HRP930107A2 - Laminated metal sheets - Google Patents
Laminated metal sheets Download PDFInfo
- Publication number
- HRP930107A2 HRP930107A2 HR930107A HRP930107A HRP930107A2 HR P930107 A2 HRP930107 A2 HR P930107A2 HR 930107 A HR930107 A HR 930107A HR P930107 A HRP930107 A HR P930107A HR P930107 A2 HRP930107 A2 HR P930107A2
- Authority
- HR
- Croatia
- Prior art keywords
- film
- polyolefin
- temperature
- layer
- polyester
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 50
- 239000002184 metal Substances 0.000 title claims description 50
- 239000010410 layer Substances 0.000 claims description 81
- 229920000642 polymer Polymers 0.000 claims description 44
- 229920000728 polyester Polymers 0.000 claims description 43
- 229920000098 polyolefin Polymers 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- -1 trichlorohexane-dimethanol Chemical compound 0.000 claims description 28
- 229920006254 polymer film Polymers 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 229920002647 polyamide Polymers 0.000 claims description 17
- 239000004952 Polyamide Substances 0.000 claims description 16
- 229920006267 polyester film Polymers 0.000 claims description 15
- 238000003475 lamination Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229920002799 BoPET Polymers 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Chemical class 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Chemical class 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 150000008064 anhydrides Chemical group 0.000 description 6
- 238000002207 thermal evaporation Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000003776 cleavage reaction Methods 0.000 description 5
- 230000007017 scission Effects 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000005025 cast polypropylene Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 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 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical class C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000009957 hemming Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002897 polymer film coating Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
Područje tehnike The field of technology
Ovaj izum odnosi se na postupak proizvodnje laminiranih limova. This invention relates to the production process of laminated sheets.
Tehnički problem Technical problem
Nanošenje polimernih materijala na limove, kao što su metalne trake, predstavlja dobro poznatu i dobro dokumentiranu tehniku. Proizvedeni laminati imaju mnogo primjene kao što je npr. upotreba za izradu bačava i posuda za spremanje prehrambenih proizvoda i napitaka, te za rubne dijelove poklopaca s ventilima za posude s aerosolima. The application of polymeric materials to sheets, such as metal strips, is a well-known and well-documented technique. The laminates produced have many applications such as use for making barrels and containers for storing food products and beverages, and for the edge parts of lids with valves for aerosol cans.
U mnogim primjenama sloj polimera nanosi se na obje glavne površine lima. Općenito, većina poznati polimernih filmova istog ili sličnog sastava na suprotnu površinu lima ili na opis nanošenja polimernih filmova čiji su sastavi drugačiji od sastava suprotnog lima, pri čemu se svaki od dva razičita polimera nanose na lim u odvojenim stupnjevima, češće nego istovremeno. In many applications, a layer of polymer is applied to both major surfaces of the sheet. In general, most known polymer films of the same or similar composition to the opposite surface of the sheet or to the description of the application of polymer films whose compositions are different from the composition of the opposite sheet, where each of the two different polymers is applied to the sheet in separate stages, more often than simultaneously.
Iako metalni laminati, koji imaju slične prevlake na obje strane lima ili trake, imaju neke prednosti, ipak se oni mogu koristiti za sve namjene. Tako npr. dok poliesterske prevlake, koje su opisane u GB 2125746, imaju izuzetnu sposobnost oblikovanja, nisu potpuno primjenljive za završetke koji se zatvaraju toplinom, one se teško pigmentiraju na prihvatljivu razinu neprozirnosti uz dostupnu cijenu koštanja i s vremenom mijenjaju vanjski izgled. Although metal laminates, which have similar coatings on both sides of the sheet or strip, have some advantages, they can be used for all purposes. Thus, for example, while polyester coatings, which are described in GB 2125746, have an exceptional formability, they are not fully applicable for heat-sealed finishes, they are difficult to pigment to an acceptable level of opacity at an affordable cost and change the external appearance over time.
Stanje tehnike State of the art
Polipropilenske ili polietilenske prevlake, kao što su one opisane npr. GB 1324952 i EP 0062385, pokazuju prihvatljivu otpornost prema koroziji kad su u pitanju limovi, ali su relativno meke, lako se oštećuju, imaju nisko talište i relativno nizak sjaj površine. Polypropylene or polyethylene coatings, such as those described in e.g. GB 1324952 and EP 0062385, show acceptable corrosion resistance when it comes to sheets, but are relatively soft, easily damaged, have a low melting point and a relatively low surface gloss.
Ni jedan polimer sam ne može zadovoljiti sve različite fizičke osobine koji su namijenjeni upotrebi za metal/polimerne laminate koji su namijenjeni upotrebi za bačve za skladištenje. Zbog toga, pronađeno je, da je mnogo pogodnije primijeniti kombinaciju različitih polimera u jednostavnom laminatu polimer/metal/polimer i da se na odgovarajući način koriste osobine svakog polimera. No single polymer can satisfy all the different physical properties intended for use in metal/polymer laminates intended for use in storage drums. Therefore, it has been found that it is much more convenient to use a combination of different polymers in a simple polymer/metal/polymer laminate and to use the properties of each polymer appropriately.
U mnogim slučajevima poželjno je koristiti različite polimere nanesene na dvije površine lima i na taj način omogućiti primjenu različitih svojstava različitih polimera. In many cases, it is desirable to use different polymers applied to the two surfaces of the sheet and thus enable the application of different properties of different polymers.
Sa stajališta ekonomičnosti bolje je primijeniti prevlake različitih polimera na limove istovremenim postupkom, pri čemu se smanjuju radni troškovi. Istovremeno nanošenje dvaju različitih polimera može se postići primjenom ljepila koje se nanosi u dva različita polimerna filma, a zatim istovremenim nanošenjem ovih filmova na lim. Na drugi način, željeni polimerni filmovi mogu se istovremeno prevući jednim postupkom na dvije površine metalne trake. From the point of view of economy, it is better to apply coatings of different polymers to sheets in a simultaneous process, thereby reducing labor costs. The simultaneous application of two different polymers can be achieved by applying an adhesive that is applied in two different polymer films, and then by simultaneously applying these films to the sheet. Alternatively, the desired polymer films can be simultaneously coated in one process on two surfaces of the metal strip.
Međutim, prva metoda nepoželjna je zbog zahtjeva upotrebe materijala na osnovi otapala koja mogu sadržavati biološki opisane kemikalije, kao što su izocijanati, a također povlači sa sobom i dugi popis lijekova. Druga metoda, koja zahtjeva koekstrudiranje polimernih talina, može narušiti izuzetna svojstva biaksijalno orijentiranih poliesterskih materijala, kao što je polietilenteraftalat (PET), s obzirom da se takovi biaksijalno orijentirani materijali ne mogu prevući estrudiranjem i zadržati svoja izvanredna svojstva. However, the first method is undesirable due to the requirement to use solvent-based materials that may contain biologically described chemicals, such as isocyanates, and also entails a long list of drugs. The second method, which requires coextrusion of polymer melts, can impair the exceptional properties of biaxially oriented polyester materials, such as polyethylene terephthalate (PET), since such biaxially oriented materials cannot be extruded and retain their outstanding properties.
Toplinsko nanošenje biaksijalno orijentiranih PET-a na metalnu traku poznato je, npr. iz GB 2123746. Slično tome, toplinsko nanošenje polipropilenskih filmova na metalnu traku opisano je npr. u GB 1324952 i US 3679513, dok je toplinsko nanošenje polietilenskih filmova na metalnu traku opisano npr. u EP 0062385 i US 4452375. Međutim, uvjeti opisani u ovim dokumentima za toplinsko nanošenje polimernih filmova s tako različitim svojstvima nisu pogodni za istovremeno toplinsko nanošenje poliesterskog filma, posebno biaksijalno orijentiranog polietilen tereftalatnog filma, na jednu stranu metalne trake, dok se istovremeno na drugu stranu metalne trake toplinski nanosi film koji sadrži poliolefin ili poliamid debljine gospodarski i tehnički pogodne za izradu bačava za skladištenje. Thermal deposition of biaxially oriented PET on metal tape is known, e.g., from GB 2123746. Similarly, thermal deposition of polypropylene films on metal tape is described, e.g., in GB 1324952 and US 3679513, while thermal deposition of polyethylene films on metal tape is described eg in EP 0062385 and US 4452375. However, the conditions described in these documents for the thermal deposition of polymer films with such different properties are not suitable for the simultaneous thermal deposition of a polyester film, especially a biaxially oriented polyethylene terephthalate film, on one side of a metal strip, while simultaneously on the other side of the metal strip, he thermally applies a film containing polyolefin or polyamide with a thickness economically and technically suitable for making storage barrels.
Opis rješenja tehničkog problema s izvedbenim primjerima Description of the solution to the technical problem with practical examples
Otkrili smo da se istovremeno toplinsko nanošenje poliesterskog filma na jednu stranu lima i filma koji sadrži poliolefin ili poliamid na drugu stranu lima može lako postići mjerenjem značajki mekoće različitih polimera na svakoj strani lima, osiguravaju intermedijarni sloj nekristaliničnog poliestera koji ima određene specifične fizičke značajke između lima i poliesterskog sloja, a za kojeg se želi da se prilijepi za lim, i nanošenjem polimernih filmova na lim postupkom toplinskih nanošenja, pri čemu se u prvom stupnju polimerni filmovi nanose na lim pri prvobitnoj temperaturi koja ne oštećuje vanjsku površinu filmova pri prolazu kroz kadu za nanošenje, i u slijedećem stupnju dobiveni laminat se ponovno posredno zagrijava do druge više temperature, što uvjetuje da polimerni filmovi reagiraju s limom uz čvrsto sjedinjavanje. We found that simultaneous thermal deposition of a polyester film on one side of the sheet and a film containing polyolefin or polyamide on the other side of the sheet can be easily achieved by measuring the softness characteristics of the different polymers on each side of the sheet, providing an intermediate layer of non-crystalline polyester having certain specific physical properties between the sheets and polyester layer, which is desired to adhere to the sheet, and by applying polymer films to the sheet by the process of thermal applications, whereby in the first stage, the polymer films are applied to the sheet at the original temperature that does not damage the outer surface of the films when passing through the bath for application, and in the next step the resulting laminate is indirectly heated again to a second higher temperature, which conditions the polymer films to react with the sheet with a solid union.
Prema prvom aspektu ovog izuma predviđen je proizvodni proces za laminate polimer/metal/polimer s istovremenim nanošenjem pri čemu ovaj postupak obuhvaća nanošenje poliesterskog filma (A) koji sadrži unutrašnji sloj A1) uglavnom nekristaličnog poleistera, čija je temperatura mekšanja ispod 150ºC, a talište iznad 150ºC ali ispod 240ºC, na jednu od glavnih površina lima, i unutrašnji sloj (A2) linearnog poliestera, čije je talište iznad 220ºC, i istovremeno nanošenje filma (B) koji sadrže poliolefin, a što podrazumijeva vezanje kiselinski modificirane poliolefinske smole koje sadrže karboksilne ili anhidridne skupine, na drugu glavnu površinu lima, pri čemu se lim zagrijava do temperature T1 pri kojoj film polimera omekšava i dolazi u posredan dodir s limom, s tim da je temperatura T1 niža od temperature pri kojoj se vanjska površina filma koja sadrži poliolefin oštećenja tijekom nanošenja i dobiveni laminat se ponovno zagrijava do temperature T2, koja omogućuje da oba polimerna filma (A) i (B) međusobno reagiraju s odgovarajućim vezivom i površinom lima. According to the first aspect of this invention, a production process for polymer/metal/polymer laminates with simultaneous application is provided, wherein this process includes the application of a polyester film (A) containing an inner layer A1) of mainly non-crystalline polyester, the softening temperature of which is below 150ºC, and the melting point above 150ºC but below 240ºC, on one of the main surfaces of the sheet, and the inner layer (A2) of linear polyester, whose melting point is above 220ºC, and the simultaneous application of film (B) containing polyolefin, which implies the bonding of acid-modified polyolefin resin containing carboxylic or anhydride groups, to the second main surface of the sheet, whereby the sheet is heated to a temperature T1 at which the polymer film softens and comes into indirect contact with the sheet, with the temperature T1 being lower than the temperature at which the outer surface of the film containing the polyolefin is damaged during application and the resulting laminate is heated again to temperature T2, which allows both polymer films (A ) and (B) react with each other with the appropriate binder and sheet surface.
Prema drugom aspektu ovog izuma predviđen je laminat polimer/metal/polimer koji se sastoji od lima na čijoj se svakoj velikoj površini nalazi polimerni film koji je istovremeno toplinski nanešen na lim, pri čemu jedan od filmova, nanešen na jednu veliku površinu lima, predstavlja poliesterski film (A) koji sadrži unutrašnji sloj (A1), obično nekristaličnog linearnog poliestera, s temperaturom mekšanja iznad 150ºC ali ispod 240ºC, i vanjski sloj (A2) linearnog poliestera čije je talište iznad 220ºC, i polimerni film (B), nanesen na drugu veliku površinu lima koji sadrži poliolefin s vezivnim kiselinski modificiranom poliolefinskom smolom s karbokislnim ili anhidridnim skupinama. According to another aspect of this invention, a polymer/metal/polymer laminate is provided, which consists of a sheet, on each large surface of which there is a polymer film that is simultaneously thermally applied to the sheet, whereby one of the films, applied to one large surface of the sheet, represents a polyester film (A) containing an inner layer (A1), usually of non-crystalline linear polyester, with a softening temperature above 150ºC but below 240ºC, and an outer layer (A2) of linear polyester whose melting point is above 220ºC, and a polymer film (B), applied to the other a large surface area of sheet containing polyolefin with a binder acid-modified polyolefin resin with carboxylic acid or anhydride groups.
Film (B) koji sadrži poliolefin može biti jednoslojni film vezivne smole koja je kiselinski modificirana i sadrži karbokislne ili anhidridne skupine, ili može biti višeslojni film ili anhidridne skupine, ili može biti višeslojni film koji sadrži vanjski sloj (B2) poliolefina ili poliamida pričvršćen za unutrašnji (ili vezivni) sloj (B1) vezivne smole, kako što je eć definirano. The polyolefin-containing film (B) may be a single-layer film of a binder resin which is acid-modified and contains carboxylic acid or anhydride groups, or it may be a multilayer film or anhydride groups, or it may be a multilayer film containing an outer layer (B2) of polyolefin or polyamide attached to inner (or binding) layer (B1) of binding resin, as already defined.
U daljnjem rješenju ovog izuma složeni film (B) može sadržavati i polietilneski ili poliamidni sloj (B4) priljubljen za spomenuti vanjski sloj (B2) posredstvom međusloja (B3) vezivne smole koja je definirana kod sloja (B1). In a further solution of this invention, the composite film (B) may also contain a polyethylene or polyamide layer (B4) attached to the mentioned outer layer (B2) by means of an intermediate layer (B3) of the binding resin defined by the layer (B1).
Pogodnije složeni filmovi (A) i (B) predstavljaju filmove koji su pripremljeni koekstrudiranjem. More conveniently, composite films (A) and (B) represent films prepared by coextrusion.
Koristeći proces ovog izuma laminat metal/polimer može se dobiti nanošenjem biaksijalno orijentiranih poliesterskih materijala, kao što je polietilen tereftalat na jednu stranu lima i prevlaku s poliolefinom ili poliamidom na drugu stranu lima. Primjenom ovog postupka obje polimerne prevlake mogu se nanijeti istovremeno bez otapala koje sadrži ljepila nepoželjna za okolinu. Using the process of this invention, a metal/polymer laminate can be obtained by applying biaxially oriented polyester materials, such as polyethylene terephthalate to one side of the sheet and a polyolefin or polyamide coating to the other side of the sheet. Using this procedure, both polymer coatings can be applied simultaneously without solvents containing adhesives that are undesirable for the environment.
Proces ovog izuma odvija se u više stupnjeva. U prvom stupnju, metal se prethodno zagrijava do temperature T1 opsega 120 do 240ºC, a najmanje između 140 i 220ºC, tako da vanjska površina filma (B) ne dosegne temperaturu svoj tališta u kadi za prevlačenje, a poželjno je da ne dosegne niti svoju temperaturu mekšanja. The process of this invention takes place in several stages. In the first stage, the metal is preheated to a temperature T1 of 120 to 240ºC, and at least between 140 and 220ºC, so that the outer surface of the film (B) does not reach the temperature of its melting point in the coating bath, and preferably does not even reach its temperature softening.
U drugom stupnju, filmovi i metal zajedno se dovode u kadu za prevlačenje kako bi se upostavio blizak i ujednačen dodir bez nabiranja. U ovom stupnju dodirni slojevi su unutrašnji sloj (A) amorfnog poliestera i metala, a na suprotnoj stani metala i unutrašnje površine filma poliolefina ili poliamida (B). In the second stage, the films and metal are brought together in a coating bath to establish a close and uniform contact without wrinkling. In this stage, the contact layers are the inner layer (A) of amorphous polyester and metal, and on the opposite side of the metal and the inner surface of the polyolefin or polyamide film (B).
U trećem stupnju, dobiveni laminat ponovno se zagrijava, najbolje indukcijskim zagrijavanjem metalne jezgre do temperature T2 koja je viša od 250ºC, ali je ispod temperature toplinske ili oksidacijske razgradnje vanjske površine filma (B) koji sadrži poliolefin ili poliamid, ili temperature pri kojoj se vanjski sloj fizički razgrađuje kad se naglo prelila vodom. Po želji može se primijeniti i grijanje infracrvenim zračenjem. In the third stage, the resulting laminate is heated again, preferably by induction heating of the metal core to a temperature T2 that is higher than 250ºC, but below the thermal or oxidative decomposition temperature of the outer surface of the film (B) containing polyolefin or polyamide, or the temperature at which the outer the layer physically decomposes when it is suddenly filled with water. If desired, heating with infrared radiation can also be applied.
U uvjetima kad se vanjska površina poliesterskog filma (A) održava ispod njenog tališta, ali s jezgrom metala iznad tališta poliestera, dolazi do brze interakcije između metala, unutrašnjeg sloja poliestera (A1) i poliolefinskog sloja (B). Da bi se dostigla ova intakcija, laminat se drži iznad 200ºC tijekom 1 do 30 sekundi, a najbolje pri pribl. 250ºC tijekom 2 sekunde, a zatim se laminat brzo i ravnomjerno ispere vodom do temperature ispod točke mekšanja smole koja ima najnižu temperaturu omekšavanja. In conditions where the outer surface of the polyester film (A) is kept below its melting point, but with the metal core above the melting point of the polyester, a rapid interaction occurs between the metal, the inner polyester layer (A1) and the polyolefin layer (B). To achieve this effect, the laminate is kept above 200ºC for 1 to 30 seconds, and best at approx. 250ºC for 2 seconds and then the laminate is quickly and evenly rinsed with water to a temperature below the softening point of the resin which has the lowest softening temperature.
Mi smo otkrili da, uz osiguranje da vanjska površina filma (A) biaksijalno orijentiranog poliestera ostane ispod svog tališta, mogu postići odlična svojstva biaksijalno orijentiranog poliestera, tj. polietilen teraftalata. Temperatura u zoni iza nanošenja može se mijenjati kako bi se kontrolira svojstva, posebno sposobnost oblikovanja, što se naročito traži kod poliesterskih prevlaka. ovo kontroliranje može se obaviti posebno dobro ako se primjeni indukcijsko zagrijavanje za ponovno zagrijavanje laminata nakon kade na nanošenje. Radi mejrenja temperature poliestera najbolje je koristiti odgovarajući pirometar. Ista tako, mogu se koristiti i uređaji za otkrivanje promjena iz biaksijalno orijentiranog do kristaličnog neorijentiranog ili amorfnog poleistera, kako bi se definiralo kritično stanje poliesterskog filma (npr. difraktometar pomoću X-zraka). We have found that by ensuring that the outer surface of the biaxially oriented polyester film (A) remains below its melting point, we can achieve the excellent properties of the biaxially oriented polyester, ie polyethylene terephthalate. The temperature in the post-coating zone can be varied in order to control the properties, especially the formability, which is particularly required for polyester coatings. this control can be done particularly well if induction heating is used to reheat the laminate after the application bath. In order to measure the temperature of polyester, it is best to use a suitable pyrometer. Likewise, devices for detecting changes from biaxially oriented to crystalline non-oriented or amorphous polyester can be used to define the critical state of the polyester film (eg X-ray diffractometer).
Točna temperatura T1 do koje se lim mora zgrijati prije nanošenja ovisi o debljini filmova koji se nanose, kao i o kemijskoj prirodi spomenutih filmova. Na taj način temperature od pribl. 120º i više obično 140ºC, pogodne su za lijevani polipropilenski film od 20 mikrona, a do 230ºC za debljine polipropilenskog filma od 200 mikrona. The exact temperature T1 to which the sheet must be heated before application depends on the thickness of the films that are applied, as well as on the chemical nature of said films. In this way, temperatures of approx. 120º and above, usually 140ºC, are suitable for cast polypropylene film of 20 microns, and up to 230ºC for polypropylene film thicknesses of 200 microns.
Temperature od 140 do 270ºC pogodne su za koekstrudirani biaksijalno orijentirani polietilem teraftalat. Temperatures from 140 to 270ºC are suitable for coextruded biaxially oriented polyethylene terephthalate.
Filmovi koji sadrže poliamid mogu podnijeti nešto više temperature metala nego lijevani polipropilen, a orijentirani polipropilen zahtjeva više temperature nego lijevani polipropilen, obično 200ºC za ml od 20 mikrona. Films containing polyamide can withstand slightly higher metal temperatures than cast polypropylene, and oriented polypropylene requires higher temperatures than cast polypropylene, typically 200ºC for a 20 micron ml.
Temperatura T2 koja se primjenjuje za ponovno zagrijavanje laminata iznad kade za prevlačenje obično se nalazi u području od 230 do 270ºC. Stvarna temperatura koja se mora primijeniti ovisi o vremenu zastoja do potapanja u vodu temperature iznad 270ºC dovode do fizičkog oštećenja poliolefinskog filma kad on dođe u dodir s vodom za hlađenje i dovodi do taljenja polietilen teraftalatnih filmova. Temperatura pri donjoj granici spomenutog područja kontrolira se zbog postizanja zadovoljavajuće čvrstoće veze između lima i polimernih filmova koji su priljubljeni uz lim vrlo kratko vrijeme tijekom kojeg se laminat zagrijava do željene temperature. Ekonomični postupci obično zahtijevaju vrijeme zastoja od pribl. samo 3 sekunde. The temperature T2 applied to reheat the laminate above the coating bath is usually in the range of 230 to 270ºC. The actual temperature that must be applied depends on the dwell time until immersion in water temperatures above 270ºC lead to physical damage to the polyolefin film when it comes into contact with the cooling water and lead to melting of the polyethylene terephthalate films. The temperature at the lower limit of the mentioned area is controlled in order to achieve a satisfactory strength of the connection between the sheet and the polymer films that are stuck to the sheet for a very short time during which the laminate is heated to the desired temperature. Economic procedures usually require a downtime of approx. just 3 seconds.
Metalna podloga na koju se nanose polimerni filmovi obično je u obliku metalne trake i to od čelika ili aluminija ili njihovih legura koje se dalje upotrebljavaju u industriji pakiranja. The metal substrate on which polymer films are applied is usually in the form of a metal strip made of steel or aluminum or their alloys, which are further used in the packaging industry.
Područje izmjera obično je 0,05 mm do 0,4 mm za čelik i 0,02 do 0,4 mm za aluminij. The measurement range is usually 0.05 mm to 0.4 mm for steel and 0.02 to 0.4 mm for aluminum.
Čelik može biti prevučen kositrom, najbolje pasivnim uobičajenom kromnom obradom, ili galvaniziran s niklom ili cinkom, crni željezni lim ili fosfatiran crni željezni lim koji se obično ispere kromatima nakon fosfatiranja. The steel may be tin-plated, preferably by a passive common chromium treatment, or electroplated with nickel or zinc, black iron sheet, or phosphated black iron sheet, which is usually chromate-washed after phosphating.
Najbolja obrada čelika je elekotrolitičko kromno prevlačenje čelika (ECCS) s dvostrukim slojem metalnog kroma i okisda kroma. Kod takovih čelika količine metalnog kroma i okisda mogu mnogo varirati. Obično sadržaj metalnog kroma je u području od 0,10 do 0,20 gm/m2, a sadržaj okisda kroma od 0,005 do 0,05 gm/m2. ECCS proveden je taložnih sistema koji sadrže katalizatore na osnovi sumpora ili fluora. The best steel treatment is electrolytic chromium plating of steel (ECCS) with a double layer of metallic chromium and chromium oxide. With such steels, the amounts of metallic chromium and oxides can vary greatly. Usually, the content of metallic chromium is in the range of 0.10 to 0.20 gm/m2, and the content of chromium oxide is from 0.005 to 0.05 gm/m2. ECCS was carried out on precipitation systems containing catalysts based on sulfur or fluorine.
Složeni poliesterski film (A) najpogodnije se može dobiti koekstrudiranjem prije nanošenja na metalnu traku. Složeni poliesterski film (A) sadrži tanji unutrašnji sloj (A) uglavnom nekristaliničnog (tj. amorfnog) linearnog poliestera čija je temperatura mekšanja ispod 150ºC, a talište oko 150ºC, ali ispod 240ºC, i deblji vanjski sloj (A2) čije je talište 220ºC i najbolje je da ima unutrašnju viskoznost od 0,5 do 1,1, najbolje od 0,6 do 0,8. The composite polyester film (A) can most conveniently be obtained by coextrusion before application to the metal strip. Composite polyester film (A) contains a thinner inner layer (A) of mostly non-crystalline (i.e. amorphous) linear polyester with a softening temperature below 150ºC and a melting point around 150ºC but below 240ºC, and a thicker outer layer (A2) with a melting point of 220ºC and preferably it has an intrinsic viscosity of 0.5 to 1.1, most preferably 0.6 to 0.8.
Najpovoljnije je da je vanjski sloj (A2) biaksijalno orijentirani polester, kao što je polietilen tereftalat. Najpovoljnije je da unutrašnji sloj (A1) bude linearni kopoliester, npr. neki amorfni kopolimer od približno 80% molnih % etilen tereftalata i 20 molnih % etilenizoftalata. Za unutrašnji sloj (A1) također su pogodni kopoliesteri tereftalne kiseline i dva alkohola, npr. etilen glikol i cikloheksan-dimetanol. It is most advantageous that the outer layer (A2) is a biaxially oriented polyester, such as polyethylene terephthalate. It is most favorable for the inner layer (A1) to be a linear copolyester, for example an amorphous copolymer of approximately 80% mol% ethylene terephthalate and 20 mol% ethylene isophthalate. Copolyesters of terephthalic acid and two alcohols, eg ethylene glycol and cyclohexane-dimethanol, are also suitable for the inner layer (A1).
Obično, biaksijalno orijentirani poliester u vanjskom sloju (A2) ima kristaliničnost veću od 30%, a najbolje od 40 do 50%. Typically, the biaxially oriented polyester in the outer layer (A2) has a crystallinity greater than 30%, preferably 40 to 50%.
Kristaliničnost poliesterskog materijala može se odrediti postupcima difrakcije pomoću X-zraka, kao što je opisano u GB 1566422, ili mjerenjem gustoće i formulom The crystallinity of the polyester material can be determined by X-ray diffraction methods, as described in GB 1566422, or by density measurement and the formula
Vc = (P - Pa) · (Pc - Pa)-1 Vc = (P - Pa) · (Pc - Pa)-1
Vc je volumna frakcija kristaliničnosti, Vc is the volume fraction of crystallinity,
P je gustoća uzorka, P is the density of the sample,
Pa je gustoća amorfnog materijala, So the density of the amorphous material is,
Pc je gustoća kristaliničnog materijala Pc is the density of the crystalline material
P se može izmjeriti u koloni za mjerenje gustoće pomoću mješavine cink klorida/voda ili n-heptana/ugljik tetraklorida. P can be measured in a density column using a mixture of zinc chloride/water or n-heptane/carbon tetrachloride.
Biaksijalno orijentirani film koji se može koristi kao vanjski sloj može se oblikovati izvlačenjem amorfnog ekstrudiranog polimera u uzdužnom smjeru pri temperaturama iznad temperature staklastog prijelaza tog polimera za faktor 2,2 do 3,8 i slično u poprečnom smjeru za faktor 2,2 do 4,2. Kad se nanesene prevlake žele koristiti za duboko izvlačene metalne posude, orijentacija je uglavnom svedena na izvlačenje s faktorom oko 2,5 i u uzdužnom i u poprečnom smjeru. A biaxially oriented film which can be used as an outer layer can be formed by drawing an amorphous extruded polymer in the longitudinal direction at temperatures above the glass transition temperature of that polymer by a factor of 2.2 to 3.8 and similarly in the transverse direction by a factor of 2.2 to 4, 2. When the applied coatings are to be used for deep-drawn metal vessels, the orientation is generally reduced to drawing by a factor of about 2.5 in both longitudinal and transverse directions.
Najbolja namještena temperatura biaksijalnog PET filma je u području od 215 do 220ºC. Može se primijeniti i niža temperatura zagrijavanja, ali to je obično praćeno povećanom sklonošću skupljanja tijekom nanošenja. The best set temperature of biaxial PET film is in the range of 215 to 220ºC. A lower heating temperature can also be used, but this is usually accompanied by an increased tendency to shrink during application.
Obično unutrašnji sloj (A1) treba biti kontinuiran i to debljine od 2 do 4 mikrona. Odnos debljine vanjskog poliesterskog sloja (A2) prema unutrašnjem poliesterskom sloju (A1) iznosi između 12 i 4, pri čemu je ukupna debljina kombiniranih slojeva od 12 do 25 mikrona. Usually, the inner layer (A1) should be continuous with a thickness of 2 to 4 microns. The ratio of the thickness of the outer polyester layer (A2) to the inner polyester layer (A1) is between 12 and 4, whereby the total thickness of the combined layers is from 12 to 25 microns.
Ako je potrebno poliesterski slojevi mogu sadržavati anti-blok sredstva, kao što je sintetilčki silicij diokisd čija prosječna veličina čestica je 0,5 do 5 mikrona. If necessary, the polyester layers can contain anti-blocking agents, such as synthetic silicon dioxide, the average particle size of which is 0.5 to 5 microns.
Također, ako je potrebno, vanjski poliesterski sloj (A2) može biti obojen uobičajenim pigmentima kao što je titan dioksid. Also, if necessary, the outer polyester layer (A2) can be colored with common pigments such as titanium dioxide.
Osnovna funkcija unutrašnjeg poliesterskog sloja (A1) je da se djelovanjem topline prilijepi za metalnu površinu pri temperaturama ispod tališta tako da unutrašnji sloj može zadržati svoju amorfnu strukturu nakon orijentacije i toplog prevlačenja filmom. Osim toga, unutrašnji poliesterski sloj (A1) mora se vezati za metal pri temperaturama koje su u skladu s istovremenim laminiranjem suprotne strane trake s prevlakom koja sadrži poliamid ili poliolefin. Ovi zahtjevi su postavljeni uz uvjet da uunutrašnji sloj poliestera (A1) ima točku mekšanja u skladu s temperaturama koje su potrebne za laminiranje širokog opsega prevlake na osnovi poliolefina ili poliamida. Stoga temperatura mekšanja mora biti niža od 150ºC, a posebno ne veća od 130ºC. The basic function of the inner polyester layer (A1) is to adhere to the metal surface by the action of heat at temperatures below the melting point, so that the inner layer can retain its amorphous structure after orientation and hot film coating. In addition, the inner polyester layer (A1) must be bonded to the metal at temperatures consistent with the simultaneous lamination of the opposite side of the tape with a coating containing polyamide or polyolefin. These requirements are set with the condition that the inner layer of polyester (A1) has a softening point in accordance with the temperatures required for laminating a wide range of polyolefin or polyamide based coatings. Therefore, the softening temperature must be lower than 150ºC, and especially not higher than 130ºC.
Film koji sadrži poliolefin (B) ii sloj vezivne smole (B1) u složenom filmu (B) je kiselinski modificirana poliolefinska smola koja sadrži karbokislne ili anhidridne skupine. Tipične kiseline za pripremanje ovakovih kiselinski modoficiranih polimera su etilenski nezasičene karbokislne kiseline, kao što je akrilna kiselina, metakrilna kiselina, maleinska kiselina, fumarna kiselina, metakrilna kiselina, maleinska kiselina, fumarna kiselina, krotonska kiselina i itakonska kiselina. Tipični anhidridi koji se koriste u iste svrhe jesu etilenski nezasićeni karbokislni anhidridi, kao što je maleinski. The film containing the polyolefin (B) and the binder resin layer (B1) in the composite film (B) is an acid-modified polyolefin resin containing carboxylic acid or anhydride groups. Typical acids for preparing such acid-modified polymers are ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid. Typical anhydrides used for the same purpose are ethylenically unsaturated carboxylic anhydrides, such as maleic.
Kiselinske skupine mogu biti prisutne kao etilenski polimeri, npr. etilen/akrilna kiselina (EAA) ii etilne/metakrilna kiselina (EMMA). Koncentracija kiseline je obično 5 do 15%. The acid groups may be present as ethylene polymers, eg ethylene/acrylic acid (EAA) and ethyl/methacrylic acid (EMMA). The acid concentration is usually 5 to 15%.
Kiselinska modifikacija kiselinom modificiranih polimera može se dobiti npr. cijepanjem maleinskog anhidrida do poliolefina, kao što je polipropilen, polietilne etilen-propilen ili etilen-vinilacetat kopolimer. Cijepanje se može postići postupkom kao što je reakcija maleinskog anhidrida s poliolefinom u otopini u organskom otapalu uz slobodno radikalski katalizator, kao što je dibenziil perokisd. Alternativno, može se uvesti neki aktivni centar u polimer primjernom zračenja visoke energije, kao što je gama zračenje, a zatim reakcijom dobivene tvari s anhidridom. Acid modification of acid-modified polymers can be obtained, for example, by cleavage of maleic anhydride to polyolefins, such as polypropylene, polyethylene ethylene-propylene or ethylene-vinyl acetate copolymer. Cleavage can be achieved by a process such as the reaction of maleic anhydride with a polyolefin in solution in an organic solvent with a free radical catalyst such as dibenzyl peroxide. Alternatively, some active center can be introduced into the polymer by, for example, high-energy radiation, such as gamma radiation, and then reacting the resulting substance with an anhydride.
Najpogodnije je da vezna smola sadrži od 0,05% do 0,5%, a još bolje od 0,1 do 0,25% kiselinske modifikacije, mjerene analizom infracrvene asorpcije pri 1790cm-1, smole predsušene pri 200ºC kako bi se kiselinska funkcionalna skupina prevele u anhidrid. It is most suitable that the bonding resin contains from 0.05% to 0.5%, and even better from 0.1 to 0.25% acid modification, measured by infrared absorption analysis at 1790cm-1, resin pre-dried at 200ºC to make the acid functional group translated into an anhydride.
Anhidrid cijepanjem modificiran poliolefin može se razrijediti s još ne modificiranim poliolefinom da se dobije vezna smola sa sadržajem cijepanje kiseline (tj, razinom cijepanog) od 0,02 do 0,6%, a najbolje 0,2±0,5%. Nemodificirani poliolefin za razrjeđenje može biti isti poliolefin koji je upotrijebljen za proizvodnju kiselinski modificiranog poliolefina, ili može biti različit poliolefin. Tako npr. neki polietilen niske gustoće (LDPE) ili linerni polietilen niske gustoće (LLDE) modificiran kiselinom može se razrijediti s polipropilenom, ili polipropilen modificiran kiselinom može se razrijediti polipropilenom ili etileno propilenom kopolimerom. The anhydride cleavage modified polyolefin can be diluted with the unmodified polyolefin to produce a binder resin with an acid cleavage content (ie, cleavage level) of 0.02 to 0.6%, preferably 0.2±0.5%. The unmodified polyolefin for the diluent can be the same polyolefin that was used to produce the acid modified polyolefin, or it can be a different polyolefin. Thus, for example, some acid-modified low-density polyethylene (LDPE) or linear low-density polyethylene (LLDE) can be diluted with polypropylene, or acid-modified polypropylene can be diluted with polypropylene or ethylene propylene copolymer.
Svrha unutrašnejg sloja (B1) vezne smoje je da veže vanjski sloj (B2) poliolefina ili poliamida za površinu metala. Pogodnije je, kad je vanjski poliolefinski sloj (B2), da polietilenska osnova vezne smole unutrašnejg sloja (B1) bude polietilen ii etilenski kopolimer. Pogodnije je, kad je vanjski sloj polietilnski sloj (B2), polipropilenski homopolimer ili neki etilen-propilen kopolimer, da osnova vezne smole unutrašnjeg sloja (B1) bude prlipropilen ili neki etilne propilen kopolimer. Kad je vanjski sloj (B2) poliamid, sloj vezne smole može biti na osnovi polietilena ili polipropilena. The purpose of the inner layer (B1) of bonding resin is to bind the outer layer (B2) of polyolefin or polyamide to the metal surface. It is more convenient, when the outer polyolefin layer (B2), that the polyethylene base of the binding resin of the inner layer (B1) is polyethylene and ethylene copolymer. It is more convenient, when the outer layer is a polyethylene layer (B2), a polypropylene homopolymer or an ethylene-propylene copolymer, that the base of the binding resin of the inner layer (B1) is polypropylene or an ethylene-propylene copolymer. When the outer layer (B2) is polyamide, the binding resin layer can be based on polyethylene or polypropylene.
Najbolje je da za sloj vezne smole na osnovi polipropilena masenog protoka taline vezne smole bude 3 do 30 g/10 min, mjereno pri 230ºC metodom ASTM D 1238. It is best that for a layer of bonding resin based on polypropylene, the mass flow rate of the bonding resin melt is 3 to 30 g/10 min, measured at 230ºC by the ASTM D 1238 method.
Posebno pogodni vezni slojevi vezne smole su na osnovi eltilen-propilen kopolimera ili mješavine linearnog polietilena male gustoće (LLDPE) s polipropilenom. Especially suitable bonding layers of bonding resin are based on ethylene-propylene copolymer or a mixture of linear low-density polyethylene (LLDPE) with polypropylene.
Posebno pogodan olefinski kopolimer modificiran kiselinom je etilen vinil acetat modificiran maleinskim anhidridom. A particularly suitable acid-modified olefinic copolymer is ethylene vinyl acetate modified with maleic anhydride.
Za sloj vezne smole (B1) u složenom polimernom filmu (B) najbolje je da ima debljinu od 1 do 10 mikrona. For the bonding resin layer (B1) in the composite polymer film (B), it is best to have a thickness of 1 to 10 microns.
U daljnjem rješenju ovog izuma, za vanjski sloj (B2) pomoću slijedećeg sloja vezne smole (B3) može se prilijepiti još i poliamidni ili polioledinskim sloj (B4) kao što je definirano za vezni sloj (B1). Ako je potrebno, svaki od slojeva (B1) do (B4) može se obojiti na uobičajeni način, npr. s titan diokisdom. Pogodnije je da boja bude u sloju (B2) ili u slojevima (B2) i (B4). Pogodno je da vanjski poliolefinski ili poliamidni sloj može sadržavati anti-blok sredstvo, kao što je sintetički silicij diokisd veličine čestica od 0,5 do5 mikrona. In a further solution of this invention, a polyamide or polyoledine layer (B4) can also be adhered to the outer layer (B2) using the next layer of bonding resin (B3), as defined for the bonding layer (B1). If necessary, each of the layers (B1) to (B4) can be painted in the usual way, for example with titanium dioxide. It is more convenient for the color to be in layer (B2) or in layers (B2) and (B4). Conveniently, the outer polyolefin or polyamide layer may contain an anti-blocking agent, such as synthetic silicon dioxide with a particle size of 0.5 to 5 microns.
U ovom opisu stvarna viskoznost mjerenja je pri 25ºC u o-klorofenolnim otopinama pri koncentraciji od 5 g/l. Slijedeći primjeri predstavljaju dalju ilustraciju ovog izuma. In this description, the actual viscosity is measured at 25ºC in o-chlorophenol solutions at a concentration of 5 g/l. The following examples further illustrate this invention.
Primjeri 1 do 42 Examples 1 to 42
Laminati polimer/metan/polimer pripremljeni su postupkom laminiranja provedenom u uređaju koji je shematski prikazan na slici 11 ili slici 12, na priloženim crtežima. Metalna traka M predgrijava se do odgovarajuće temperature T1 pomoću grijala 1. Temperatura T1 obično je u području 120 do 220ºC. Poliesterski film A dovodi se iz valjka za napajanje 2, a film sadrži poliolefin iz valjka za napajanje 4, koji se laminira na suprotne strane predgrijane metalne trake između valjka za laminiranje 6 i 8, čiji promjer je obično 100-400 mm. Laminiranje se obično provodi pomoću prihvatne sile od 200-400 N/m između valjaka za laminiranje. Polymer/methane/polymer laminates were prepared by the lamination process carried out in the device schematically shown in Figure 11 or Figure 12, in the attached drawings. The metal strip M is preheated to the appropriate temperature T1 by the heater 1. The temperature T1 is usually in the range of 120 to 220ºC. Polyester film A is fed from feed roller 2, and the film contains polyolefin from feed roller 4, which is laminated on opposite sides of the preheated metal strip between lamination rollers 6 and 8, the diameter of which is usually 100-400 mm. Lamination is usually carried out using a holding force of 200-400 N/m between the laminating rollers.
Pri bliskom i ujednačenom zahvatu laminiranje uspostavlja se dodir bez gužvanja metalne trake i polimernih filmova. Iza valjaka za laminiranje dobiveni laminat se ponovno grije pomoću indukcijskog grijala 10 do temperature T2 pri kojoj oba polimerna filma A i B reagiraju međusobno stvarajući vezu s metalnom trakom. Temperaturu T2 obično je u području 230 do 270ºC. Metalpolimerni laminat drži se pri temperaturi T2 ili pri temperaturi malo nižoj od T2, kratko vrijeme, obično ne dulje od 2 sekunde, a onda se brzo i ravnomjerno uranja u vodu do temperature ispod tališta filma koji sadrži poliolefin (B). Potapanje se može provesti na bilo koji od uobičajenih načina, ali uglavnom se provodi prolaskom laminata kroz kadu s vodom 12 koja je prikazana na slici 11 ili prolaskom laminata kroz vodenu zavjesu 14, što se vidi na slici 12. With a close and uniform grip, lamination establishes contact without wrinkling the metal strip and polymer films. Behind the laminating rollers, the obtained laminate is reheated using the induction heater 10 to the temperature T2 at which both polymer films A and B react with each other creating a bond with the metal strip. The temperature T2 is usually in the range of 230 to 270ºC. The metal-polymer laminate is held at temperature T2 or at a temperature slightly below T2 for a short time, usually no longer than 2 seconds, and then rapidly and evenly immersed in water to a temperature below the melting point of the polyolefin-containing film (B). Immersion can be carried out in any of the usual ways, but it is mainly carried out by passing the laminate through a bath of water 12, which is shown in Figure 11, or by passing the laminate through a water curtain 14, which is seen in Figure 12.
Načelno bolji je postupak prikazana na slici 11 kojim se laminiranje provodi okomito. Okomito kretanje metalne trake kroz stupanj laminiranja omogućuje veću brzinu uranjanja, a samo uranjanje je bolje i ravnomjernije. In principle, the procedure shown in Figure 11 is better, in which the lamination is carried out vertically. The vertical movement of the metal strip through the lamination stage enables a higher speed of immersion, and the immersion itself is better and more uniform.
Slika 11 također prikazuje shematski dijagram profila temperature u procesu čiji uređaj je prikazan na slici 11. Figure 11 also shows a schematic diagram of the temperature profile in the process whose device is shown in Figure 11.
U tablici 1 navedeni su tipovi polimera koji su laminirani na metalnu traku, kao i debljine svakog sloja. Uvjeti laminiranja i rezultati koji se pri tome dobiju prikazani su ua tablici 2. Table 1 lists the types of polymers laminated to the metal strip, as well as the thicknesses of each layer. Lamination conditions and the results obtained are shown in table 2.
Poliesterski film A koji se nanosi na metalnu traku može biti u obliku filma s jednostrukim slojem (kao u primjerima 11 do 14 koji su dati radi usporedbe). U tim slučajevima priroda polimera navedena je u tablici 1 u stupcu A1. Alternativno, poliesterski film A može biti složeni film koji se sastoji od unutrašnjeg sloja A1 i vanjskog sloja A2 i obično je pripremljen koekstrudiranjem odgovarajućih polimernih filmova. Ovakovi filmovi predstavljaju filmove u skladu s ovim izumom. The polyester film A applied to the metal strip may be in the form of a single layer film (as in Examples 11 to 14 provided for comparison). In these cases, the nature of the polymer is listed in Table 1 in column A1. Alternatively, the polyester film A may be a composite film consisting of an inner layer A1 and an outer layer A2 and is usually prepared by coextruding the corresponding polymer films. Such films represent films in accordance with the present invention.
Poliolefinski film može imati samo jedan jednostruki sloj B1, kao što je to u slučaju laminata prikazanog na slici 1, ili može sadržavati veći broj slojeva B1, B2, B3, B4, koji se obično pripremaju koekstrudiranjem odgovarajućih polimernih filmova. The polyolefin film can have only one single layer B1, as in the case of the laminate shown in Figure 1, or it can contain a number of layers B1, B2, B3, B4, which are usually prepared by coextruding the corresponding polymer films.
Slika 1 prikazuje laminat polimer/metal/polimer koji ima složeni poliesterski film A1/A2 nanesen na jednu stranu metalne trake M s jednostrukim slojem filma koji sadrži poliolefin, a nanesen je na suprotnu stranu filma. Laminati predstavljeni u primjerima 1 do 3, 17 i 18 imaju ovakvu strukturu. Figure 1 shows a polymer/metal/polymer laminate having a composite polyester film A1/A2 applied to one side of a metal strip M with a single layer of polyolefin-containing film applied to the opposite side of the film. The laminates presented in examples 1 to 3, 17 and 18 have this structure.
Slika 2 prikazuje laminat polimer/metal/polimer koji sadrži složeni poliesterski film A1/A2 na jednoj strani metalne trake i složeni film koji sadrži poliolefin B1/B2 na drugoj strani. Laminati iz promjera 4 do 8, 15, 16 i 19 do 24 imaju ovu strukturu. Primjeri 9 i 10 imaju ovu strukturu, ali sadrže i dva dodatna vanjska sloja B3 i B4 na ovoj strani metalne trake koja je prevučena poliolefinom. Figure 2 shows a polymer/metal/polymer laminate containing a composite polyester film A1/A2 on one side of the metal strip and a composite film containing polyolefin B1/B2 on the other side. Laminates from diameters 4 to 8, 15, 16 and 19 to 24 have this structure. Examples 9 and 10 have this structure, but also contain two additional outer layers B3 and B4 on this side of the metal strip which is coated with polyolefin.
Slika 3 prikazuje laminat polimer/metal/polimer kod kojeg oba polimerna filma A i B imaju po jedan sloj. Filmovi iz primjera 11 i 12 imaju ovaj tim slojeva. Figure 3 shows a polymer/metal/polymer laminate where both polymer films A and B have one layer each. The films of examples 11 and 12 have this team of layers.
Strukture laminata metal/polimer iz primjera 1 do 10 i 15 do 23 pogodne su za izradu u skladu s ovim izumom. Tablica 2 prikazuje primjere ponašanja laminata u različitim uvjetima i to raznih struktura laminata prikazanih u tablici 1. The metal/polymer laminate structures from examples 1 to 10 and 15 to 23 are suitable for production in accordance with this invention. Table 2 shows examples of the behavior of laminates in different conditions and of various laminate structures shown in table 1.
Tablica 2 pokazuje da ako se temperatura metalne trake pri laminiranju podigne do previsoke vrijednosti, poliolefinske prevlake se lijepe za valjke (slučaj D, E, F i I). Osim toga ako je temperatura preniska i ne postoji poliesterski unutrašnji sloj (A1) u skladu s izumom, poliesterski sloj neće se pravilno prilijepiti za metalnu traku (slučaj G i H). Table 2 shows that if the temperature of the metal strip during lamination rises to too high a value, the polyolefin coatings stick to the rollers (Case D, E, F and I). In addition, if the temperature is too low and there is no polyester inner layer (A1) according to the invention, the polyester layer will not adhere properly to the metal strip (case G and H).
Tablica 1: Sastav metal-polimernih laminata. Table 1: Composition of metal-polymer laminates.
[image] Objašnjenje uz tablicu 1: [image] Explanation to table 1:
Poliester A: Polyester A:
U primjerima od 1 do 10, 15, 17-22 i 23 upotrijebljen je nekristaličan (tj. amorfan) poliester koji je 80:20 kopolimer tereftalata i etilen izoftalata. Temperatura mekšanja poliestera bila je ispod 150ºC i talište 210ºC. Unutrašnja viskoznost poliestera bila je 0,6 do 0,7. In examples 1 to 10, 15, 17-22 and 23, non-crystalline (i.e. amorphous) polyester was used, which is an 80:20 copolymer of terephthalate and ethylene isophthalate. The softening temperature of polyester was below 150ºC and the melting point was 210ºC. The intrinsic viscosity of the polyester was 0.6 to 0.7.
U primjeru 16 amorfni poliester bio je kopolimer tereftalne kiseline i etilne glikola i cikloheksan dimetanola. Temperatura mekšanja poliestera bila je ispod 150ºC, a talište poliestera 180ºC. Unutrašnja viskoznost poliestera bila je oko 0,9 i ispod 1,1. In Example 16, the amorphous polyester was a copolymer of terephthalic acid and ethyl glycol and cyclohexane dimethanol. The softening temperature of polyester was below 150ºC, and the melting point of polyester was 180ºC. The intrinsic viscosity of polyester was around 0.9 and below 1.1.
Vezna smola 1: Bonding resin 1:
Etilen propilen slučajni kopolimer modificiran cijepljenjem s moleinskim anhidridom s razinom cijepljenja oko 0,2 do 0,05. An ethylene propylene random copolymer modified by maleic anhydride grafting with a degree of grafting of about 0.2 to 0.05.
Vezna smola 2: Bonding resin 2:
Polietilen modificiran cijepljenjem s maleinskim anhidridom s razinom cijepljenja otprilike od 0,08±0,05. Polyethylene modified by maleic anhydride grafting with a grafting level of approximately 0.08±0.05.
Vezna smola 3: Bonding resin 3:
Etilen/akrilna kiselina kopolimer (EAA) koji obično ima 6% ili 9% akrilne kiseline. Ethylene/acrylic acid copolymer (EAA) which usually has 6% or 9% acrylic acid.
Vezna smola 4: Bonding resin 4:
Etilen/metakrilna kisleina kopolimer (EMAA) obično ima 9% ili 12% metakrilne kiseline. Ethylene/methacrylic acid copolymer (EMAA) typically has 9% or 12% methacrylic acid.
Vezna smola 5: Bonding resin 5:
Etilen vinilacetat kopolimer modificiran cijepljenjem s maleinskim anhidridom s razinom cijepljenja otprilike od 0,08%±0,05. Maleic anhydride graft modified ethylene vinyl acetate copolymer with a grafting level of approximately 0.08%±0.05.
Vezna smola 6: Bonding resin 6:
Polipropilen kopolimer modificiran cijepljenjem s maleinskim anhidridom koji ima razinu cijepljenja otprilike od 0,2±0,05%. A graft-modified polypropylene copolymer with maleic anhydride having a grafting level of approximately 0.2±0.05%.
Vezna smola 7: Bonding resin 7:
Etilen-propilen blok kopolimer modificiran cijepljenjem s maleinskim anhidridom s razinom cijepljenja otprilike od 0,2±0,05. Maleic anhydride graft-modified ethylene-propylene block copolymer with a grafting level of approximately 0.2±0.05.
PET: FIVE:
Polietilen tereftalat. Polyethylene terephthalate.
Biaksijalni PET: Biaxial PET:
Biaksijalno orijentiran polietilen tereftalat s talištem 255ºC. Biaxially oriented polyethylene terephthalate with a melting point of 255ºC.
Poliamid: Polyamide:
Najlon 6. Nylon 6.
Metalna traka M: Metal strip M:
Može biti ECCS (označeno s E), aluminij ili neka njegova legura (označena s A), kositrena ploča (označeno s T) ili crni željezni lim (označeno s B). It can be ECCS (marked with E), aluminum or some of its alloys (marked with A), tin plate (marked with T) or black iron sheet (marked with B).
[image] [image]
Napomena Remark
Slučajevi A, B i C ilustriraju materijale i postupke opisane u ovom izumu koji su primijenjeni uspješno. Cases A, B and C illustrate the materials and processes described in the present invention that have been applied successfully.
Slučajevi D, E i F ilustriraju ograničenja koja nameću poliolefinske prevlake u svezi s temperaturom laminiranja. Poliester se uspješno laminira u D-F. Cases D, E and F illustrate the limitations imposed by polyolefin coatings on lamination temperature. Polyester is successfully laminated in D-F.
Slučajevi G, H i I: Kombinacije s već opisanim materijalom koje pokazuju nekompatibilnost pri niskim (G, H) i visokim (I) temperaturama laminiranja i zahtijevaju laminiranje poliolefina i biaksijalno orijentiranih PET filmova. Cases G, H and I: Combinations with already described material that show incompatibility at low (G, H) and high (I) lamination temperatures and require lamination of polyolefin and biaxially oriented PET films.
Primjeri 25 do 51 (vidi tablicu 3) Examples 25 to 51 (see Table 3)
Ovi primjeri ilustrijraju određen broj sastojaka za metalne posude za pakiranje, kao i njihove zatvarače, koji se mogu uspješno izraditi od laminata polimer/metal/polimer proizvedenih u skladu s ovim izumom. Ilustracije tipičnih oblika uobičajenih proizvoda prikazane su na slikama od 4 do 10 priloženih crteža. These examples illustrate a number of components for metal packaging containers, as well as their closures, which can be successfully made from polymer/metal/polymer laminates produced in accordance with the present invention. Illustrations of typical shapes of common products are shown in Figures 4 to 10 of the attached drawings.
Tablica 3 sadrži prirodu metalne trake (M), tipove polimernih filmova (A) i (B) koji se na nju laminiraju i za svaku primjenu navodi se sastav polimernog filma za vanjske prevlake (C) proizvoda i sastav polimernog filma unutrašnje prevlake (D) proizvoda. Table 3 contains the nature of the metal strip (M), the types of polymer films (A) and (B) that are laminated to it and for each application the composition of the polymer film for the outer coating (C) of the product and the composition of the polymer film for the inner coating (D) are listed. products.
Laminati opisani u primjerima 25 do 31 obrađeni su uobičajenim postupcima u poklopce za posude za prehrambene proizvode koji su prikazani na slici 4 priloženih crteža. The laminates described in examples 25 to 31 were processed by conventional methods into lids for containers for food products which are shown in Figure 4 of the attached drawings.
Laminati opisani u primjerima 32 do 34 i 51 oblikovani su uobičajenim postupcima dubokog izvlačenja u posude (izvlačeno - ponovno duboko izvlačenje posude), kao što su one prikazane na slici 5 priloženih crteža. The laminates described in Examples 32 to 34 and 51 were formed by conventional deep drawing into containers (drawn - again deep drawing into containers), such as those shown in Figure 5 of the attached drawings.
Laminati opisani u primjerima 35 do 38 obrađeni su uobičajenim postupcima u poklopce posude za napitke, kao što je prikazano na slici 6 priloženih crteža. The laminates described in examples 35 to 38 were processed by conventional methods into lids for beverage containers, as shown in Figure 6 of the attached drawings.
Laminati opisani u primjerima 39 i 40 obrađeni su na uobičajena način u željezne posude s duboko izvlačenim stijenkama kao što su one prikazane na slici 7 priloženih crteža. The laminates described in Examples 39 and 40 were processed in the usual manner into iron pans with deep drawn walls such as those shown in Figure 7 of the accompanying drawings.
Laminati opisani u primjerima 41 do 43, 44, 45 i 46 do 50 obrađeni su na uobičajen način u posude za aerosole, kupole za aerosole i stošce za aerosole, kao što su oni prikazani na slikama 8, 9 i 10 priloženih crteža. The laminates described in Examples 41 to 43, 44, 45 and 46 to 50 were processed in a conventional manner into aerosol containers, aerosol domes and aerosol cones, such as those shown in Figures 8, 9 and 10 of the accompanying drawings.
ECCS koji se primjenjuje u primjerima 25-29, 31-36 i 41-51 predstavlja komercijalni proizvod tvrtke British Steel Corporation i podvrgava svoj ECC obradi u kromnoj kiselini koja sadrži katalizator sumpornu kiselinu (tip 1). ECC obrada primijenjena na čeliku u primjeru 30 bila je kromna kiselina koja je sadržavala HBF4 kao katalizator (tip 2). The ECCS used in Examples 25-29, 31-36 and 41-51 is a commercial product of British Steel Corporation and undergoes its ECC treatment in chromic acid containing a sulfuric acid catalyst (type 1). The ECC treatment applied to the steel in Example 30 was chromic acid containing HBF4 as a catalyst (type 2).
Aluminij koji je upotrijebljen u primjerima 37-40 obrađen je u mediju kromna kiselina - fosforna kiselina u mlinu za aluminijske trake nakon hladnog valjanja i čišćenja. The aluminum used in Examples 37-40 was treated in a chromic acid - phosphoric acid medium in an aluminum strip mill after cold rolling and cleaning.
Kositrene ploče koje se primjenjuju u primjeru 22 imale su prevlaku od kositra težine 0,5 g/m2 i 2,8 g/m2. The tin plates used in Example 22 had a tin coating of 0.5 g/m 2 and 2.8 g/m 2 .
Tablica 3. Table 3.
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Svojstva prevlaka od polimernih filmova laminiranih na proizvodima iz primjera 25 do 51 provjerena su podvrgavanjem proizvoda različitim ispitivanjima uključiv slijedeća: The properties of the polymer film coatings laminated on the products from examples 25 to 51 were verified by subjecting the products to various tests including the following:
Dvostruko obrubljivanje Double hemming
Poklopci posuda promjera 73 mm oblikovani su iz laminata i savijeni. Poklopci su čeonom stranom zavareni na tijelo posude pomoću konvencionalnog uređaja za obrubljivanje poklopaca. Prevlaka je ispitana prema fibrilaciji, struganju i oštećenjima. Poklopac je provjeren potapanjem u zakiseljeni bakar sulfat u trajanju od 2 minute i očnim pregledom dali ilma naslaga bakra. The lids of the containers with a diameter of 73 mm are formed from laminate and bent. The lids are butt-welded to the body of the container using a conventional device for edging the lids. The coating was tested for fibrillation, scraping and damage. The lid was checked by immersing it in acidified copper sulfate for 2 minutes and visual inspection for copper deposits.
Sposobnost oblikovanja The ability to shape
Sposobnost oblikovanja provjerena je oblaganjem prevlake nakon što je posuda već oblikovana, Oblog se provjerava kao što je opisano kod dvostrukog obrubljivanja. Formability is checked by coating the coating after the vessel has already been formed, The coating is checked as described for double lining.
Zaštita Protection
Zaštita se procjenjuje ubrzanim ispitivanjem kojima se simuliraju pakiranje agresivnih proizvoda u trajanju od 6 do 12 mjeseci, procjenjuju se vrijednosti cakline i određuje se trajanje s raznim specifičnim proizvodima. Protection is assessed by accelerated tests simulating the packaging of aggressive products for 6 to 12 months, evaluating enamel values and determining duration with various specific products.
Uobičajena sredstva za ubrzavanja: Common accelerators:
- octena kiselina (1,5%), natrij klorid (1,0%) u vodi, - acetic acid (1.5%), sodium chloride (1.0%) in water,
- limunska kiselina (0,63%), natrij klorid (1,0%), - citric acid (0.63%), sodium chloride (1.0%),
- jabučna kiselina (0,42%), voda do pH 4. - malic acid (0.42%), water up to pH 4.
Uobičajeni uvjeti ispitivanja: Usual test conditions:
- reterta pri 121ºC, jedan sat, - retort at 121ºC, one hour,
držanje 24 sata, holding for 24 hours,
Sastojci ili posude pregledane su nakon ispitivanja i uspoređena je korozija s konvencionalno prevučenim posudama. The components or containers were inspected after the test and the corrosion compared to conventionally coated containers.
Procjenjivanje vrijednosti cakline: Assessing the value of enamel:
- otopina natrij klorida, - sodium chloride solution,
- 6,4 V, - 6.4 V,
- struja monitora, - monitor current,
- 2 mA prihvatljiva granica - 2 mA acceptable limit
Zatvaranje poklopca Closing the lid
Poklopci prevučeni polimerom leme se ili zakivaju u slučaju kupole s ventilom na tijelo posude bez dijelova za obrubljivanje. Posude su bile napunjene s proizvodom i pritisnute. Mjeren je gubitak težine radi usporedbe brzine gubitka sadržaja u slučaju konvencionalnih dijelova koji imaju dijelova za obrubljivanje. Ako je ta brzina manja od uobičajenih poklopci se smatraju prihvatljivim. Polymer coated caps are soldered or riveted in the case of a valve dome to the body of the vessel without trim pieces. The containers were filled with the product and pressed. Weight loss was measured to compare the rate of content loss to conventional parts having trim parts. If this speed is lower than usual, the covers are considered acceptable.
Stanovite prednosti u svojstvima proizvoda iz primjera 25 do 51 navedene su u slijedećem prikazu. Certain advantages in the properties of the products from examples 25 to 51 are listed in the following presentation.
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Claims (19)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8724237A GB8724237D0 (en) | 1987-10-15 | 1987-10-15 | Laminated metal sheet |
YU190488A YU190488A (en) | 1987-10-15 | 1988-10-13 | Process for producing laminated metallic thin plates |
Publications (1)
Publication Number | Publication Date |
---|---|
HRP930107A2 true HRP930107A2 (en) | 1995-06-30 |
Family
ID=26292887
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
HR930107A HRP930107A2 (en) | 1987-10-15 | 1993-02-03 | Laminated metal sheets |
Country Status (1)
Country | Link |
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HR (1) | HRP930107A2 (en) |
-
1993
- 1993-02-03 HR HR930107A patent/HRP930107A2/en not_active Application Discontinuation
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