WO2004011569A1 - Hybrid plastisol/hot melt compositions - Google Patents
Hybrid plastisol/hot melt compositions Download PDFInfo
- Publication number
- WO2004011569A1 WO2004011569A1 PCT/US2003/023873 US0323873W WO2004011569A1 WO 2004011569 A1 WO2004011569 A1 WO 2004011569A1 US 0323873 W US0323873 W US 0323873W WO 2004011569 A1 WO2004011569 A1 WO 2004011569A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- comprised
- liquid
- phase component
- adhesive
- acid
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 259
- 239000012943 hotmelt Substances 0.000 title abstract description 33
- 229920001944 Plastisol Polymers 0.000 title description 9
- 239000004999 plastisol Substances 0.000 title description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 172
- 230000001070 adhesive effect Effects 0.000 claims abstract description 172
- 239000007788 liquid Substances 0.000 claims abstract description 150
- 239000003463 adsorbent Substances 0.000 claims abstract description 91
- 239000006185 dispersion Substances 0.000 claims abstract description 83
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 67
- 239000002105 nanoparticle Substances 0.000 claims abstract description 63
- 238000002156 mixing Methods 0.000 claims abstract description 49
- 239000007787 solid Substances 0.000 claims abstract description 42
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 239000012071 phase Substances 0.000 claims description 142
- 239000002480 mineral oil Substances 0.000 claims description 74
- 235000010446 mineral oil Nutrition 0.000 claims description 74
- 239000004743 Polypropylene Substances 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 68
- 229920001155 polypropylene Polymers 0.000 claims description 68
- -1 mono carboxylic acid compound Chemical class 0.000 claims description 65
- 229920000642 polymer Polymers 0.000 claims description 62
- 239000007791 liquid phase Substances 0.000 claims description 52
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 46
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 42
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 33
- 239000004615 ingredient Substances 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 24
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 24
- 235000021355 Stearic acid Nutrition 0.000 claims description 23
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 23
- 239000008117 stearic acid Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 19
- 239000004698 Polyethylene Substances 0.000 claims description 18
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 claims description 17
- 239000004831 Hot glue Substances 0.000 claims description 16
- 229920001897 terpolymer Polymers 0.000 claims description 16
- 229940117958 vinyl acetate Drugs 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 14
- 239000003921 oil Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 235000019198 oils Nutrition 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 11
- 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 claims description 11
- 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 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- 229920001054 Poly(ethylene‐co‐vinyl acetate) Polymers 0.000 claims description 10
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 10
- 238000004299 exfoliation Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001038 ethylene copolymer Polymers 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 239000004088 foaming agent Substances 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000003017 thermal stabilizer Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000565 sealant Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000002666 chemical blowing agent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims 4
- 235000014666 liquid concentrate Nutrition 0.000 claims 4
- 229920001400 block copolymer Polymers 0.000 claims 3
- 229920000578 graft copolymer Polymers 0.000 claims 3
- 239000005639 Lauric acid Substances 0.000 claims 2
- 235000021314 Palmitic acid Nutrition 0.000 claims 2
- 239000001361 adipic acid Substances 0.000 claims 2
- 235000011037 adipic acid Nutrition 0.000 claims 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- 239000013032 Hydrocarbon resin Substances 0.000 claims 1
- 239000005642 Oleic acid Substances 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims 1
- 229920002457 flexible plastic Polymers 0.000 claims 1
- 150000004677 hydrates Chemical class 0.000 claims 1
- 229920006270 hydrocarbon resin Polymers 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- 235000014655 lactic acid Nutrition 0.000 claims 1
- 235000012243 magnesium silicates Nutrition 0.000 claims 1
- 239000012768 molten material Substances 0.000 claims 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 239000000049 pigment Substances 0.000 claims 1
- 229920005638 polyethylene monopolymer Polymers 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 238000009472 formulation Methods 0.000 description 76
- 239000000123 paper Substances 0.000 description 43
- 239000005038 ethylene vinyl acetate Substances 0.000 description 36
- 230000000694 effects Effects 0.000 description 17
- 229920001903 high density polyethylene Polymers 0.000 description 16
- 239000004700 high-density polyethylene Substances 0.000 description 16
- 239000000654 additive Substances 0.000 description 14
- 230000008901 benefit Effects 0.000 description 14
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 14
- 239000000499 gel Substances 0.000 description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 13
- 239000012190 activator Substances 0.000 description 11
- 238000004806 packaging method and process Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000002114 nanocomposite Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229920003298 Nucrel® Polymers 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920003345 Elvax® Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000011093 chipboard Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000003466 anti-cipated effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000001010 compromised effect Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 229960002380 dibutyl phthalate Drugs 0.000 description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000010128 melt processing Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- AFSHUZFNMVJNKX-UHFFFAOYSA-N 1,2-di-(9Z-octadecenoyl)glycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCC=CCCCCCCCC AFSHUZFNMVJNKX-UHFFFAOYSA-N 0.000 description 2
- AFSHUZFNMVJNKX-LLWMBOQKSA-N 1,2-dioleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](CO)OC(=O)CCCCCCC\C=C/CCCCCCCC AFSHUZFNMVJNKX-LLWMBOQKSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 102100041003 Glutamate carboxypeptidase 2 Human genes 0.000 description 2
- 101000892862 Homo sapiens Glutamate carboxypeptidase 2 Proteins 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 2
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 2
- 229940073769 methyl oleate Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920001481 poly(stearyl methacrylate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 101100389815 Caenorhabditis elegans eva-1 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 229960002685 biotin Drugs 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical compound C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 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
- 230000002349 favourable effect Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 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
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/12—Polypropene
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
Definitions
- the invention relates to adhesive compositions and, more specifically, to a hybrid plastisol/hot melt composition especially suited as an adhesive for packaging and the like.
- Hot-melt adhesives are adhesives which are solid at room temperature and which are applied to the substrates to be joined in the form of a melt, solidifying on cooling after the substrates have been joined together. In the case of thermoplastic adhesives, this operation can be repeated indefinitely because they do not cross-link.
- polymers are essentially based, on polymers,; such as polyamides, polyesters or polyolefms.
- Hot melt adhesives are used widely in the packaging industry for such applications as case and carton sealing, tray forming and box forming.
- the substrates to be bonded include virgin and recycled kraft, high and low density kraft, chipboard and various types of treated and coated kraft and chipboard.
- Composite materials are also used for packaging applications such as for the packaging of alcoholic beverages.
- These composite materials may include chipboard laminated to an aluminum foil which is further laminated to film materials such as polyethylene, Mylar, polypropylene, polyvinylidene chloride, ethylene vinyl acetate and various other types of films.
- film materials such as polyethylene, Mylar, polypropylene, polyvinylidene chloride, ethylene vinyl acetate and various other types of films.
- these film materials also may be bonded directly to chipboard or kraft.
- an adhesive that meets as many of the following technical specifications as possible: liquid at room temperature; stable over long periods (at least one year); chlorine free; low volatility; easily pumped by gravity feed to a gear or piston pump; largely unaffected by storage at 140 degrees F°; low cost; ready to use as received (no mixing); will not "pack out," separate, or change when pumped or pressurized; fuses to become a molten adhesive at elevated temperatures; FDA approved for indirect food contact; has good heat stability at fusion temperature; melt viscosity ⁇ 10,000 cps; T g similar to conventional EVA packaging grade hot melts; open molten time of about 7 seconds when applied at 350 degrees F°; set time after compression between two substrates of about 2 seconds; capable of producing fiber tear adhesion to clay coated printed paperboard; foamable to a 50% density reduction while maintaining other adhesion specifications; and able to be compounded with up to 30 phr filler.
- the invention relates to a liquid plastisol/hot melt hybrid adhesive technology that has been developed based on a blend of functionally specific materials.
- the adhesive is in the form of a liquid dispersion at room temperature, and is stable as a liquid when stored at temperatures of up to approximately 140°F.
- the liquid adhesive is designed to fuse and melt when the dispersion is exposed to temperatures in excess of 300°F. With adequate mixing, the dispersed ingredients form a soluble, molten "hot- melt" solution, which can be dispensed like other hot melt adhesives onto various substrates for industrial adhesive and packaging applications. Once dispensed, the molten hot melt cools to form a solid adhesive which is capable of producing fiber tear when adhered to common clay coated paper stock.
- the hot melt may be thermally stable for periods in excess of five hours at process temperatures, and like other thermoplastic adhesives, it can be remelted, and reused after cooling.
- the achievement of fiber tear adhesion is strongly dependent on mixing (since there are two polymer components), and on activation temperature. Inadequate mixing will result in cohesive failure of the adhesive.
- the adhesive is preferably molten and mixed at temperatures in excess of 350°F to activate the chemistry; otherwise, the adhesive may cohesively fail.
- the adhesive compositions of the invention are based on blends of materials, each of which is dispersed as particulates within a liquid vehicle. Unique processes for mixing and applying the adhesive compositions have also been developed.
- the particulates are chosen based on their ability to impart a specific function in the finished adhesive, and on their ability to resist liquid adsorption at storage temperatures. More specifically, it has been discovered that the plastisol/hot melt hybrid of this invention contains a liquid phase, which serves as the vehicle for dispersion of the ingredients; a reinforcing phase, which gives the adhesive the requisite cohesive strength for the end use application; and an adsorbent phase, which prevents exudation of the liquid phase during hot melt processing, during application, and during end-use.
- the adhesive compositions also preferably include an activator, which activates the chemistry and helps to prevent exudation in the finished product; a thermal stabilizer, which provides thermal stability at process temperatures; and secondary additives (optional) for the purpose of controlling viscosity, cost, set time, foaming, etc.
- the liquid phase is comprised of mineral oil;
- the reinforcing phase is comprised of either poly(ethylene-co-vinyl acetate), a poIy(ethylene-co ⁇ vinyl acetate-co-methacrylic acid) terpolymer, a poly(ethylene-co- vinyl acetate-co-maleic anhydride) terpolymer, or a mixture thereof;
- the adsorbent phase is comprised of poly(propylene-co-maleic anhydride), either alone or mixed with other ingredients such as a polypropylene homopolymer, a tackifier such as a rosin ester of pentaerythritol, or a mixture thereof;
- the activator is comprised of a dicarboxylic acid such as sebacic acid or dodecanedioic acid;
- the thermal stabilizer is comprised of a mixture of Irganox 1010 (a hindered phenol), and Irganox PS 800 (dilau
- the ratios of the ingredients are controlled so that the reinforcing phase is in excess of the adsorbent phase. In this way, sufficient cohesive strength is maintained, and liquid exudation is prevented in the finished product.
- cohesive strength and stiffness are further enhanced through the incorporation of nanoparticles, where it has been found that the method of mixing these particles is important to the achievement of optimum properties.
- nanoparticle aggregates are exfoliated in the hot-melt molten state, while in a second scenario, they are pre-exfoliated in the dispersion state. In the first scenario, nanoparticle aggregates are added to the dispersion with little to no change in the dispersion state viscosity.
- the aggregates are then exfoliated during the melt- processing stage to yield a true nanocomposite adhesive.
- the advantage of this scenario is that the liquid dispersion can be easily prepared through simple low shear mixing. Also, the resultant dispersion is relatively low in viscosity, and as such is it easily processed as a liquid (i.e., through pumping, pouring, etc.).
- the aggregates are purposely pre-exfoliated (either partially or completely) in the dispersion state to yield a mixture with controllable rheological characteristics ranging from those of a liquid to those of a gel — independent of the organic ingredient concentrations.
- the advantage of this scenario is that the dispersion can be processed in applications where higher viscosities are required (with no change in the chemical composition). However, regardless of which scenario is employed, enhanced physical properties are only achieved when the nanoparticle aggregates are exfoliated in the finished solid adhesive.
- the overall ratio of liquid to polymer is also controlled so as to maintain a balance between storage stability, hot melt viscosity, and cohesive strength of the finished product.
- higher levels of liquid necessitate the use of higher levels of the adsorbent phase (to prevent exudation), which diminishes the cohesive strength of the adhesive.
- a minimum level of activator (diacid) may be required to both prevent exudation, and to activate the chemical component of the adhesive. Surprisingly, the activator has no effect in the absence of the adsorbent phase.
- liquid phase enables the composition to be packaged as a liquid • at room temperature, which is a unique and desirable aspect of this invention.
- the choice of liquid may be limited by several constraints including cost, compatibility with the adsorbent phase, volatility at both elevated temperatures (during processing) and at end-use temperatures, and acceptability for indirect food contact applications.
- mineral oil comprises the liquid phase.
- the liquid phase can be any low volatility liquid compound, as long as it is compatible with the adsorbent phase in the finished formulation.
- Such liquids can be either reactive (e.g., acrylic, epoxy, isocyanate-based materials, trialkoxysilane and hydrolyzed and/or oligomerized products thereof, acid functional compounds like isostearic acid); or non-reactive (e.g., aliphatic hydrocarbons, hydrocarbon esters of diacids like adipic, sebacic, and phthalic acid, esters of monoacids, esters of natural fatty acids such as methyloleate, glyceroldioleate, vegetable oils such as soy oil, epoxidized soy oil, etc.), or combinations thereof.
- reactive e.g., acrylic, epoxy, isocyanate-based materials, trialkoxysilane and hydrolyzed and/or oligomerized products thereof, acid functional compounds like isostearic acid
- the reinforcing phase and the adsorbent phase are of higher polarity, then other liquids could include water, glycerol, ethylene glycol, propylene glycol, and mixtures, etc. If reactive liquids are employed, photo and thermal initiators can be used to crosslink the liquids either during the processing of the finished product, or after thermoforming (in which case a photoinitiator, or higher temperature decomposing thermal initiator could be used to finish the cure).
- the reinforcing phase provides the finished adhesive with its mechanical integrity, and as such it must have the ability to fuse, melt, and quickly cool to become a solid after it is applied to a substrate. It has been discovered that polymeric materials such as polyolefins are best suited for this purpose.
- a polymeric reinforcing phase preferably exists in the form of discrete particles that are dispersed in the liquid phase at room temperature. It is important that the particles do not adsorb the liquid at temperatures below 140°F. In this way, the stability of the liquid adhesive is maintained both during storage and during shipping.
- the polymeric particles (which will comprise the reinforcing phase in the finished adhesive) fuse with the liquid phase to form a molten blend.
- the temperature of fusion is dictated by the rheological characteristics of the polymer in the presence of the liquid. These characteristics are controlled by several variables including polymer molecular weight, copolymer composition, solubility with the liquid phase, solubility with the other ingredients, and the composition ratios of all ingredients.
- the reinforcing polymer phase should be miscible with both the liquid and adsorbent phases at elevated processing temperatures (i.e., in the fused, molten state). Incompatibility at elevated process temperatures can result in incomplete mixing, exudation of the liquid, and exudation of the other ingredients; all of which can interfere with adhesion to the substrate, and can deter from the end-use performance properties. Further, it has been surprisingly found that the liquid phase should not be completely compatible with the reinforcing phase upon cooling. Although partial compatibility is acceptable, it is more desirable for the liquid phase to separate from the reinforcing phase upon cooling.
- the reinforcing phase polymer prefferably incompatible with the liquid phase at temperatures below 140°F (to maintain storage stability of the liquid dispersion), and to be compatible with the liquid phase at higher temperatures.
- the balance between compatibility at elevated temperatures and incompatibility at storage temperatures depends on the solubility of the liquid in the reinforcing phase, which in turn depends on copolymer composition, the choice of polyolefin, the choice of liquid, and the ratio of the ingredients.
- the reinforcing phase is comprised of a poly(ethylene-co-vinyI acetate) polymer (EVA).
- EVA poly(ethylene-co-vinyI acetate) polymer
- the reinforcing phase could conceivably be any polyolefin copolymer or terpolymer (linear, graft, or block) as long as it meets the criteria described above.
- Such polymers can include copolymers prepared with monomers of ethylene, butylene, propylene or butadiene, etc; copolymerized with other monomers such as vinyl acetate, methyl acrylate, methyl methacrylate, butyl acrylate, styrene (like IndexTM polymers from Dow, and KratonTM polymers from Shell), maleic anhydride, maleic acid, acrylic acid, methacrylic acid, vinyl methyl ether, glycidyl ethers, trimethylolpropanemonoallylether, vinyl chloride, etc.
- copolymers prepared with monomers of ethylene, butylene, propylene or butadiene, etc copolymerized with other monomers such as vinyl acetate, methyl acrylate, methyl methacrylate, butyl acrylate, styrene (like IndexTM polymers from Dow, and KratonTM polymers from Shell), maleic anhydride, maleic acid, acrylic acid, methacrylic acid
- the reinforcing phase could also be comprised of higher polarity polymers such as polyvinyl alcohol and its copolymers (polyvinylbutyral, polyvinylformal, ethylene vinyl alcohol), polyamides (nylons), and polyvinylpyrrolidone copolymers.
- polyvinyl alcohol and its copolymers polyvinylbutyral, polyvinylformal, ethylene vinyl alcohol), polyamides (nylons), and polyvinylpyrrolidone copolymers.
- acid, alcohol, or anyhydride functional polymers can enhance adhesion to multiple substrates, and can also provide the capacity to chemically react with a reactive liquid phase and/or adsorbent phase if so desired.
- thermally activated curing agents can be incorporated to cross-link the reinforcing phase and/or the adsorbent phase so as to further improve the physical properties of the finished adhesive.
- the thermosetting embodiment of the present invention can be achieved via many conventional chemical pathways (familiar to those skilled in the art), one example of which may include the use of a thermally activated peroxide additive such as t-butylperoxide in combination with an ethylene copolymer as the reinforcing phase.
- the curing agent could also be chosen so as to not react at the temperatures required for mixing and application, but instead to react in either a post- thermal curing process, in a post UV/visible light activated process, or in a moisture activated curing process step.
- These embodiments could be further formulated to make useful coatings and sealants for metals, wood, plastic, and the like.
- blends of the aforementioned polymers can be employed, where blending can either be accomplished through physical mixing of polymers followed by pulverizing into powder form; or through the polymerization process as would be accomplished in a core-shell emulsion or dispersion polymerization.
- a core-shell emulsion or dispersion process could be used to produce a core of the desired composition for end-use mechanical properties (like a terpolymer of polyethylene-co-vinylacetate-co-methacrylic acid with a VA content of greater than 15%), and a shell which provides shelf stability when the particles are dispersed in the liquid phase of the invention (like a copolymer of ethylene and vinylacetate where the VA content is less than 9%).
- the shell could also be comprised of the adsorbent phase for the system (as long as shelf stability can be maintained during the storage of the dispersion).
- polypropylene homopolymers and copolymers are capable of fusing with mineral oil to form soluble molten compositions at elevated process temperatures; but unlike EVA, these compositions remain surprisingly compatible upon cooling to temperatures below 140°F (as evidenced by minimal to no exudation of liquid from the blends after cooling).
- polypropylene and its copolymers are more compatible with the liquid phase than EVA (a positive benefit for minimizing liquid exudation in the finished adhesive), this same attribute deteriorates the resultant cohesive strength, making these polymers poor choices for the reinforcing phase.
- this same "detrimental" attribute has been employed as an important aspect of the present invention.
- this invention makes use of a reinforcing phase that must be accompanied by an adsorbent phase to prevent exudation of liquid from the fused solid adhesive.
- the reinforcing and adsorbent phases must be employed at a ratio where the reinforcing phase is in excess of the adsorbent phase. Otherwise, cohesive strength and interfacial adhesion are compromised.
- the adsorbent phase polymers or other material should be initially dispersed as particulates material into the liquid phase, together with the dispersed reinforcing phase polymer. In this way, the adhesive can be stored and processed as a liquid dispersion (a desirable feature of this invention).
- the composition of the adsorbent phase is also not limited to polymeric materials. In fact, stearic acid has been shown to adequately perform this function.
- a copolymer of polypropylene with maleic anhydride has been found to be the preferred adsorbent phase material, either alone, or in combination with a polypropylene homopolymer.
- stearic acid is capable of preventing exudation, this same attribute results in poor shelf stability at temperatures below 140°F. This is because stearic acid melts and becomes compatible with the mineral oil at a relatively low temperature.
- particulates of stearic acid can remain dispersed in mineral oil at room temperature for indefinite periods, the particulates prematurely gel with the mineral oil at temperatures below 140°F.
- particles of polypropylene and its copolymers do not adsorb the mineral oil at storage temperatures, yet they help to prevent exudation of the liquid from the finished, solid product.
- These polymers also result in an adhesive composition with a greatly reduced set time, which can be an important attribute for economic reasons.
- poly(propylene-co-maleic anhydride) and polypropylene enable the adhesive composition to display good liquid shelf stability, low exudation, and a fast set time.
- the choice of adsorbent phase also depends greatly on the choice of liquid (for reasons related to compatibility).
- the adsorbent phase can be comprised of a polymeric material, a low molecular weight compound, a high surface area inorganic material, or a combination of the three.
- Polymers can include relatively non-polar materials such as polyolefins (like polypropylene and its copolymers, polyethylene and its copolymers, polystyrene copolymers); or relatively polar polymers like nylon, polycaprolactone, polyvinyl alcohol and its copolymers, etc.
- resinous materials can include higher molecular weight aliphatic hydrocarbon waxes, esters, terpene resins, and rosin esters like pentaerythritol ester of tall oil rosin, etc.
- Low molecular weight compounds can include materials that are capable of gelling with the liquid phase like the aforementioned stearic acid, or like others including azelaic acid, benzoic acid, stearic acid, citric acid, tartaric acid, biotin, niacin, etc.
- the adsorbent phase can also include traditional micron-sized inorganic fillers, or high surface area inorganic materials, especially nano materials with surface areas in excess of 30 m 2 /g, and more preferably 100 m 2 /g and higher.
- Such nano-materials can be surface treated with compounds that further enhance their ability to adsorb the liquid phase.
- Surface treatments can include organosilanes such as n-octyltriethoxysilane, monoacids like stearic acid, quaternary ammonium compounds, or others.
- the upper storage temperature limit of the liquid dispersion appears to be related to the melt temperature of the adsorbent phase material, and to the compatibility of the liquid phase with the molten product.
- Polypropylene (PP) homopolymer has a higher melt temperature than that of its copolymers, and thus the upper storage temperatures for compositions with a PP adsorbent phase will be the highest.
- acceptable adhesion is only achieved when a PP copolymer is employed, either alone, or in combination with PP homopolymer, where maleic anhydride is the preferred comonomer in the copolymer composition.
- the adsorbent phase material, the liquid phase material, or both in combination can be comprised of components that yield finished materials with excellent release characteristics.
- Such "release” components have the surprising capacity to prevent exudation (like their adhesion promoting counterparts), while enabling the solid material to be easily peeled away from the substrate over which it is applied.
- An example of an adsorbent phase material that suits this purpose is N,N'- ethylenebisstearamide, while an example of a liquid phase material includes isostearic acid.
- Uses for this embodiment can include molded parts, or applications where temporary protective coatings are desired for metals, paper products, wood products, glass products, and others.
- Such compounds could be aqueous-based, and as such they could be optionally dispersed in the oil phase with appropriate surfactants.
- dicarboxylic acid compounds could be neutralized and rendered water soluble for dispersion in the oil phase to form water-in-oil emulsions.
- the choice of activator is limited by several constraints including cost, compatibility with the other components, volatility at both elevated temperatures (during processing) and at end-use temperatures, and acceptability for indirect food contact applications.
- dodecanedioic acid comprises the activator.
- sebacic acid comprises the activator.
- the diacids have the ability to react with the comonomer constituents, and thus can both catalyze the ring opening of maleic groups, and can graft onto the polymer. It has also been found that there is an upper limit of diacid beyond which no additional improvements are achieved.
- the diacid compounds are dispersed in the liquid phase together with the other dispersed ingredients. It is important that the diacid particles do not become soluble in the liquid at temperatures below 140°F. In this way, the stability of the liquid adhesive is maintained both during storage and during shipping.
- the preferred formulation should also contain a thermal stabilizer so that adequate process stability can be achieved.
- a thermal stabilizer Two stabilizers that have been found to be adequate for this purpose include Irganox
- the aforementioned dispersion state ingredients can be further mixed with inorganic nano-materials such as montmorillonites (aluminum silicates), aluminum oxide and its hydrate forms, titanium dioxide, zinc oxide, iron oxide, etc.
- nanoparticles have the added benefit of increasing the modulus, the cohesive strength, and the heat distortion temperature of the finished adhesive. However, such improvements are only realized when the nanoparticles are properly mixed and exfoliated in the finished solid adhesive.
- the nanometer-sized platelets have a major influence on the molecular configuration of the polymer chains (since the dimensions of a nanoparticle are on the same scale as the dimensions of a polymer chain).
- An unperturbed polymer chain has a characteristic radius of gyration that roughly depends on its molecular weight, and bond rotational barriers (stiffness).
- the polymer can adopt an extended chain configuration as it stretches out and adsorbs onto the nano-surface. This has the effect of raising bond rotational barrier energies, and making the chain stiffer. Consequently, macroscopic properties like modulus, toughness, diffusion, and heat distortion are all affected.
- montmorillonite can be exfoliated with the aforementioned dispersion ingredients in any combination to form a nanocomposite adhesive. Aside from having a higher modulus, the nanocomposite also exhibits a higher heat distortion temperature, and improved adhesion at elevated temperatures. The heat distortion temperature increases by as much as 25°F to 30°F with as little as 3% to 6% montmorillonite by weight.
- molten-state mixing is critical.
- the adhesive cools to form a solid, which in turn can be re-melted and used as a traditional hot melt adhesive.
- the adhesive could be fabricated into solid pellets, which would render it useful with traditional hot melt adhesive equipment if so desired.
- solidified pellets or powders of the formulations encompassed by this invention could in themselves be used as formulation additives for traditional, extruded and/or pelletized, hot melt adhesives.
- traditional hot melts could reap the benefits of improved adhesion as well as enhanced physical properties from exfoliated nanoparticles.
- the solidified versions of the formulations encompassed by this invention are indeed useful and novel, the liquid nature of this adhesive and its shelf stability are an especially advantageous aspect of the invention.
- the adsorbent phase and reinforcing phase polymers could be premixed together with the remaining solid ingredients (through melt or solution blending), pulverized, and subsequently dispersed as particulates into a liquid medium.
- a process could be employed that performs both the premixing function, and facilitates the application of the molten, blended adhesive composition directly onto the substrates that are to be adhered.
- nanoparticle aggregates are exfoliated in the hot-melt molten state, while in another embodiment, they are pre-exfoliated in the dispersion state.
- nanoparticle aggregates are added to the dispersion with surprisingly little to no change in the dispersion state viscosity. The aggregates are then exfoliated during the melt- processing stage to yield a true nanocomposite adhesive. This method offers a process advantage from the standpoint that nanocomposite materials can be formed from relatively low-viscosity liquid dispersions.
- nanoparticles when incorporated as aggregates, they have little to no effect on viscosity, and no special process equipment is required to pump or mix the liquid dispersions. Instead, partial or complete exfoliation is accomplished later, through high shear mixing during the final application process.
- the aggregates are purposely pre-exfoliated (either partially or completely) in the dispersion state to yield controlled rheological characteristics ranging from those of a liquid to those of a gel, independent of the organic ingredient concentrations. Exfoliation (either in the dispersion state or in the molten state) can be achieved through any combination of methods, including those that employ high shear mixing, and/or ultrasound.
- enhanced physical properties are only achieved when the nanoparticle aggregates are exfoliated (either partially or completely) in the finished solid adhesive.
- other polymer solutions and dispersions can also benefit from the processing advantages of incorporating nanoparticles through the unique methods of exfoliation as described above.
- Some of these polymer dispersions and solutions may include but are not limited to plastisols, caulks, sealants, paints, and coatings.
- MicrotheneTM FE532 EVA [24937-78-8], 8 to 9% vinyl acetate, melt index 9.5, from Equistar b. MicrotheneTM FN519 LDPE [9002-88-4] from Equistar c. MicrotheneTM FP800 PP [9003-07-0] from Equistar d. MicrotheneTM FN510 LDPE [9002-88-4] from Equistar e. MicrotheneTM FN501 LDPE [9002-88-4] from Equistar f. MicrotheneTM FA700 HDPE [25087-34-7] from Equistar g. Epolene E43P maleated polypropylene from Eastman h. Epolene C16P maleated polyethylene from Eastman i. Diisononylphthalate (DINP) j. Dioctylphthalate (DOP) k. Dibutylphthalate (DBP)
- EQM-PE maleated polyethylene from Equistar v. Permalyn 3100; rosin ester of pentaerythritol (Eastman) w. Piccotac B; mixed hydrocarbon tackifier (Eastman) x. EQ-EVA; poly(ethylene-co-vinyl acetate), 18% vinyl acetate from Equistar y. Isostearic Acid [2724-58-5], Emersol 875 from Henkel z. Omya, 30 micron, calcium carbonate powder aa. Capa 6501, polycaprolactone from Solvay bb. Nanomer 1-44, surface treated nano-sized montmorillonite (Nanocor) cc.
- the "liquid form” of the adhesives was prepared by dispersing the solid ingredients into the liquids at room temperature (into 40 ml glass jars with lids). The dispersions were hand mixed with a spatula. An aliquot of the adhesive (1 to 2 grams) was placed onto a 4"x4" piece of aluminum foil. The foil was placed onto a hot plate at a specified temperature, and was allowed to set for one minute. The "hot melt” form of the adhesives were then mixed with a spatula until visual homogeneity was achieved.
- Example 1 This example illustrates the relative adhesion performance and compatibility of several solid/liquid dispersions (Table 1).
- the solid/liquid ratio was chosen in each case to insure that the dispersions behaved as liquids at room temperature.
- the liquid dispersions in Table 1 fused to become molten liquids at elevated temperatures. All samples except for 1-16 and 1-17 gelled to become solid blends upon cooling.
- solubility parameters in MPa 1/2 for PE, EVA, and PP range respectively from 15.76 to 17.99 for PE; 17.0 to 18.6 for EVA; and 18.8 to 19.2 for PP.
- solubility parameters for paraffinic hydrocarbons range from 15 to 18 (see
- EVA/DINP blends are not; especially given that DINP is more polar than mineral oil, and EVA is more polar than PP. It is also of interest that the finished HDPE/DOP blends are compatible, whereas the higher molecular weight DINP shows signs of exudation. Furthermore, unlike the other polyolefins, HDPE appears to be less compatible with the liquid in the molten state. Placing the molten HDPE/DOP and
- HDPE/DINP blends directly onto adsorbent paper towels served to further verify this visual observation.
- the paper became immediately saturated with the liquid.
- Similar tests were also performed with maleated PP/mineral oil blends, but no visual evidence of saturation was observed.
- the results in Table 2 also show that with the exception of HDPE/DOP blends, liquid adsorption is accompanied by a qualitative decrease in strength as can be seen by comparing neat PP (1-12) with the liquid/PP blends.
- the other polyolefin/liquid blends tend to retain higher levels of toughness and strength, their exudation is extreme.
- stearic acid like PP and maleated PP
- stearic acid is capable of adsorbing liquids like mineral oil.
- the resultant low molecular weight gel has even less cohesive strength than the compatible PP/liquid blends, and thus it cannot be used as an adhesive by itself.
- Acrawax C and PSMA are also capable of adsorbing mineral oil and DBP, respectively, but no adhesion is achieved.
- the solid tackifiers, Piccotac B and Permalyn 3100 fuse with mineral oil to produce compatible, liquid solutions at room temperature. Needless to say, these liquids have no cohesive strength.
- Example 2 This example demonstrates the feasibility of using multiple component liquid dispersions to both minimize exudation and to maintain sufficient cohesive strength in the finished adhesive.
- the candidates for "Component B” in these formulations are chosen based on their ability to prevent liquid exudation by themselves as shown in Example 1.
- the "diacid” in this example refers to dodecanedioic acid.
- the formulations are provided in Table 3.
- Samples 2-1 to 2-3 show that when stearic acid is blended with EVA, exudation is greatly decreased, but no adhesion is observed. Surprisingly, when a second acid is added (dodecanedioic acid), exudation is further reduced, and adhesion to paper stock is excellent. Samples 2-4 to 2-11 also show that stearic acid prevents exudation of mineral oil from both HDPE and LDPE. Dodecanedioic acid also provides some benefit. However, only the EVA/stearic acid/dodecanedioic acid blend provides adhesion. Thus, the prevention of exudation alone is not enough to insure adhesion. Instead, at least one of the components must have functionality that is capable of bonding with the substrate, either alone or through activation with another additive.
- Samples 2-12 to 2-15 make use of polypropylene and maleated polypropylene as alternatives to stearic acid. Like stearic acid, these polymers also prevent exudation of liquids from EVA. Surprisingly however, only maleated polypropylene with mineral oil provides adequate adhesion. Even though exudation is minimal, adhesion does not occur with polypropylene homopolymer (even in the presence of dodecanedioic acid).
- Samples 2-16 to 2-19 make use of the "adsorbent" polymer/liquid combinations that were discussed in Example 1, but with alternatives to EVA as the primary polymer component.
- Sample 2-16 makes use of polypropylene blended with maleated polypropylene and mineral oil. Unlike EVA, polypropylene is capable of adsorbing mineral oil (see Example 1). However, the resultant finished adhesive is cohesively weak and waxy, and no adhesion is observed. Thus, it is important that the blend contain a primary polymer component (the "reinforcing phase” as defined in this invention), which by itself, is incompatible with the liquid.
- the primary component can provide the adhesive with strength
- the secondary component i.e., the "adsorbent phase”
- the liquid can prevent exudation.
- sample 2-25 which contains an excess of maleated polypropylene as the adsorbent polymer blended with EVA. This blend does not exude, but unlike its sample 2-14 counterpart (with EVA in excess), no adhesion is observed. Instead, this blend is cohesively weak and waxy like sample 2-16.
- Sample 2-17 makes use of maleated polyethylene blended with an HDPE adsorbent phase, and DOP.
- This adhesive qualitatively has moderate cohesive strength, and it exhibits no exudation. However, it also exhibits no adhesion to paper, much like its sample 2-20 counterpart (with EVA instead of maleated polyethylene). Even the addition of dodecanedioic acid (sample 2-18) does not improve adhesion. Again, these results further illustrate that minimizing exudation is in itself not enough to enable adhesion. Instead, the combination- of low exudation, polymer functionality, liquid . type, and secondary additives may all be important.
- the reinforcing polymer must also be present at an adequate level in the overall formulation.
- Acids other than dodecanedioic acid can also be used to produce adequate adhesion as shown by sample 2-26, which makes use of sebacic acid together with maleated polypropylene as the adsorbent phase.
- Tackifiers can also be employed to reduce the melt viscosity of the formulation, and to help prevent exudation of the liquid phase.
- Permalyn 3100 a pentaerythritol rosin ester "tackifier”
- tackifier a pentaerythritol rosin ester
- tackifier additives are often used in traditional hot melt adhesive applications to achieve lower melt viscosities, and to improve adhesion to certain substrates.
- tackifiers like Permalyn 3100 and Piccotac B can be incorporated, but only insofar as the cohesive strength of the resultant adhesive is not unduly compromised.
- Samples 2-31 and 2-33 make use of isostearic acid as an alternative liquid phase to mineral oil.
- isostearic acid is compatible with maleated PP after melt blending.
- This effect is also manifested in the multi-component blends of this example, where both adhesives exhibit qualitatively moderate cohesive strengths without signs of exudation.
- the adhesives with isostearic acid as the liquid phase do not adhere to paper, unlike their 2-26 and 2-32 mineral oil counterparts (with EVA and maleated polyethylene as the reinforcing phases, respectively).
- Samples 2-34 and 2-35 are also non-exuding as might be anticipated from the results presented in Example 1. Surprisingly however, these samples do not adhere to paper. Again, these results further illustrate that minimizing exudation is in itself not enough to enable adhesion.
- Example 3 This example demonstrates the surprising effect that the adsorbent phase can have on the moderate temperature storage stability of the liquid dispersions.
- certain adsorbent phase candidates are capable of producing finished adhesives that exhibit minimal exudation, and excellent adhesion to paper.
- many of these adsorbent phase candidates tend to negatively impact the storage stability of the liquid dispersions.
- certain adsorbent phase materials do not negatively affect the storage stability; and as such, they define a preferred embodiment of this invention.
- a good adsorbent phase for this application is a crystalline or semicrystallme material that does not adsorb the liquid phase until it is molten.
- the melt point of the adsorbent phase should be higher than the highest anticipated storage temperature for the liquid dispersion.
- stearic acid dissolves and melts in the mineral oil at moderate temperatures. Upon cooling, the stearic acid then phase separates, recrystallizes, and gels with the mineral oil.
- the adsorbent phase material Upon recrystallization, the adsorbent phase material must also be able to retain the liquid phase. This is indeed the case for both stearic acid and maleated PP with mineral oil, and for HDPE with DOP. However, of the three examples cited here, only the maleated PP displays the unique capability of providing adequate end-use adhesion, and acceptable storage stability.
- Example 4 This example demonstrates the effect of mixing (and hence the effect of the application process) on the resultant adhesion.
- Sample 2-30 was heated on a hot plate at 385°F, and was mixed according to the procedure outlined above.
- a second sample of the same formulation was heated, but without mixing.
- Adhesion coupons were prepared in both cases for relative comparison.
- the mixed sample exhibited fiber tear adhesion 5 out of 5 times, whereas the unmixed sample provided no adhesion. In the absence of mixing, the cohesive strength of the adhesive was significantly reduced.
- this example demonstrates a preferred method for applying the adhesive of this invention.
- the adhesive must either be premixed, or it must be mixed during the application process, otherwise the adhesive will not produce adequate adhesion to the substrate.
- Example 5 This example demonstrates the effect of temperature on adhesion in the presence and absence of diacid. It also demonstrates the effect of mixed dicarboxylic acid additives on adhesion. The procedures are the same as those used in Example 2, except samples were processed at temperatures of 345°F, 385°F, and 430°F. Table 7 provides the comparative formulations for this example, and Table 8 provides the results, including exudation upon cooling, exudation after 24 hours, and adhesion to paper. The exudation results were judged for samples that were processed at 385°F, whereas adhesion was judged at all three temperatures.
- the composition should contain preferably between zero and 15% of a dicarboxylic acid "activator" by weight.
- a mixture of dicarboxylic acids e.g. Corfree Ml, which contains fractions of both dodecanedioic acid and sebacic acid
- the preferred adhesive of this invention is comprised of a dicarboxylic acid "activator" additive such as dodecanedioic acid or sebacic acid.
- a dicarboxylic acid "activator” additive such as dodecanedioic acid or sebacic acid.
- these additives not only minimize exudation as shown here- and in Example 2, but they also lower the minimum threshold temperature required to achieve adhesion.
- the preferred method of application not only involves mixing as shown in Example 4, it involves heating the adhesive to a certain minimum threshold temperature so as to achieve adhesion, where the minimum threshold temperature is affected by the presence or absence of a dicarboxylic acid in the formulation.
- Example 6 This example describes the effect of component ratios on viscosity, shelf stability, and adhesion.
- Table 9 were made according to procedures outlined in Examples 1 and 2.
- the level of sebacic acid was kept constant (at 0.7g) as was the total level of resin (at 6.5g), while the ratio of adsorbent phase to reinforcing phase was varied, as was the level of liquid.
- the level of exudation generally increases as the level of the adsorbent phase is decreased, and as the level of liquid phase is increased.
- the samples with the best adhesion are those that have higher ratios of the adsorbent phase to the liquid phase (i.e. those that exhibit the lowest levels of exudation).
- Example 7 This example demonstrates the use of heat stabilizers and inorganic additives in the adhesive formulations of this invention.
- the formulations (shown in Table 11) were made according to procedures outlined in Examples 1 and 2. After hot melt mixing at 385°F, adhesion coupons were prepared, and the remainder of each sample was allowed to cool to room temperature on aluminum foil. The samples were visually inspected for exudation after 24 hours. Paper adhesion was tested (as described in Example 2) after 1 day. Each adhesive (in liquid dispersion form) was also placed in a 45°C oven for 24 hours to test shelf stability as judged by the relative increase in viscosity. The results reported in Table 12 show that the formulations exhibit good adhesion, minimal exudation, and good shelf stability at moderate temperatures.
- Example 8 This example demonstrates the effect of the liquid adsorbent phase on the "set time” of the adhesive.
- the “set time” in this example is defined as the time required for the adhesive to change from a molten liquid to a solid.
- 1.0 g of each formulation was melt- blended at 385°F according to procedures in Examples 1 and 2.
- the samples were removed from the hot plate and placed on a bench top at room temperature to cool.
- the adhesives were visually monitored for the "onset time of set,” or the time required for the first sign of crystallization to appear as visually monitored by the appearance of any sign of opacity.
- the "set time” of the adhesives was recorded as the time required for the entire adhesive to appear opaque. At this point, the adhesive was also observed to be solid as judged by pressing it with a metal spatula.
- Formulations for this example are provided in Table 13, and results are presented in Table 14. TABLE 13: Formulations used in Example 8.
- Example 9 This example demonstrates the effect of the reinforcing phase copolymer composition on adhesive performance.
- an ethylene copolymer with a higher level of vinyl acetate of 18% VA (sample 3-4) was shown to have worse shelf stability than a copolymer with 9% VA when the polymer particles were dispersed in mineral oil.
- a higher vinyl acetate level particularly when copolymerized with an additional monomer such as methacrylic acid, or maleic anhydride, can yield a particularly useful polymer for the purposes of this invention.
- polymer particles of this type should be protected with a coating layer of a polymer that is not permeated by the liquid phase until the temperature is raised beyond some critical level.
- Such a coating could be for example, an ethylene copolymer with a lower vinyl acetate content, a copolymer of ethylene and methacrylic acid, a polysiloxane, polyethylene, polypropylene, a polypropylene copolymer, or others.
- the polymer pellets were placed into separate glass vials at a 1/1-weight ratio of mineral oil to polymer.
- the vials were placed into an oven set at 50°C, and were removed after overnight exposure.
- the samples were allowed to cool to room temperature, and were then evaluated for gelation.
- the Elvax 4355 pellets (25%VA, 0.7 to 1.4%MA) were completely gelled with one another, whereas the Nucrel 3990 (9%MA) pellets were still free flowing. This result was consistent with earlier observations that showed the detrimental effect of higher vinyl acetate levels on shelf storage stability.
- Formulations were prepared with 4.5g of each pelletized polymer, 2.0g of E43P maleated polypropylene, 0.7g sebacic acid, and 4g of mineral oil. Table 15 shows the results for paper adhesion, and 24-hour exudation evaluations for the two comparative formulations. TABLE 15. Comparative paper adhesion and exudation of formulations made with Nucrel 3990 and Elvax 4355.
- Example 10 This example demonstrates the possibility of using a different adsorbent phase (polycaprolactone) and a different liquid phase (dibutylphthalate) to produce a shelf-stable liquid dispersion that could be fused to form a non-exuding, solid product.
- adsorbent phase polycaprolactone
- a different liquid phase dibutylphthalate
- the formulations in this example were found to exhibit low levels of adhesion to paper.
- the results still demonstrate the broad scope of the invention: namely, stable, non-exuding solids can be fused from liquid dispersions when the appropriate adsorbent phase and liquid phase are chosen.
- a similar formulation was prepared using 4g FE532 EVA, 2.5g Capa 6501, 0.7g sebacic acid, and 4.5g DBP.
- the finished adhesives with Capa/DBP produced no exudation. However, they were cohesively weaker (qualitatively). Also, unlike E43/mineral oil formulations, the Capa/DBP formulations did not adhere to paper stock.
- this example also serves to further demonstrate the surprising uniqueness of E43P/mineral oil formulations. Namely, even though both Capa DBP and E43P/mineral oil formulations do not exude, only the E43P/mineral oil formulations provide excellent adhesion to paper stock. Thus, minimal exudation is not in itself a guarantee of good adhesion.
- Example 11 This example demonstrates the effect of nanoparticles on the heat distortion temperature, as judged by the upper temperature for cohesive failure of paper stock, and the relative adhesive stiffness. The example also demonstrates the sensitivity of end-use performance to the method by which the mixture is processed.
- the formulations for this example were melt blended with a spatula over a hot plate for 1 minute at 385°F, and were then tested for both exudation and paper adhesion (via methods and procedures outlined in prior examples). Paper adhesion was also evaluated at elevated temperatures by allowing coupons to equilibrate for 30 minutes in an oven at various preset temperatures prior to tear testing.
- the nanoparticle material for this example was Nanomer 1-44 montmorillonite from Nanocor.
- the nanoparticles were incorporated in one of two ways: they were either directly added to the formulation (in their aggregated form as-received); or they were pre-blended to form a mineral oil/nanoparticle concentrate, which was then subsequently diluted into the formulation at the appropriate level.
- Mineral oil/nanoparticle concentrates were prepared by blending 70/30 ratios of oil to powder in a small Hobart mixer. Simple stirring of the 70/30 mixture produced a low viscosity slurry. However, high intensity blending with the Hobart mixer provided the shear required to at least partially exfoliate the aggregated particles, as evidenced by the formation of a high viscosity gel. This gel was then diluted into the finished fo ⁇ nulation with simple low shear stirring (using a hand held spatula) to produce a pourable liquid dispersion with the desired level of Nanomer 1-44.
- this invention provides a method by which nanoparticles can be exfoliated and subsequently incorporated into fusible liquid formulations to produce adhesives with substantial property improvements.
- Example 12 This example further demonstrates the sensitivity of end-use performance to the method by which the nanocomposites are processed.
- the formulations for this example were melt blended with a spatula over a hot plate at 385°F for a specified time, and were then tested for both exudation and paper adhesion (via methods and procedures outlined in prior examples). Paper adhesion was also evaluated at elevated temperatures by allowing coupons to equilibrate for 30 minutes in an oven at various preset temperatures prior to tear testing.
- the nanoparticle material for this example was Nanomer 1-44 montmorillonite from Nanocor.
- the nanoparticles were incorporated in one of two ways. In sample 12- 1, they were directly added "as-received" to the formulation (in their aggregated form).
- mineral oil/nanoparticle concentrates were first prepared by blending 70/30 ratios of oil to powder in a small Hobart mixer. As noted in Example 11, simple stirring of the 70/30 mixture produced a low viscosity slurry. High intensity blending with the Hobart mixer provided the shear required to exfoliate the aggregated particles, as evidenced by the formation of a high viscosity gel. Using simple low shear stirring (with a hand held spatula), the concentrated gel was then diluted into neat mineral oil (minus the other ingredients). The resultant low viscosity dispersion of Nanomer 1-44 in oil was then exposed to an ultrasound bath for one hour in an attempt to further exfoliate the nanoparticles.
- the Nanomer I-44/oil mixture Upon removal from the ultrasound bath, the Nanomer I-44/oil mixture was observed to be a translucent gel, indicative of a higher degree of exfoliation than was achieved with a similar sample, 11-3. At this point, the remainder of the formulation ingredients was added to yield a gelled version of the adhesive, with otherwise the same composition as sample 12-1. Thus, the dispersions differed only in the methods used to prepare them.
- the ingredients in both 12-1 and 12-2 were as follows: FE 532 EVA, 4.5 g (35.9%), E43P, 2.0 g (16.0%),
- Sebacic acid 0.7 g (5.6%), Mineral oil, 5.0 g (39.9%), and Nanomer 1-44, 0.32g (2.6%).
- Samples 12-1 and 12-2 were hot plate blended for one minute at 385°F (with the usual one minute pre-heat period). In addition, a second aliquot of sample 12-1 was hot plate blended (with rigorous stirring) until the degree of translucency was qualitatively equivalent to the translucency of sample 12-2 (approximately five minutes of mixing time was required). Thus, the hot-melts differed only in the time and shear applied during blending. Table 19 provides a summary of the comparisons. Table 20 compares the adhesion results at room temperature and at a substrate temperature of 140°F. TABLE 19: Comparison of methods used to process Nanomer 1-44 in comparative samples from Example 12.
- a gel or paste could be useful in a continuous application process where it is important to maintain a bond-line during the working period between an adhesive's application, and its final "cure.”
- a gel or paste could also be useful in a caulking application where a continuous bead is to be applied, and then heated to achieve final fusion.
- the aggregate dispersion form of this invention enables the use of simple processing equipment for low viscosity liquids. Subsequent shear can then be applied during the stage of molten hot-melt mixing to achieve adequate exfoliation, together with adequate mixing of the reinforcing and adsorbent phases of the dispersion.
- any intermediate stage i.e., partial pre- exfoliation
- the nanoparticle aggregates could be added directly to any hot melt-adhesive formulation (either the conventional solid-types or the novel hybrid types of this invention) with the objective of postponing the exfoliation step until the pellets or liquids are subjected to the final process of application to a packaging substrate.
- any hot melt-adhesive formulation either the conventional solid-types or the novel hybrid types of this invention
- the process costs associated with pre- exfoliation could be minimized, and the benefits of nanocomposite enhancement could be achieved by subjecting the adhesives to sufficient shear during the process of applying the adhesive to a substrate.
- Example 13 Formulations were made for the purpose of determining the effect of reinforcing phase molecular weight and vinyl acetate level on adhesion. All formulations were prepared with 4.5g of the reinforcing phase polymer, 2.0g E43P adsorbent phase, 0.7g sebacic acid activator, and 5.0g mineral oil. The procedures for mixing were the same as those reported in Examples 1 and 2. Paper tear coupons were also made as described in prior examples. Paper tear adhesion was tested as a function of substrate temperature using the procedures as outlined in Examples 11 and 12. Comparative polymers for this example are listed in Table 21. The results of paper tear adhesion vs. temperature are provided in Table 22.
- an increase in the molecular weight of the reinforcing phase leads to improved adhesion at elevated temperatures.
- the preferred molecular weight of the reinforcing phase will depend on the desired end-use temperature range, as well as the desired melt-process characteristics (the viscosity of the molten state will increase with increasing molecular weight).
- an increase in the VA% at an otherwise constant molecular weight leads to a decrease in the upper adhesion temperature.
- the preferred VA content will also depend on the desired end-use temperature range, as well as the desired melt-process characteristics (the viscosity of the molten state will generally decrease with increasing VA content).
- the upper VA limit is also dependent on the desired storage temperature characteristics for the liquid dispersion (higher VA level leads to a lower storage temperature limit for reasons related to gelation). It can also be appreciated from prior examples that the heat distortion temperature and hence the upper temperature adhesion threshold can be increased through the incorporation of nanoparticles ⁇ independent of molecular weight and VA content.
- the embodiments of this invention provide the capability to produce adhesives with a wide range of processing and end-use characteristics.
- Example 14 Formulations were prepared for the purpose of illustrating the utility of an adsorbent phase comprised of a blend of polypropylene homopolymer and maleated polypropylene. The results of show that little to no adhesion is achieved when the adsorbent phase is comprised of polypropylene homopolymer. However, when maleated PP is blended with PP to form the adsorbent phase, acceptable adhesion is achieved. This result shows that the preferred adhesive is one where the adsorbent phase is comprised of maleated PP, or PP blended with maleated PP.
- the formulations for this example were made and tested in accordance with the aforementioned procedures. The formulations and results are provided in Table 23.
- Example 15 The purpose of this example is to demonstrate that density reduction can be achieved through the incorporation of foaming agents.
- hot-melt adhesives When hot-melt adhesives are dispensed as a cellular foam, they provide significant economical advantages by decreasing the mass of adhesive required to obtain any given adhesive bead volume or dimension. For example, adding 30% gas by volume to a given hot-melt will decrease its mass by the same amount; therefore decreasing the cost per bead by the same amount.
- Formulation 15-1 was pumped under pressure from its ambient container through a heat exchanger to elevate its temperature to 350°F.
- the liquid became molten as it passed through the heater. Viscous drag in the heater provided adequate shear for mixing the polymer blend to form a homogeneous melt.
- the chemical blowing agent decomposed to liberate nitrogen gas into the molten adhesive. The gas remained solvated at a pressure of 300 psi.
- Solvation of the gas was audibly detected as the molten liquid was dispensed to atmospheric pressure.
- audible crackling and hissing sounds were observed to emanate from the dispensing nozzle tip. Crackling sounds were readily observed at 100 psi, and the audible level was observed to gradually decrease until no sound could be heard at 300 psi.
- the extruded material was observed to expand to form a closed cell foam.
- the formulation did not foam, and at 150 psi, the cellular foam structure started to appear with relatively large combinations of open and closed cells. The cell structure was observed to become finer and predominantly closed-cell in nature as the pressure approached 300 psi.
- the resulting extrudate produced a fine, closed-cell foam.
- the resultant 15-1 extrudate provided a density reduction of approximately 49%.
- the foamed hot-melt adhesive provided excellent paper-tear adhesion.
- the invention described herein provides for many additional potential uses. These uses include, but are not limited to, adhesives for other materials; caulking materials; sealants; gaskets; encapsulants to facilitate controlled release of natural and synthetic products in applications ranging from agricultural to medical applications; low adhesion strippable protective coatings for metals and wires (as such they could be formulated with corrosion inhibitors); textile coatings; thermoset coatings for applications demanding abrasion resistance such as floor tiles, wood, and furniture; wear layers for flexible sheet flooring; chemically embossable foamed layers for flexible sheet flooring; safety glass interlayers and solar cell encapsulants; injection molded parts for toys; components for consumer goods; components for industrial and automotive applications; components for construction applications, plumbing applications, electrical applications; and others.
- both release and adhering embodiments of this invention could be formulated to serve as barrier coatings for civil and military defense applications.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
- Packages (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03772123A EP1543086A4 (en) | 2002-07-30 | 2003-07-30 | Hybrid plastisol/hot melt compositions |
JP2004524226A JP4792223B2 (en) | 2002-07-30 | 2003-07-30 | Plastisol / hot melt composite composition |
MXPA05001103A MXPA05001103A (en) | 2002-07-30 | 2003-07-30 | Hybrid plastisol/hot melt compositions. |
AU2003257047A AU2003257047B2 (en) | 2002-07-30 | 2003-07-30 | Hybrid plastisol/hot melt compositions |
CA2493515A CA2493515C (en) | 2002-07-30 | 2003-07-30 | Hybrid plastisol/hot melt compositions |
CN038229498A CN1685025B (en) | 2002-07-30 | 2003-07-30 | Hybrid plastisol/hot melt compositions |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US39953502P | 2002-07-30 | 2002-07-30 | |
US60/399,535 | 2002-07-30 | ||
US41290702P | 2002-09-23 | 2002-09-23 | |
US60/412,907 | 2002-09-23 | ||
US43384002P | 2002-12-16 | 2002-12-16 | |
US60/433,840 | 2002-12-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004011569A1 true WO2004011569A1 (en) | 2004-02-05 |
Family
ID=31192101
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2003/023873 WO2004011569A1 (en) | 2002-07-30 | 2003-07-30 | Hybrid plastisol/hot melt compositions |
Country Status (7)
Country | Link |
---|---|
US (5) | US7285583B2 (en) |
EP (1) | EP1543086A4 (en) |
JP (1) | JP4792223B2 (en) |
CN (1) | CN1685025B (en) |
CA (1) | CA2493515C (en) |
MX (1) | MXPA05001103A (en) |
WO (1) | WO2004011569A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005087889A1 (en) * | 2004-03-18 | 2005-09-22 | Siew Puat Yeo | Adhesive composition |
WO2006004750A1 (en) * | 2004-06-28 | 2006-01-12 | Dow Global Technoligies Inc. | Adhesion promoters for multistrucural laminates |
US8012540B2 (en) | 2006-04-07 | 2011-09-06 | Addcomp Holland Bv | Aqueous emulsion comprising a functionalized polyolefin and carbon nanotubes |
Families Citing this family (102)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7285583B2 (en) * | 2002-07-30 | 2007-10-23 | Liquamelt Licensing Llc | Hybrid plastisol/hot melt compositions |
US20050097046A1 (en) | 2003-10-30 | 2005-05-05 | Singfield Joy S. | Wireless electronic check deposit scanning and cashing machine with web-based online account cash management computer application system |
EP1570831A1 (en) * | 2004-03-02 | 2005-09-07 | Ernst Mühlbauer GmbH & Co.KG | Polymerisable dental material containing a filler |
US7381035B2 (en) * | 2004-04-14 | 2008-06-03 | Nordson Corporation | Piston pump with check shaft |
US20050230423A1 (en) * | 2004-04-14 | 2005-10-20 | Riney John M | Applicators for liquid hot melt adhesive and methods of applying liquid hot melt adhesive |
US7237578B2 (en) * | 2004-07-21 | 2007-07-03 | Nordson Corporation | Rechargeable dispensing head |
US7221859B2 (en) * | 2004-12-01 | 2007-05-22 | Liquamelt Corp. | Multi-function heat exchanger |
US7456233B2 (en) * | 2005-02-16 | 2008-11-25 | Nordson Corporation | Adhesive composition |
US20070249771A1 (en) * | 2006-04-21 | 2007-10-25 | Paul Charles W | Hot melt adhesive for packaging applications |
US7876949B1 (en) | 2006-10-31 | 2011-01-25 | United Services Automobile Association | Systems and methods for remote deposit of checks |
US8708227B1 (en) | 2006-10-31 | 2014-04-29 | United Services Automobile Association (Usaa) | Systems and methods for remote deposit of checks |
US8351677B1 (en) | 2006-10-31 | 2013-01-08 | United Services Automobile Association (Usaa) | Systems and methods for remote deposit of checks |
US7885451B1 (en) | 2006-10-31 | 2011-02-08 | United Services Automobile Association (Usaa) | Systems and methods for displaying negotiable instruments derived from various sources |
US8799147B1 (en) | 2006-10-31 | 2014-08-05 | United Services Automobile Association (Usaa) | Systems and methods for remote deposit of negotiable instruments with non-payee institutions |
US7873200B1 (en) | 2006-10-31 | 2011-01-18 | United Services Automobile Association (Usaa) | Systems and methods for remote deposit of checks |
US8959033B1 (en) | 2007-03-15 | 2015-02-17 | United Services Automobile Association (Usaa) | Systems and methods for verification of remotely deposited checks |
US10380559B1 (en) | 2007-03-15 | 2019-08-13 | United Services Automobile Association (Usaa) | Systems and methods for check representment prevention |
US8475621B2 (en) * | 2007-04-24 | 2013-07-02 | Honeywell International Inc. | Adhesion promotion to difficult substrates for hot melt adhesives |
US8433127B1 (en) | 2007-05-10 | 2013-04-30 | United Services Automobile Association (Usaa) | Systems and methods for real-time validation of check image quality |
US8538124B1 (en) | 2007-05-10 | 2013-09-17 | United Services Auto Association (USAA) | Systems and methods for real-time validation of check image quality |
US7741395B2 (en) * | 2007-08-21 | 2010-06-22 | Eastman Chemical Company | Low volatile organic content viscosity reducer |
US9058512B1 (en) | 2007-09-28 | 2015-06-16 | United Services Automobile Association (Usaa) | Systems and methods for digital signature detection |
SI2047891T1 (en) | 2007-10-10 | 2012-04-30 | Todi Sport Ag Glarus | Climbing assistance for snow sport equipment |
US9892454B1 (en) | 2007-10-23 | 2018-02-13 | United Services Automobile Association (Usaa) | Systems and methods for obtaining an image of a check to be deposited |
US9159101B1 (en) | 2007-10-23 | 2015-10-13 | United Services Automobile Association (Usaa) | Image processing |
US9898778B1 (en) | 2007-10-23 | 2018-02-20 | United Services Automobile Association (Usaa) | Systems and methods for obtaining an image of a check to be deposited |
US8358826B1 (en) | 2007-10-23 | 2013-01-22 | United Services Automobile Association (Usaa) | Systems and methods for receiving and orienting an image of one or more checks |
US7996315B1 (en) | 2007-10-30 | 2011-08-09 | United Services Automobile Association (Usaa) | Systems and methods to modify a negotiable instrument |
US7996316B1 (en) | 2007-10-30 | 2011-08-09 | United Services Automobile Association | Systems and methods to modify a negotiable instrument |
US7996314B1 (en) | 2007-10-30 | 2011-08-09 | United Services Automobile Association (Usaa) | Systems and methods to modify a negotiable instrument |
US8046301B1 (en) | 2007-10-30 | 2011-10-25 | United Services Automobile Association (Usaa) | Systems and methods to modify a negotiable instrument |
US8001051B1 (en) | 2007-10-30 | 2011-08-16 | United Services Automobile Association (Usaa) | Systems and methods to modify a negotiable instrument |
US8290237B1 (en) | 2007-10-31 | 2012-10-16 | United Services Automobile Association (Usaa) | Systems and methods to use a digital camera to remotely deposit a negotiable instrument |
US8320657B1 (en) | 2007-10-31 | 2012-11-27 | United Services Automobile Association (Usaa) | Systems and methods to use a digital camera to remotely deposit a negotiable instrument |
US7900822B1 (en) | 2007-11-06 | 2011-03-08 | United Services Automobile Association (Usaa) | Systems, methods, and apparatus for receiving images of one or more checks |
US7896232B1 (en) | 2007-11-06 | 2011-03-01 | United Services Automobile Association (Usaa) | Systems, methods, and apparatus for receiving images of one or more checks |
US20090124737A1 (en) * | 2007-11-12 | 2009-05-14 | Eastman Chemical Company | Acrylic plastisol viscosity reducers |
JP2011506634A (en) * | 2007-12-07 | 2011-03-03 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Binder composition and asphalt mixture |
EP2072028A1 (en) * | 2007-12-21 | 2009-06-24 | Ernst Mühlbauer GmbH & Co.KG | Stump construction |
US10380562B1 (en) | 2008-02-07 | 2019-08-13 | United Services Automobile Association (Usaa) | Systems and methods for mobile deposit of negotiable instruments |
AU2013202086B2 (en) * | 2008-02-26 | 2015-02-26 | H.B. Fuller Company | Energy-activated room temperature-pumpable polymer compositions and devices for activating and dispensing the same |
CN104194029A (en) * | 2008-02-26 | 2014-12-10 | H.B.富勒公司 | Energy-activated room temperature-pumpable polymer compositions and devices for activating and dispensing the same |
US8351678B1 (en) | 2008-06-11 | 2013-01-08 | United Services Automobile Association (Usaa) | Duplicate check detection |
US8422758B1 (en) | 2008-09-02 | 2013-04-16 | United Services Automobile Association (Usaa) | Systems and methods of check re-presentment deterrent |
US10504185B1 (en) | 2008-09-08 | 2019-12-10 | United Services Automobile Association (Usaa) | Systems and methods for live video financial deposit |
CA2734411C (en) * | 2008-09-10 | 2014-05-06 | Stephen D. Horton | Soft, pelletized poly(vinyl chloride) plastisol |
CN102159658A (en) * | 2008-09-23 | 2011-08-17 | 芬欧汇川木业公司 | Glue line material for wood board and wood board |
US8275710B1 (en) | 2008-09-30 | 2012-09-25 | United Services Automobile Association (Usaa) | Systems and methods for automatic bill pay enrollment |
US7962411B1 (en) | 2008-09-30 | 2011-06-14 | United Services Automobile Association (Usaa) | Atomic deposit transaction |
US7974899B1 (en) | 2008-09-30 | 2011-07-05 | United Services Automobile Association (Usaa) | Atomic deposit transaction |
US7885880B1 (en) | 2008-09-30 | 2011-02-08 | United Services Automobile Association (Usaa) | Atomic deposit transaction |
US8391599B1 (en) | 2008-10-17 | 2013-03-05 | United Services Automobile Association (Usaa) | Systems and methods for adaptive binarization of an image |
US7970677B1 (en) | 2008-10-24 | 2011-06-28 | United Services Automobile Association (Usaa) | Systems and methods for financial deposits by electronic message |
US7949587B1 (en) | 2008-10-24 | 2011-05-24 | United States Automobile Association (USAA) | Systems and methods for financial deposits by electronic message |
JP5465865B2 (en) * | 2008-11-06 | 2014-04-09 | 理研ビタミン株式会社 | Hot melt adhesive composition |
US8323749B2 (en) * | 2009-01-29 | 2012-12-04 | Questech Corporation | Method for applying and curing by UV radiation a sealant system onto natural stone tiles to provide permanent sealing, protection, abrasion resistance, stain and mold resistance |
US8452689B1 (en) | 2009-02-18 | 2013-05-28 | United Services Automobile Association (Usaa) | Systems and methods of check detection |
US10956728B1 (en) | 2009-03-04 | 2021-03-23 | United Services Automobile Association (Usaa) | Systems and methods of check processing with background removal |
CN102439058B (en) * | 2009-03-06 | 2015-07-29 | 生物高聚物技术有限公司 | Foam materials containing albumen, their manufacture and purposes |
CA2753866C (en) | 2009-03-06 | 2020-04-28 | Biopolymer Technologies, Ltd. | Protein-containing emulsions and adhesives, and manufacture and use thereof |
US20100282706A1 (en) * | 2009-05-05 | 2010-11-11 | Gilliam James R | Lift lever crown cap system and method |
US9499311B1 (en) * | 2009-05-05 | 2016-11-22 | Super Closure International, Llc | Tamper evident crown cap system and method |
WO2010128105A1 (en) | 2009-05-07 | 2010-11-11 | Shell Internationale Research Maatschappij B.V. | Binder composition and asphalt mixture |
US8542921B1 (en) | 2009-07-27 | 2013-09-24 | United Services Automobile Association (Usaa) | Systems and methods for remote deposit of negotiable instrument using brightness correction |
US9779392B1 (en) | 2009-08-19 | 2017-10-03 | United Services Automobile Association (Usaa) | Apparatuses, methods and systems for a publishing and subscribing platform of depositing negotiable instruments |
US8977571B1 (en) | 2009-08-21 | 2015-03-10 | United Services Automobile Association (Usaa) | Systems and methods for image monitoring of check during mobile deposit |
US8699779B1 (en) | 2009-08-28 | 2014-04-15 | United Services Automobile Association (Usaa) | Systems and methods for alignment of check during mobile deposit |
US20130186913A1 (en) * | 2009-12-11 | 2013-07-25 | H.B. Fuller Company | Improved, low viscosity, shelf stable, energy-actiivated compositions, equipment, sytems and methods for producing same |
PL2576661T3 (en) | 2010-06-07 | 2017-07-31 | Evertree | Protein-containing adhesives, and manufacture and use thereof |
US9129340B1 (en) | 2010-06-08 | 2015-09-08 | United Services Automobile Association (Usaa) | Apparatuses, methods and systems for remote deposit capture with enhanced image detection |
WO2011162324A1 (en) * | 2010-06-25 | 2011-12-29 | 日本ポリエチレン株式会社 | Resin composition for solar cell sealing material, and solar cell sealing material and solar cell module using same |
JP5517162B2 (en) | 2010-09-22 | 2014-06-11 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Method, computer program, apparatus, and system for determining confidential label of document information |
CN102532918A (en) * | 2010-12-07 | 2012-07-04 | 上海富驰高科技有限公司 | Notebook computer CPU (Central Processing Unit) connector switch device material and manufacturing method thereof |
JP5859567B2 (en) | 2010-12-30 | 2016-02-10 | ダウ グローバル テクノロジーズ エルエルシー | Anti-bleeding oil-extended olefin block copolymer composition containing microcrystalline wax |
US9034972B2 (en) | 2010-12-30 | 2015-05-19 | Dow Global Technologies Llc | Bleed resistant, oil-extended olefin block copolymer composition with precipitated silica |
WO2012160929A1 (en) * | 2011-05-26 | 2012-11-29 | 日東電工株式会社 | Water-dispersed adhesive composition, adhesive and adhesive sheet |
US8673462B2 (en) | 2011-09-02 | 2014-03-18 | International Business Machines Corporation | Low viscosity electrostatic discharge (ESD) dissipating adhesive substantially free of agglomerates |
CA3075143C (en) | 2011-09-09 | 2023-03-28 | Evertree | Protein-containing adhesives, and manufacture and use thereof |
WO2013036744A1 (en) | 2011-09-09 | 2013-03-14 | Biopolymer Technologies, Ltd. | Protein-containing adhesives, and manufacture and use thereof |
CN103184026B (en) * | 2011-12-29 | 2015-11-25 | 深圳市宏商材料科技股份有限公司 | A kind of polyester type hot melt adhesive and complete processing thereof |
US10380565B1 (en) | 2012-01-05 | 2019-08-13 | United Services Automobile Association (Usaa) | System and method for storefront bank deposits |
EP2880116B1 (en) | 2012-07-30 | 2020-02-05 | Evertree | Protein adhesives containing an anhydride, carboxylic acid, and/or carboxylate salt compound and their use |
US10552810B1 (en) | 2012-12-19 | 2020-02-04 | United Services Automobile Association (Usaa) | System and method for remote deposit of financial instruments |
MX2015015309A (en) * | 2013-05-10 | 2016-08-11 | Fuller H B Co | Improved strength room temperature fluid adhesive composition and articles made with the same. |
US11138578B1 (en) | 2013-09-09 | 2021-10-05 | United Services Automobile Association (Usaa) | Systems and methods for remote deposit of currency |
US9286514B1 (en) | 2013-10-17 | 2016-03-15 | United Services Automobile Association (Usaa) | Character count determination for a digital image |
CN104031567B (en) * | 2013-12-27 | 2015-06-17 | 杭州福斯特光伏材料股份有限公司 | Rapid crosslinking EVA adhesive film with dual initiation |
US10279361B2 (en) * | 2014-08-17 | 2019-05-07 | Foammatick, Llc | Self-foaming hot melt adhesive compositions and methods of making and using same |
CN104263260B (en) * | 2014-09-19 | 2016-02-24 | 广州保均塑料科技有限公司 | Inorganic nano photo-crosslinking promotor and nano compound light crosslinked EVA glued membrane and preparation method thereof |
ES2625621T3 (en) * | 2014-12-04 | 2017-07-20 | Exxonmobil Chemical Patents Inc. | Multimodal polymer blend, melt application adhesive comprising the same and use thereof |
CN104745109A (en) * | 2015-04-16 | 2015-07-01 | 中天光伏材料有限公司 | White EVA adhesive film for photovoltaic module encapsulation |
US10402790B1 (en) | 2015-05-28 | 2019-09-03 | United Services Automobile Association (Usaa) | Composing a focused document image from multiple image captures or portions of multiple image captures |
BR112018002946B1 (en) * | 2015-08-31 | 2022-06-14 | Dow Global Technologies Llc | POLYPROPYLENE COMPOSITION, DRY MIX OR FUSION MIX, MULTI-LAYER STRUCTURE AND ARTICLE |
DE102015224997A1 (en) * | 2015-12-11 | 2017-06-14 | Henkel Ag & Co. Kgaa | Process for the preparation and application of adhesives |
RU2625849C1 (en) * | 2016-03-18 | 2017-07-19 | Общество с ограниченной ответственностью "Куранты" | Adhesive composition and aluminium layered structure containing it with increased adhesive joints interlaminar strength |
EP3625297A4 (en) * | 2017-05-19 | 2021-03-17 | Honeywell International Inc. | Compositions including copolymer formulations for improving adhesion to low surface energy substrates |
US11030752B1 (en) | 2018-04-27 | 2021-06-08 | United Services Automobile Association (Usaa) | System, computing device, and method for document detection |
CN109266231B (en) * | 2018-06-27 | 2021-04-02 | 广东隆兴防水隔热科技有限公司 | High-molecular anticorrosive waterproof coiled material and preparation method thereof |
CN109207072A (en) * | 2018-08-15 | 2019-01-15 | 广东尚联新材料科技有限公司 | It is a kind of applied between wooden boards or wooden boards and PVC board bonding EVA adhesive film and preparation method |
DE102018124663A1 (en) | 2018-10-05 | 2020-04-09 | Vermes Microdispensing GmbH | Dosing system with dosing agent cooling device |
US11292857B2 (en) | 2019-10-31 | 2022-04-05 | Exxonmobil Chemical Patents Inc. | Methods and systems for the production of high molecular weight ethylene-based polymers |
US11900755B1 (en) | 2020-11-30 | 2024-02-13 | United Services Automobile Association (Usaa) | System, computing device, and method for document detection and deposit processing |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
UST969011I4 (en) * | 1977-08-04 | 1978-04-04 | Shell Oil Company | Hot melt adhesive emulsion process |
US4906497A (en) * | 1987-11-16 | 1990-03-06 | Uzin-Werk Georg Utz Gmbh & Co. Kg | Microwave-activatable hot-melt adhesive |
US6316088B1 (en) * | 1999-02-26 | 2001-11-13 | Nagoya Oilchemical Co., Ltd. | Hot-melt adhesive powder dispersed in water with alkali thickener |
US6548579B2 (en) * | 2000-03-30 | 2003-04-15 | H. B. Fuller Licensing & Financing, Inc. | Adhesive composition comprising a particulate thermoplastic component |
Family Cites Families (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3644245A (en) * | 1969-06-25 | 1972-02-22 | Nat Starch Chem Corp | Hot melt adhesives containing silane compounds |
US4020966A (en) | 1975-03-28 | 1977-05-03 | W. R. Grace & Co. | Plastisol composition and container closure gasket made therefrom |
EP0042008B1 (en) * | 1979-12-21 | 1986-04-09 | Toray Industries, Inc. | Polyester amides and adhesives therefrom |
JPS56120780A (en) * | 1980-02-27 | 1981-09-22 | Asahi Chem Ind Co Ltd | Aqueous dispersion and heat-sensitive adhesive sheet treated with the same |
US4365044A (en) * | 1981-05-15 | 1982-12-21 | Hercules Incorporated | Polypropylene composition for extrusion coating |
US4497941A (en) | 1981-10-16 | 1985-02-05 | Exxon Research & Engineering Co. | Ethylene copolymers for hot melt systems |
JPS59149944A (en) * | 1983-02-15 | 1984-08-28 | Toyo Seikan Kaisha Ltd | Hot-melt adhesive |
JPS6020977A (en) | 1983-07-13 | 1985-02-02 | Arakawa Chem Ind Co Ltd | Pressure-sensitive adhesive composition |
US4623588A (en) | 1984-02-06 | 1986-11-18 | Biotek, Inc. | Controlled release composite core coated microparticles |
US4537805A (en) | 1984-03-26 | 1985-08-27 | W. R. Grace & Co. | Reactive plastisol dispersion |
JPS6231015A (en) | 1985-08-02 | 1987-02-10 | Hitachi Ltd | Thin-film magnetic head |
DE3633777C2 (en) | 1985-10-03 | 1996-08-22 | Mitsubishi Gas Chemical Co | Hot melt adhesive composition |
JPS644681A (en) * | 1987-06-26 | 1989-01-09 | Mitsubishi Paper Mills Ltd | Heat-sensitive sustainedly self-adhesive composition and heat-sensitive sustainedly self-adhesive sheet |
JPS644681U (en) | 1987-06-30 | 1989-01-12 | ||
US4822653A (en) | 1987-08-05 | 1989-04-18 | National Starch And Chemical Corporation | Recyclable hot melt adhesive compositions |
US4900711A (en) * | 1988-03-23 | 1990-02-13 | Harshaw/Filtrol Partnership | Hydrotreating catalyst |
US5310803A (en) | 1988-05-04 | 1994-05-10 | Minnesota Mining And Manufacturing Company | Hot-melt composition that have good open time and form creep-resistant bonds when applied in thin layers |
US5627229A (en) | 1992-07-25 | 1997-05-06 | H.B. Fuller Licensing & Financing, Inc. | Hot melt adhesive having controlled property change |
US5091454A (en) | 1988-08-03 | 1992-02-25 | Velsicol Chemical Corporation | Hot melt adhesive composition |
US4900771A (en) * | 1989-01-26 | 1990-02-13 | Aster, Inc. | Hot applied plastisol compositions |
DE4027140A1 (en) | 1990-08-28 | 1992-03-05 | Basf Ag | ETHYLENE / VINYL ACETATE COPOLYMERISATES WITH INCREASED RESISTANCE POINT |
JPH06505762A (en) | 1991-03-20 | 1994-06-30 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン | hot melt adhesive |
US5120781A (en) | 1991-05-07 | 1992-06-09 | Union Camp Corporation | Acid-modified polyhydric alcohol rosin ester tackifiers and hot melt adhesive compositions containing those tackifiers |
DE4217914A1 (en) * | 1992-05-30 | 1993-12-02 | Basf Ag | Process for the preparation of a curable molding material |
DE4226081A1 (en) | 1992-08-06 | 1994-02-10 | Henkel Kgaa | Thermoplastic hot melt adhesive |
US5427702A (en) * | 1992-12-11 | 1995-06-27 | Exxon Chemical Patents Inc. | Mixed ethylene alpha olefin copolymer multifunctional viscosity modifiers useful in lube oil compositions |
EP0694054B1 (en) * | 1993-04-16 | 1997-06-04 | Exxon Chemical Patents Inc. | Ethylene based hot melt adhesives |
DE4315191A1 (en) * | 1993-05-07 | 1994-12-08 | Teroson Gmbh | plastisol |
EP0624606B2 (en) * | 1993-05-14 | 2003-08-27 | Mitsui Takeda Chemicals, Inc. | Core-shell polymer and plastisol therefrom |
US5840786A (en) * | 1993-12-10 | 1998-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Plastisol composition |
US6107430A (en) | 1996-03-14 | 2000-08-22 | The Dow Chemical Company | Low application temperature hot melt adhesive comprising ethylene α-olefin |
JPH10168417A (en) * | 1996-12-11 | 1998-06-23 | Sekisui Chem Co Ltd | Hot-melt adhesive |
DE19652762A1 (en) * | 1996-12-18 | 1998-08-06 | Henkel Kgaa | Swellable hot melt adhesive |
US6143818A (en) * | 1999-08-04 | 2000-11-07 | Ato Findley, Inc. | Hot melt adhesive based on ethylene-propylene rubber (EPR) and semicrystalline olefinic polymers |
US6447973B1 (en) * | 1999-08-24 | 2002-09-10 | Ricoh Company, Ltd. | Liquid developer for developing electrostatic image and image forming method |
US6649888B2 (en) * | 1999-09-23 | 2003-11-18 | Codaco, Inc. | Radio frequency (RF) heating system |
KR100675717B1 (en) * | 1999-10-15 | 2007-02-05 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Conformable Multilayer Films |
DE19951599A1 (en) * | 1999-10-27 | 2001-05-23 | Henkel Kgaa | Process for adhesive separation of adhesive bonds |
JP4511660B2 (en) * | 1999-12-24 | 2010-07-28 | 三井化学株式会社 | Heat seal adhesive composition |
WO2001053389A1 (en) | 2000-01-19 | 2001-07-26 | Illinois Tool Works, Inc. | Thermoplastic adhesive |
JP4462691B2 (en) * | 2000-01-27 | 2010-05-12 | 東洋化成工業株式会社 | Propylene / α-olefin copolymer resin dispersion |
US6403231B1 (en) * | 2000-05-12 | 2002-06-11 | Pechiney Emballage Flexible Europe | Thermoplastic film structures having improved barrier and mechanical properties |
WO2001088009A1 (en) | 2000-05-16 | 2001-11-22 | Sunstar Giken Kabushiki Kaisha | Thermosetting composition |
ES2227247T3 (en) * | 2000-07-27 | 2005-04-01 | Slaweyko Prof. Dr. Marinow | PLASTISOL AND ORGANOSOL FREE OF CHLORINE-BASED POLYOLEFINS AND PROCEDURE FOR PREPARATION. |
GB0029198D0 (en) * | 2000-11-30 | 2001-01-17 | Ciba Sc Holding Ag | Liquid dispersion polymer compositions their preparation and their use |
US6664309B2 (en) * | 2000-12-07 | 2003-12-16 | Bostik Findley, Inc. | Antimicrobial hot melt adhesive |
US6586483B2 (en) * | 2001-01-08 | 2003-07-01 | 3M Innovative Properties Company | Foam including surface-modified nanoparticles |
US6884833B2 (en) * | 2001-06-29 | 2005-04-26 | 3M Innovative Properties Company | Devices, compositions, and methods incorporating adhesives whose performance is enhanced by organophilic clay constituents |
US20030083413A1 (en) * | 2002-07-19 | 2003-05-01 | Stumphauzer William C | Thermoplastic adhesive |
US7285583B2 (en) * | 2002-07-30 | 2007-10-23 | Liquamelt Licensing Llc | Hybrid plastisol/hot melt compositions |
US7456233B2 (en) * | 2005-02-16 | 2008-11-25 | Nordson Corporation | Adhesive composition |
-
2003
- 2003-07-29 US US10/629,876 patent/US7285583B2/en not_active Expired - Fee Related
- 2003-07-30 WO PCT/US2003/023873 patent/WO2004011569A1/en active Application Filing
- 2003-07-30 CN CN038229498A patent/CN1685025B/en not_active Expired - Fee Related
- 2003-07-30 CA CA2493515A patent/CA2493515C/en not_active Expired - Fee Related
- 2003-07-30 JP JP2004524226A patent/JP4792223B2/en not_active Expired - Fee Related
- 2003-07-30 MX MXPA05001103A patent/MXPA05001103A/en active IP Right Grant
- 2003-07-30 EP EP03772123A patent/EP1543086A4/en not_active Withdrawn
-
2006
- 2006-10-17 US US11/582,234 patent/US20070036970A1/en not_active Abandoned
-
2007
- 2007-10-16 US US11/872,912 patent/US7501468B2/en not_active Expired - Fee Related
- 2007-10-16 US US11/872,929 patent/US20080156438A1/en not_active Abandoned
-
2009
- 2009-01-29 US US12/361,815 patent/US7772313B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
UST969011I4 (en) * | 1977-08-04 | 1978-04-04 | Shell Oil Company | Hot melt adhesive emulsion process |
US4906497A (en) * | 1987-11-16 | 1990-03-06 | Uzin-Werk Georg Utz Gmbh & Co. Kg | Microwave-activatable hot-melt adhesive |
US6316088B1 (en) * | 1999-02-26 | 2001-11-13 | Nagoya Oilchemical Co., Ltd. | Hot-melt adhesive powder dispersed in water with alkali thickener |
US6548579B2 (en) * | 2000-03-30 | 2003-04-15 | H. B. Fuller Licensing & Financing, Inc. | Adhesive composition comprising a particulate thermoplastic component |
Non-Patent Citations (1)
Title |
---|
See also references of EP1543086A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005087889A1 (en) * | 2004-03-18 | 2005-09-22 | Siew Puat Yeo | Adhesive composition |
WO2006004750A1 (en) * | 2004-06-28 | 2006-01-12 | Dow Global Technoligies Inc. | Adhesion promoters for multistrucural laminates |
KR101197933B1 (en) * | 2004-06-28 | 2012-11-05 | 다우 글로벌 테크놀로지스 엘엘씨 | Adhesion Promoters for Multistructural Laminates |
US8012540B2 (en) | 2006-04-07 | 2011-09-06 | Addcomp Holland Bv | Aqueous emulsion comprising a functionalized polyolefin and carbon nanotubes |
Also Published As
Publication number | Publication date |
---|---|
EP1543086A1 (en) | 2005-06-22 |
US7501468B2 (en) | 2009-03-10 |
CN1685025B (en) | 2010-12-01 |
US20090133826A1 (en) | 2009-05-28 |
JP2005534745A (en) | 2005-11-17 |
US20040029980A1 (en) | 2004-02-12 |
EP1543086A4 (en) | 2010-12-29 |
CA2493515A1 (en) | 2004-02-05 |
US20080156438A1 (en) | 2008-07-03 |
CN1685025A (en) | 2005-10-19 |
MXPA05001103A (en) | 2005-08-03 |
JP4792223B2 (en) | 2011-10-12 |
US7285583B2 (en) | 2007-10-23 |
AU2003257047A1 (en) | 2004-02-16 |
US7772313B2 (en) | 2010-08-10 |
US20080161496A1 (en) | 2008-07-03 |
CA2493515C (en) | 2012-01-03 |
US20070036970A1 (en) | 2007-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7285583B2 (en) | Hybrid plastisol/hot melt compositions | |
EP2054482B1 (en) | Hotmelt adhesive with improved adhesion | |
TWI600673B (en) | Linear low-density polyethylene grafted with maleic anhydride, process for preparing the same and its applications | |
KR101632770B1 (en) | - -3-20- contact adhesive based on metallocene-catalyzed olefin-3-20-olefin copolymers | |
US20200392319A1 (en) | Hot-Melt Formulations Utilizing Depolymerized Polymeric Material | |
JPH0464352B2 (en) | ||
US20120064337A1 (en) | Peelable multilayer surface protecting film and product | |
JP5754688B2 (en) | Sealant film, laminate using the sealant film, packaging container using the laminate, and method for producing the sealant film | |
EP0753032B1 (en) | Extrudable adhesive compositions and methods relating thereto | |
WO1998021286A1 (en) | Hot melt adhesives with excellent heat resistance | |
AU2003257047B2 (en) | Hybrid plastisol/hot melt compositions | |
JP2022514913A (en) | Articles containing water-based top coats | |
US20040020589A1 (en) | Hot melt adhesive | |
JP2015063701A (en) | Sealant film, laminate using the sealant film, packaging container using the laminate | |
JPS58215437A (en) | Heat seal composition | |
EP2586841B1 (en) | Hot adhesive formulation for adhering plastic materials | |
US20110311803A1 (en) | Delayed-tack material | |
JPH0151342B2 (en) | ||
RU2005105685A (en) | HYBRID PLASTIZOLE / THERMAL ADHESIVES | |
JPH0481486A (en) | Bonding composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2493515 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2005/001103 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004524226 Country of ref document: JP Ref document number: 2003772123 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2003257047 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 538395 Country of ref document: NZ |
|
ENP | Entry into the national phase |
Ref document number: 2005105685 Country of ref document: RU Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 299/KOLNP/2005 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20038229498 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 2003772123 Country of ref document: EP |
|
ENPW | Started to enter national phase and was withdrawn or failed for other reasons |
Ref document number: PI0313065 Country of ref document: BR Free format text: PEDIDO RETIRADO FACE A IMPOSSIBILIDADE DE ACEITACAO DA ENTRADA NA FASE NACIONAL POR TER SIDO INTEMPESTIVA. O PRAZO PARA ENTRADA NA FASE NACIONAL EXPIRAVA EM 30.03.2004 ( 20 MESES - BR DESIGNADO APENAS), ELEICAO NAO COMPROVADA, E A PRETENSA ENTRADA NA FASE NACIONAL SO OCORREU EM 28.01.2005. |