CN103052503B - 层压薄膜 - Google Patents
层压薄膜 Download PDFInfo
- Publication number
- CN103052503B CN103052503B CN201180038268.9A CN201180038268A CN103052503B CN 103052503 B CN103052503 B CN 103052503B CN 201180038268 A CN201180038268 A CN 201180038268A CN 103052503 B CN103052503 B CN 103052503B
- Authority
- CN
- China
- Prior art keywords
- adhesive coating
- polyamine resin
- laminate film
- film
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000005001 laminate film Substances 0.000 title claims abstract description 33
- 239000000853 adhesive Substances 0.000 claims abstract description 125
- 230000001070 adhesive effect Effects 0.000 claims abstract description 125
- 239000011248 coating agent Substances 0.000 claims abstract description 116
- 238000000576 coating method Methods 0.000 claims abstract description 115
- 229920000768 polyamine Polymers 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000011347 resin Substances 0.000 claims abstract description 72
- 239000010410 layer Substances 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000011247 coating layer Substances 0.000 claims abstract description 25
- 239000000565 sealant Substances 0.000 claims abstract description 15
- 125000004429 atom Chemical group 0.000 claims abstract description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- -1 aliphatic amines Chemical class 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- 230000035699 permeability Effects 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 150000001408 amides Chemical group 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 150000004982 aromatic amines Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 description 111
- 239000000463 material Substances 0.000 description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 238000003475 lamination Methods 0.000 description 38
- 230000004888 barrier function Effects 0.000 description 36
- 239000007789 gas Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 29
- 239000002904 solvent Substances 0.000 description 20
- 238000007789 sealing Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 10
- 239000005022 packaging material Substances 0.000 description 10
- 238000004806 packaging method and process Methods 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 235000013305 food Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000003368 amide group Chemical group 0.000 description 7
- 238000009820 dry lamination Methods 0.000 description 7
- 238000010030 laminating Methods 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 3
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 3
- 235000019688 fish Nutrition 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000005033 polyvinylidene chloride Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- 244000099147 Ananas comosus Species 0.000 description 2
- 235000007119 Ananas comosus Nutrition 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 229930003427 Vitamin E Natural products 0.000 description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 235000012970 cakes Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000009459 flexible packaging Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 235000011087 fumaric acid Nutrition 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 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 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012939 laminating adhesive Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002633 protecting effect Effects 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000013580 sausages Nutrition 0.000 description 2
- 235000011888 snacks Nutrition 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- 235000019165 vitamin E Nutrition 0.000 description 2
- 229940046009 vitamin E Drugs 0.000 description 2
- 239000011709 vitamin E Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- SINZNVHKJJDTSC-UHFFFAOYSA-N 1,4-bis(isocyanatomethylidene)cyclohexane Chemical compound O=C=NC=C1CCC(=CN=C=O)CC1 SINZNVHKJJDTSC-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- 229940054273 1-propoxy-2-propanol Drugs 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 244000291564 Allium cepa Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 241000962514 Alosa chrysochloris Species 0.000 description 1
- 244000247812 Amorphophallus rivieri Species 0.000 description 1
- 235000001206 Amorphophallus rivieri Nutrition 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920002752 Konjac Polymers 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 241000220225 Malus Species 0.000 description 1
- 235000011430 Malus pumila Nutrition 0.000 description 1
- 235000015103 Malus silvestris Nutrition 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ABWDWYZSKJSXRD-UHFFFAOYSA-N N=C=O.N=C=O.C1CC=CC1 Chemical compound N=C=O.N=C=O.C1CC=CC1 ABWDWYZSKJSXRD-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 241000195474 Sargassum Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- 235000013527 bean curd Nutrition 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 235000013330 chicken meat Nutrition 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000014510 cooky Nutrition 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 235000021438 curry Nutrition 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 235000015220 hamburgers Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000008446 instant noodles Nutrition 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000252 konjac Substances 0.000 description 1
- 235000010485 konjac Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- 235000013557 nattō Nutrition 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 235000015108 pies Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 235000021395 porridge Nutrition 0.000 description 1
- 235000013324 preserved food Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000021251 pulses Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 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 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- 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
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
-
- 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
- B32B2439/40—Closed containers
- B32B2439/46—Bags
-
- 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
-
- 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
- B32B2439/80—Medical packaging
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
- Sealing Material Composition (AREA)
Abstract
本发明提供对各种基材赋予良好的粘接性且是单剂型的、包含含有多胺树脂的粘接性涂料层的气体阻隔性层压薄膜。该层压薄膜的特征在于,其是至少基材、粘接性涂料层和密封层按照该顺序层压而成的层压薄膜,形成该粘接性涂料层的粘接性涂料含有多胺树脂,该多胺树脂含有40质量%以上的下述式(1)所示的骨架结构,并且相对于该多胺树脂中所含的氮原子,该多胺树脂含有2.0~20mol%的金属原子。
Description
技术领域
本发明涉及层压薄膜。具体地涉及下述层压薄膜:使用了各种气体的阻隔方面优异的粘接性涂料,以内容物的保存为目的,食品、医药品等的包装材料所使用的层压薄膜。
背景技术
近年来,由于作为包装材料的强度、商品保护性、操作适应性、印刷等带来的宣传效果等原因,将不同种类的聚合物材料组合的复合挠性膜逐渐成为主流。这样的复合薄膜一般由作为具有商品保护作用的外层的热塑性塑料薄膜层等和作为密封层的热塑性塑料薄膜层等构成,它们的贴合采用下述方法:干式层压法,在层压薄膜层上涂布粘接剂并与密封层粘接;挤出层压法,根据需要在层压薄膜层上涂布锚固涂层剂(anchorcoating agent),并压接熔融的作为密封层的塑料薄膜,从而层压为薄膜状。
另外,关于这些方法中使用的粘接剂,从粘接性能高的方面考虑,一般由具有羟基等活性氢基团的主剂和具有异氰酸酯基的固化剂构成的二液型聚氨酯系粘接剂成为主流(参照专利文献1~2)。
然而,这些二液型聚氨酯系粘接剂由于其固化反应通常不是那么迅速,所以为了确保充分的粘接性,需要在贴合后通过长达1~5天的长时间的熟化来促进固化。另外,由于使用具有异氰酸酯基的固化剂,所以固化后未反应的异氰酸酯基残留时,会出现该残留异氰酸酯基与大气中的水分反应生成二氧化碳而使层压薄膜内产生气泡等问题。
另一方面,作为解决这些问题的方法,提出了聚氨酯系粘接剂、以及环氧系层压用粘接剂(参照专利文献3~4)。
然而,由于上述各聚氨酯系粘接剂、环氧系层压用粘接剂的气体阻隔性并不高,因此对于包装材料要求气体阻隔性时,需要在下述各种气体阻隔层与作为密封层的挠性聚合物薄膜层之间另外层压粘接剂层、锚固涂层等起粘接作用的层(参照专利文献5),从而给层压薄膜的制造成本、层压的操作工序带来不利,所述各种气体阻隔层如:PVDC涂层、聚乙烯醇(PVA)涂层;乙烯-乙烯醇共聚物(EVOH)薄膜层;聚己二酰间苯二甲胺薄膜层;蒸镀了氧化铝、二氧化硅等的无机蒸镀薄膜层等。
作为解决这些问题的方法,提出了气体阻隔性层压用粘接剂(专利文献6参照),虽然上述环氧树脂组合物体现了良好的气体阻隔性,但是由于是二液型粘接剂、适用期短,因而期盼具有气体阻隔性、操作性良好的单剂型粘接性涂料。
现有技术文献
专利文献
专利文献1:日本特开平5-51574号公报
专利文献2:日本特开平9-316422号公报
专利文献3:日本特开2000-154365号公报
专利文献4:国际公开第99/60068号
专利文献5:日本特开平10-71664号公报
专利文献6:日本特开2002-256208号公报
发明内容
发明要解决的问题
本发明的课题在于提供对各种基材赋予良好的粘接性且是单剂型的、包含含有多胺树脂的粘接性涂料层的气体阻隔性层压薄膜。
用于解决问题的方案
本发明人等为了解决上述课题进行了深入研究,结果发现,由于含有特定的多胺树脂的粘接性涂料具有多胺树脂的优异性能、高的气体阻隔性、对各种基材的良好粘接性且是单剂型的,所以使适用期大幅延长并赋予良好的操作性,通过使用该粘接性涂料将基材薄膜与密封薄膜贴合,能够经济地获得具有气体阻隔性、粘接性优异的层压薄膜,从而完成本发明。
即,本发明如下所述。
1.层压薄膜,其特征在于,其是至少基材、粘接性涂料层和密封层按照该顺序层压而成的层压薄膜,形成该粘接性涂料层的粘接性涂料含有多胺树脂,该多胺树脂含有40质量%以上的下述式(1)所示的骨架结构,并且相对于该多胺树脂中所含的氮原子,该多胺树脂含有2.0~20mol%的金属原子。
2.根据第1项记载的层压薄膜,其中,前述金属原子选自由锌、铝、镁、钙、锡、铜、镍、钯、铁、铬、钼、钛、铷、铯、锶、钡、锆、铪和锰组成的组中的1种以上。
3.根据第1项或第2项记载的层压薄膜,其中,前述多胺树脂为下述(A)、(B)和(C)的反应产物,
(A)选自由具有芳香环的脂肪族胺、脂肪族胺、脂环式胺和芳香族胺组成的组中的1种以上的多胺;
(B)能够与多胺反应形成酰胺基部位、并且能够形成低聚物的、具有至少1个酰基的多官能化合物;
(C)(甲基)丙烯酸金属盐
4.根据第3项记载的层压薄膜,其中,前述(A)为间苯二甲胺或对苯二甲胺。
5.根据第3项记载的层压薄膜,其中,前述(B)为丙烯酸、甲基丙烯酸或者它们的酯、酰胺、酸酐或酰氯。
6.根据第3项记载的层压薄膜,其中,前述(C)为丙烯酸锌、丙烯酸镁或丙烯酸钙。
7.根据第3项记载的层压薄膜,其中,前述(A)与前述(C)的反应摩尔比((C)/(A))为0.05~0.35。
8.根据第1项~第7项中任一项记载的层压薄膜,其中,前述多胺树脂的透氧系数为2.0ml·mm/(m2·天·MPa)(23℃、60%RH)以下。
发明的效果
本发明的层压薄膜所使用的粘接性涂料由于气体阻隔性以及粘接性良好且是单剂型涂料,所以适用期长、操作性优异。因此,使用该粘接性涂料得到的本发明的层压薄膜的气体阻隔性、粘接性优异,作为非卤系气体阻隔材料应用于各种用途。另外,由于可经济地且操作性有利地获得该层压薄膜,所以工业上是有用的。
具体实施方式
本发明的层压薄膜是至少基材、粘接性涂料层和密封层按照该顺序层压而成的层压薄膜,将层压薄膜制袋时,基材层用作袋外表面,密封层用作袋内表面。
〔基材〕
作为本发明的层压薄膜的基材,例如可以使用:聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等聚酯系薄膜;尼龙6、尼龙6,6、聚己二酰间苯二甲胺(N-MXD6)等聚酰胺系薄膜;低密度聚乙烯、高密度聚乙烯、直线状低密度聚乙烯、聚丙烯等聚烯烃系薄膜;聚丙烯腈系薄膜;聚(甲基)丙烯酸(酯)系薄膜;聚苯乙烯系薄膜;聚碳酸酯系薄膜;乙烯-乙烯醇共聚物(EVOH)系薄膜;聚乙烯醇系薄膜;聚丙烯腈系薄膜;聚碳酸酯系薄膜;聚乳酸等生物降解性薄膜;卡片纸等纸类;铝、铜等金属箔;以及对于这些用作基材的各种材料,利用聚偏二氯乙烯(PVDC)树脂、聚乙烯醇树脂、乙烯-乙酸乙烯酯共聚物皂化物系树脂、丙烯酸(酯)系树脂等各种聚合物实施涂覆后的薄膜,蒸镀铝等金属后的薄膜,分散无机填料等后的薄膜,赋予氧捕集功能后的薄膜等。
另外,涂覆的各种聚合物中也可以分散无机填料。作为无机填料,可举出二氧化硅、氧化铝、云母、滑石、铝粉、玻璃鳞片等,优选蒙脱石等层状硅酸盐,另外作为无机填料的分散方法例如可以使用挤出混炼法、树脂溶液中的混合分散法等以往公知的方法。
作为赋予氧捕集功能的方法,例如,可举出至少部分地使用含有下述化合物的组合物的方法等,所述化合物为:受阻酚类、维生素C、维生素E、有机磷化合物、没食子酸、焦棓酚等与氧反应的低分子有机化合物;钴、锰、镍、铁、铜等的过渡金属化合物等。
这些薄膜材料的厚度实用的为10~300μm左右、优选为10~100μm左右,塑料薄膜的情况下也可以进行过单轴或双轴方向地拉伸。
另外,本发明中,作为上述基材、粘接性涂料层和密封层以外的层,可以层压聚烯烃、聚酯等上述薄膜材料(例如,粘接性涂料层与密封层之间等)。此时,该薄膜材料还可以蒸镀有二氧化硅或蒸镀有氧化铝。层压各种材料时,也可以将粘接性涂料层设为多层。另外,也可以组合使用本发明的粘接性涂料以外的涂料和/或粘接剂。
〔密封层〕
作为本发明的层压薄膜的密封层,优选使用挠性聚合物薄膜,考虑到体现良好的热封性,优选选择聚乙烯薄膜、聚丙烯薄膜、乙烯-乙酸乙烯酯共聚物等聚烯烃系薄膜。这些薄膜的厚度实用的为10~300μm左右、优选为10~100μm左右,也可以对薄膜表面实施火焰处理、电晕放电处理等各种表面处理。
〔粘接性涂料层〕
本发明的层压薄膜的粘接性涂料层的特征在于由含有多胺树脂的粘接性涂料形成,该多胺树脂含有40质量%以上的下述式(1)所示的骨架结构、优选45质量%以上、更优选50质量%以上,并且相对于该多胺树脂中所含的氮原子,该多胺树脂含有2.0~20mol%、优选3.0~20mol%、更优选5.0~17.5mol%、进一步优选7.5~15mol%、特别优选7.5~12.5mol%的金属原子。
由于多胺树脂中高水平地含有上述式(1)所示的骨架结构和金属原子,所以维持粘接性,并且体现高的气体阻隔性。采用本发明,可以得到23℃、60%RH下透氧系数为2.0ml·mm/(m2·天·MPa)以下的多胺树脂。以下,对多胺树脂进行说明。
(多胺树脂)
作为本发明的多胺树脂,可举出由多胺类与具有至少1个酰基或异氰酸酯基的多官能化合物反应而得到的酰胺低聚物或尿素低聚物。
作为多胺类,可举出:乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺等脂肪族胺;间苯二甲胺、对苯二甲胺等具有芳香环的脂肪族胺;1,3-双(氨甲基)环己烷、异佛尔酮二胺、降冰片烷二胺(norbornane diamine)等脂环式胺;二氨基二苯甲烷、间苯二胺等芳香族胺;或杂环式化合物等,这些可以单独使用或者组合使用。
作为具有至少1个酰基的多官能化合物,可举出:丙烯酸、甲基丙烯酸、马来酸、富马酸、琥珀酸、苹果酸、酒石酸、己二酸、间苯二甲酸、对苯二甲酸、均苯四甲酸、偏苯三酸等羧酸以及它们的衍生物、例如酯、酰胺、酸酐、酰氯等。
作为具有至少1个异氰酸酯基的多官能化合物,可举出:对苯二异氰酸酯、4,4’-二苯基二异氰酸酯、1,5-萘二异氰酸酯(NDI)、4,4’-、2,4’-或2,2’-二苯基甲烷二异氰酸酯或其混合物(MDI)、2,4-或2,6-甲苯二异氰酸酯或其混合物(TDI)、4,4’-甲苯胺二异氰酸酯(TODI)、4,4’-二苯醚二异氰酸酯、1,3-或1,4-苯二甲基二异氰酸酯或其混合物(XDI)、1,3-或1,4-四甲基苯二甲基二异氰酸酯或其混合物(TMXDI)、ω,ω′-二异氰酸酯基-1,4-二乙基苯、1,3-环戊烯二异氰酸酯、1,4-环己烷二异氰酸酯、1,3-环己烷二异氰酸酯、3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯(异佛尔酮二异氰酸酯;IPDI)、4,4’-、2,4’-或2,2’-二环己基甲烷二异氰酸酯或其混合物(加氢MDI)、甲基-2,4-环己烷二异氰酸酯、甲基-2,6-环己烷二异氰酸酯、1,3-或1,4-双(异氰酸酯基亚甲基)环己烷或其混合物(加氢XDI)、双(异氰酸酯基亚甲基)降冰片烷、六甲撑二异氰酸酯、以及它们的改性物等。
作为多胺树脂中所含的金属原子,优选二价以上的金属。作为二价以上的金属,可举出锌、铝、镁、钙、锡、铜、镍、钯、铁、铬、钼、钛、铷、铯、锶、钡、锆、铪、锰等,尤其优选锌、镁、钙。向多胺树脂中导入金属原子例如可使后述那样的(甲基)丙烯酸的金属盐与多胺类反应来实现。
作为本发明的多胺树脂,优选使用下述(A)、(B)和(C)的反应产物。由此体现高的气体阻隔性以及良好的粘接性。
(A)选自由具有芳香环的脂肪族胺、脂肪族胺、脂环式胺和芳香族胺组成的组中的1种以上的多胺;
(B)能够与多胺反应形成酰胺基部位、并且能够形成低聚物的、具有至少1个酰基的多官能化合物;
(C)(甲基)丙烯酸金属盐。
作为前述(A),可使用选自由具有芳香环的脂肪族胺、脂肪族胺、脂环式胺和芳香族胺组成的组中的1种以上的多胺,作为具有芳香环的脂肪族胺可举出间苯二甲胺、对苯二甲胺等,作为脂肪族胺可举出乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺等,作为脂环式胺可举出1,3-双(氨甲基)环己烷、异佛尔酮二胺、降冰片烷二胺等,作为芳香族胺可举出二氨基二苯甲烷、间苯二胺等。特别优选间苯二甲胺或对苯二甲胺。该化合物可单独使用,也可以2种以上混合使用。
作为能够与前述(B)多胺反应形成酰胺基部位、并且能够形成低聚物的、具有至少1个酰基的多官能化合物,可举出:丙烯酸、甲基丙烯酸、马来酸、富马酸、琥珀酸、苹果酸、酒石酸、己二酸、间苯二甲酸、对苯二甲酸、均苯四甲酸、偏苯三酸等羧酸以及它们的衍生物、例如酯、酰胺、酸酐、酰氯等,特别优选丙烯酸、甲基丙烯酸以及它们的衍生物。
另外,也可以将甲酸、乙酸、丙酸、丁酸、乳酸、乙醇酸、苯甲酸等碳原子数1~8的一元羧酸以及它们的衍生物、例如酯、酰胺、酸酐、酰氯等,与上述(B)多官能化合物一起使用而与多胺反应。由反应导入的酰胺基部位具有高的内聚力,通过使酰胺基部位以高比例存在于多胺树脂中,可获得更高的气体阻隔性和良好的粘接强度。
作为(甲基)丙烯酸金属盐(前述(C))所使用的金属,可举出锌、铝、镁、钙、锡、铜、镍、钯、铁、铬、钼、钛、铷、铯、锶、钡、锆、铪、锰等二价以上的金属。特别优选锌、镁、钙。另外,可以使用这些金属盐的水溶液。前述(C)可以单独使用也可以2种以上组合使用。
另外,在本说明书中,有时将“丙烯酸”和“甲基丙烯酸”总称为(甲基)丙烯酸。
从工业上容易获取的方面考虑,前述(C)更优选为丙烯酸锌、丙烯酸镁或丙烯酸钙。
前述(A)、(B)和(C)的反应通过下述方式来实施:首先在0~100℃的条件下将(A)、(B)和(C)混合,接着在100~300℃、优选120~250℃的条件下脱水、脱醇、脱胺来进行酰胺基形成反应。
另外,关于混合的顺序也可以任意,优选先加入(A)和(C),接着添加(B)进行加成反应。
酰胺基形成反应时,为了结束反应,还可以根据需要在反应的最终阶段对反应装置内进行减压处理。另外,也可以根据需要使用非反应性的溶剂进行稀释。此外还可以添加亚磷酸酯类等催化剂作为脱水剂、脱醇剂。
另一方面,作为(B)使用酸酐、酰氯的情况下,在0~150℃、优选0~100℃的条件下混合后,通过进行酰胺基形成反应来实施。
酰胺基形成反应时,为了结束反应,还可以根据需要在反应的最终阶段对反应装置内进行减压处理。另外,也可以根据需要使用非反应性的溶剂进行稀释。此外还可以添加吡啶、甲基吡啶、二甲基吡啶、三烷基胺等叔胺。
由上述反应导入的酰胺基部位具有高的内聚力,通过使酰胺基部位以高比例存在于多胺树脂中,可获得更高的气体阻隔性以及对金属、混凝土、塑料等基材的良好的粘接强度。
另外,关于(A)与(B)的反应比,摩尔比((B)/(A))优选为0.3~1.5的范围、更优选为0.5~1.4的范围、进一步优选为0.6~1.3的范围。通过设为上述范围,多胺树脂中有足够量的酰胺基生成,并且可以得到成为形成粘接性涂料的涂膜的足够分子量、体现高的气体阻隔性和优异涂膜性能、且操作性也良好的多胺树脂。
关于(A)与(C)的反应比,摩尔比((C)/(A))优选为0.05~0.35的范围、更优选为0.15~0.30的范围、进一步优选为0.15~0.25的范围。该摩尔比为0.05以上时,体现良好的气体阻隔性和粘接性;为0.35以下时,操作性良好。进而,关于(B)和(C)与(A)的反应比,摩尔比(((B)+(C))/(A))优选为0.4~1.8的范围。该摩尔比为0.4以上时,多胺树脂中有足够量的酰胺基生成,体现良好的气体阻隔性和粘接性。另外,适当地维持多胺树脂中残留的挥发性分子的比例,从而不产生来自于得到的多胺树脂的臭味。另外,该摩尔比为1.8以下时,在有机溶剂中的溶解性良好。
尤其在考虑得到的多胺树脂的高气体阻隔性、高粘接性、臭味产生的抑制以及高湿度环境下的高气体阻隔性的情况下,多官能化合物与多胺成分的摩尔比(((B)+(C))/(A))更优选为0.6~1.5的范围。
本发明的多胺树脂的透氧系数优选为2.0ml·mm/m2·天·MPa(23℃、60%RH)以下。
其中,使用本发明的粘接性涂料制作的层压薄膜在刚层压后300mm/min的剥离速度下的层压强度优选为30g/15mm以上、更优选为40g/15mm以上、进一步优选为50g/15mm以上。该层压强度足够时,层压薄膜的隧穿(tunneling)、卷取薄膜时的卷边不齐等问题不发生。
为了防止卷边不齐,需要设为高剪切强度,在考虑体现高剪切强度的情况下,例如优选使用下述多胺树脂:优选将前述摩尔比(((B)+(C))/(A))设为0.6~1.8、更优选设为0.7~1.6、进一步优选设为0.8~1.5的范围,提高了反应产物的低聚物的平均分子量。更优选的多胺树脂是间苯二甲胺、与丙烯酸、甲基丙烯酸和/或它们的衍生物、及(甲基)丙烯酸金属盐的反应产物。其中,丙烯酸、甲基丙烯酸和/或它们的衍生物及(甲基)丙烯酸金属盐与间苯二甲胺的反应摩尔比优选为0.8~1.5的范围。
〔粘接性涂料〕
本发明的粘接性涂料含有上述多胺树脂,用于形成本发明的层压薄膜中的粘接性涂料层。本发明的粘接性涂料将上述多胺树脂作为主要成分,从气体阻隔性和粘接性的观点考虑,该粘接性涂料中该多胺树脂的含量优选为50~100质量%、更优选为60~100质量%。
在不损害本发明的效果的范围内,还可以根据需要在本发明的粘接性涂料中混合聚氨酯系树脂组合物、聚丙烯酸(酯)系树脂组合物、聚脲系树脂组合物等热固化性树脂组合物。
为了有助于将本发明的粘接性涂料涂布到各种材料上时表面的润湿,还可以根据需要在本发明的粘接性涂料中添加硅酮或丙烯酸(酯)系化合物之类的润湿剂。作为合适的润湿剂,有能够从BYK-Chemie GmbH获取的BYK331、BYK333、BYK340、BYK347、BYK348、BYK354、BYK380、BYK381等。添加它们的情况下,优选以多胺树脂的质量作基准为0.01~2.0质量%的范围。
为了提高刚涂布后对于各种材料的粘着性,还可以根据需要在本发明的粘接性涂料中添加二甲苯树脂、萜烯树脂、酚醛树脂、松香树脂等粘接赋予剂。添加它们的情况下,优选以多胺树脂的质量作基准为0.01~5.0质量%的范围。
另外,为了提高气体阻隔性、粘接性,还可以在本发明的粘接性涂料中添加甲醛、乙醛、乙二醛等醛、乙酸酐、丙酸酐等羧酸酐等。添加它们的情况下,优选相对于前述多胺树脂中所含的氮原子为10~80mol%的范围。
另外,为了提高由本发明的粘接性涂料(以下,有时将其称为“多胺树脂组合物”。)形成的粘接性涂料层的气体阻隔性、耐冲击性、耐热性等诸性能,还可以在粘接性涂料之中添加二氧化硅、氧化铝、云母、滑石、铝粉、玻璃鳞片等无机充填剂。考虑薄膜的透明性的情况下,优选这样的无机填料为平板状。添加它们的情况下,优选以多胺树脂的质量作基准为0.01~10.0质量%的范围。
另外,根据需要还可以在本发明的粘接性涂料中添加具有氧捕集作用的化合物等。作为具有氧捕集作用的化合物,例如,可举出:受阻酚类、维生素C、维生素E、有机磷化合物、没食子酸、焦棓酚等与氧反应的低分子有机化合物;钴、锰、镍、铁、铜等的过渡金属化合物等。
此外,为了提高由本发明的粘接性涂料形成的粘接性涂料层的粘接性,还可以在粘接性涂料之中添加硅烷偶联剂、钛偶联剂等偶联剂。添加它们的情况下,优选以多胺树脂的质量作基准为0.01~5.0质量%的范围。
本发明的粘接性涂料的特征在于具有良好的粘接性、高的气体阻隔性。因此,使用了本发明的粘接性涂料的层压薄膜体现了非常高水平的气体阻隔性而并没有使用PVDC涂层、聚乙烯醇(PVA)涂层、乙烯-乙烯醇共聚物(EVOH)薄膜层、聚己二酰间苯二甲胺薄膜层等通常所使用的气体阻隔性材料。此外,通过使用该粘接性涂料作为贴合这些以往的气体阻隔性材料与密封材料的涂料,还能够显著地提高得到的层压薄膜的气体阻隔性。
〔层压薄膜的制造方法〕
使用本发明的粘接性涂料层压各种薄膜材料时,可以使用干式层压、无溶剂层压(non-solvent laminate)、挤出层压等公知的层压法,在本发明中,优选干式层压。
在对各种材料涂布本发明的粘接性涂料并层压的情况下,虽然是在获得粘接性涂料层的充分的多胺树脂组合物的浓度和温度下进行实施的,但粘接性涂料可根据起始材料以及层压方法的选择进行改变。即,多胺树脂组合物的浓度可根据选择的材料的种类及摩尔比、层压方法等而采取从不使用溶剂的情况至使用某种合适的有机溶剂和/或水稀释至约5质量%左右的组合物浓度从而调制涂布液的情况的各种状态。
作为所使用的有机溶剂,可以使用与粘接性涂料具有溶解性的所有溶剂。例如可举出:甲苯、二甲苯、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮、甲乙酮等非水溶性系溶剂;2-甲氧基乙醇、2-乙氧基乙醇、2-丙氧基乙醇、2-丁氧基乙醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丙氧基-2-丙醇等二醇醚类;甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇等醇类;乙醛、丙醛等醛类;N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮等非质子性极性溶剂等。
用溶剂稀释的粘接性涂料(以下,有时将其称为“涂布液”。)可以被稀释至其察恩杯(No.3)粘度为5~30秒(25℃)的范围那样的浓度。察恩杯(No.3)粘度为5秒以上时,可对被涂物充分涂布粘接性涂料,而不产生辊的污染等。另外察恩杯(No.3)粘度为30秒以下时,粘接性涂料可充分地转移至辊上,容易形成均匀的粘接性涂料层。例如采用干式层压时优选察恩杯(No.3)粘度在粘接性涂料使用中为10~20秒(25℃)。
调制本发明的涂布液时,为了抑制涂布液的起泡,还可以在涂布液之中添加硅酮或丙烯酸(酯)系化合物之类的消泡剂。作为合适的消泡剂,可举出:能够从BYK-Chemie GmbH公司获取的BYK019、BYK052、BYK063、BYK065、BYK066N、BYK067N、BYK070、BYK080;能够从楠本化成(株)获取的DISPARLON1930N、1934等,特别优选BYK065。另外,添加这些消泡剂的情况下,优选以涂布液中的多胺树脂的质量作基准为0.001~3.0质量%的范围、更优选为0.005~2.0质量%。
另外,使用溶剂的情况下,涂布粘接性涂料后的溶剂干燥温度可以是从20℃至140℃之间的各种温度,期望为接近溶剂的沸点、且不对被涂物造成影响的温度。干燥温度小于20℃时,层压薄膜中溶剂残留,成为粘接不良、臭味的原因。另外,干燥温度超过140℃时,由于聚合物薄膜的软化等,所以难以获得良好外观的层压薄膜。例如,在拉伸聚丙烯薄膜上涂布粘接性涂料时,期望为40~120℃。
作为涂布粘接性涂料时的涂装形式,可任意地使用辊涂、喷涂、吹拂器涂布、浸渍、刷涂等通常所使用的涂装形式,优选辊涂或喷涂。例如,在聚合物薄膜上涂布聚氨酯系粘接剂成分,可应用与层压时同样的辊涂覆或喷涂技术及设备。
接着,对各层压方法中具体的操作进行说明。
干式层压法的情况下,可以通过使用凹印辊等辊在基材上涂布前述涂布液后,干燥溶剂后立即使用轧辊(nip roll)在其表面贴合新的薄膜材料,从而得到层压薄膜。
干式层压法的情况,作为调制粘接性涂料时的溶剂,优选溶解性好、沸点较低、含有碳原子数3以下的醇的溶剂,可例示出将选自由甲醇、乙醇、异丙醇和正丙醇组成的组中的1种以上作为主要成分的溶剂。另外,还可以混合具有酯基、酮基等官能团的溶剂,作为具有酯基、酮基等任一官能团的溶剂,可例示出沸点较低且混合了选自由乙酸甲酯、乙酸乙酯、丙酮、甲乙酮组成的组中的1种以上的混合液。为了得到残留在所得层压薄膜中的溶剂量少的薄膜,具有酯基、酮基、醛基任一官能团的溶剂的含量优选为全部溶剂中的20质量%以下。其中,残留在层压薄膜中的溶剂多时,成为恶臭的原因,因而残留的溶剂量实用的为7mg/m2以下,多于7mg/m2时,成为感受到薄膜发出的异臭的原因。严格管理薄膜的臭味的情况下,优选为5mg/m2以下、更优选为3mg/m2以下。
干式层压法中,粘接性涂料也可以涂布在密封层上,可以通过涂布在聚乙烯薄膜、聚丙烯薄膜、乙烯-乙酸乙烯酯共聚物等聚烯烃系薄膜上,干燥后,贴合拉伸聚丙烯、聚酰胺系薄膜、聚对苯二甲酸乙二醇酯薄膜等基材,从而制造层压薄膜。
使用轧辊贴合时,轧辊可以加热至20~120℃进行贴合,期望为40~100℃。
另外,无溶剂层压法的情况下,可以通过使用加热至40~120℃的凹印辊等辊在包含基材的薄膜材料上涂布预先加热至40~100℃左右的本发明的粘接性涂料后,立即在其表面贴合新的薄膜材料,从而得到层压薄膜。
挤出层压法的情况下,可以通过使用凹印辊等辊在包含基材的薄膜材料上涂布粘接辅助剂(锚固涂层剂),20~140℃下进行溶剂的干燥、固化反应后,层压利用挤出机熔融的聚合物材料,从而得到层压薄膜,所述粘接辅助剂是作为本发明的粘接性涂料的主要成分的多胺树脂的被有机溶剂和/或水稀释得到的稀释溶液。熔融的聚合物材料优选低密度聚乙烯树脂、线性低密度聚乙烯树脂、乙烯-乙酸乙烯酯共聚物树脂等聚烯烃系树脂。这些层压法以及其它通常可使用的层压法也可以根据需要进行组合,层压薄膜的层构成可以根据用途、形态发生变化。
在各种材料等上涂布本发明的粘接性涂料,进行干燥、贴合,热处理后的粘接性涂料层的厚度实用的优选为0.1~100μm、更优选为0.5~10μm。0.1μm以上时,能够体现足够的气体阻隔性和粘接性,另一方面,100μm以下时,能够容易形成均一厚度的粘接性涂料层。
[层压薄膜]
本发明的层压薄膜具有优异的层压强度。虽然300mm/min的剥离速度下的层压强度根据基材、密封层的材质不同而不同,例如,基材为拉伸聚丙烯时,优选为80g/15mm以上、更优选为100g/15mm以上、进一步优选为120g/15mm以上。另一方面,基材为拉伸尼龙、聚对苯二甲酸乙二醇酯时,密封层为低密度聚乙烯或未拉伸聚丙烯时,优选为120g/15mm以上、更优选为250g/15mm以上、进一步优选为300g/15mm以上。上述层压强度可以按照实施例记载的方法进行测定。
使用本发明的粘接性涂料制造的层压薄膜可以用作以保护食品、医药品等为目的的多层包装材料。用作多层包装材料的情况下,层压薄膜的层构成可以根据内容物、使用环境、使用形态发生变化。即,本发明的层压薄膜可直接作为多层包装材料使用,也可以根据需要在本发明的层压薄膜上进一步层压氧吸收层、热塑性树脂薄膜层、纸层、金属箔层等。此时,可以使用本发明的粘接性涂料进行层压,也可以使用其它的涂料、粘接剂、锚固涂层剂进行层压。
对由使用前述多层包装材料制造的软包装用袋等构成的包装用袋进行说明。所述由软包装用袋等构成的包装用袋可以通过下述方式来制造:使用前述多层包装材料,将其热封性树脂层面对向叠置合拢后,将其周边端部热封而形成密封部。作为包装用袋的制袋方法,例如,可以举出将前述多层包装材料弯折或叠置,使其内层面对向,进而对其周边端部例如采用侧面密封型、双向密封型、三向密封型、四向密封型、信封式密封型、合掌贴型密封型(枕型密封型)、带槽密封型(gathersealing)、平底密封型(flat bottom sealing)、方底密封型(squarebottom sealing)、报刊型(gazette sealing)、其他等热封方式进行热封的方法。包装用袋可以根据内容物、使用环境、使用形态采用各种形态。其它例如也可以为自立性包装用袋(自立袋)等。作为热封的方法,例如,可以采用棒封合(bar sealing)、旋转辊封合、带式封合、脉冲封合、高频封合、超声波封合等公知的方法进行。
可以通过从前述包装用袋的开口部填充内容物、合拢后,对其开口部进行热封,从而制造使用了本发明的包装用袋的包装制品。作为可填充的内容物,可举出:米糕、豆糕、坚果类、饼干/曲奇、威化糕点(wafers)、棉花糖(marshmallows)、馅饼、半生蛋糕、糖果、零食(snack foods)等糕点类;面包、干脆面、方便面、干面条、意大利面食、无菌包装米饭、杂烩粥、粥、包装年糕、谷类食品等主食类;咸菜、煮豆、纳豆、酱、冻豆腐、豆腐、酱油煮的金针菇(cooked enoki mushrooms)、魔芋、野菜加工品、果酱类、花生膏、色拉类、冷冻蔬菜、土豆加工品等农产加工品;火腿类、培根、香肠类、鸡肉加工品、牛肉罐头类等畜产加工品;鱼肉火腿/香肠、水产熬制品、鱼糕、海藻、咸烹海味(佃煮)、干制鲣鱼、腌鱼、熏鲑鱼、芥末鳕鱼子等水产加工品;桃、橘子、菠萝、苹果、凤梨、樱桃等果肉类;玉米、芦笋、蘑菇、洋葱、胡萝卜、萝卜、土豆等蔬菜类;以汉堡、肉丸、炸制水产、饺子、炸丸子等为代表的冷冻副食、冷藏副食等已烹制食品;黄油、人造黄油、乳酪、奶油、速溶奶粉、育儿用调整奶粉等乳制品;液体调味料、速食咖喱、宠物食品等食品类。另外,也可以用作香烟、一次性取暖袋、医药品、化妆品等的包装材料。
实施例
下面根据实施例具体地说明本发明。然而,本发明并不受到这些实施例的任何限制。
另外,含有多胺树脂的粘接性涂料溶液A~F按照以下方法调制。
粘接性涂料溶液A
在反应容器中加入1mol的间苯二甲胺和0.23mol的丙烯酸锌。氮气流下升温至60℃,花费1小时滴加0.70mol的丙烯酸甲酯。馏去生成的甲醇并升温至165℃,保持165℃1.0小时。花费1.5小时滴加相当于固形分浓度45%的甲醇,从而得到含有多胺树脂的粘接性涂料溶液A。
粘接性涂料溶液B
在反应容器中加入1mol的间苯二甲胺和0.20mol的丙烯酸锌。氮气流下升温至60℃,花费1小时滴加0.70mol的丙烯酸甲酯。馏去生成的甲醇并升温至165℃,保持165℃1.0小时。花费1.5小时滴加相当于固形分浓度45%的甲醇,从而得到含有多胺树脂的粘接性涂料溶液B。
粘接性涂料溶液C
在反应容器中加入1mol的间苯二甲胺和0.20mol的丙烯酸镁。氮气流下升温至60℃,花费1小时滴加0.70mol的丙烯酸甲酯。馏去生成的甲醇并升温至165℃,保持165℃1.0小时。花费1.5小时滴加相当于固形分浓度45%的甲醇,从而得到含有多胺树脂的粘接性涂料溶液C。
粘接性涂料溶液D
在前述粘接性涂料溶液A中加入0.31mol的丙烯酸,氮气流下升温至60℃,保持3小时。花费1.5小时滴加相当于固形分浓度45%的甲醇,从而得到含有多胺树脂的粘接性涂料溶液D。
粘接性涂料溶液E
在反应容器中加入1mol的间苯二甲胺。氮气流下升温至60℃,花费1小时滴加0.93mol的丙烯酸甲酯。馏去生成的甲醇并升温至165℃,保持165℃2.5小时。花费1.5小时滴加相当于固形分浓度45%的甲醇,从而得到含有多胺树脂的粘接性涂料溶液E。
粘接性涂料溶液F
在反应容器中加入1mol的间苯二甲胺和0.10mol的丙烯酸锌。氮气流下升温至60℃,花费1小时滴加0.80mol的丙烯酸甲酯。馏去生成的甲醇并升温至165℃,保持165℃1.0小时。花费1.5小时滴加相当于固形分浓度45%的甲醇,从而得到含有多胺树脂的粘接性涂料溶液F。
另外,气体阻隔性、层压强度的评价方法如下所述。
<透氧系数(ml·mm/m2·天·MPa)>
使用透氧率测定装置(MOCON公司制造、OX-TRAN2/21),在23℃、相对湿度60%的条件下测定下述物质的透氧率:在基材上涂布含有上述多胺树脂的粘接性涂料溶液并贴合密封薄膜而得到的层压薄膜、以及基材、密封薄膜,使用以下的式子计算粘接性涂料的涂膜的透氧系数:
1/R1=1/R2+DFT/P+1/R3
其中,
R1=层压薄膜的透氧率(ml/m2·天·MPa)
R2=基材的透氧率(ml/m2·天·MPa)
R3=密封薄膜的透氧率(ml/m2·天·MPa)
DFT=粘接性涂料的涂膜的厚度(mm)
P=粘接性涂料的涂膜的透氧系数
<层压强度(g/15mm)>
使用JISK-6854指定的方法,通过T型剥离试验以300mm/min的剥离速度测定层压薄膜的层压强度。
实施例1
<透氧系数和层压强度的测定>
在作为基材的厚20μm的双轴拉伸聚丙烯薄膜(TOYOBOCO.,LTD制造;P2161)上,使用100线/英寸、深度100μm凹印辊涂布粘接性涂料溶液A,接着用60℃(入口附近)~90℃(出口附近)的干燥炉干燥后,通过用加热至70℃的轧辊贴合作为密封层的厚40μm的直链状聚乙烯薄膜(MC TOHCELLOCO.,LTD制造T.U.X.MC-S),以卷取速度130m/min进行卷取,从而得到由基材/含有多胺树脂的粘接性涂料层/密封层构成的层压薄膜(L1)。
评价得到的层压薄膜(L1)的气体阻隔性、层压强度。透氧系数和层压强度示于表1。
实施例2
<透氧系数和层压强度的测定>
除了使用粘接性涂料溶液B替代粘接性涂料溶液A以外,按照与实施例1同样的方法制作层压薄膜(L2),测定透氧系数和层压强度。结果示于表1。
实施例3
<透氧系数的测定>
按照与实施例2同样的方法测定透氧系数。结果示于表1。
<层压强度的测定>
在厚15μm的双轴拉伸尼龙薄膜(TOYOBO CO.,LTD制;N1102)上涂布聚氨酯系粘接剂,所述聚氨酯系粘结剂是含有50质量份聚醚成分(Toyo-Morton,Ltd制造;TM-319)、50质量份多异氰酸酯成分(Toyo-Morton,Ltd制造;CAT-19B)的乙酸乙酯溶液(固形分浓度;30质量%),85℃下干燥10秒后,通过用轧辊贴合厚12μm的拉伸酯薄膜(TOYOBO CO.,LTD制;E5200),从而得到作为基材的层压薄膜(X)。
作为基材使用上述层压薄膜(X)替代双轴拉伸聚丙烯薄膜(TOYOBO CO.,LTD制;P2161),除此之外,按照与实施例2同样的方法制作层压薄膜(L3),测定层压强度。结果示于表1。
实施例4
<透氧系数的测定>
除了使用粘接性涂料溶液C替代粘接性涂料溶液A以外,按照与实施例1同样的方法测定透氧系数。结果示于表1。
<层压强度的测定>
除了使用粘接性涂料溶液C替代粘接性涂料溶液B以外,按照与实施例3同样的方法制作层压薄膜(L4),测定透氧系数和层压强度。结果示于表1。
实施例5
<透氧系数的测定>
按照与实施例4同样的方法测定透氧系数。结果示于表1。
<层压强度的测定>
作为基材使用厚8μm的铝箔(Toyo Aluminium K.K.;铝箔1N30)替代层压薄膜(X),除此之外,按照与实施例4同样的方法制作层压薄膜(L5),测定层压强度。结果示于表1。
实施例6
<透氧系数的测定>
除了使用粘接性涂料溶液D替代粘接性涂料溶液A以外,按照与实施例1同样的方法测定透氧系数。结果示于表1。
<层压强度的测定>
除了使用粘接性涂料溶液D替代粘接性涂料溶液B以外,按照与实施例3同样的方法制作层压薄膜(L6),测定透氧系数和层压强度。结果示于表1。
实施例7
<透氧系数和层压强度的测定>
除了使用粘接性涂料溶液F替代粘接性涂料溶液A以外,按照与实施例1同样的方法制作层压薄膜(L9),测定透氧系数和层压强度。结果示于表1。
比较例1
<透氧系数和层压强度的测定>
除了使用粘接性涂料溶液E替代粘接性涂料溶液A以外,按照与实施例1同样的方法制作层压薄膜(L7),测定透氧系数和层压强度。结果示于表1。
比较例2
<透氧系数的测定>
按照与比较例1同样的方法测定透氧系数。结果示于表1。
<层压强度的测定>
作为基材使用层压薄膜(X)替代双轴拉伸聚丙烯薄膜(TOYOBO CO.,LTD制;P2161),除此之外,按照与比较例1同样的方法制作层压薄膜(L8),测定层压强度。结果示于表1。
[表1]
产业上的可利用性
由于本发明的层压薄膜所使用的粘接性涂料具有高的气体阻隔性和良好的粘接性、且是单剂型,所以适用期长且赋予良好的操作性。因此,使用该粘接性涂料将基材与密封薄膜贴合得到的本发明的层压薄膜的气体阻隔性和粘接性优异,可作为非卤系气体阻隔材料应用于各种用途,并且经济性优异、工业上有用。
Claims (8)
1.一种层压薄膜,其特征在于,其是至少基材、粘接性涂料层和密封层按照该顺序层压而成的层压薄膜,形成该粘接性涂料层的粘接性涂料是单剂型粘接性涂料且含有多胺树脂,该多胺树脂含有40质量%以上的下述式(1)所示的骨架结构,并且相对于该多胺树脂中所含的氮原子,该多胺树脂含有2.0~20mol%的金属原子,
2.根据权利要求1所述的层压薄膜,其中,所述金属原子选自由锌、铝、镁、钙、锡、铜、镍、钯、铁、铬、钼、钛、铷、铯、锶、钡、锆、铪和锰组成的组中的1种以上。
3.根据权利要求1所述的层压薄膜,其中,所述多胺树脂为下述(A)、(B)和(C)的反应产物,
(A)选自由具有芳香环的脂肪族胺、脂肪族胺、脂环式胺和芳香族胺组成的组中的1种以上的多胺;
(B)能够与多胺反应形成酰胺基部位、并且能够形成低聚物的、具有至少1个酰基的多官能化合物;
(C)(甲基)丙烯酸金属盐。
4.根据权利要求3所述的层压薄膜,其中,所述(A)为间苯二甲胺或对苯二甲胺。
5.根据权利要求3所述的层压薄膜,其中,所述(B)为丙烯酸、甲基丙烯酸或者它们的酯、酰胺、酸酐或酰氯。
6.根据权利要求3所述的层压薄膜,其中,所述(C)为丙烯酸锌、丙烯酸镁或丙烯酸钙。
7.根据权利要求3所述的层压薄膜,其中,所述(A)与所述(C)的反应摩尔比(C)/(A)为0.05~0.35。
8.根据权利要求1~7中任一项所述的层压薄膜,其中,在23℃、60%RH下,所述多胺树脂的透氧系数为2.0ml·mm/(m2·天·MPa)以下。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-176284 | 2010-08-05 | ||
JP2010176284 | 2010-08-05 | ||
PCT/JP2011/066995 WO2012017866A1 (ja) | 2010-08-05 | 2011-07-26 | ラミネートフィルム |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103052503A CN103052503A (zh) | 2013-04-17 |
CN103052503B true CN103052503B (zh) | 2014-12-17 |
Family
ID=45559368
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201180038268.9A Expired - Fee Related CN103052503B (zh) | 2010-08-05 | 2011-07-26 | 层压薄膜 |
Country Status (9)
Country | Link |
---|---|
US (1) | US9162431B2 (zh) |
EP (1) | EP2602107B1 (zh) |
JP (1) | JP5780241B2 (zh) |
KR (1) | KR20130085411A (zh) |
CN (1) | CN103052503B (zh) |
ES (1) | ES2538823T3 (zh) |
HK (1) | HK1183649A1 (zh) |
TW (1) | TWI551460B (zh) |
WO (1) | WO2012017866A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5641043B2 (ja) * | 2010-04-21 | 2014-12-17 | 三菱瓦斯化学株式会社 | エポキシ樹脂硬化剤、エポキシ樹脂組成物及びラミネート用接着剤 |
TW201400367A (zh) * | 2012-06-19 | 2014-01-01 | Taipei Pack Ind Corp | 食品包裝材(二) |
US20170183426A1 (en) * | 2014-07-11 | 2017-06-29 | Kuraray Co., Ltd. | Ethylene-vinyl alcohol copolymer and resin composition, and molded product obtained using the same |
JP6956563B2 (ja) * | 2017-08-14 | 2021-11-02 | 三井化学東セロ株式会社 | ガスバリア性積層体およびその製造方法ならびに包装体 |
WO2021132127A1 (ja) * | 2019-12-27 | 2021-07-01 | 三井化学東セロ株式会社 | ガスバリア用塗材、ガスバリア性フィルム、ガスバリア性積層体およびガスバリア性積層体の製造方法 |
JP7372147B2 (ja) * | 2019-12-27 | 2023-10-31 | 三井化学東セロ株式会社 | ガスバリア性フィルムおよびガスバリア性積層体 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102858838A (zh) * | 2010-04-21 | 2013-01-02 | 三菱瓦斯化学株式会社 | 环氧树脂固化剂、环氧树脂组合物和层压用粘接剂 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2848047B2 (ja) | 1991-08-23 | 1999-01-20 | 東洋インキ製造株式会社 | 接着剤組成物 |
US5536775A (en) * | 1994-02-28 | 1996-07-16 | Sandoz Ltd. | Amine curable compositions |
JPH09316422A (ja) | 1996-05-28 | 1997-12-09 | Nippon Polyurethane Ind Co Ltd | ラミネート用接着剤組成物、およびそれを用いたラミネートフィルムの製造方法 |
JPH1071664A (ja) | 1996-07-03 | 1998-03-17 | Toppan Printing Co Ltd | ラミネートフィルム及びその製造方法 |
US6495624B1 (en) * | 1997-02-03 | 2002-12-17 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
US7268179B2 (en) * | 1997-02-03 | 2007-09-11 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
US20020006484A1 (en) | 1998-05-20 | 2002-01-17 | Balasubramaniam Ramalingam | Adhesive and coating formulations for flexible packaging |
JP2000154365A (ja) | 1998-11-18 | 2000-06-06 | Takeda Chem Ind Ltd | ドライラミネート用接着剤 |
JP4763190B2 (ja) | 2000-12-26 | 2011-08-31 | 三菱瓦斯化学株式会社 | ガスバリア性塗料用組成物および塗料 |
JP4035693B2 (ja) * | 2001-10-25 | 2008-01-23 | 三菱瓦斯化学株式会社 | 物品の保存方法 |
JP2004323053A (ja) * | 2003-04-24 | 2004-11-18 | Mitsubishi Gas Chem Co Inc | 層間剥離の改良された多層容器 |
JP2006045528A (ja) * | 2004-07-02 | 2006-02-16 | Mitsubishi Gas Chem Co Inc | ポリアミド樹脂及び多層成形体 |
JP5515194B2 (ja) * | 2006-09-26 | 2014-06-11 | 大日本印刷株式会社 | バリア性共押出多層シーラントフィルムを用いた包装材料、包装袋および包装製品 |
JP2008188975A (ja) * | 2007-02-08 | 2008-08-21 | Mitsubishi Gas Chem Co Inc | 多層構造物 |
JP5170427B2 (ja) * | 2007-12-21 | 2013-03-27 | 三菱瓦斯化学株式会社 | 食品、薬品等の保存に適した袋状容器 |
-
2011
- 2011-07-26 EP EP11814494.8A patent/EP2602107B1/en not_active Not-in-force
- 2011-07-26 ES ES11814494.8T patent/ES2538823T3/es active Active
- 2011-07-26 JP JP2012527673A patent/JP5780241B2/ja active Active
- 2011-07-26 US US13/813,012 patent/US9162431B2/en not_active Expired - Fee Related
- 2011-07-26 KR KR1020137001930A patent/KR20130085411A/ko not_active Application Discontinuation
- 2011-07-26 CN CN201180038268.9A patent/CN103052503B/zh not_active Expired - Fee Related
- 2011-07-26 WO PCT/JP2011/066995 patent/WO2012017866A1/ja active Application Filing
- 2011-08-02 TW TW100127436A patent/TWI551460B/zh not_active IP Right Cessation
-
2013
- 2013-09-27 HK HK13111089.4A patent/HK1183649A1/zh not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102858838A (zh) * | 2010-04-21 | 2013-01-02 | 三菱瓦斯化学株式会社 | 环氧树脂固化剂、环氧树脂组合物和层压用粘接剂 |
Also Published As
Publication number | Publication date |
---|---|
TWI551460B (zh) | 2016-10-01 |
HK1183649A1 (zh) | 2014-01-03 |
CN103052503A (zh) | 2013-04-17 |
US20130130062A1 (en) | 2013-05-23 |
JP5780241B2 (ja) | 2015-09-16 |
KR20130085411A (ko) | 2013-07-29 |
TW201208884A (en) | 2012-03-01 |
EP2602107A4 (en) | 2014-01-08 |
JPWO2012017866A1 (ja) | 2013-10-03 |
WO2012017866A1 (ja) | 2012-02-09 |
EP2602107B1 (en) | 2015-03-18 |
US9162431B2 (en) | 2015-10-20 |
ES2538823T3 (es) | 2015-06-24 |
EP2602107A1 (en) | 2013-06-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI425022B (zh) | 胺系環氧樹脂硬化劑、含有它之氣體障壁性環氧樹脂組成物、塗料及積層用黏著劑 | |
CN102858838B (zh) | 环氧树脂固化剂、环氧树脂组合物和层压用粘接剂 | |
EP2842982B1 (en) | Epoxy resin curing agent, epoxy resin composition, gas barrier adhesive agent, and gas barrier laminate body | |
JP5776685B2 (ja) | エポキシ樹脂硬化剤、エポキシ樹脂組成物及びラミネート用接着剤 | |
JP6241674B2 (ja) | エポキシ樹脂硬化剤、エポキシ樹脂組成物、及びガスバリア性接着剤、並びにガスバリア性積層体 | |
AU2002328410B2 (en) | Adhesive for gas barrier laminates and laminated films | |
CN103052503B (zh) | 层压薄膜 | |
JP5966511B2 (ja) | ラミネートフィルム | |
JP4876399B2 (ja) | ラミネートフィルム | |
JP4857721B2 (ja) | ラミネートフィルム | |
JP2007050686A (ja) | ラミネートフィルム | |
JP4433153B2 (ja) | ラミネートフィルムの製造方法 | |
JP5640770B2 (ja) | エポキシ樹脂硬化剤の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1183649 Country of ref document: HK |
|
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1183649 Country of ref document: HK |
|
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141217 Termination date: 20180726 |