarboxylic acid was adjusted to be greater than that of Example 1, thereby obtaining a number average molecular weight (Mn) of 8,900, A polyester polyol having a weight average molecular weight (Mw) of 15,000 and a ratio Mw / Mn of 1.69.
以上述之聚酯多元醇替代實施例1之聚酯多元醇，並摻合作為硬化劑之甲苯二異氰酸酯(TDI)與三羥甲基丙烷的加合物(NCO%13．0%、固體成分75%；芳香族系多官能異氰酸酯化合物)4．8質量份，使著色油墨組成物中，硬化劑之異氰酸酯官能基(NCO)與聚酯多元醇羥基(OH)的莫爾比(NCO/OH)為5。除此之外，皆與實施例1相同，得到圖1所示之成形用包裝材1。 The polyester polyol of Example 1 was replaced by the above-mentioned polyester polyol, and the adduct of toluene diisocyanate (TDI) and trimethylolpropane (NCO% 13.0%, solid content) blended as a hardener 75%; aromatic polyfunctional isocyanate compound) 4.8 parts by mass, in the colored ink composition, the molar ratio of the isocyanate functional group (NCO) of the hardener and the polyester polyol hydroxyl group (OH) (NCO / OH ) Is 5. Other than that, it was the same as Example 1, and obtained the packaging material 1 for shaping | molding shown in FIG.
<實施例3> <Example 3>
將實施例1的硬化劑的二異氰酸酯成分，變更成係芳香族的甲苯二異氰酸酯(TDI)70莫爾%與脂肪族異氰酸酯化合物的六亞甲基二異氰酸酯(HDI)30莫爾%所成之混合異氰酸酯和三羥甲基丙烷反應而得之加合物的多官能異氰酸酯化合物(NCO%13．0%、固形分75%)，除此之外，皆與實施例1相同，得到圖1所示之成形用包裝材1。 The diisocyanate component of the hardener of Example 1 was changed to 70 mol% of aromatic toluene diisocyanate (TDI) and 30 mol% of hexamethylene diisocyanate (HDI) of an aliphatic isocyanate compound. A polyfunctional isocyanate compound (NCO% 13.0%, solid content 75%) obtained by mixing an isocyanate and trimethylolpropane as an adduct, was the same as in Example 1 except that Shown the packaging material 1 for molding.
<實施例4> <Example 4>
將平均粒徑1．0μm之碳黑4．4質量份、聚酯多元醇樹脂溶液100質量份、乙酸乙酯43．6質量份混合以替代實施例1的將平均粒徑1．0μm之碳黑13．3質量份、聚酯多元醇樹脂溶液100質量份、乙酸乙酯64．4質量份混合之方式，藉此將相對於聚酯樹脂與碳黑之合計質量之碳黑之含有比例設定為10質量%，除此之外，皆與實施例1相同，得到圖1所示之成形用包裝材1。 4.4 parts by mass of carbon black having an average particle diameter of 1.0 μm, 100 parts by mass of a polyester polyol resin solution, and 43.6 parts by mass of ethyl acetate were mixed in place of the carbon having an average particle diameter of 1.0 μm in Example 1. By mixing 13.3 parts by mass of black, 100 parts by mass of polyester polyol resin solution, and 64.4 parts by mass of ethyl acetate, the content ratio of carbon black to the total mass of polyester resin and carbon black is set. Except that it was 10% by mass, it was the same as in Example 1 to obtain a molding packaging material 1 shown in FIG. 1.
<實施例5> <Example 5>
不採用實施例1中相對於主劑油墨組成物100質量份摻合作為硬化劑之甲苯二異氰酸酯(TDI)與三羥甲基丙烷所成的加合物(NCO%13．0%、固體成分75%；芳香族系多官能異氰酸酯化合物)7．1質量份，再摻合乙酸乙酯34．1質量份而得到著色油墨組成物之方式，而改採相對於主劑油墨組成物100質量份摻合作為硬化劑之甲苯二異氰酸酯(TDI)與三羥甲基丙烷所成的加合物(NCO%13．0%、固體成分75%；芳香族系多官能異氰酸酯化合物)3．6質量份， 再摻合乙酸乙酯31質量份而得到著色油墨組成物之方式，藉此使硬化劑之異氰酸酯官能基(NCO)與聚酯多元醇羥基(OH)的莫爾比(NCO/OH)為5，除此之外，皆與實施例1相同，得到圖1所示之成形用包裝材1。 The adduct (NCO% 13.0%, solid content) of toluene diisocyanate (TDI) and trimethylolpropane blended as a hardener with respect to 100 parts by mass of the main component ink composition in Example 1 was not used. 75%; aromatic polyfunctional isocyanate compound) 7.1 parts by mass, and 34.1 parts by mass of ethyl acetate was blended to obtain a colored ink composition. Instead, 100 parts by mass of the ink composition relative to the main agent was used. 3.6 mass parts of adduct (NCO% 13.0%, solid content 75%; aromatic polyfunctional isocyanate compound) formed by toluene diisocyanate (TDI) and trimethylolpropane blended as hardener , A method of blending 31 parts by mass of ethyl acetate to obtain a colored ink composition, whereby the molar ratio (NCO / OH) of the isocyanate functional group (NCO) of the hardener and the hydroxyl group (OH) of the polyester polyol is 5 Other than that, it was the same as in Example 1 to obtain a molding packaging material 1 shown in FIG. 1.
<實施例6> <Example 6>
將氟乙烯乙烯基酯(耐熱性樹脂)80質量份、硫酸鋇(無機微粒子)10質量份、粉狀二氧化矽(無機微粒子)10質量份混合而製得馬特塗層組成物。接續在實施例1之二軸延伸尼龍薄膜(耐熱性樹脂層)2的貼合步驟後，將此馬特塗層組成物，塗佈於二軸延伸尼龍薄膜(耐熱性樹脂層)2之表面，形成乾燥後之厚度為2μm之馬特塗層20，除此之外，皆與實施例1相同，得到圖2所示構成之成形用包裝材1。 80 parts by mass of vinyl fluoride vinyl (heat-resistant resin), 10 parts by mass of barium sulfate (inorganic fine particles), and 10 parts by mass of powdered silicon dioxide (inorganic fine particles) were mixed to obtain a Matt coating composition. Following the bonding step of the biaxially stretched nylon film (heat-resistant resin layer) 2 of Example 1, this Matt coating composition was applied to the surface of the biaxially stretched nylon film (heat-resistant resin layer) 2. Except that the Matt coating 20 having a thickness of 2 μm after drying was formed, it was the same as in Example 1 to obtain a molding packaging material 1 having the structure shown in FIG. 2.
針對前述馬特塗層20之表面，以BYK社製的總值(gloss value)測定器「micro-TRI-gloss-s」於60°反射角測定光澤度，結果馬特塗層20之表面的總值(基於JIS Z8741之60°反射角測定值)為1．9%。 The gloss of the surface of the Matt Coating 20 was measured with a reflectance meter "micro-TRI-gloss-s" manufactured by BYK at a reflection angle of 60 °. The total value (measurement value of 60 ° reflection angle based on JIS Z8741) was 1.9%.
<比較例1> <Comparative example 1>
使用與實施例1相同的起始材料，並改變反應條件(將二醇成分全量相對於二羧酸全量之摻合莫爾比調整為較實施例1多)，藉此獲得數目平均分子量(Mn)為6700、重量平均分子量(Mw)為8400、此等之比率(Mw/Mn)為1．25之聚酯多元醇。 The same starting material as in Example 1 was used, and the reaction conditions were changed (the blended mole ratio of the total amount of the diol component to the total amount of the dicarboxylic acid was adjusted to be more than that of Example 1), thereby obtaining the number average molecular weight (Mn ) Is a polyester polyol of 6700, a weight average molecular weight (Mw) of 8400, and a ratio (Mw / Mn) of these is 1.25.
以上述之聚酯多元醇替代實施例1之聚酯多元醇，除此之外，皆與實施例1相同，得到成形用包裝材。又，著色油墨組成物中，異 氰酸酯官能基(NCO)與聚酯多元醇羥基(OH)的莫爾比(NCO/OH)為4。 Except that the polyester polyol described in Example 1 was used in place of the polyester polyol described above, it was the same as in Example 1 to obtain a packaging material for molding. In the coloring ink composition, The molar ratio (NCO / OH) of the cyanate ester functional group (NCO) to the polyester polyol hydroxyl group (OH) was 4.
<比較例2> <Comparative example 2>
不使用實施例1之甲苯二異氰酸酯(TDI)與三羥甲基丙烷所成的加合物(NCO%13．0%、固體成分75質量%；芳香族系多官能異氰酸酯化合物)7．1質量份，而改用由甲苯二異氰酸酯(TDI)30莫爾%與六亞甲基二異氰酸酯(HDI)70莫爾%構成之混合異氰酸酯和三羥甲基丙烷反應而得之加合物(NCO%13．0%、固體成分75%；多官能異氰酸酯化合物)7．1質量份作為硬化劑，除此之外，皆與實施例1相同，得到成形用包裝材。 Adduct of toluene diisocyanate (TDI) and trimethylolpropane (NCO% 13.0%, solid content 75% by mass; aromatic polyfunctional isocyanate compound) of Example 1 was not used 7.1 mass And use an adduct (NCO%) obtained by reacting a mixed isocyanate composed of 30 mole% of toluene diisocyanate (TDI) and 70 mole% of hexamethylene diisocyanate (HDI) and trimethylolpropane. 13.0%, solid content 75%; polyfunctional isocyanate compound) 7.1 parts by mass as a hardener, except that all were the same as in Example 1 to obtain a molding packaging material.
<比較例3> <Comparative example 3>
不使用實施例2之甲苯二異氰酸酯(TDI)與三羥甲基丙烷所成的加合物(NCO%13．0%、固體成分75質量%；芳香族系多官能異氰酸酯化合物)4．8質量份，而改用由甲苯二異氰酸酯(TDI)30莫爾%與六亞甲基二異氰酸酯(HDI)70莫爾%構成之混合異氰酸酯和三羥甲基丙烷反應而得之加合物(NCO%13．0%、固體成分75%；多官能異氰酸酯化合物)4．8質量份作為硬化劑，除此之外，皆與實施例2相同，得到成形用包裝材。 Adduct formed from toluene diisocyanate (TDI) and trimethylolpropane (NCO% 13.0%, solid content 75% by mass; aromatic polyfunctional isocyanate compound) of Example 2 was not used And use an adduct (NCO%) obtained by reacting a mixed isocyanate composed of 30 mole% of toluene diisocyanate (TDI) and 70 mole% of hexamethylene diisocyanate (HDI) and trimethylolpropane. 13.0%, solid content 75%; polyfunctional isocyanate compound) 4.8 parts by mass as a hardener, the same as in Example 2 to obtain a packaging material for molding.
針對上述所得的各成形用包裝材，以下述評估法作為基準進行性能評估。其等之結果如表1所示。 For each of the molding packaging materials obtained above, performance evaluation was performed using the following evaluation method as a reference. The results are shown in Table 1.
<成形品的外觀(有無色彩不均)的評估法> <Evaluation method of appearance (presence or absence of color unevenness) of a molded article>
對各實施例、各比較例的每個例子，分別製作30個成形用包裝材，以肉眼確認此些中耐熱性樹脂層2並未由鋁箔4剝離後，使用衝頭及模頭等，以使內側的熱可塑性樹脂層3與衝頭接觸的型態，進行深引伸成形而形成縱50mm×橫35mm×深5．5mm之直方體形狀，製作出周圍具有輪緣部的成形用外殼。 For each of the examples and comparative examples, 30 forming packaging materials were produced, and the medium heat-resistant resin layer 2 was not visually confirmed to be peeled off from the aluminum foil 4 by a naked eye. The shape in which the inner thermoplastic resin layer 3 was in contact with the punch was deep-drawn and formed into a cuboid shape with a length of 50 mm × a width of 35 mm × a depth of 5.5 mm, and a molding case having a rim portion around it was produced.
從耐熱性樹脂層側目測觀察已製成的成形用外殼的外觀，並根據下列判定基準評估於成形處等有無色彩不均。 The appearance of the finished molding case was visually observed from the heat-resistant resin layer side, and the presence or absence of color unevenness at the molding place was evaluated according to the following criteria.
「○」...30個成形品皆無色彩不均 "○" ... No color unevenness in 30 molded products
「△」...有少量色彩不均之成形品存在 "△" ... A small amount of uneven molded products
「×」...有明顯色彩不均之成形品存在 "×" ... There is a molded product with obvious uneven color
<剝離有無的評估法> <Evaluation method of presence or absence of peeling>
對各實施例及各比較例的每個例子，分別製造30個成形用包裝材，並對此等包裝材在下列a)、b)、c)的3個狀態下以肉眼觀察耐熱性樹脂層有無剝離，並根據下列判定基準來評估。 For each of the examples and comparative examples, 30 forming packaging materials were produced, and the heat-resistant resin layers were visually observed with respect to these packaging materials in the following three states a), b), and c). The presence or absence of peeling was evaluated based on the following criteria.
(判定基準) (Judgment criteria)
「◎」...耐熱性樹脂層從鋁箔剝離者，於30個中為0個 "◎" ... the number of the heat-resistant resin layer peeled from the aluminum foil was 0 out of 30
「○」...耐熱性樹脂層從鋁箔剝離者，於30個中有1個或2個 "○" ... One or two of the 30 heat-resistant resin layers peeled from the aluminum foil
「△」...耐熱性樹脂層從鋁箔剝離者，於30個中有3個~5個 "△" ... Three to five of 30 peeled heat-resistant resin layers from aluminum foil
「×」...耐熱性樹脂層從鋁箔剝離者，於30個中有6個~30個。 "×" ... 6 to 30 of the 30 heat-resistant resin layers were peeled from the aluminum foil.
a)深引伸成形後不久的成形用包裝材。(亦即進行上述成形品外觀評估後之成形外殼) a) A packaging material for molding shortly after deep drawing. (That is, the molded case after the above-mentioned appearance evaluation of the molded product)
b)準備與上述a)的成形外殼相同構成的成形前的平面之成形用包裝材(以下，稱為「蓋材」)。另一方面，由上述a)的成形外殼僅選出耐熱性樹脂層未剝離者，將此無剝離的成形外殼的輪緣部與上述蓋材(的邊緣部)重合，以200℃×0．3MPa×6秒的條件進行熱封，此熱封後不久的成形用包裝材。 b) A packaging material for molding (hereinafter referred to as a "cover material") having a flat surface before molding having the same configuration as the molding case of a) above is prepared. On the other hand, only the heat-resistant resin layer without peeling was selected from the molded shell of a), and the rim portion of the molded shell without peeling was overlapped with the cover material (edge portion), and the temperature was 200 ° C × 0.3 MPa. Heat-sealing was performed under the conditions of × 6 seconds, and the packaging material for molding was shortly after this heat-sealing.
c)由上述a)的成形外殼僅選出耐熱性樹脂層未剝離者，將此無剝離的成形外殼，放入60℃×95%RH的高溫高濕試驗機中持續72小時後，取出並於常溫下放置5日後的成形用包裝材。 c) Only the heat-resistant resin layer without peeling is selected from the molded shell of a) above, and the molded shell without peeling is put into a high-temperature and high-humidity testing machine at 60 ° C. 95% RH for 72 hours, then taken out and The packaging material for molding was left at room temperature for 5 days.
<硬化膜的物性評估> <Physical evaluation of hardened film>
製作出實施例1~6、比較例1~3所使用的二液硬化型聚酯聚氨酯樹脂接著劑的硬化膜(亦即，由各著色油墨組成物中除去作為著色劑的碳黑後之組成的組成物之硬化膜；換言之，主劑與硬化劑反應而成之硬化膜)，並評估此硬化膜之物性。 Hardened films of the two-liquid curable polyester polyurethane resin adhesives used in Examples 1 to 6 and Comparative Examples 1 to 3 were produced (that is, the composition obtained by removing carbon black as a colorant from each colored ink composition) The hardened film of the composition; in other words, the hardened film formed by the reaction of the main agent and the hardener), and the physical properties of the hardened film were evaluated.
亦即，在非接著性的未處理PP薄膜上，塗佈二液硬化型聚酯聚氨酯樹脂接著劑，使乾燥後的厚度成為50μm，使溶劑乾燥後，於60℃進行老化使其硬化至殘存的異氰酸酯為5%以下為止而形成硬化膜。從未處理PP薄膜剝離硬化膜後，將該硬化膜裁切成寬15mm、長100mm之長尺材並以此作為試驗片。 That is, a non-adhesive untreated PP film is coated with a two-liquid curable polyester polyurethane resin adhesive so that the thickness after drying becomes 50 μm. After the solvent is dried, it is aged at 60 ° C. to be hardened to remain. The isocyanate is less than 5% to form a cured film. After the cured film was peeled from the untreated PP film, the cured film was cut into a long ruler having a width of 15 mm and a length of 100 mm, and this was used as a test piece.
對於製作的試驗片，在標點距離50mm、拉伸速度200mm/min的條件下，依據JIS K7162進行拉伸試驗，測定楊氏模量、斷裂強度及斷裂伸長率。此外，求取此拉伸試驗的S-S曲線，實施例1~6為圖3所示的模式A，比較例1~3為圖3所示的模式B。 The produced test piece was subjected to a tensile test in accordance with JIS K7162 under conditions of a punctuation point distance of 50 mm and a tensile speed of 200 mm / min, and the Young's modulus, breaking strength, and breaking elongation were measured. In addition, the S-S curve of this tensile test was obtained. Examples 1 to 6 are the mode A shown in FIG. 3, and Comparative examples 1 to 3 are the mode B shown in FIG. 3.
由表1可明確得知，本發明的實施例1~6的成形用包裝材，於成形時及熱封時，其耐熱性樹脂層不會剝離，即使於高溫多濕的環境下使用時耐熱性樹脂層也幾乎不剝離。 It is clear from Table 1 that the heat-resistant resin layer of the packaging materials for molding of Examples 1 to 6 of the present invention does not peel off during molding and heat sealing, and is heat-resistant even when used in a high-temperature and humid environment. The resin layer is hardly peeled.
相較於此，作為主劑使用的聚酯樹脂之分子量等偏離本發明之規定範圍的比較例1之成形用包裝材，於熱封時及在高溫多濕的環境下使用後，耐熱性樹脂層剝離的情形較多。此外，作為硬化劑的多官能異氰酸酯化合物中的芳香族系多官能異氰酸酯化合物之含有率未達50莫爾%的比較例2、3之成形用包裝材，於熱封時及在高溫多濕的環境下使用後，耐熱性樹脂層剝離的情形較多。 In comparison, the molding packaging material of Comparative Example 1 whose molecular weight, etc. of the polyester resin used as the main agent deviates from the specified range of the present invention, is heat-resistant resin during heat sealing and after use in a high temperature and humidity environment. There are many cases where the layer is peeled. In addition, the molding packaging materials of Comparative Examples 2 and 3 in which the content of the aromatic polyfunctional isocyanate compound in the polyfunctional isocyanate compound as the hardener was less than 50 mol% were heat-sealed and at high temperature and humidity. After use in an environment, the heat-resistant resin layer often peels off.
本發明的成形用包裝材，係可較佳地作為筆記型電腦用、行動電話用、車載用、固定型的鋰離子聚合物蓄電池等的電池外殼使用；除此之外，亦可較佳地作為食品的包裝材、醫藥品的包裝材，且並無限定僅能作為此等用途。其中，特佳係作為電池外殼使用。 The molding packaging material of the present invention can be preferably used as a battery case for a notebook computer, a mobile phone, a car, a fixed type lithium ion polymer battery, etc. It is not limited as a packaging material for food and a packaging material for pharmaceuticals, and can be used only for these purposes. Among them, the special good series is used as a battery case.
本申請案，係伴隨著在2014年5月16日提出申請的日本專利申請案的特願2014-102149號的優先權主張，其揭示內容直接構成本申請案的一部分。 This application claims priority from Japanese Patent Application No. 2014-102149, filed on May 16, 2014, and the disclosure content directly forms a part of this application.
在此所使用的用語及說明，係用以說明本發明的實施形態所使用，但本發明並不限定於此。在本發明所揭示且敘述的特徵事項的任何均等物皆不應被排除，且在本發明所請求的範圍內的各種變形亦應被理解為係可被接受的。 The terms and descriptions used herein are used to describe embodiments of the present invention, but the present invention is not limited thereto. Any equivalents of the features disclosed and described in the present invention should not be excluded, and various modifications within the scope claimed by the present invention should also be understood as acceptable.
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| JP2014102149A JP6279973B2 (en) | 2014-05-16 | 2014-05-16 | Molding packaging material and molding case |
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| JP6090522B1 (en) * | 2016-03-29 | 2017-03-08 | 東洋インキＳｃホールディングス株式会社 | Laminated body and manufacturing method thereof |
| JP2017220331A (en) * | 2016-06-06 | 2017-12-14 | 住友電気工業株式会社 | Lead member |
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| JP7203483B2 (en) * | 2016-12-28 | 2023-01-13 | 昭和電工パッケージング株式会社 | Exterior material for power storage device, exterior case for power storage device, and power storage device |
| JP6581120B2 (en) * | 2017-01-05 | 2019-09-25 | ロックペイント株式会社 | Laminate adhesive resin composition for battery packaging |
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Also Published As
| Publication number | Publication date |
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| CN105098104A (en) | 2015-11-25 |
| KR20230025836A (en) | 2023-02-23 |
| KR20210151759A (en) | 2021-12-14 |
| KR102438980B1 (en) | 2022-09-01 |
| TW201544313A (en) | 2015-12-01 |
| KR102500875B1 (en) | 2023-02-21 |
| KR20150131982A (en) | 2015-11-25 |
| CN105098104B (en) | 2019-05-14 |
| JP6279973B2 (en) | 2018-02-14 |
| KR102619739B1 (en) | 2024-01-02 |
| JP2015217577A (en) | 2015-12-07 |
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