WO2015153226A1 - Bio-based hot melt adhesives - Google Patents
Bio-based hot melt adhesives Download PDFInfo
- Publication number
- WO2015153226A1 WO2015153226A1 PCT/US2015/022489 US2015022489W WO2015153226A1 WO 2015153226 A1 WO2015153226 A1 WO 2015153226A1 US 2015022489 W US2015022489 W US 2015022489W WO 2015153226 A1 WO2015153226 A1 WO 2015153226A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hot melt
- lactide
- melt adhesive
- poly
- molecular weight
- Prior art date
Links
- 239000004831 Hot glue Substances 0.000 title claims abstract description 164
- 239000000203 mixture Substances 0.000 claims abstract description 163
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 114
- -1 poly(lactide) Polymers 0.000 claims abstract description 49
- 239000004014 plasticizer Substances 0.000 claims abstract description 47
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- 229940065514 poly(lactide) Drugs 0.000 claims abstract description 23
- 229920001519 homopolymer Polymers 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 75
- 235000015165 citric acid Nutrition 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 15
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 7
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 229920001434 poly(D-lactide) Polymers 0.000 claims description 3
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 claims description 2
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims 1
- 150000007527 lewis bases Chemical class 0.000 claims 1
- 239000000155 melt Substances 0.000 description 39
- 238000001542 size-exclusion chromatography Methods 0.000 description 31
- 238000009826 distribution Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
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- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- 238000005259 measurement Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
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- 238000002474 experimental method Methods 0.000 description 10
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
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- CVPZXHCZKMFVOZ-UHFFFAOYSA-N [4-(benzoyloxymethyl)cyclohexyl]methyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(CC1)CCC1COC(=O)C1=CC=CC=C1 CVPZXHCZKMFVOZ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000008035 bio-based plasticizer Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
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- 239000000047 product Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 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 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 3
- 239000004353 Polyethylene glycol 8000 Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
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- 229940085678 polyethylene glycol 8000 Drugs 0.000 description 3
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 description 3
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- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 3
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- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
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- 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 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 239000012790 adhesive layer Substances 0.000 description 2
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- 125000003700 epoxy group Chemical group 0.000 description 2
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
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- 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
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UQGPCEVQKLOLLM-UHFFFAOYSA-N pentaneperoxoic acid Chemical compound CCCCC(=O)OO UQGPCEVQKLOLLM-UHFFFAOYSA-N 0.000 description 1
- ABOYDMHGKWRPFD-UHFFFAOYSA-N phenylmethanesulfonamide Chemical class NS(=O)(=O)CC1=CC=CC=C1 ABOYDMHGKWRPFD-UHFFFAOYSA-N 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- KHLAZQIVJFSQDS-UHFFFAOYSA-N tert-butyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OC(C)(C)C)OC1=CC=CC=C1 KHLAZQIVJFSQDS-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WCLDITPGPXSPGV-UHFFFAOYSA-N tricamba Chemical compound COC1=C(Cl)C=C(Cl)C(Cl)=C1C(O)=O WCLDITPGPXSPGV-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/018—Additives for biodegradable polymeric composition
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
Definitions
- Hot melt adhesives are solids at room temperature, but when heated form a liquid adhesive layer that cools and bonds rapidly to a substrate. HMAs can be useful for high speed manufacturing and applications that require bonding versatility, large gap filling, and minimal shrinkage. HMAs do not require a carrier fluid such as an organic solvent or water, which eliminates the need for drying the liquid adhesive layer once it is applied to a substrate. Elimination of the drying step reduces solvent usage, increases production line speeds, and lowers transportation costs.
- a carrier fluid such as an organic solvent or water
- HMA compositions have historically been based on petroleum-derived polymers, and these compositions are further tackified, plasticized, and reinforced with a variety of resins, oils and waxes that can be derived from both petroleum and naturally occurring feedstocks such as wood, gum and tall oil rosin, and terpenes. These HMA compositions are subject to the cyclical price cycles common to all petroleum-derived materials, and also are generally very resistant to degradation once the articles employing them (such as cardboard boxes and the like) are disposed.
- HMA compositions made from raw materials derived from renewable, natural resources can be composted or degrade naturally after coming in contact with the soil.
- HMA compositions prepared from homopolymers or copolymers of poly(lactide) (the bimolecular cyclic ester of lactic acid), also referred to herein as PLA, can be useful in many bonding applications.
- the present disclosure is directed to HMA compositions that, in various embodiments, include at least 50 wt%, or at least 75 wt%, or at least 85 wt%, or at least 95 wt%, of components derived from renewable, natural resources.
- the HMA compositions utilize raw materials that demonstrate some level of natural degradation when composted or contacted with soil.
- the HMA compositions utilize poly(lactic acid), which is derived from a non-petroleum feedstock, as a base polymer. Poly(lactic acid) polymers have a high molecular weight previously considered unsuitable for use in HMA compositions, and for use in these applications required compounding with significant amounts of petroleum-derived tackifying resins, diluents or other modifiers.
- the present disclosure is directed to a method for modifying the molecular weight of poly(lactic acid) polymers using a molecular weight reducing compound such as a weak acid, an alcohol, a base, an amine, or a combination thereof, which can provide a low melt viscosity material that is suitable for HMA applications.
- a molecular weight reducing compound such as a weak acid, an alcohol, a base, an amine, or a combination thereof, which can provide a low melt viscosity material that is suitable for HMA applications.
- the method of this disclosure differs from conventional techniques in which HMA compositions are made from monomeric lactide with comonomers to build up molecule chains, or rely on high molecular weight base polymers, which can require significant amounts of tackifier and other modifying additives from non-renewable sources to achieve a desired level of HMA performance.
- the method of this disclosure can produce base polymers with tailored molecular weight distribution, which in some embodiments require no tackifier, and in some embodiments can require fewer modifying additives to achieve good performance as a HMA.
- the present disclosure is directed to low-melt viscosity HMA compositions that have good hot tack characteristics and require either no tackifiers or a reduced amount of tackifying agents/compounds.
- the HMA compositions require a minimum amount of plasticization and/or diluents to achieve the desirable wetting characteristics typical of a HMA at application temperatures of 300-375 °F (150- 190 °C).
- the present disclosure is directed to a hot melt adhesive including a poly(lactide) homopolymer or copolymer with a molecular weight (Mn) of about 1000 to about 40000 Daltons; and a plasticizer including an ester with about 50% to about 99% bio-based content; wherein the viscosity of the hot melt adhesive composition is about 500 to about 15,000 cPs at 350°F, and wherein the hot melt adhesive composition is substantially free of tackifying resins.
- Mn molecular weight
- the present disclosure is directed to a hot melt adhesive including 60 wt% to 99 wt% of a poly(lactide) homopolymer or copolymer with a molecular weight of about 1000 to about 40000 Daltons; 1 wt% to 40% wt% of a plasticizer including an ester with about 50% to about 99% bio-based content; and 1 wt% to 25 wt% of an epoxy resin.
- the present disclosure is directed to a hot melt adhesive composition including 60 wt% to 99 wt% of a poly(lactide) homopolymer or copolymer; 1 wt% to 40% wt% of a plasticizer including an ester with about 50% to about 99% bio-based content; 0 wt% to 25 wt% of an epoxy resin; and 0.1 wt% to 10 wt% of a molecular weight reducing compound selected from weak acids, amines, strong bases, alcohols, lewis acids, and combinations thereof, wherein the hot melt adhesive is substantially free of tackifying resins.
- the present disclosure is directed to a method for making a hot melt adhesive, including heating to a temperature of 180°C to 210°C a hot melt adhesive composition including 60 wt% to 99 wt% of a poly(lactide) homopolymer or copolymer; 1 wt% to 40% wt% of a plasticizer including an ester with about 50% to about 99% bio-based content; and 0.1 wt% to 10 wt% of a molecular weight reducing compound selected from weak acids, amines, lewis acids, and combinations thereof.
- a hot melt adhesive composition including 60 wt% to 99 wt% of a poly(lactide) homopolymer or copolymer; 1 wt% to 40% wt% of a plasticizer including an ester with about 50% to about 99% bio-based content; and 0.1 wt% to 10 wt% of a molecular weight reducing compound selected from weak acids, amines, lewis acids, and combinations thereof.
- FIG. 1 is a plot of the melt viscosity measurements of the HMA composition of Example 1.
- FIG. 2 is a plot of the molecular weight distribution of the HMA composition of
- FIG. 3 is a plot of the melt viscosity measurements of the HMA composition of Example 2.
- FIG. 4 is a plot of the molecular weight distribution of the HMA composition of Example 2 using SEC.
- FIG. 5 is a plot of the melt viscosity measurements of the HMA composition of Example 3.
- FIG. 6 is a plot of the molecular weight distribution of the HMA composition of Example 3 using SEC.
- FIG. 7 is a plot of the melt viscosity measurements of the HMA composition of
- FIG. 8 is a plot of the molecular weight distribution of the HMA composition of Example 4 using SEC.
- FIG. 9 is a plot of the melt viscosity measurements of the HMA composition of Example 5.
- FIG. 10 is a plot of the molecular weight distribution of the HMA composition of Example 5 using SEC.
- FIG. 11 is a plot of the melt viscosity measurements of the HMA composition of Example 6.
- FIG. 12 is a plot of the molecular weight distribution of the HMA composition of
- FIG. 13 is a plot of the melt viscosity measurements of the HMA composition of Example 7.
- FIG. 14 is a plot of the molecular weight distribution of the HMA composition of Example 7.
- FIG. 15 is a plot of the melt viscosity measurements of the HMA composition of Example 8.
- FIG. 16 is a plot of the molecular weight distribution of the HMA composition of Example 8 using SEC.
- FIG. 17 is a plot of the melt viscosity measurements of the HMA composition of Example 9.
- FIG. 18 is a plot of the molecular weight distribution of the HMA composition of Example 9 using SEC.
- FIG. 19 is a plot of the melt viscosity measurements of the HMA composition of Example 10.
- FIG. 20 is a plot of the molecular weight distribution of the HMA composition of Example 10 using SEC.
- FIG. 21 is a plot of the melt viscosity measurements of the HMA composition of Example 11.
- FIG. 22 is a plot of the molecular weight distribution of the HMA composition of
- FIG. 23 is a plot of the melt viscosity measurements of the HMA composition of Example 12.
- FIG. 24 is a plot of the molecular weight distribution of the HMA composition of Example 12 using SEC.
- FIG. 25 is a plot of the melt viscosity measurements of the HMA composition of Example 13.
- FIG. 26 is a plot of the molecular weight distribution of the HMA composition of Example 13 using SEC.
- FIG. 27 is a plot of the melt viscosity measurements of the HMA composition of
- FIG. 28 is a plot of the molecular weight distribution of the HMA composition of Example 14 using SEC.
- FIG. 29 is a plot of elastic modulus (G') vs. temperature for the HMA compositions of Examples 1 -2 and various neat PLA polymers and Ethylene Vinyl Acetate (EVA) HMA compositions.
- FIG. 30 is a plot of melt viscosity measurements for the HMA composition of Example 15.
- FIG. 31 is a plot of melt viscosity measurements for the HMA composition of Example 16.
- FIG. 32 is a plot of melt viscosity measurements for the HMA composition of Example 17.
- the present disclosure is directed to HMA compositions including a polylactide compound (the bimolecular cyclic ester of lactic acid, also referred to herein as PLA) or copolymers thereof with other lactones such as glycolide and caprolactone, a plasticizer, a weak organic acid, and optional additives.
- the HMA composition is substantially free of tackifying resins, which in this application means that the HMA composition includes less than 5 wt%, or less than 1 wt%, or less than 0.5 wt%, or less than 0.1 wt% of tackifying resin, or 0% tackifying resins.
- the HMA composition can include less than 25 wt%, or less than 15 wt%, or less than 10 wt% of an epoxy tackifying resin.
- tackifying resin as used herein means a material included in the HMA composition to enhance the tack, or stickiness, or adhesion to a substrate. In addition to enhancing adhesion, the tackifying resin may cause the HMA composition to harden faster, or increase the temperature at which hardening occurs, thus building cohesive strength rapidly in the HMA product.
- the major component of the HMA composition which is present in an amount of about 60 wt% to about 99 wt% of the composition, includes a homo- or copolymer of poly(lactic acid), referred to herein generally as PLA:
- Lactide is a chiral molecule and exists in two distinct optically active forms, L-lactide and D-lactide, which can be polymerized to form a crystalline polymer.
- Polymerization of a racemic mixture of L- and D-lactide monomeric units forms poly-D,L-lactide (PDLLA), which is amorphous and has a glass transition temperature of 55-60°C.
- the degree of crystallinity in the poly(lactide) polymer also can be tuned by altering the ratio of D to L enantiomers within the polymer. Selection of the PLA stereochemistry can have a major effect on polymer properties, processability and biodegradability.
- poly (L-lactide) or PLLA is used in the HMA precursor composition because it breaks down into L(+)-lactic acid units, a naturally occurring stereoisomer, and would be expected to degrade more quickly in the environment.
- Suitable polylactide polymers can include, for example, homopolymers or copolymers made up of (L-lactide), (D-lactide), and (meso-lactide) monomeric units. As noted above, while poly(D,L-lactide) and poly(meso-lactide) are essentially amorphous, poly(L-lactide,
- the PLA polymer in the HMA precursor composition includes a predominant amount of (L-lactide) and (D-lactide) monomeric units, and in some embodiments the PLA polymer is a crystalline homopolymer or copolymer including (L-lactide) and (D-lactide) monomeric units. In other embodiments, the PLA polymer is a crystalline homopolymer including (L-lactide) monomeric units.
- suitable PLAs for use in the HMA composition have a number average molecular weight (Mn) of about 100,000 to about 200,000 Daltons, and a viscosity of about 1 x 10 6 cP at 350°F (177 °C).
- Mn number average molecular weight
- Viscosity about 1 x 10 6 cP at 350°F (177 °C).
- the poly(lactide) polymers may be prepared by ring-opening
- the poly(lactide) polymers may be obtained commercially from, for example, Nature Works, LLC, Minnetonka, MN, under the trade designations PLA 4060D and 6252D, or from Sigma Aldrich Corp., St. Louis, MO, under the trade designation RESOMER, including RESOMER 206, 202, and 203.
- suitable polymers for use in the HMA composition may also be prepared by copolymerization of polylactides with other lactones such as glycolide or caprolactone.
- Both L- and DL-lactides can be used for co-polymerization, and the ratio of lactone to lactide at different compositions allows control of the degree of crystallinity of the resulting copolymers:
- Suitable poly(D,L-lactide-co-glycolide) polymers containing equimolar amounts of the lactide and glycolide components are available from Sigma Aldrich under the trade designation RESOMER, including RG502, 503, 504, 505 and 506.
- RESOMER poly(D,L-lactide-co- glycolide) polymers such as RESOMER RG 653 (including 65% of the lactide component), or RESOMER RG752, 755 and 756 (containing 75% of the lactide component), as well as RESOMER 858 (contains 85% lactide) are also suitable for use in the HMA composition.
- the HMA composition further includes about 0.1 wt% to about 40 wt%, or about 1 wt% to about 20 wt%, based on the total weight of the composition, of a plasticizer, which in some embodiments is a bio-based plasticizer.
- a plasticizer refers to a material that increases the flexibility and/or toughness of the final HMA product by solvation of the poly(lactide) base polymer.
- bio-based means that the plasticizer includes more than 50% and up to 100% of materials that are biodegradable and/or are made from renewable materials that are not derived from petroleum.
- the plasticizer should be used in an amount sufficient to reduce the viscosity of the HMA composition to about 500 to about 15,000 cPs, or from about 800 to about 3000 cPs, at 350°F (177 °C).
- Useful commercially available bio-based plasticizers include, but are not limited to, those available under the following trade designations:
- CITROFLEX 2, CITROFLEX A-2, CITROFLEX 4 and CITROFLEX A-4 from Morflex Inc. (Greensboro, NC); ester plasticizers from HallStar, Chicago, IL such as HALLGREEN R-3000, R-3010, R-3020, R-4010, R-4028, R-8010, and R-9010; and SGP9300D from Segetis, Golden Valley, MN.
- the HALLGREEN bio-based plasticizers are certified by the U.S. Department of Agriculture as a USDA Bio-based Product as defined under the USDA BioPreferred program created by the Farm Security and Rural Investment Act of 2002 (2002 Farm Bill), and expanded by the Food, Conservation, and Energy Act of 2008 (2008 Farm Bill).
- the HALLGREEN plasticizers are esters with about 50% to about 100%, or about 50% to about 99%, bio-based content, which means that the esters are composed of and/or derived primarily from agricultural, forestry, or marine materials, and would be expected to degrade naturally in the environment.
- the bio-based plasticizers may be used alone or in combination with other petroleum- derived plasticizers, but it is preferred that the amount of petroleum-based plasticizer be limited to preserve the biodegradable nature of the HMA compositions.
- additional plasticizers include, but are not limited to, for example, SANTICIZER 160 and SANTICIZER 154 t-butyl diphenyl phosphate from Monsanto (St. Louis, MO); DYNACOL 720 liquid plasticizer from Degussa (Piscataway, NJ); liquid polymeric plasticizers from CP.
- BENZOFLEX 352 1 ,4-cyclohexane dimethanol dibenzoate BENZOFLEX 50 diethylene glycol/dipropylene glycol dibenzoate
- BENZOFLEX P200 polyethylene glycol dibenzoate BENZOFLEX 9-88 and BENZOFLEX 2088 dipropylene glycol dibenzoates
- BENZOFLEX 400 polypropylene glycol dibenzoate
- BENZOFLEX 2-45 diethylene glycol dibenzoate having from 0.5 to 0.95 mole faction esterified hydroxyl groups all from Velsicol (Rosemont, IL);
- the HMA composition further includes about 0.1 wt% to about 10 wt%, based on the total weight of the composition, of at least one molecular weight reducing compound.
- the molecular weight reducing compound may be selected from any compound or combination of compounds that reduces the molecular weight of the poly(lactic acid) polymer or copolymer when employed with the plasticizers listed above.
- the molecular weight reducing compound reduces the molecular weight of the poly(lactic acid) polymer to provide a HMA composition with sufficiently low melt viscosity to function as a HMA. In some embodiments, the molecular weight reducing compound reduces the molecular weight (Mn) of the poly(lactic acid) homopolymer or copolymer in the HMA precursor composition to about 1000 to about 40,000 Daltons, or about 1000 to about 20,000 Daltons.
- the molecular weight reducing compound reduces the viscosity of the HMA composition to about 500 to about 15,000 cPs, or about 800 to about 2000 cPs, at 350°F (177 °C).
- the molecular weight reducing compound is a weak organic or inorganic acid.
- Suitable weak organic acids include, but are not limited to, citric acid, oxalic acid, adipic acid, undecanoic acid, p-toluenesulfonic acid, stearic acid, and combinations thereof.
- Suitable weak inorganic acids include, but are not limited to, phosphoric acid, boric acid, Lewis acids such as, for example, MgCh., and the like.
- the molecular weight reducing compound can be a strong base such as, for example, sodium hydroxide (NaOH), Ca(OH)2 , Mg(OH)2, an alcohol such as, for example, undecan- 1 -ol, or an amine such as, for example, diethanolamine or triethanolamine, and combinations thereof.
- the HMA composition can include about 1 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, or about 8 wt% to about 10 wt% of a tackifying resin to enhance crosslinking.
- Suitable resin crosslinkers include, for example, di- and polyepoxides that are capable of reacting with the hydroxyl and carboxylic acid end groups of the low molecular weight PLA, as well as di- and poly carbonates and anhydrides, and combinations thereof. Suitable examples include di- and polyepoxides such as glycidal ethers of bisphenol A, bisphenol F, bisphenol M, Novolac, melamines, polyglycols, and their modified derivatives, and epoxides of polyolefins and vegetable oils. Di- and polyanhydrides, di- and polycarbonates, methylolated ureas and amines and other PLA reactive chain extenders may also be used.
- suitable epoxides can include bisphenol A diglycidyl ether of the formula below, wherein n denotes the number of polymerized subunits and is about 0 to about 25:
- the epoxide may be bisphenol F diglycidal ether epoxy resin: or an epoxidised novolac, such as an epoxy phenol novolac and epoxy cresol with typical mean epoxide functionality of around 2 to 6:
- glycidyl epoxy resins such as the following may be used:
- the epoxy resins can be liquid, solid, or a combination thereof, and include, but are not limited to, the epoxies available under the trade designation EPON from Momentive,
- Suitable examples include, but are not limited to, difunctional bisphenol A/epichlorohydrin derived liquid epoxy resins such as EPON 828, solid bisphenol- A/epichlorohydrin resins such as EPON 2004, and combinations thereof.
- the PLA can be heated to about 180 °C to about 195 °C in the presence of the molecular weight reducing compounds listed above, and the tackifiers can be added to allow them to react before or after adding plasticizers.
- the HMAs prepared in this manner can have better adhesion and cohesion forces with somewhat better thermal stabilities.
- the HMA composition can optionally further include wax diluents to reduce the melt viscosity or cohesive characteristics of the HMA without appreciably decreasing their adhesive bonding characteristics.
- wax diluents are often used in adhesives which do not exhibit pressure sensitive properties.
- Suitable waxes include 12-hydroxystearamide wax, hydrogenated castor oil, oxidized synthetic waxes, poly(ethylene oxide) having a weight average molecular weight above about 1000 and functionalized synthetic waxes such as carbonyl containing Escomer HI 01 from Exxon. It should be recognized that some HMA compositions may contain both wax and plasticizer components so that the presence of one or the other is not mutually exclusive.
- the HMA composition can further optionally include stabilizers or antioxidants such as, for example, high molecular weight hindered phenols and multifunctional phenols such as sulfur and phosphorous-containing phenols.
- stabilizers or antioxidants include: 1,3,5- trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene; pentaerythritol tetrakis-3-(3,5- di-tert-butyl-4-hydroxyphenyl)propionate; n-octadecyl 3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4,4'-methylenebis (2,6-di-tert-butylphenol); 4,4'-thiobis (6-tert-butyl-o-cresol); 2,6- di-tert-butylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octylthio)- 1
- HMA composition there may also be present in the HMA composition small amounts (e.g., less than about 20% by weight, and preferably 5 to 20% by weight) of certain thermoplastic polymers such as ethylene vinyl acetate containing 12 to 50% vinyl acetate, ethylene acrylic acid, ethylene methyl acrylate and ethylene n-butyl acrylate copolymers as well as caprolactone polymers.
- these polymers can impart flexibility, toughness and strength to the HMA.
- HMA composition it may be desirable to incorporate into the HMA composition up to 20% by weight of certain hydrophilic polymers such as polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl methyl ether, poly(ethylene oxide), or poly (hydroxy butyrate/hydroxy valerate), which can increase the water sensitivity of the adhesives as desired for some applications.
- hydrophilic polymers such as polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl methyl ether, poly(ethylene oxide), or poly (hydroxy butyrate/hydroxy valerate), which can increase the water sensitivity of the adhesives as desired for some applications.
- the present disclosure is directed to a HMA derived from the HMA compositions described above.
- the viscosity of the HMA is about 500 to about 15,000 cPs, or about 800 to about 2000 cPs, at 350°F (177 °C).
- the molecular weight of the poly(lactic acid) homopolymer or copolymer in the HMA is about 1000 to about 40,000 Daltons, or about 1000 to about 20,000 Daltons.
- the HMA includes 10 wt% to 99 wt% of a poly(lactide) homo- or copolymer (L-, D- and -D, L or meso or mixtures thereof) with a molecular weight of about 1000 to about 40,000 Daltons, or about 1000 to about 20,000 Daltons; 1 wt% to 50 wt% of a bio-based ester plasticizer; 0 wt% to 20 wt% of an epoxy resin, 0 wt% to 30 wt% of a wax diluents, and 0 wt% to 3 wt% of a stabilizer.
- a poly(lactide) homo- or copolymer L-, D- and -D, L or meso or mixtures thereof
- a molecular weight of about 1000 to about 40,000 Daltons, or about 1000 to about 20,000 Daltons
- 1 wt% to 50 wt% of a bio-based ester plasticizer 0 wt% to 20
- a non-pressure sensitive HMA composition can be prepared using 20 wt% to 70 wt% of the polylactide homo- or copolymer with a molecular weight of about 1000 to about 40,000 Daltons, or about 1000 to about 20,000 Daltons; 1 wt% to 20 wt% of a bio-based plasticizer; 0 wt% to 10 wt% of an epoxy resin; and 0 wt% to 3 wt% of a stabilizer.
- Lower levels of plasticizer may also be employed to produce adhesives useful for various end uses such as in construction adhesives for disposable products where some initial degree of tack is needed but no residual pressure sensitive properties are required.
- non-pressure sensitive adhesives can be prepared using 20 wt% to 98 wt% of the polylactide homo- or copolymer with a molecular weight of about 1000 to about 40,000 Daltons, or about 1000 to about 20,000 Daltons; 1 wt% to 20 wt% plasticizer, 0 wt% to 10 wt% epoxy resin, and 0 wt% to 3 wt% of a stabilizer.
- the present disclosure is directed to a method for making a HMA from the HMA compositions described above.
- the poly(lactic acid) polymer, plasticizer, optional tackifier, and any additional optional additives are placed in a mixer with stirring and heated to a temperature of about 180°C to about 210°C, or about 190°C to about 200°C.
- the weak organic acid is added, and the mixture is heated for a time sufficient to form a smooth, homogeneous HMA with a desired viscosity. Reaction times may vary widely, but a time of about 0.1 hours to about 2 hours, or about 1 hour to 2 hours, is typically used to form the HMA.
- the HMA may optionally be formed into sticks, pellets, blocks, pillows and the like.
- the HMAs disclosed herein may be employed in a wide variety of uses, including packaging and carton sealing applications, bookbinding operations, or laminating tissue and/or screen-reinforced tissue layers such as are used in individual or roll use applications as in wipers, paper towels, toilet tissue and other consumer or industrial end uses.
- the adhesives may be used in the assembly or construction of various disposable applications including, but not limited to, sanitary napkins, disposable diapers, hospital gowns, bed pads and the like. In particular, adhesives are useful for the assembly of disposable articles using 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.
- the adhesives may be useful in the bonding of elastic to polyethylene, polypropylene or non- woven substrate so as, for example, to impart elongation resistant gathers thereto.
- the adhesive may also be utilized in less demanding disposable construction applications such as for end or perimeter sealing.
- compositions and method of the present disclosure will now be further illustrated by the following non-limiting examples.
- the PLAs were obtained from Nature Works, Minnetonka, MN.
- Hallgreen plasticizers were obtained from HallStar, Chicago, IL.
- the SGP9300D plasticizer was obtained from Segetis, Golden Valley, MN.
- the epoxies were obtained from Momentive, Columbus, OH.
- SEC Size Exclusion Chromatography
- Syringe filter type 0.45 micron PTFE
- An AR-G2 rheometer from TA instruments was used for monitoring melt viscosity of the starting material and reaction mixtures.
- About 3 gms of test material was set between two circular parallel plates of the rheometer at a gap of 1.1 mm.
- the top plate measured 20 mm in diameter while the bottom plate measured 100 mm in diameter.
- the bottom plate was a peltier temperature controlled plate and held at a steady temperature of 177 ° C.
- each sample was subjected to a fixed 5% small amplitude oscillatory stress varying in frequency from 1 Hz to 10 Hz. The response of the test material to this oscillatory stress was then reported as the complex viscosity in units of Pa.sec.
- Example 3 Preparation of PLA Hot Melt Adhesive Composition 162455-33-1
- the PLA adhesive was prepared similarly as previous examples except using 69 g of PLA 6252, 137 g of PLA 4060, 46 g of Hallgreen R8010, 22 g of SGP9300D (from Segetis) and 19 g of each citric acid. After the melt viscosity reached about 600 cps, another 69 g of PLA 6252D was added and dissolved at 190°C to become the final product mixture. The melt viscosity and the molecular weight were measured by rheometer and exclusion
- a PLA adhesive composition was prepared using 296.4 g of PLA 6252, 76 g of
- a PLA adhesive composition was prepared using 296.4 g of PLA 6252, 76 g of SGP9300D (from Segetis) and 7.6 g of citric acid.
- SGP9300D from Segetis
- 76 g of SGP9300D plasticizer from Segetis
- 148.2 g of the PLA 6252 was slowly added; after the contents became solution, all of the 7.6 g of citric acid was slowly introduced and the mixture allowed to react with agitation for 1 hour.
- the remaining 148.2 g of PLA 6252 was slowly added, allowed to mix and become solution. The heat was removed, ending the experiment. Samples were collected and the melt viscosity and molecular weight were measured by rheometer and size exclusion chromatography.
- a PLA adhesive composition was prepared using 296.4 g of PLA 6252, 76 g of SGP9300D (from Segetis) and 7.6 g of citric acid.
- SGP9300D from Segetis
- 76 g of SGP9300D plasticizer from Segetis
- 222.3 g of the PLA 6252 was slowly added; after the contents became solution, all of the 7.6 g of citric acid was slowly introduced and the mixture was allowed to react with agitation for 1 hour.
- the remaining 74.1 g of PLA 6252 was slowly added, allowed to mix and become solution. The heat was then removed, ending the experiment.
- a PLA adhesive composition was prepared using 31 1.6 g of PLA 6252, 57 g of SGP9300D (from Segetis) and 1 1.4 g of citric acid.
- 57 g of SGP9300D plasticizer from Segetis
- 103.9 g of the PLA 6252 was slowly added; after the contents became solution, 3.8 g of citric acid was slowly introduced and the mixture was allowed to react with agitation for 5 min.
- a PLA adhesive composition was prepared using 315.4 g of PLA 4060, 57 g of SGP9300D (from Segetis) and 7.6 g of citric acid.
- 57 g of SGP9300D plasticizer from Segetis
- 78.85 g of the PLA 4060 was slowly added; after the contents became solution, 1.9 g of citric acid was slowly introduced and the mixture was allowed to react with agitation for 5 mins.
- a PLA adhesive composition was prepared using 302.1 g of PLA 6252, 76 g of
- a PLA adhesive composition was prepared using 285 g of PLA 6252, 76 g of
- a PLA adhesive composition was prepared using 296.4 g of PLA 6252, 76 g of SGP9300D (from Segetis) and 7.6 g of undecanoic acid.
- SGP9300D from Segetis
- 76 g of SGP9300D plasticizer from Segetis
- 148.2 g of the PLA 6252 was slowly added; after the contents became solution, 3.8 g of undecanoic acid was slowly introduced and the mixture was allowed to react with agitation for about 10 mins.
- a PLA adhesive composition was prepared using 300.2 g of PLA 6252, 76 g of SGP9300D (from Segetis) and 3.8 g of p-toluenesulfonic acid. To a 500 ml three-necked flask equipped with mechanical stirrer, thermometer, and condenser, 76 g of SGP9300D plasticizer (from Segetis) was charged and heated to 190°C. Then, 150.1 g of the PLA
- a PLA adhesive composition was prepared using 282.7 g of PLA 6252, 76 g of SGP9300D (from Segetis) and 15.2 g of stearic acid.
- SGP9300D from Segetis
- 76 g of SGP9300D plasticizer from Segetis
- 141.35 g of the PLA 6252 was slowly added; after the contents became solution, 7.6g of stearic acid was slowly introduced and the mixture was allowed to react with agitation for about 10 mins.
- a PLA adhesive composition was prepared using 296.4 g of PLA 6252, 76 g of SGP9300D (from Segetis) and 7.6 g of diethanolamine.
- SGP9300D from Segetis
- diethanolamine 7.6 g
- each sample was held between two plates of the rheometer: an 8mm spindle and a heated hot plate that measured 80mm at a gap of 650 microns.
- the samples were then each simultaneously subjected to a sinusoidal strain of 5% while the temperature was ramped from 180°C to 45°C at a rate of 5°C a minute.
- the instrument then collected data of the elastic modulus (G') in Pa at intervals of 10 sec. These data are shown in FIG. 29.
- Example 15 Preparation of Hot Melt Adhesive Composition 165161-72-1
- the melt mixer was heated to 180 °C and the CAM blades set to mix at a rate of 65 rpm.
- 44.4 g of PLA 4060 pellets were slowly added to the mixing bowl with CAM blades rotating ensuring all the polymer was melted and well mixed before moving to the next step.
- 0.6 g of triethanolamine, reagent grade, obtained from J.T. Baker, Phillipsburg, NJ was slowly added via a plastic 3 ml dropper - a few drops every 5 sees.
- the resulting polymer was evaluated for hot melt adhesive application.
- the melt viscosity was measured by a rheometer model AR-G2 from TA instruments (New Castle, DE) and results are summarized in FIG. 30.
- a Type Six melt mixer with CAM blade from Brabender was heated to 180 °C and the CAM blades set to mix at a rate of 65 rpm. 41.4 g of PLA 4060 pellets were slowly added to the mixing bowl with CAM blades rotating ensuring all polymer was melted and well mixed before moving to the next step. Then, 0.6 g of Triethanolamine, reagent grade, obtained from J.T. Baker, was slowly added via a plastic 3 ml dropper - a few drops every 5 sec. After the contents were visually well mixed, 6.0g of CARBOWAX SENTRY Polyethylene Glycol-8000 powder was slowly added until it completely dissolved and was well mixed into the molten polymer.
- the resulting polymer was evaluated for use as a hot melt adhesive.
- the melt viscosity was measured by a rheometer model AR-G2 from TA instruments, and results are summarized in FIG. 31.
- a Type Six melt mixer with CAM blade from Brabender was heated to 180 °C and the CAM blades set to mix at a rate of 65 rpm. 41.4 g of PLA 4060 pellets were slowly added to the mixing bowl with CAM blades rotating ensuring all polymer was melted and well mixed before moving to the next step. Then, 0.6 g of Triethanolamine, reagent grade, obtained from J.T. Baker, was slowly added via a plastic 3 ml dropper - a few drops every 5 sec. After the contents were visually well mixed, 3.0g of CARBOWAX SENTRY Polyethylene Glycol- 8000 powder was slowly added until it completely dissolved and was well mixed into the molten polymer.
- the resulting polymer was evaluated for use in hot melt adhesive applications.
- the melt viscosity was measured by a rheometer model AR-G2 and results are summarized in FIG. 32.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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KR1020167028186A KR20160140718A (en) | 2014-03-31 | 2015-03-25 | Bio-based hot melt adhesives |
US15/300,858 US20170037218A1 (en) | 2014-03-31 | 2015-03-25 | Bio-based hot melt adhesives |
JP2016559859A JP2017512873A (en) | 2014-03-31 | 2015-03-25 | Bio-based hot melt adhesive |
EP15772338.8A EP3126464A4 (en) | 2014-03-31 | 2015-03-25 | Bio-based hot melt adhesives |
CN201580017923.0A CN106133101A (en) | 2014-03-31 | 2015-03-25 | Bio-based hot-melt adhesive |
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US201461972790P | 2014-03-31 | 2014-03-31 | |
US61/972,790 | 2014-03-31 |
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WO2015153226A1 true WO2015153226A1 (en) | 2015-10-08 |
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PCT/US2015/022489 WO2015153226A1 (en) | 2014-03-31 | 2015-03-25 | Bio-based hot melt adhesives |
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US (1) | US20170037218A1 (en) |
EP (1) | EP3126464A4 (en) |
JP (1) | JP2017512873A (en) |
KR (1) | KR20160140718A (en) |
CN (1) | CN106133101A (en) |
WO (1) | WO2015153226A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022073006A1 (en) * | 2020-09-29 | 2022-04-07 | H.B. Fuller Company | Bio-based and compostable hot melt adhesive compositions and articles including the same |
WO2024023795A1 (en) | 2022-07-29 | 2024-02-01 | Università Di Pisa | Hot-melt biobased polymeric formulations for coating applications containing active biomolecules |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EA033746B1 (en) * | 2015-10-01 | 2019-11-21 | Purac Biochem Bv | Non-reactive hot-melt adhesive with set time improver |
JP6419376B1 (en) * | 2018-05-18 | 2018-11-07 | 株式会社Bpコンサルティング | Method for producing polylactic acid hot melt adhesive |
JP7240501B2 (en) * | 2018-12-21 | 2023-03-15 | ピュラック バイオケム ビー. ブイ. | Tackifier for lactic acid-based hot melt adhesives |
KR20210105350A (en) * | 2018-12-21 | 2021-08-26 | 헨켈 아이피 앤드 홀딩 게엠베하 | Hot melt adhesive composition and uses thereof |
KR20220114578A (en) | 2019-12-10 | 2022-08-17 | 티코나 엘엘씨 | Cellulose Ester Compositions Containing Bloom-Resistant or Bio-Based Plasticizers |
US12012503B2 (en) | 2019-12-10 | 2024-06-18 | Ticona Llc. | Impact-modified biodegradable polymer compositions |
CN111675888B (en) * | 2020-07-20 | 2021-04-13 | 四川大学 | High-strength high-toughness polylactic acid-based composite material and preparation method thereof |
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- 2015-03-25 EP EP15772338.8A patent/EP3126464A4/en not_active Withdrawn
- 2015-03-25 US US15/300,858 patent/US20170037218A1/en not_active Abandoned
- 2015-03-25 WO PCT/US2015/022489 patent/WO2015153226A1/en active Application Filing
- 2015-03-25 JP JP2016559859A patent/JP2017512873A/en not_active Withdrawn
- 2015-03-25 CN CN201580017923.0A patent/CN106133101A/en active Pending
- 2015-03-25 KR KR1020167028186A patent/KR20160140718A/en unknown
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WO2022073006A1 (en) * | 2020-09-29 | 2022-04-07 | H.B. Fuller Company | Bio-based and compostable hot melt adhesive compositions and articles including the same |
WO2024023795A1 (en) | 2022-07-29 | 2024-02-01 | Università Di Pisa | Hot-melt biobased polymeric formulations for coating applications containing active biomolecules |
Also Published As
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US20170037218A1 (en) | 2017-02-09 |
JP2017512873A (en) | 2017-05-25 |
KR20160140718A (en) | 2016-12-07 |
CN106133101A (en) | 2016-11-16 |
EP3126464A1 (en) | 2017-02-08 |
EP3126464A4 (en) | 2017-11-08 |
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