TW202332710A - 用於數位油墨印刷層壓體之黏著劑 - Google Patents
用於數位油墨印刷層壓體之黏著劑 Download PDFInfo
- Publication number
- TW202332710A TW202332710A TW111150567A TW111150567A TW202332710A TW 202332710 A TW202332710 A TW 202332710A TW 111150567 A TW111150567 A TW 111150567A TW 111150567 A TW111150567 A TW 111150567A TW 202332710 A TW202332710 A TW 202332710A
- Authority
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- Taiwan
- Prior art keywords
- component
- isocyanate
- adhesive composition
- polyol
- solvent
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 65
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 65
- 239000012948 isocyanate Substances 0.000 claims abstract description 70
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 68
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 150000003077 polyols Chemical class 0.000 claims abstract description 33
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 23
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 16
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 15
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 23
- -1 phosphate ester Chemical class 0.000 claims description 20
- 239000002318 adhesion promoter Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 claims 1
- 239000012939 laminating adhesive Substances 0.000 abstract description 13
- 238000003475 lamination Methods 0.000 abstract description 9
- 238000010030 laminating Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 19
- 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 15
- 239000000376 reactant Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 238000007639 printing Methods 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920013701 VORANOL™ Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 5
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 5
- 239000011888 foil Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MZNYWPRCVDMOJG-UHFFFAOYSA-N N-(1-naphthyl)ethylenediamine dihydrochloride Chemical compound [Cl-].[Cl-].C1=CC=C2C([NH2+]CC[NH3+])=CC=CC2=C1 MZNYWPRCVDMOJG-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000012156 elution solvent Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 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 2
- FDYWJVHETVDSRA-UHFFFAOYSA-N 1,1-diisocyanatobutane Chemical compound CCCC(N=C=O)N=C=O FDYWJVHETVDSRA-UHFFFAOYSA-N 0.000 description 1
- VKLNMSFSTCXMSB-UHFFFAOYSA-N 1,1-diisocyanatopentane Chemical compound CCCCC(N=C=O)N=C=O VKLNMSFSTCXMSB-UHFFFAOYSA-N 0.000 description 1
- KEZMBAQUUXDDDQ-UHFFFAOYSA-N CCC.N=C=O.N=C=O Chemical compound CCC.N=C=O.N=C=O KEZMBAQUUXDDDQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 101100437784 Drosophila melanogaster bocks gene Proteins 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 1
- FUCRTFHCJZBKBB-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCCCCC Chemical compound N=C=O.N=C=O.CCCCCCCCC FUCRTFHCJZBKBB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- STBLQDMGPBQTMI-UHFFFAOYSA-N heptane;isocyanic acid Chemical compound N=C=O.N=C=O.CCCCCCC STBLQDMGPBQTMI-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 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
- 238000009776 industrial production Methods 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000009928 pasteurization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
具有改良之數位油墨層壓特性之層壓黏著劑,其包含異氰酸酯組分及多元醇組分。異氰酸酯組分包含異氰酸酯預聚物及脂族聚異氰酸酯。多元醇組分包含由芳族聚酯多元醇及天然油製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑。異氰酸酯組分內之異氰酸酯預聚物包含異氰酸酯與聚伸烷基二醇聚合物之反應產物。層壓體結構可藉由用黏著劑塗佈基材之至少部分且使第一基材與第二基材接觸。
Description
本揭示案係關於層壓黏著劑,且更具體地係關於具有包含異氰酸酯組分及異氰酸酯組分之多元醇組分之數位油墨印刷層壓體之組分層壓黏著劑,其中異氰酸酯組分包含經改質異氰酸酯與聚伸烷基二醇反應之反應產物、及脂族聚異氰酸酯;及多元醇組分包含由芳族聚酯多元醇及天然油製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑。
數位或噴墨印刷致能經濟的短版印刷工作,其用於定製及個人化封裝。非噴墨印刷方法不允許經濟的短路印刷工作,且因此製造經濟的個人化封裝所有但不可能。
使用聚乙烯、聚丙烯、聚酯、聚醯胺或纖維素基材,使用聚乙烯、聚丙烯、聚酯、聚醯胺或纖維素基材來產生大量包裝。層壓黏著劑通常係分類為基於溶劑、水基或無溶劑。
無溶劑層壓黏著劑可在高執行速度下施加,因為無水或有機溶劑必須在施加時自黏著劑乾燥。此使無溶劑黏著劑在需要快速黏著劑施加之應用中較佳,諸如短版噴墨個人化封裝印刷工作。
然而,當前層壓黏著劑與數位油墨不相容,導致較低黏合性效能。因此,層壓黏著劑與數位油墨相容,從而實現噴墨印刷為未滿足的需求。
本揭示案係關於雙組分無溶劑黏著劑組合物,其包含異氰酸酯組分及多元醇組分。異氰酸酯組分可包含經改質異氰酸酯與聚伸烷基二醇反應之反應產物、及脂族聚異氰酸酯。多元醇組分可包含由芳族聚酯多元醇及天然油製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑。亦揭示一種包含基材及設置在該基材之至少一部分上之雙組分無溶劑黏著劑組合物之塗佈膜。設置於基材之一側之表面之至少一部分上之黏著劑可包含異氰酸酯組分及多元醇組分。異氰酸酯組分可包含經改質異氰酸酯與聚伸烷基二醇反應之反應產物、及脂族聚異氰酸酯。多元醇組分可包含由芳族聚酯多元醇及天然油製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑。
如上文所述,根據本揭示案之雙組分無溶劑黏著劑組合物包括異氰酸酯組分及多元醇組分。
異氰酸酯組分:
異氰酸酯組分包括至少一種異氰酸酯。至少一種異氰酸酯可選自由以下組成之群:異氰酸酯預聚物、異氰酸酯單體、聚異氰酸酯(例如二聚體、三聚物等)及其兩種或更多種之組合。如本文所用,「聚異氰酸酯(polyisocyanate)」係含有二或更多個異氰酸酯基團之任何化合物。異氰酸酯預聚物為包含至少一種異氰酸酯及至少一種多元醇之反應物的反應產物。如本文所用,「異氰酸酯預聚物(isocyanate prepolymer)」可為聚異氰酸酯本身。
至少一種異氰酸酯包含1.5至10,或1.8至5,或2至3的官能度。如關於異氰酸酯組分所使用,「官能度(functionality)」係指每分子之羥基反應性位點的數目。具有異氰酸酯基團之化合物(諸如異氰酸酯組分)可藉由參數「%NCO」表徵,該參數為以化合物重量計的以重量計之異氰酸酯基團之量。參數%NCO係藉由ASTM D 2572-97(2010)之方法測量。所揭示異氰酸酯組分之%NCO為至少3%、或至少6%、或至少10%。較佳地,異氰酸酯組分具有%NCO不超過25%、或18%、或14%。
此外,至少一種異氰酸酯包括0至50%、5至40%或10至30%之游離單體含量。再者,至少一種異氰酸酯包括200至6,000 g/mol或500至5,000 g/mol或1000至4,000 g/mol之平均分子量。甚至進一步,如藉由ASTM D2196之方法所測量,異氰酸酯組分在25℃下具有300至40,000 mPa-s或500至20,000 mPa-s或1,000至10,000 mPa-s。
異氰酸酯組分之異氰酸酯可為亞甲基二苯基二異氰酸酯(「MDI」)之芳族異構物,諸如但不限於4-4-MDI、2,2-MDI、2,4 -MDI及甲苯二異氰酸酯(TDI)。如本文所用,芳族異氰酸酯(aromatic isocyanate)為含有一或多個芳族環之異氰酸酯。
以黏著劑組合物之重量(亦即異氰酸酯組分及多元醇組分之總重量)計,黏著劑組合物中之至少一種異氰酸酯的量(以重量計)為至少5 wt %,或至少10 wt %,或至少20 wt %。以黏著劑組合物之重量計,黏著劑組合物中之至少一種異氰酸酯的量(以重量計)為不超過100 wt %,或不超過75 wt %,或不超過50 wt %。
異氰酸酯組分亦可含有聚伸烷基二醇與NCO終止基團反應。如本文所用,聚伸烷基二醇可為但不限於聚丙二醇、聚乙二醇、或乙烯/丙烯共聚物二醇。異氰酸酯組分亦可含有脂族聚異氰酸酯。以異氰酸酯組分之重量計,脂族聚異氰酸酯之量為0.1至10或0.1至5重量百分比。如本文所用,脂族聚異氰酸酯(aliphatic polyisocyanate)為不含芳族環之異氰酸酯。如適用於使用之脂族聚異氰酸酯之實例包括但不限於六亞甲基二異氰酸酯(「HDI」)、丙烷二異氰酸酯、丁烷二異氰酸酯、戊烷二異氰酸酯、己烷二異氰酸酯、庚烷二異氰酸酯、壬烷二異氰酸酯、環脂族聚異氰酸酯或其摻合物之摻合物或其摻合物。
多元醇組分:
多元醇組分可包含與天然油酯交換之芳族聚酯多元醇。天然油可為但不限於蓖麻油、水解環氧化大豆油、水解環氧化的亞麻籽油或此等混合物。在一些實施例中,酯交換芳族聚酯多元醇具有100至600 g/mol的當量。適合於根據本揭示案使用之酯交換芳族聚酯多元醇之市售實例包括但不限於以商品名MOR -FREE
™C-156購自陶氏化學公司之產品。多元醇組分亦可包含磷酸酯助黏劑,諸如MOR -FREE
™88-138。
酯交換芳族聚酯多元醇之含量可為5至50重量%,或10至40%或20至35%;聚丙二醇之含量可為40至80%、或50至70%、或55至65%;在總多元醇組分中,磷酸酯助黏劑可為0.1至20%、或1至15%、或5至10%。
用於製造本揭示案之雙組分無溶劑層壓黏著劑組合物之方法可包含混合、混合或摻合異氰酸酯組分及多元醇組分。異氰酸酯組分可包含經改質之異氰酸酯與聚伸烷基二醇之反應產物、及脂族聚異氰酸酯。多元醇組分可包含由芳族聚酯多元醇及天然油製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑。
黏著劑調配物組分可藉由任何已知混合製程及設備混合在一起。異氰酸酯組分及多元醇組分可彼此分開地製備且彼此分開地儲存。組分可在施加之前或立即與彼此混合。
使用本揭示案之雙組分無溶劑黏著劑組合物形成層壓體結構之方法可包含以下步驟:(1)將一層該黏著劑組合物施加至第一基材之表面,(2)藉由層壓機使該黏著劑之該層與第二基材之表面接觸,以形成層壓體結構,以及(3)固化該黏著劑組合物,該黏著劑組合物在環境溫度或升高之溫度下將該第一基材及第二基材之該等表面黏合在一起。
本發明揭示一種用於形成層壓體結構之方法。在本發明所揭示之方法中,異氰酸酯組分可與多元醇組分混合。異氰酸酯組分可包含經改質之異氰酸酯與聚伸烷基二醇多元醇或多於一種聚烷二醇之混合物之反應產物、及脂族聚異氰酸酯。多元醇組分可包含由芳族聚酯多元醇及天然油製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑。
因此形成之層壓黏著劑可施加至至少一個基材之表面之至少一部分,接著可藉由層壓機與至少一個第二基材之表面接觸而形成層壓體結構。接著可將黏著劑組合物固化且將基材黏合在一起。
本發明所揭示之雙組分無溶劑層壓黏著劑組合物可在25℃下呈液體或半固態。若在25℃下半固態,可加熱本發明所揭示之無溶劑層壓黏著劑直至無溶劑層壓黏著劑在液態中為止。在一些實施例中,將一層混合黏著劑組合物施加於第一基材之表面,例如聚合物膜上。「膜」為在一個維度為2毫米(mm)或更小且在其他兩個維度均為1公分(cm)或更大的任何結構。聚合物膜為由單一聚合物或二或更多種聚合物之混合物製成的膜。此外,膜可為金屬化聚合物膜及箔。在一些實施例中,可固化黏著劑混合物中異氰酸酯組分與多元醇組分的重量比為1:1.5至2:1,且NCO指數為1.6至1。
在一些實施例中,在固化黏著劑之前,使第二基材的表面或膜與第一基材上的可固化黏著劑混合物的層接觸,以形成未固化複合層壓體。未固化層壓體可經受壓力,例如藉由穿過軋輥,該軋輥可經或可不經加熱。可加熱未固化之層壓體以加速固化反應。
根據本發明使用的適合之基材(例如,第一及第二基材)包含但不限於膜,諸如紙、編織及非編織織品、金屬箔、聚合物及金屬塗佈之聚合物。膜可選地具有上面用油墨印有影像的表面;油墨可與黏著劑組合物接觸。
層壓體可為黏合在一起之兩個基材,可為結合在一起之三個基材,或可為以黏著劑黏合在一起之多個基材。
一般而言,可在用於生產大量層壓產品之工業規模下進行使用本發明之無溶劑層壓黏著劑組合物黏合兩個基材。有利地,將兩種組分填充且儲存於單獨的容器中,諸如大桶(drum)或化工桶(hob bock)中,直至組分準備好使用為止。如前述,在施加黏著劑組合物之前,將兩種組分分離;且僅在施加黏著劑之前或立即在黏著劑之前為與彼此混合之兩種組分。在施加期間,藉助於饋料泵迫使組分自儲存容器中排出,且經由饋料線計量至混合設備中,諸如在工業生產中常用於混合雙組分黏著劑的彼等混合設備。舉例而言,可經由靜態混合器或藉助於動態混合器進行兩種組分之混合。當混合兩種組分時,注意確保兩種組分儘可能均勻混合。若兩種組分不佳地混合,則將存在與有利混合比之局部偏差,此可在使用黏著劑製成之所得產物之機械特性劣化方面具有影響。為在視覺上檢查混合品質,若兩種組分具有兩種不同顏色,則其可為有利的。當混合黏著劑具有均勻混合顏色而無可見條痕或污跡時,視為存在良好混合。控制及維持兩種組分之混合比對於達成黏著劑之所要目標效能為較佳的。
本揭示案之雙組分聚胺基甲酸酯黏著劑可用於所有類別之層壓體,包括例如:經層壓之膜對膜或膜對箔複合物或膜對紙;且黏著劑可用於需要三個效能位準的封裝應用中:「通用」、「中性能」及「高效能」層壓體。通常,最終封裝產品及其填充製程判定用於各種應用中之黏著劑材料類型。舉例而言,通用層壓體包含膜對膜或膜對紙複合物且一般用於封裝儲存於室溫下之乾燥食品。中等效能層壓體通常用於脂肪或酸性食品封裝,高達巴氏殺菌(pasteurization)溫度之溫度處理及箔層壓體。且,高效能層壓體通常用於蒸煮袋應用、熱灌裝、諸如高達140℃之高溫下的滅菌製程,製藥等。
實例
所有原料及數位油墨印刷膜列於表1中。
表1.實例中所用之原料
預聚物1:
材料名稱 | 供應商 | 特徵 |
ISONATE ™143L | The Dow Chemical Company | 液體MDI |
ISONATE 125M | The Dow Chemical Company | 固體MDI |
VORANOL ™232-034N | The Dow Chemical Company | 聚丙二醇 |
MOR-FREE ™L75-197 | The Dow Chemical Company | MDI預聚物 |
CR-5 ™ | The Dow Chemical Company | 共反應物,摻合物聚丙二醇 |
VORANOL ™CP-1055 | The Dow Chemical Company | 甘油引發丙氧基化聚醚三醇 |
MOR -FREE ™88-138 | The Dow Chemical Company | 助黏劑 |
CR-89 ™ | The Dow Chemical Company | 共反應物,摻合物聚醚多元醇 |
PACACEL ™L75-191 | The Dow Chemical Company | MDI預聚物 |
CR 88-141 | The Dow Chemical Company | 共反應物,摻合物聚酯多元醇及聚醚多元醇 |
MOR -FREE ™L75-164 | The Dow Chemical Company | MDI預聚物 |
C-411 | The Dow Chemical Company | 共反應物,摻合物聚酯多元醇及聚醚多元醇 |
芳族聚酯 | 酯交換聚酯多元醇 | |
C-33 | The Dow Chemical Company | 脂族異氰酸酯(HDI三聚物) |
數位印刷60 g BOPP | Kodak, NAA | PP膜 |
1,5密耳線性低密度聚乙烯(GF-19) | Berry Plastics Corp | PE膜 |
數位印刷48 g PET | Kodak, NAA | 聚對苯二甲酸乙二酯膜 |
2.25密耳EVOH coex LLDPE | 由來自Charter之 TC Transcontinental供應 | EVOH coex LLDPE膜 |
48 g PET | FilmQuest | 聚對苯二甲酸乙二酯膜 |
預聚物1之配方展示於下表2中。藉由首先將經乾燥之2L三口燒瓶吹掃至冷凝器、頂部混合器、熱電偶溫度控制器及氮氣鼓泡器而製備預聚物1。ISONATE
™125M及ISONATE
™143L接著在預溫熱至45℃之後加入VORANOL
™232-034N及VORANOL CP-1055多元醇。接著,在氮氣中持續鼓泡至少兩分鐘,使反應器逐漸加熱至78℃。在反應器溫度已維持在78℃下兩小時後,停止反應,且將產物倒入玻璃瓶中。預聚物1具有總重量11%之NCO%。
表2. NCO封端之聚胺甲酸酯預聚物之組成:
共反應物1:
材料 | 量(g) |
VORANOL ™CP 1055(多元醇) | 135.5 |
VORANOL ™232-034N(PPG) | 425.4 |
ISONATE ™125 M(固體MDI) | 314.6 |
ISONATE ™143L(液體MDI) | 124.5 |
總計 | 1000.0 |
設計NCO% | 11.5 |
藉由將表3中之組分使用高速混合器以1,800 rpm混合2分鐘來製備共反應物1。
表3. 共反應物1之組成:
預聚物2:
描述 | AMT(pbw) |
MOR -FREE ™88-138 | 8.25 |
酯交換聚酯多元醇 | 29.29 |
VORANOL™ CP 1055 | 62.46 |
總計 | 100.00 |
藉由將預聚物1與2重量%之C-33脂族聚異氰酸酯(以預聚物1之重量計)用高速混合器以1,800 rpm混合達2分鐘來製備預聚物2。
預聚物3係藉由將預聚物1與5重量%之C-33脂族聚異氰酸酯混合來製備
藉由將預聚物1與10重量%之C-33脂族聚異氰酸酯混合來製備預聚物4。
下表中之實例1係藉由使預聚物1與共反應物1在混合、塗佈、接著層壓後在室溫反應而製備。實例2係藉由使預聚物2與共反應物1在混合、塗佈、接著層壓後在室溫反應而製備。實例3係藉由使預聚物3與共反應物1在混合、塗佈、接著層壓後在室溫反應而製備。實例4係藉由使預聚物4與共反應物1在混合、塗佈、接著層壓後在室溫反應而製備。
比較實例1為MOR-FREE
™L75-164/C-411及比較實例2為PACACEL
™L75-191/CR 88-141。NCO%係根據ASTM D2572-70在環境溫度下藉由滴定方法確定。
本揭示案之雙組分聚胺基甲酸酯黏著劑之適用期係藉由測量黏度變化與固化時間在40℃下,具有20 rpm之心軸27之DV II Brookfield Viscometer。黏著劑之適用期定義為黏度之固化時間,其在混合黏著劑達到4000 mPa.s時達到混合黏度或固化時間。混合黏度在混合後且穩定於40℃後界定黏著劑之最低黏度
表4顯示本發明黏著劑之黏著劑之混合黏度、適用期(兩倍混合黏度之固化時間)。
表4 具有不同混合比率之層壓黏著劑預聚物1/共反應物1之適用期:
表5層壓黏著劑之適用期:
預聚物1/共反應物1混合比率 | 100/62.6 | 100/67.4 | 100/73.1 |
混合黏度mPa.s | 1625 | 1575 | 1550 |
在兩倍混合黏度的適用期(分鐘) | 28 | 27 | 27 |
在4000 mPa.s黏度的適用期(分鐘) | 33 | 33 | 33 |
樣本 | 實例1 | 實例2 | 實例3 | 實例4 | 比較實例1 | 比較實例2 |
混合黏度mPa.s | 1575 | 1600 | 1637 | 1525 | 1400 | 1525 |
在兩倍混合黏度的適用期(分鐘) | 27 | 27 | 27 | 29 | 27 | 28 |
在4000 mPa.s黏度的適用期(分鐘) | 33 | 33 | 33 | 37 | 39 | 37 |
如可見,在例如四次較高含量之脂族聚異氰酸酯導致可忽略性能增加時間更長固化時間。用數位油墨印刷之BOPP//GF-19及數位油墨印刷PET//EVOH-PE來評估透過手動層壓及前導層壓機(pilot-laminator)試驗兩者之黏著效能。在數位油墨印刷之BOPP//GF-19結構、150℉軋溫度及40 psi軋壓力下,以27 in/min速度用熱油手動層壓機進行手動層壓試驗。前導層壓機試驗在LABO-COMBI
™400層壓機上進行,可購自Nordmeccanica Group,在100 ft/min以數位油墨印刷PET//EVOH-PE、120℉軋溫度及100℉計量輥溫度可購得。
T-剝離黏合強度係在具有200 N荷重元之Thwing-Albert拉伸測試儀上使用1吋樣品條及10吋/分鐘速率固化1天、6天及14天後測量。對各層壓體樣品測試三個條帶,且記錄高黏合強度及平均黏合強度以及失效模式。對於膜撕裂、膜拉伸及油墨轉移(總或部分油墨轉移),重新報導;在其他失效模式(黏著劑轉移、黏著失效及黏著劑分離時),報導平均平均T-剝離黏合強度。典型故障模式包括:
AF-黏著劑失效(一次黏著);
AT-黏著劑轉移(二次黏著);
AS-黏著劑破裂(黏著劑之內聚失效);
FT-膜撕裂(破壞黏合)。
IT-全部油墨轉移。
PIT-部分油墨轉移。
表6. 印刷BOPP/GF-19層壓體中之不同NCO指數之預聚物1/共反應物1之黏合:橙色、粉紅色、藍色之不同顏色印刷區域:
表7. 實例1及實例2黏著劑在印刷BOPP/GF-19層壓體中之黏合強度比較:橙色、粉紅色、藍色之不同顏色印刷區域:
表8. 實例2與比較實例2 (PACACEL L75-191/CR 88-141)在不同色彩印刷區域中之數位印刷PET//EVOH-PE結構中比較之黏合強度:
NCO 指數1.2 | NCO 指數1.3 | NCO 指數1.4 | |
1 天黏合強度 | |||
橙色 | 276 | 452 | 389 |
標準 | 4 | 58 | 24 |
失效 | AT,無明顯油墨轉移。 | 油墨轉移/FT | 油墨轉移/FT |
粉紅色 | 511 | 597 | 560 |
標準 | 48 | 75 | 75 |
油墨轉移/FT | 油墨轉移/FT | 油墨轉移/FT | |
藍色 | 609 | 458 | 383 |
標準 | 95 | 26 | 12 |
油墨轉移/Ft | 油墨轉移 | 油墨轉移/FT | |
6 天黏合強度 | |||
橙色 | 275 | 374 | 315 |
標準 | 20 | 45 | 12 |
失效 | 輕微PIT | 輕微,PIT | 輕微,PIT |
粉紅色 | 535 | 535 | 481 |
標準 | 21 | 80 | 33 |
失效 | PIT/FT | PIT/FT | PIT/FT |
藍色 | 493 | 357 | 359 |
標準 | 79 | 8 | 20 |
失效 | PIT | PIT/FT | PIT |
14 天黏合強度 | |||
橙色 | 314 | 310 | 未測試 |
標準 | 23 | 40 | |
失效 | 輕微,PIT | 輕微,PIT | |
粉紅色 | 505 | 471 | |
標準 | 12 | 6.2 | |
失效 | PIT/FT | PIT | |
藍色 | 447 | 374 | |
標準 | 96 | 16 | |
失效 | PIT/FT | PIT |
實例2 | 實例1 | |
橙色 | 511 | 374 |
標準 | 69 | 45 |
失效 | PIT,FT | 輕微,PIT |
粉紅色 | 666 | 535 |
標準 | 147 | 80 |
PIT,FT | PIT/FT | |
藍色 | 376 | 357 |
標準 | 95 | 8 |
PIT,FT | PIT/FT |
藍色 | 黑色 | 橙色 | 白色 | |
實例2 | 512 | 522 | 313 | 426 |
標準 | 33 | 4 | 4 | 67 |
失效 | AS/FT | AS/FT | AS/FT | AS/FT |
比較實例2 | 185 | 135 | 134 | 307 |
標準 | 35 | 31 | 38 | 42 |
失效 | AS | AS | PIT | FT |
在固化9天後,將層壓體熱封在320℉、40 psi壓力及1.0秒密封時間。熱封抗性藉由將一個嵌入寬帶拉動,以12 in/min的拉力速度為1.5吋。下文報導三份資料之平均值。
表9. 實例2黏著劑與比較實例1在不同色彩印刷區域中之數位印刷PET//EVOH-PE結構中的熱封抗性比較:
熱封 | ||||
藍色 | 黑色 | 橙色 | 白色 | |
L75-164/C-411-100/40 | 3949 | 3471 | 3801 | 5077 |
標準 | 299 | 41 | 293 | 670 |
失效 | PET FT,PE應力 | 脫層,PE應力 | 脫層 | PET FT,PE應力 |
實例2 | 4369 | 3919 | 3717 | 5106 |
標準 | 56 | 88 | 121 | 419 |
失效 | 全膜snape | 全膜snape | 脫層,PE FT | PET FT, snape |
在樣品在25℃、50%相對濕度下固化2天及3天且藉由PAA之二氮雜交來測試PAA衰減,使得PAA之濃度可經確定著色金屬黴素。在氯化物溶液中對測試溶液中存在的芳族胺進行重氮化,且隨後與N-(1-萘基)-乙二胺二鹽酸鹽偶聯,得到紫色溶液。藉由固定相萃取管柱來富集顏色。在550 nm的波長下以光度方式測定PAA的量。
如上文所述製備層壓體。袋子係使用上述層壓體藉由自層壓體之中間部分切割約30.5 cm × 16.5 cm寬的條帶而形成。將各條帶摺疊以形成14 cm × 16.3 cm表面積,且沿摺疊帶之各開口縱向邊緣熱封約1 cm的邊緣,以形成內表面積為14 cm × 14.3 cm的袋子。用於熱封邊緣之設備為Brugger HSG-C熱封機。層壓體之密封條件為1.3至1.5巴及130至160℃。
將各自內表面積為約14.0 cm × 14.3 cm的四個袋子(兩個空白及兩個測試袋子)用於實例的各膜。在形成個別層壓體兩天後形成各袋子。在形成袋子之前,將層壓體儲存於環境氛圍的室溫下。
為進行測試,各袋子填充有 100 ml之3%乙酸水溶液,用作食品模擬物。小袋在空氣循環烘箱中於70℃儲存兩小時。在將小袋冷卻至室溫後,將100 ml測試溶液與12.5 ml鹽酸溶液(1N)及2.5 ml亞硝酸鈉溶液混合(每100 ml溶液0.5 g),並使內容物反應十分鐘。磺酸銨(5 ml;添加2.5 g/100 ml水溶液),並使其反應十分鐘。偶合試劑(5 ml;添加每100 g水溶液之N-(1 -萘基)-乙二胺二鹽酸鹽之1 g),且使其反應2小時。在每次添加後,將所得混合物用玻璃棒攪拌。對於「空白袋子」,除亞硝酸鈉外,將100 ml之測試溶液與上述衍生試劑混合在一起。
經由ODS固相萃取管柱(ODS逆相,C18封端)藉由溶離來濃縮測試溶液,且使用分光光度計(購自Perkin Elmer的Spectrophotometer Lambda)在550 nm下測量消光係數。
管柱使用第一、10 ml甲醇、接著10 ml溶離溶劑,且接著10 ml水性鹽酸溶液(0.1 N)。使用預先用3 ml鹽酸水溶液(0.1 N)沖洗兩次的玻璃燒杯將各衍生樣本添加至管柱中。該管柱經受真空(約2.5 mm Hg)拉,以移除所有沖洗一分鐘。隨後將5 ml溶離溶劑添加至管柱,且重複此步驟直至收集10 ml洗提液。
為測定PAA之濃度,對照試劑空白溶液及一系列平行處理的已知濃度苯胺鹽酸鹽的標準品,在5 cm的比色皿中,在550 nm下測量反應產物之消光係數。
如在PAA衰減下表中可見,在實例2中顯著較比較實例1更快。
表10. 新黏著劑及MOR-FREE
™L75-164/C-411之PAA衰減比較:
結構 | 實例2 | 比較實例1 (MOR-FREE ™L75-164/C-411) |
2天固化後(ppb) | 0.307 | 4.628 |
3天固化後 | 0.198 | 3.560 |
無
無
Claims (10)
- 一種雙組分無溶劑黏著劑組合物,其包含: a. 至少一種異氰酸酯組分,其包含異氰酸酯預聚物及脂族聚異氰酸酯,該異氰酸酯預聚物進一步包含異氰酸酯與聚伸烷基二醇聚合物之反應產物, b. 至少一種多元醇組分,其包含由芳族聚酯多元醇與蓖麻油反應製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑。
- 一種塗佈膜,其包含: a. 基材; b. 雙組分無溶劑黏著劑組合物,其中該雙組分無溶劑黏著劑設置於該基材之表面上之至少一部分上,且其中該雙組分無溶劑黏著劑組合物包含: i. 至少一種異氰酸酯組分,其包含異氰酸酯之反應產物,且脂族聚異氰酸酯; ii. 至少一種多元醇組分,其包含由芳族聚酯多元醇及蓖麻油製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑。
- 一種層壓體結構,其包含: a. 第一基材 b. 第二基材 c. 雙組分無溶劑黏著劑組合物,其中該雙組分無溶劑黏著劑設置於該第一基材與第二基材之間,且其中該雙組分無溶劑黏著劑組合物包含: i. 至少一種異氰酸酯組分,其包含異氰酸酯預聚物及脂族聚異氰酸酯,該異氰酸酯預聚物進一步包含異氰酸酯與聚伸烷基二醇聚合物之反應產物, ii. 至少一種多元醇組分,其包含由aa芳族聚酯多元醇及蓖麻油製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑。
- 如請求項1之雙組分無溶劑黏著劑組合物或如請求項2之塗佈膜,其中以該異氰酸酯組分之重量計,該脂族聚異氰酸酯之量係0.1至5重量百分比。
- 如前述請求項中之任一項,其中該天然油係蓖麻油。
- 如請求項3之層壓體結構,其中該黏合強度高於200 g/in。
- 如請求項3之層壓體結構,其中在固化3天後,該PAA濃度低於0.200 ppb。
- 如請求項3之層壓體結構,其中該熱封抗性黏合強度係介於3,000與6,000 g/in之間。
- 如前述請求項中之任一項,其中以該至少一種多元醇組分之重量計,該磷酸酯助黏劑之量係0.1至20重量百分比。
- 一種用於形成層壓結構之方法,其包含以下步驟: a. 提供至少一種異氰酸酯組分,其包含異氰酸酯預聚物及脂族聚異氰酸酯,該異氰酸酯預聚物進一步包含異氰酸酯與聚伸烷基二醇聚合物之反應產物, b. 提供至少一種多元醇組分,其包含由芳族聚酯多元醇及蓖麻油製成之酯交換聚酯多元醇、聚丙二醇及磷酸酯助黏劑; c. 混合至少一種異氰酸酯組分及至少一種多元醇組分以形成無溶劑黏著劑組合物; d. 將一層無溶劑黏著劑組合物施加至第一基材之表面; e. 藉由層壓機使該黏著劑之層與該第二基材之表面接觸,以形成層壓結構;及 f. 固化該黏著劑組合物以將該第一基材及該第二基材之該等表面黏合在一起。
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