ZA200103578B - Hot-melt adhesive compositions. - Google Patents
Hot-melt adhesive compositions. Download PDFInfo
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- ZA200103578B ZA200103578B ZA200103578A ZA200103578A ZA200103578B ZA 200103578 B ZA200103578 B ZA 200103578B ZA 200103578 A ZA200103578 A ZA 200103578A ZA 200103578 A ZA200103578 A ZA 200103578A ZA 200103578 B ZA200103578 B ZA 200103578B
- Authority
- ZA
- South Africa
- Prior art keywords
- hydroxy
- hot
- melt adhesive
- och
- functionalized polyether
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 46
- 239000004831 Hot glue Substances 0.000 title claims description 40
- 229920000570 polyether Polymers 0.000 claims description 33
- -1 hydroxy- Chemical class 0.000 claims description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 25
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 9
- 150000001412 amines Chemical group 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Chemical group 0.000 claims description 6
- 229910052739 hydrogen Chemical group 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 229940124530 sulfonamide Drugs 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 150000004662 dithiols Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- ZXKINMCYCKHYFR-UHFFFAOYSA-N aminooxidanide Chemical compound [O-]N ZXKINMCYCKHYFR-UHFFFAOYSA-N 0.000 claims 2
- 229930185605 Bisphenol Natural products 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 150000003456 sulfonamides Chemical class 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 13
- 239000000758 substrate Substances 0.000 description 11
- 239000001993 wax Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000000007 visual effect Effects 0.000 description 7
- 229920005601 base polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000009969 flowable effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- DNUPYEDSAQDUSO-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl benzoate Chemical compound OCCOCCOC(=O)C1=CC=CC=C1 DNUPYEDSAQDUSO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 235000012791 bagels Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WCLDITPGPXSPGV-UHFFFAOYSA-N tricamba Chemical compound COC1=C(Cl)C=C(Cl)C(Cl)=C1C(O)=O WCLDITPGPXSPGV-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 101100519432 Rattus norvegicus Pdzd2 gene Proteins 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- HGVPOWOAHALJHA-UHFFFAOYSA-N ethene;methyl prop-2-enoate Chemical compound C=C.COC(=O)C=C HGVPOWOAHALJHA-UHFFFAOYSA-N 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 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 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KKPOOQIUNLRSCM-UHFFFAOYSA-N n,n'-bis(3-hydroxyphenyl)hexanediamide Chemical compound OC1=CC=CC(NC(=O)CCCCC(=O)NC=2C=C(O)C=CC=2)=C1 KKPOOQIUNLRSCM-UHFFFAOYSA-N 0.000 description 1
- VWYIWJWRJAKRFB-UHFFFAOYSA-N n,n'-bis(3-hydroxyphenyl)pentanediamide Chemical compound OC1=CC=CC(NC(=O)CCCC(=O)NC=2C=C(O)C=CC=2)=C1 VWYIWJWRJAKRFB-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- SYDJVRWZOWPNNO-UHFFFAOYSA-N sucrose-benzoate Natural products OCC1OC(OC2(COC(=O)c3ccccc3)OC(CO)C(O)C2O)C(O)C(O)C1O SYDJVRWZOWPNNO-UHFFFAOYSA-N 0.000 description 1
- 125000004962 sulfoxyl group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- NNKSCESTDPOUKU-UHFFFAOYSA-N trioxidanylbenzene Chemical compound OOOC1=CC=CC=C1 NNKSCESTDPOUKU-UHFFFAOYSA-N 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
Description
gt] WO 00/26319 PCT/US99/25613
HOT-MELT ADHESIVE COMPOSITIONS : The present invention relates to hot-melt adhesive compositions.
Hot-melt adhesives are adhesives with a thermoplastic character, that is, they flow at an elevated temperature and are solid at a lower temperature. Such adhesives are well-known and are typically applied by extruding the heated adhesive between two articles to be bonded and then allowing the adhesive to cool. As the adhesive cools, it forms a more rigid bond between the articles. See generally, A.J. Kinloch, Adhesion and Adhesives
Science and Technology, Chapman and Hall (London, 1990), pages 175-176.
The major advantage of hot-melt adhesives is the lack of a carrier fluid which eliminates the need for drying the adhesive film once it is applied to the substrate. This elimination of the drying step overcomes hazards associated with solvent usage and also allows for faster production line speeds and lower costs. The ability to modify the properties of the adhesive composition with the addition of various resins, oils, waxes and other additives, makes hot-melt adhesives commercially useful in a wide variety of applications.
U.S. Patents 5,574,076 and 5,583,187 describe hot-melt adhesive compositions comprising thermoplastic methyiol polyesters as the base polymer or main functional adhesive material. These polyesters are prepared from the reaction of at least one dicarboxylic acid with a diglycidyl ether, a diglycidy! ester or a combination thereof.
WO 97/23564 discloses compositions of (1) a polysaccharide, a modified polysaccharide, or a naturally-occurring fiber or particulate filler and (2) a thermoplastic hydroxy-functional polyether derived from monomers containing 1 or more epoxy groups are ’ suitable for, among other things, adhesives.
It would be desirable to provide a hot-melt adhesive composition wherein the base polymer is a hydroxy functionalized polymer which does not contain ester linkages labile to hydrolytic degradation.
In one aspect, the present invention is the use as a hot melt adhesive, of a composition comprising a thermoplastic hydroxy-functionalized polyether which is essentially free of ester linkages labile to hydrolytic degradation.
In another aspect, the present invention is a hot-melt adhesive composition comprising a thermoplastic hydroxy-functionalized polyether which is not the reaction product of a dicarboxylic acid with a diglycidyl ether, optionally in combination with a compatible tackifier, a compatible plasticizer and a compatible diluent.
In another aspect, the present invention is a method of adhering a first substrate to at least one other substrate which may be of the same or different material as the first substrate, comprising contacting the first substrate and the at least one other substrate with an effective amount of a hot-melt adhesive composition comprising a thermoplastic hydroxy-functionalized polyether which is not the reaction product of a dicarboxylic acid with a diglycidyl ether, at a temperature and pressure sufficient to flow the hot-melt adhesive composition onto a portion of each substrate; bringing adjacent portions of adhesive-coated substrates into contact with each other and applying sufficient pressure to form a joint (which may be a laminate) and cooling the joint to resolidify the hot-melt adhesive composition.
The hot-melt adhesive compositions of the present invention may be employed in a wide variety of uses as are known in the art, such as, for example, packaging and carton sealing operations, bookbinding operations, metal bonding assembly such as in automotive or appliance applications, and assembly of wood articles. They may also be employed for laminating tissue and/or screen-reinforced tissue layers such as are used in individual or roll use applications as in wipers, paper towel, toilet tissue and other consumer or industrial end uses. When formulated with plasticizers, the resultant adhesives may be useful in the assembly or construction of various disposable articles, such as sanitary napkins, disposable diapers, hospital gowns, and bed pads. These adhesives may also be usetul for the assembly of disposable articles using spray or multi-line construction techniques wherein at least one flexible film substrate is bonded to at least one tissue, non- woven, polyolefin or other flexible polymeric film substrate. In addition, the adhesives may also be useful in the bonding of elastic materials to polyethylene, polypropylene or non- woven substrate so as, for example, to impart elongation resistant gathers thereto. The adhesives may also be useful in less demanding disposable construction applications such : as for end or perimeter sealing.
Preferably, the base polymer of the hot-melt adhesive composition of the present invention comprises any one of the following hydroxy-functional polyethers: (1) poly(hydroxy ethers) having repeating units represented by the formula:
OH omen nent I & n
D2.
\, : (2) poly(hydroxy amino ethers) having repeating units represented by the formula: oH oH
O— CHz-G— CH= A—CHz-C—CH,-0—B II
R R n (3) poly(hydroxy ether sulfonamides) having repeating units represented by the formula:
SE
OCH; COHN —S—R=-S— NCH, CCH, 0B IIIa
R 0 oO R or es ‘a
OCH, (CH NCH, CCH 0B IIIb
R SO; R : 13 : (4) poly(hydroxy ether sulfides) having repeating units represented by the formula:
OH OH ocH,cH, SRASCH,dCH,08 Iv
R R
(5) poly(hydroxy amide ethers) having repeating units represented independently by any one . of the formulas: i mah : OCH; CCHa0RT — NHC—R’CNHAT va
R n
IN i i
OCH CCH, OAT— CNH—R NHCAE vb
R n or no
OCH; (CHOAL CHAE Ve ;
R n or (6) poly(hydroxy amide ethers) having repeating units represented by any one of the formulas:
OH 0 0 OH
OCH, CCH, OAT — NHU— R2CNH— Ar—oCitCH;0nx i a ’
J R n
OH 0 0 OH
OCH, CCH, 0AT — UNH_R? NHC — Ax —OCH,CCH;00x VIb ,
R ® n or
OH 0 OH
OCH, CHORE — Cov — x — DCH CHP Vic ;
R R n wherein R is alkyl or hydrogen; R' and R® are independently a substituted or an unsubstituted alkyl or aryl wherein the substituent(s) is a monovalent moiety which is inert in the reactions used to prepare the hydroxy-functionalized polyethers, such as cyano, halo, amido, hydroxy and hydroxyalkyl; Ar is a divalent aromatic moiety; A is a diamino moiety or a combination of different amine moieties; B, R? and R* are independently a divalent organic moiety which is predominantly hydrocarbylene; and n is an integer from 5 to 1000.
The term "predominantly hydrocarbylene" means a divalent radical which is predominantly hydrocarbon, but which optionally contains a minor amount of heteroatomic moiety such as oxygen, sulfur, imino, sulfonyl, and sulfoxyl.
In the preferred embodiment of the present invention, R is hydrogen; R' and
R® are independently methyl, ethyl, propyl, butyl, 2-hydroxyethyl or phenyl; Ar, B, R* and R* are independently 1,3-phenylene, 1,4-phenylene, sulfonyldiphenylene, oxydiphenylene,
iY WO 00126319 PCT/US99/25613 thiodiphenylene or isopropylidenediphenylene; A is 2-hydroxyethylimino, 2-hydroxypropylimino, piperazenyl or N,N’-bis(2-hydroxyethyl)-1,2-ethylenediimino.
The hydroxy-functional polyethers having repeating units represented by
Formula | are prepared, for example, by contacting a diglycidyl ether or a combination of diglycidyl ethers with a dihydric phenol or combination of dihydric phenols using the process described in U.S. Patent 5,164,472. Alternatively, the poly(hydroxy ethers) are obtained by allowing a dihydric phenol or a combination of dihydric phenols to react with an epihalohydrin by the process described by Reinking, Barnabeo, and Hale in the Journal of Applied Polymer
Science, Volume 7, page 2135 (1963). Preferably the poly(hydroxy ether of Formula | is a poly(hydroxy phenoxyether)
The polyetheramines having repeating units represented by Formula ll are prepared by contacting one or more of the diglycidyl ethers of a dihydric phenol with a difunctional amine (an amine having two amine hydrogens) under conditions sufficient to cause the amine moieties to react with epoxy moieties to form a polymer backbone having amine linkages, ether linkages and pendant hydroxyl moieties. These polyetheramines are described in U.S. Patent 5,275,853. The polyetheramines can also be prepared by contacting a diglycidyl ether or an epihalohydrin with a difunctional amine.
The hydroxy-functional poly(ether sulfonamides) having repeating units represented by Formulas lila and lib are prepared, for example, by polymerizing an N,N'-dialkyl or N,N'-diaryldisulfonamide with a diglycidyl ether as described in U.S. Patent 5,149,768. ; The hydroxy-functional polyethers having repeating units represented by
Formula IV are prepared by reacting a diglycidyl ether and a dithiol as described in . U.S. Patents 4,048,141 and 4,171,420.
The poly(hydroxy amide ethers) represented by Formula V are prepared by contacting a bis(hydroxyphenylamido)alkane or arene, or a combination of 2 or more of these compounds, such as N,N'-bis(3-hydroxyphenyl)adipamide or N,N'-bis(3- hydroxyphenyl)glutaramide, with an epihalohydrin as described in U.S. Patent 5,134,218.
The poly(hydroxy amide ethers) represented by Formula Vi are preferably prepared by contacting an N,N'-bis(hydroxyphenylamido)alkane or arene with a diglycidyl ether as described in U.S. Patents 5,089,588 and 5,143,998.
The hydroxy-functional polyethers available from Phenoxy Associates, Inc. are also suitable for use as the base polymer in the practice of the present invention. These polymers and the process for preparing them are described in U.S. Patent 3,305,528 and 5,401,814.
Optionally, the hydroxy-functionalized polyether has a multimodal molecular weight distribution. The term "multimodal molecular weight distribution," as used herein, means that the base polymer has a molecular weight distribution determined by size exclusion chromatography that contains more than one peak value. The base polymer of this invention also can be a mixture of hydroxy-functionalized polyethers of the same or different primary structures with different molecular weights.
The tackifiers which can be employed in the practice of the present invention for preparing the hot-melt adhesive composition include terpene phenolic resins and benzoates, such as, for example, sucrose benzoate.
The amount of the tackifier most advantageously incorporated into the hydroxy-functionalized polyether is dependent on a variety of factors including the specific components used to form the hot-melt adhesive composition as well as its desired : 15 properties. Typical amounts can range from 0 to 90 weight percent based on the weight of the total composition. Generally, the hot-melt adhesive composition comprises at least about 0.1, preferably about 1, more preferably about 2, and most preferably about 4 weight percent and less than about 80, preferably about 60, more preferably about 50 weight percent of the tackifier based on the total weight of the composition.
The plasticizers which can be employed in the practice of the present invention for preparing the hot-melt adhesive composition include phthalate plasticizers, such as dioctyl phthalate; liquid polyesters such as Dynacol 720 from Hiils; benzoate : plasticizers such as diethylene glycol dibenzoate (for example, Benzofiex 50 available from
Velsicol) and diethylene glycol benzoate where the mole fraction of hydroxyl groups which } have been esterified ranges from 0.5 to 0.95 (for example, Benzofiex 2-45 High Hydroxy from Velsicol); phosphate plasticizer such as t-butylpheny! diphenyl phosphate (for example,
Santicizer 164 commercially available from Monsanto); polyalkylene glycols such as the phenyi ether of poly(ethylene glycol) (for example, Pycal 94 available commercially from (Cl); as well as liquid rosin derivatives having Ring and Ball melting points below about 60°C, such as the methyl ester of hydrogenated rosin (for example, Hercolyn D from Hercules); as well as vegetable and animal oils such as glyceryl esters of fatty acids and polymerization products thereof. If used, the plasticizer is generally present in amounts up to about 90 percent by weight, preferably 10 to 40 percent by weight.
4 WO 00/26319 PCT/US99/25613
Other applications conventionally employing hot-melt adhesives may require the use of wax diluents in order to reduce the melt viscosity or cohesive characteristics of the ’ hot-melt adhesive composition without appreciably decreasing their adhesive bonding characteristics. These waxes are often used in adhesives which do not exhibit pressure sensitive properties. If present, the waxes are used in an amount up to 90 percent by weight, preferably 5 to 35 percent by weight. Suitable waxes include N-(2-hydroxyethyl)-12- hydroxystearamanide wax, hydrogenated castor oil, oxidized synthetic waxes, poly(ethylene oxide) having a weight average molecular weight of above about 1000 and functionalized synthetic waxes such as carbonyl-containing Escomer H101 from Exxon. Mixtures of one or more of such materials may be employed.
It should be recognized that some adhesive formulations described herein may contain both wax and plasticizer components so that the presence of one or the other is not mutually exclusive.
Other optional additives may be incorporated into the hot-melt adhesive " ~ 15 compositions in order to modify certain properties thereof. Among these additives are - antioxidants or stabilizers, colorants such as titanium dioxide; and fillers, such as talc and - clay. There may also be present in the adhesive composition certain thermoplastic and/or hydrophilic polymers as are conventionally used in this class of adhesive to impart flexibility, toughness, strength and/or water sensitivity. Suitable thermoplastic polymers include ethylene vinyl acetate, ethylene acrylic acid, ethylene methyl acrylate, and ethylene n-butyl acrylate copolymers containing 12 to 50 percent vinyl or acrylate monomers. Suitable . hydrophilic polymers include polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl methyl ether, poly(ethylene oxide), and polyvinyl pyrrolidone. . Among the applicable stabilizers or antioxidants which may be included herein are high molecular weight hindered phenols such as sulfur and phosphorus-containing phenols.
In general, the hot-melt adhesive composition of the present invention can be prepared using techniques known in the art. An exemplary procedure involves placing approximately 40 percent of the total tackifying resin concentration with all the polymer, wax, plasticizers and stabilizers in a jacketed mixing kettle, preferably in a jacketed heavy duty mixer, which is equipped with rotors and thereupon raising the temperature to a range of up to about 190°C. After the resin has melted, the temperature is lowered to 150°C to 165°C.
Mixing and heating are continued until a smooth, homogeneous mass is obtained whereupon the remainder of the tackifying resin is thoroughly and uniformly admixed therewith.
Techniques for melt-blending of a polymer with additives of all types are known in the art and can typically be used in the practice of this invention. Typically, in a melt blending operation useful in the practice of the present invention, the hydroxy-functionalized polyether is heated to a temperature sufficient to form a polymer melt and combined with the desired amount of the other components in a suitable mixer, such as an extruder, a Banbury mixer, a Brabender mixer, or a continuous mixer. A physical mixture of the different components may also be heated simuitaneously and blended using one of the previously mentioned mixers.
In the practice of the present invention, the melt blending is preferably carried out in the absence of air, as for example, in the presence of an inert gas, such as argon, neon, or nitrogen. However, the present invention may be practiced in the presence of air.
The melt blending operation can be conducted in a batch or discontinuous fashion but is more preferably conducted in a continuous fashion in one or more processing zones such as in an extruder from which air is largely or completely excluded. The extrusion can be conducted in one zone or step or in a plurality of reaction zones in series or parallel.
A hydroxy-functionalized polyether melt containing the other hot-melt adhesive components may also be formed by reactive melt processing in which the other components are initially dispersed in a liquid or solid monomer or cross-linking agent which will form or be used to form the hot-melt adhesive composition. This dispersion can be injected into a polymer melt containing one or more polymers in an extruder or other mixing device. The injected liquid may result in new polymer or in chain extension, grafting or even cross-linking of the polymer initially in the melt.
The hot-melt adhesive composition of the present invention can also be formed by mixing the monomer used in forming the hydroxy-functionalized polyether with the other components in the presence or absence of a solvent and subsequently polymerizing the monomer to form the hydroxy-functionalized polyether component of the composition.
After polymerization, any solvent that is used is removed by conventional means.
Alternatively, the polymer may be granulated and dry-mixed with the other components of the hot-melt adhesive composition and the composition heated in a mixer until the hydroxy-functionalized polyether is melted to form a flowable mixture. This flowable : mixture can then be subjected to a shear in a mixer sufficient to form the desired
0 wo 00/26319 PCT/US99/25613 composition. The hydroxy-functionalized polyether may also be heated in the mixer to form a flowable mixture prior to the addition of the other components of the hot-melt adhesive composition. The hydroxy-functionalized polyether and the other components are then subjected to a shear sufficient to form the desired hot-melt adhesive composition.
The following working examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and : percentages are by weight.
Lap shear test specimens were prepared by compression molding a 1 inch (2.54 cm) by 0.5 inch (1.27 cm) film of the selected hydroxy-functional polyethers between : 0.062 inch (1.575 mm) thick cold-rolled steel test plates (1” (2.54 cm) x 4” (10.2 cm) x 0.062” (1.575 mm), 1/2 hard, ground one side), obtained from Q-Panel, Cleveland, Ohio and used without surface cleaning or treatment. Molding temperature was 100°C above the measured glass transition temperature of the respective polymer, and the following molding pressure ” 15 and time profile was used. The samples were equilibrated in the press for 10 minutes at 5000 psi (3.447 x 10’ Pa) at the molding temperature, then for 4 minutes at 80,000 psi ) (5.516 x 10° Pa), and the press was allowed to cool to 120%F (502C) under 80,000 psi (5.516 x 10° Pa) force for 5 minutes. The samples were removed and testing using an Instron testing frame at a crosshead speed of 0.05 inches (0.13 cm) per minute, following ASTM test method D-1002.
Test results are shown in Table | below. Lap Shear Strength data in psi are : converted to pascal by multiplying by 6.894757 x 10° and rounding. in the Failure Mode observation column, AF denotes visual observation of apparent adhesive failure, CF denotes . apparent cohesive failure, and %CF the apparent percent of cohesive failure in tests where there was apparent partial cohesive failure.
Table | £
S
Failure Mode S
Structure lps Papin) | Visual Observation N : <4 fe } 2835 1.955 40% CF
AT J
! 3 “ 3147 2.170 AF ? Bene Wi<asY
Lo a d 4 3117 2.1489 AF 3022 2.084 50% CF i Dl OC ~ [Op 0
OH oH n & wr bh
I] a @ -
Table | (continued) <
Example Struct | Pa (x10) | Visual Observation e i’ cure | pi |pagao 2
Saf 3067 2.115 CF °
Fem sURY, +]
OH on | ¥
CH, ca, 7 Se¥ 28296 1.948 30% CF
OH - OH n
AF
=] pees =
Tv
OH
J 10% CF
Peg CL J 1.808
OH
1679 1.158 AF oo 3 oY o a 1 OH n g =
IN; a bd
Table { (continued)
EE a rr :
E | Struct | Pa (x10) | Visual Ob ti H xample ructure psi | Pa (x10" isual Observation g . . 0 w
Bagel oY 2039 | 2.026 50% CF °
OH AN n 3483 2.401 fe NN”
OH OH
OHJ)n 3773 2.601 . i” “ol
I NS
! n 14 )
Pp 3389 2.337 AF
H
A SPN ed — fc ~~ J ars n : Paey ia NN” 2881 1.986 50% CF
OH OH N oi) n 3 a [5.2] 3 .
N a i - . nn
-
Table | (continued) g }
Lap Shear Strength g
Example Structure | Failure Mode ES : | si | Pa (x10) | visual Observation 2 " ial uc ) 964 50% CF oH n 17 : 397 0.274 70% CF oO ped 1
N_/ JeManue™ 200 [8113 H 1) on 9 ! OH
H
Da Jeans 2212 AF
JT n/ dptanms™ 600 on H 09 a) n
[1] oo oth 5077 CF [+11] H © n q a wn 3
IN
2 o
Table 1 (continued) < : S
Example Structure Lap Shear Strength Visual Observation s
Psi | Pago) | 2
Nd > ior 20 BeaeUil aaa 4128 | 2846 30% CF
OH OH © a 21 “ a o
Peg Ne 4314 2.974 CF
JT Le}
CH OH n - 22 0 0 > Aa 3716 2.562 CF ls H i
OH H © n 0 0 23 . <r H 3616 2.493 AF
OH R] ? n g a g > = -« ' .
Sa £ [o] .
Table | (continued) g
S
Example Lap Shear Strength Failure Mode 2 ' Structure Psi Pa x10" Visual Observation < 24 Bagel 3288 2.67 AF
OH
2958 10% CF
H 0 oY 0 i
OH 0H n ' 0 fo AA 1616 1.114 AF ! aa vo “i
CH OH a - 30% CF 27 OC Q 2578 1.777 27 H ©
OH H . ys 2d ol,
Ls] 9 as g
IN}
Claims (11)
- CLAIMS:: 1. A hot-melt adhesive composition comprising a thermoplastic hydroxy- functionalized polyether which is not the reaction product of a dicarboxylic acid with a diglycidyl ether, optionally in combination with a compatible tackifier, a compatible plasticizer and a compatible diluent.
- 2. The hot-melt adhesive composition of Claim 1 wherein the hydroxy- : functionalized polyether has a multimodal molecular weight distribution or is a mixture of two or more hydroxy-functionalized polyethers having different molecular weights.
- 3. The hot-melt adhesive composition of Claim 1 wherein the hydroxy- functionalized polyether is a poly(hydroxy ether) having repeating units represented by the formula: oH O—CHy-C—CHz-0—B I R n wherein B is a divalent organic moiety which is predominantly hydrocarbylene, R is alkyl or hydrogen, and n is an integer from 5 to 1000.
- 4, The hot-melt adhesive composition of Claim 3 wherein the hydroxy- functionalized polyether is prepared by the reaction of a diglycidylether or epihalohydrin with a bisphenol.
- 5. The hot-melt adhesive composition of Claim 1 wherein the hydroxy- functionalized polyether is a poly(hydroxy amino ether) having repeating units represented by the formula: of oH O— CHy-C— CHp-A—CHp=C—CH,-0—B II R R n wherein A is a diamino moiety or a combination of different amine moieties; B is a divalent organic moiety which is predominantly hydrocarbylene; R is alkyl or hydrogen; and n is an integer from 5 to 1000.\ . $ WO 00/26319 PCT/US99/25613
- 6. The hot-melt adhesive composition of Claim 5 wherein the hydroxy- functionalized polyether is prepared by the reaction of a diglycidyl ether with a difunctional amine.
- 7. The hot-melt adhesive composition of Claim 1 wherein the hydroxy- functionalized polyether is a hydroxy-functional poly(hydroxy ether sulfonamide) having repeating units represented by any one of the formulas: A I OCH, CCHaN—S— RE-S— NCH, CCH OB IIIa R O O R or OCH, CCH; NCH CCH,0B IIIb R SO; R 13 ] wherein Ris hydrogen or alkyl, R' and R’are independently a substituted or an unsubstituted alkyl or aryl wherein the substituent(s) is a monovalent moiety which is inert in the reactions used to prepare the hydroxy-functionalized polyether; B and R? are independently a divalent organic moiety which is predominantly hydrocarbylene, and n is an integer from 5 to 1000.
- 8. The hot-melt adhesive of Claim 7 wherein the hydroxy-functionalized polyether is prepared by the reaction of a diglycidyl ether and a difunctional sulfonamide. . 15
- 9. The hot-melt adhesive of Claim 1 wherein the hydroxy-functionalized polyether has repeating units represented by the formula: . OH OH dc, srAscH OCH,CCH,SR"SCH,CCH,0 Iv R R n wherein R is hydrogen or alkyl, R* and B are independently a divalent organic moiety which is predominantly hydrocarbylene and n is an integer of 5 to 1000.
- 10. The hot-melt adhesive of Claim 9 wherein the hydroxy-functionalized polyether is prepared by the reaction of a diglycidyl ether and a dithiol.
- 11. The hot-melt adhesive of Claim 3 wherein the hydroxy-functionalized polyether is a poly(hydroxy amide ether) having repeating units represented independently by any one of the formulas: mtd OCH, CCH 0AT — NHC —R’CNHAT va R n NI I OCHZCCH;0Az— CNH—R NHCAY vb, R n or Lo OCH, CCH 0AX CNHAX Vc ; R n or a poly(hydroxy amide ether) having repeating units represented by any one of the formulas: in 0 OCH;CCHz0Ar —NHC—R’ Cut ar — OCH CCR; 0B via R R n . OH 0) 0 OH 1 ocH;doH;0nr — dR NHC — Ar —OCHCCH;0M: Vib , R R n or of 0 OH OCH; CCH OAT —CNH— roc: CH; OAr Aare ; R ’ R n
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US10679798P | 1998-11-03 | 1998-11-03 |
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ZA200103578B true ZA200103578B (en) | 2002-05-03 |
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ZA200103578A ZA200103578B (en) | 1998-11-03 | 2001-05-03 | Hot-melt adhesive compositions. |
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EP (1) | EP1137735A1 (en) |
JP (1) | JP2002528632A (en) |
KR (1) | KR20010080378A (en) |
CN (1) | CN1325430A (en) |
AR (1) | AR022682A1 (en) |
AU (1) | AU1460200A (en) |
BR (1) | BR9915250A (en) |
CA (1) | CA2349216A1 (en) |
WO (1) | WO2000026319A1 (en) |
ZA (1) | ZA200103578B (en) |
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CN1377286A (en) * | 1999-09-30 | 2002-10-30 | 陶氏化学公司 | Binding superabsorbent polymers to substrates |
EP3480658A4 (en) * | 2016-06-29 | 2019-07-17 | FUJIFILM Corporation | Positive photosensitive resin composition, positive lithographic printing plate, and method for manufacturing lithographic printing plates |
WO2018021331A1 (en) * | 2016-07-27 | 2018-02-01 | 東レ株式会社 | Resin composition |
CN110603305A (en) * | 2017-03-30 | 2019-12-20 | 陶氏环球技术有限责任公司 | Moisture-curable polyurethane hot-melt resin composition |
CN111662672A (en) * | 2019-03-06 | 2020-09-15 | 广州德渊精细化工有限公司 | Hydrophilic adhesive and synthesis method and application thereof |
JP7288807B2 (en) * | 2019-06-03 | 2023-06-08 | 株式会社Dnpファインケミカル | Water-based temporary fixing adhesive and method for manufacturing various members or parts using the water-based temporary fixing adhesive |
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GB1167516A (en) * | 1965-11-17 | 1969-10-15 | Hitachi Ltd | Hotmelt Adhesive Compositions |
US3505261A (en) * | 1969-01-24 | 1970-04-07 | Usm Corp | Hot melt adhesive compositions |
JPS574733A (en) * | 1980-06-12 | 1982-01-11 | Unitika Ltd | Phenoxy resin film and manufacture of the same |
DD232058A1 (en) * | 1984-11-30 | 1986-01-15 | Univ Schiller Jena | PROCESS FOR PREPARING HIGHLY MOLECULAR THERMOPLASTIC EPOXY DITHIOL POLYADDUCTS |
EP0479445B1 (en) * | 1990-10-03 | 1998-03-11 | The Dow Chemical Company | Hydroxyl functionalized polyetheramines as barrier packaging for oxygen-sensitive materials |
US5089588A (en) * | 1990-10-17 | 1992-02-18 | The Dow Chemical Company | Hydroxy-functional poly(amide ethers) as thermoplastic barrier resins |
US5149768A (en) * | 1991-06-21 | 1992-09-22 | The Dow Chemical Company | Hydroxy-functional poly(ether sulfonamides) as thermoplastic barrier resins |
-
1999
- 1999-11-01 BR BR9915250-9A patent/BR9915250A/en not_active Application Discontinuation
- 1999-11-01 JP JP2000579696A patent/JP2002528632A/en active Pending
- 1999-11-01 WO PCT/US1999/025613 patent/WO2000026319A1/en not_active Application Discontinuation
- 1999-11-01 AU AU14602/00A patent/AU1460200A/en not_active Abandoned
- 1999-11-01 CN CN99812895A patent/CN1325430A/en active Pending
- 1999-11-01 CA CA002349216A patent/CA2349216A1/en not_active Abandoned
- 1999-11-01 EP EP99971445A patent/EP1137735A1/en not_active Withdrawn
- 1999-11-01 KR KR1020017005574A patent/KR20010080378A/en not_active Application Discontinuation
- 1999-11-03 AR ARP990105551A patent/AR022682A1/en unknown
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CN1325430A (en) | 2001-12-05 |
JP2002528632A (en) | 2002-09-03 |
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WO2000026319A1 (en) | 2000-05-11 |
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