CA2833114A1 - Rosin esters for non-woven applications, methods of making and using and products therefrom - Google Patents
Rosin esters for non-woven applications, methods of making and using and products therefrom Download PDFInfo
- Publication number
- CA2833114A1 CA2833114A1 CA2833114A CA2833114A CA2833114A1 CA 2833114 A1 CA2833114 A1 CA 2833114A1 CA 2833114 A CA2833114 A CA 2833114A CA 2833114 A CA2833114 A CA 2833114A CA 2833114 A1 CA2833114 A1 CA 2833114A1
- Authority
- CA
- Canada
- Prior art keywords
- rosin
- rosin ester
- pentaerythritol
- less
- relative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 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 title claims abstract description 185
- 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 title claims abstract description 185
- 150000002148 esters Chemical class 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 61
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 80
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 54
- 239000000853 adhesive Substances 0.000 claims description 53
- 230000001070 adhesive effect Effects 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 49
- 229920005862 polyol Polymers 0.000 claims description 45
- 150000003077 polyols Chemical class 0.000 claims description 44
- 238000007323 disproportionation reaction Methods 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 24
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 16
- 239000001530 fumaric acid Substances 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- -1 iodine, iodides Chemical class 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical class OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 claims description 4
- GOWCECVOTUONTI-UHFFFAOYSA-N 3-(3-hydroxyphenyl)sulfanylphenol Chemical class OC1=CC=CC(SC=2C=C(O)C=CC=2)=C1 GOWCECVOTUONTI-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 4
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims description 3
- LJKQIQSBHFNMDV-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical class C1=CC=CC2(O)C1S2 LJKQIQSBHFNMDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000006596 Alder-ene reaction Methods 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 claims description 2
- WEMYXYMZQRSPIA-UHFFFAOYSA-N 4-(2,4-dihydroxyphenyl)sulfanylbenzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1SC1=CC=C(O)C=C1O WEMYXYMZQRSPIA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229940079877 pyrogallol Drugs 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 235000019645 odor Nutrition 0.000 description 54
- 230000008569 process Effects 0.000 description 23
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 239000003784 tall oil Substances 0.000 description 18
- 238000009472 formulation Methods 0.000 description 11
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- 230000032050 esterification Effects 0.000 description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- 239000013032 Hydrocarbon resin Substances 0.000 description 7
- 229920006270 hydrocarbon resin Polymers 0.000 description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004831 Hot glue Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 1
- WBSRIXCTCFFHEF-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinic acid Chemical compound CCOP(O)(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WBSRIXCTCFFHEF-UHFFFAOYSA-N 0.000 description 1
- VJWZOCYZDCWKSJ-UHFFFAOYSA-N 2-nonyl-3,8-dithiatricyclo[5.1.0.02,4]oct-5-en-4-ol Chemical compound C1=CC2SC2C2(CCCCCCCCC)SC21O VJWZOCYZDCWKSJ-UHFFFAOYSA-N 0.000 description 1
- RIIWOXJAAGZDLD-UHFFFAOYSA-N 2-pentyl-3,8-dithiatricyclo[5.1.0.02,4]oct-5-en-4-ol Chemical compound C1=CC2SC2C2(CCCCC)SC21O RIIWOXJAAGZDLD-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 1
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 1
- RWWVEQKPFPXLGL-ONCXSQPRSA-N L-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC=C(C(C)C)C=C2CC1 RWWVEQKPFPXLGL-ONCXSQPRSA-N 0.000 description 1
- RWWVEQKPFPXLGL-UHFFFAOYSA-N Levopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CC=C(C(C)C)C=C1CC2 RWWVEQKPFPXLGL-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940064002 calcium hypophosphite Drugs 0.000 description 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 1
- 229940118781 dehydroabietic acid Drugs 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- RCIMBBZXSXFZBV-UHFFFAOYSA-N piromidic acid Chemical class N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CN=C1N1CCCC1 RCIMBBZXSXFZBV-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical group C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- 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
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Rosin esters having suitable color, color stability and/or odor to make them useful for non-woven applications, to non-woven products made from and/or comprising rosin esters, and to methods of making and using such rosin esters and products.
Description
=
PCT/US11/31884 02-09-2011 PCT/US2011/031884 10.01.2013 Atty Docket ARZ-109007-WO 2 September ROSIN ESTERS FOR NON-WOVEN APPLICATIONS, METHODS OF MAKING AND
USING AND PRODUCTS THEREFROM
RELATED APPLICATION DATA.
[0001] Not applicable.
BACKGROUND OF THE INVENTION
1. Field of the Invention [0002] The present invention relates to rosin esters, to products made from or comprising rosin esters, and to methods of making and using such rosin esters or products. In another aspect, the present invention relates to rosin esters useful for non-woven applications, to non-woven products made from andlor comprising rosin esters, and to methods of making and using such rosin esters and products. In even another aspect, the present invention relates to rosin esters having suitable color, color stability and/or odor to make them useful for non-woven applications, to non-woven products made from and/or comprising rosin esters, and to methods of making and using such rosin esters and products.
2. Brief Description of the Related Art [0003] Currently, rosin esters are not acceptable for the non-woven adhesives industry, for example, for employment as adhesives used in construction of disposable baby diapers. Hydrogenated hydrocarbon resin based tackifiers are most commonly accepted for utilization in non-woven applications.
PCT/US11/31884 02-09-2011 PCT/US2011/031884 10.01.2013 Atty Docket ARZ-109007-WO 2 September ROSIN ESTERS FOR NON-WOVEN APPLICATIONS, METHODS OF MAKING AND
USING AND PRODUCTS THEREFROM
RELATED APPLICATION DATA.
[0001] Not applicable.
BACKGROUND OF THE INVENTION
1. Field of the Invention [0002] The present invention relates to rosin esters, to products made from or comprising rosin esters, and to methods of making and using such rosin esters or products. In another aspect, the present invention relates to rosin esters useful for non-woven applications, to non-woven products made from andlor comprising rosin esters, and to methods of making and using such rosin esters and products. In even another aspect, the present invention relates to rosin esters having suitable color, color stability and/or odor to make them useful for non-woven applications, to non-woven products made from and/or comprising rosin esters, and to methods of making and using such rosin esters and products.
2. Brief Description of the Related Art [0003] Currently, rosin esters are not acceptable for the non-woven adhesives industry, for example, for employment as adhesives used in construction of disposable baby diapers. Hydrogenated hydrocarbon resin based tackifiers are most commonly accepted for utilization in non-woven applications.
[0004] While there are a number of reasons for why rosin esters are not acceptable for use in the non-woven adhesives applications, the main ones are presently that previous and current tall oil rosin based rosin esters neither have the color, color stability nor the low odor for use in non-woven adhesives.
REPLACEMENT SHEET
AMENDED SHEET - WEA/US
REPLACEMENT SHEET
AMENDED SHEET - WEA/US
[0005] U.S. Patent No. 4,302,371, issued on November 24, 1981, to Matsu , et al., discloses a stabilized rosin ester and pressure-sensitive adhesive and hot-melt composition based thereon. The process for preparing a stabilized rosin ester having a higher softening point comprises subjecting a rosin to disproportionation and purification, and esterifying the resulting purified disproportionated rosin with a tri- or more valent polyhydric alcohol to give a rosin ester having a softening point (according to ring and ball method) of 65° to 140° C. The resulting rosin ester has superior heat resistance and aging resistance as well as a high softening point and is suitably employed as a tackifier for pressure-sensitive adhesive compositions and hot-melt compositions.
[0007] U. S. Patent No. 4,643,848, issued February 17, 1987, to Thomas , et al., discloses a modified rosin ester preparation. Phosphinic acid (also called hypophosphorous acid), when used in very small quantities, is disclosed to act as a catalyst to accelerate the reaction of rosin with an unsaturated dibasic acid to form a modified rosin for subsequent esterification with a polyhydric alcohol. According to the process of the invention, a rosin is reacted with an unsaturated dibasic acid such as maleic anhydride or fumaric acid in the presence of phosphinic acid at a temperature of from about I80° C. to about 220° C. When the modified rosin is subsequently esterified, the rosin ester exhibits improved color, softening point, and viscosity in a specified solution.
[0008] U. S. Patent No. 4,657,703, issued April 14, 1987, to Durkee, discloses a method of improving the color of tall oil rosin esters. The method of improving the color of tall oil rosin esters comprises the sequential steps of (a) heating and stirring a tall oil rosin in the presence of a Lewis acid catalyst to form a mixture, (b) distilling the mixture to provide a tall oil rosin distillate, and (c) esterifying the tall oil rosin distillate with a polyol in the presence of a phenol sulfide compound. The improved tall oil rosin esters produced thereby are useful in the manufacture of a variety of products, such as paper and textile sizes, plasticizers for polyolefin films, paints, varnishes, hot melt adhesives and pressure sensitive adhesives.
[0009] U.S. Patent No. 5,162,496, issued November 10, 1992 to Johnson, Jr., discloses a method for the preparation of light-colored rosin esters. The catalytic combination of a phosphite ester and a phenol sulfide accelerates and mediates the esterification reaction of rosin with a polyhydric alcohol, resulting in esterified rosins having numerous advantageous characteristics and particular utility as tackifiers in hot melt adhesives.
[00010] U. S. Patent No. 5,504,152, issued April 2, 1996, to Schluenz , et al., discloses esterification of rosin. The method for esterifying rosins with a polyol which comprises contacting rosin with the polyol in the presence of a bleaching mixture which includes both an alkaline earth hypophosphite and hypophosphorous acid and, preferably also, an organic sulfide, under esterification conditions to produce a rosin ester. The method enables production of rosin esters which have a color of less than about 5 Gardner neat. The preferred bleaching mixture includes from about 0.01% to about 0.10% of the alkaline earth hypophosphite and from about 0.10% to about 0.15% of active hypophosphorous acid, where the amounts are based on the weight of the rosin. The most preferred alkaline earth hypophosphite is calcium hypophosphite. The specification also describes a method for preparing an adhesive from the rosin ester.
[00011] U. S. Patent No. 5,830,992, issued November 3, 1998, to Whalen, disclosesa light color, color stable rosin esters and methods for preparing same. Rosin esters that are both light colored and color stable are produced by reacting polyhydric alcohol with an equivalent excess of rosin, in the presence of calcium bis(monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate. When phosphinic acid is added to the reaction mixture, light colored and color stable rosin esters are produced regardless of whether the rosin or polyol are in equivalent excess, although preferably the rosin is in equivalent excess. It is preferred to include a phenol sulfide compound, such as Vultac® 2, with the calcium bis(morioethyl(3,5-di-tert-butyl-4-hydroxybenzyDphosphonate, and to add the phosphinic acid incrementally after the acid nutnber of the rosin and polyhydric alcohol reaction mixture has dropped to about 100. Excess rosin is preferably stripped from the product mixture at about 275° C.
[00012] U. S. Patent No. 5,969,092, issued October 19, 1999, to Karvo, discloses preparation of a tall oil rosin ester with a low odor level. This process for the preparation of a tall oil rosin ester with a low odor level, comprises an esterification step wherein a tall oil rosin is esterified with a polyol in order to form a product which contains a tall oil rosin ester, and evaporation is carried out on this product in order to remove odor components and other volatile components from the product, which evaporation is carried out in a short-path evaporator which has an evaporation surface and, in the vicinity of this surface, a condenser on which the vaporized components to be removed condense, whereupon a tall oil rosin ester with a low odor level is recovered from the evaporator.
[00013] U. S. Patent No. 6,562,888, issued May 13, 2003, to Frihart, et al., discloses light-colored rosin esters and adhesive compositions. These rosin esters are both light-colored and color stable may be produced by reacting rosin with an organic compound containing two or more hydroxyl groups each separated from each other by at least four carbon atoms. With appropriate choices for the esterification catalyst and antioxidant(s), the rosin ester tnay be useful as a tackifier, and can be formulated into an adhesive composition.
The adhesive compositions will further comprise an appropriate adhesive polymer.
[00014] WO 2007092250 pubished August 16, 2007, and US Publication 20070179277 pubished August 2, 2007, both to Anthony Dallavia, disclosed a rosin ester with low color and process for preparing same. The process for producing light color rosins ester resin, preferably based on tall rosin is conducted in the presence of less than 10 weight % of an acid functional organic compound and avoids the need for use of a stoichiometric excess of rosin acid, or a stoichiometric excess of polyol hydroxy groups. The process allows for the use of lower colored or darker tall oil rosin in the production of low color rosin esters.
[00015] All of the patents, applications and publications cited in this specification, are herein incorporated by reference.
[00016] However, in spite of the above advancements, there exists a need in the art for rosin esters, for products there from, and for methods of making and using such resin esters and products.
[00017] There is another need for alternative adhesives to the hydrogenated hydrocarbon resin based tackifiers that have been found acceptable in non-woven applications.
[00018] There is even another need in the art for rosin esters with suitable color, color stability and./or odor, for example for non-woven applications.
[00019] There is still another need in the art for tackifiers.
[00020] There is yet another need in the art for tackifiers for EVA
packaging adhesives that give increased viscosity stability to the adhesive.
[00021] There is even still another need in the art for new tackifiers for pressure sensitive adhesives (PSA) with a low color at a lower cost than with the use of hydrogenated hydrocarbon resin based tackifiers.
[00022] There is even still a need in the art for new tackifiers for bookbinding adhesives that offer a low color and improved viscosity stability at a low cost.
[00023] These and other needs in the art will become apparent to those of skill in the art upon review of this specification, including its drawings and claims.
SUMMARY OF THE INVENTION
5 [00024] Various embodiments of the present invention may fulfill none, one or more of the following objects.
[00025] It is an object of the present invention to provide for rosin esters, for products there from, and for methods of making and using such resin esters and products.
[00026] It is another object of the present invention to provide for alternative adhesives to the hydrogenated hydrocarbon resin based tackifiers that have been found acceptable in non-woven applications.
[00027] It is even another object of the present invention to provide for rosin esters with suitable color, color stability and/or odor.
[00028] 11 is still another object of the present invention to provide for tackifiers.
[00029] It is yet another object of the present invention to provide for tackifiers for EVA packaging adhesives that give increased viscosity stability to the adhesive.
[00030] It is even still another object of the present invention to provide for tackifiers for pressure sensitive adhesives (PSA) with a low color at a lower cost than with the use of hydrogenated hydrocarbon resin based tackifiers.
[00031] It is even yet another object of the present invention to provide for tackifiers for bookbinding adhesives that offer a low color and improved viscosity stability at a low cost.
[00032] These and other objects of the present invention will become apparent to those of skill in the art upon review of this specification, including its drawings and claims.
[00033] According to one embodiment of the present invention, there is provided method of producing a rosin ester. The method may include any one or more of the following steps in any order: contacting a rosin having PAN isomers with disproportionation agent to provide a rosin having a PAN number less than 45 providing a disproportionated rosin; contacting the disproportionated rosin with an adduction agent to further reduce the PAN number to provide an adducted rosin; and/or contacting the adducted rosin with a polyhydric polyol to form a rosin ester.
[00034] According to another embodiment of the present invention, there is also provided a method of producing a rosin ester. The method may include one or more of the following steps in any order: contacting rosin having a PAN number less than 45 with an adduction agent to further reduce the PAN number to provide an adducted rosin;
contacting the adducted rosin with a polyhydric polyol to form a rosin ester.
[00035] According to even another embodiment of the present invention, there is provided a rosin ester composition having an odor intensity of less than 80%
relative to comparison rosin ester made from 100% pentaerythritol.
[00036] According to still another embodiment of the present invention, there is provided an adhesive comprising a rosin ester composition having an odor intensity of less than 80% relative to comparison rosin ester made from 100% pentaerythritol.
[00037] According to yet another embodiment of the present invention, there is provided a non-woven product comprising an adhesive comprising a rosin ester composition having an odor intensity of less than 80% relative to comparison rosin ester made from 100%
pentaerythritol.
DETAILED DESCRIPTION OF THE INVENTION
[00038] In the practice of certain non-limiting embodiments of the present invention, a process has been developed to synthesize rosin esters with lower odor, lighter color, and/or improved color stability compared to prior art technology. Certain embodiments of the rosin ester compositions of the present invention have substantially improved color stability at temperatures up to 150C and/or these compositions impart excellent thermal stability to a hot melt adhesive upon aging at temperatures up to 150C. These certain resulting rosin esters are suitable for use in conventional packaging and pressure sensitive adhesives, and unlike conventional rosin esters it can also be used for odor and color sensitive applications such as non-woven adhesives (diaper construction adhesives) or other high-end packaging adhesives.
[00039] In the practice of the present invention, possible approaches for providing a low odor RE adhesive included using a polyol other than pentaerythritol (PE), using a mixture of polyols, or to significantly reduce the PE content in rosin ester forrnulations by replacement of part or all of the PE with one or more other types of polyols.
[00040] Specifically one non-limiting embodiment of the present invention provides fumaric-modified esters based upon a polyol component that may be a blend of polyols, a non-limiting example of which includes glycerol and PE. Some of the embodiments may provide lighter color and lower odor as compared to cotnmercial SYLVALITETm Rosin Ester and !nay also provide superior color stability and viscosity stability upon aging or storage at elevated temperatures simulating warehouse conditions.
[0007] U. S. Patent No. 4,643,848, issued February 17, 1987, to Thomas , et al., discloses a modified rosin ester preparation. Phosphinic acid (also called hypophosphorous acid), when used in very small quantities, is disclosed to act as a catalyst to accelerate the reaction of rosin with an unsaturated dibasic acid to form a modified rosin for subsequent esterification with a polyhydric alcohol. According to the process of the invention, a rosin is reacted with an unsaturated dibasic acid such as maleic anhydride or fumaric acid in the presence of phosphinic acid at a temperature of from about I80° C. to about 220° C. When the modified rosin is subsequently esterified, the rosin ester exhibits improved color, softening point, and viscosity in a specified solution.
[0008] U. S. Patent No. 4,657,703, issued April 14, 1987, to Durkee, discloses a method of improving the color of tall oil rosin esters. The method of improving the color of tall oil rosin esters comprises the sequential steps of (a) heating and stirring a tall oil rosin in the presence of a Lewis acid catalyst to form a mixture, (b) distilling the mixture to provide a tall oil rosin distillate, and (c) esterifying the tall oil rosin distillate with a polyol in the presence of a phenol sulfide compound. The improved tall oil rosin esters produced thereby are useful in the manufacture of a variety of products, such as paper and textile sizes, plasticizers for polyolefin films, paints, varnishes, hot melt adhesives and pressure sensitive adhesives.
[0009] U.S. Patent No. 5,162,496, issued November 10, 1992 to Johnson, Jr., discloses a method for the preparation of light-colored rosin esters. The catalytic combination of a phosphite ester and a phenol sulfide accelerates and mediates the esterification reaction of rosin with a polyhydric alcohol, resulting in esterified rosins having numerous advantageous characteristics and particular utility as tackifiers in hot melt adhesives.
[00010] U. S. Patent No. 5,504,152, issued April 2, 1996, to Schluenz , et al., discloses esterification of rosin. The method for esterifying rosins with a polyol which comprises contacting rosin with the polyol in the presence of a bleaching mixture which includes both an alkaline earth hypophosphite and hypophosphorous acid and, preferably also, an organic sulfide, under esterification conditions to produce a rosin ester. The method enables production of rosin esters which have a color of less than about 5 Gardner neat. The preferred bleaching mixture includes from about 0.01% to about 0.10% of the alkaline earth hypophosphite and from about 0.10% to about 0.15% of active hypophosphorous acid, where the amounts are based on the weight of the rosin. The most preferred alkaline earth hypophosphite is calcium hypophosphite. The specification also describes a method for preparing an adhesive from the rosin ester.
[00011] U. S. Patent No. 5,830,992, issued November 3, 1998, to Whalen, disclosesa light color, color stable rosin esters and methods for preparing same. Rosin esters that are both light colored and color stable are produced by reacting polyhydric alcohol with an equivalent excess of rosin, in the presence of calcium bis(monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate. When phosphinic acid is added to the reaction mixture, light colored and color stable rosin esters are produced regardless of whether the rosin or polyol are in equivalent excess, although preferably the rosin is in equivalent excess. It is preferred to include a phenol sulfide compound, such as Vultac® 2, with the calcium bis(morioethyl(3,5-di-tert-butyl-4-hydroxybenzyDphosphonate, and to add the phosphinic acid incrementally after the acid nutnber of the rosin and polyhydric alcohol reaction mixture has dropped to about 100. Excess rosin is preferably stripped from the product mixture at about 275° C.
[00012] U. S. Patent No. 5,969,092, issued October 19, 1999, to Karvo, discloses preparation of a tall oil rosin ester with a low odor level. This process for the preparation of a tall oil rosin ester with a low odor level, comprises an esterification step wherein a tall oil rosin is esterified with a polyol in order to form a product which contains a tall oil rosin ester, and evaporation is carried out on this product in order to remove odor components and other volatile components from the product, which evaporation is carried out in a short-path evaporator which has an evaporation surface and, in the vicinity of this surface, a condenser on which the vaporized components to be removed condense, whereupon a tall oil rosin ester with a low odor level is recovered from the evaporator.
[00013] U. S. Patent No. 6,562,888, issued May 13, 2003, to Frihart, et al., discloses light-colored rosin esters and adhesive compositions. These rosin esters are both light-colored and color stable may be produced by reacting rosin with an organic compound containing two or more hydroxyl groups each separated from each other by at least four carbon atoms. With appropriate choices for the esterification catalyst and antioxidant(s), the rosin ester tnay be useful as a tackifier, and can be formulated into an adhesive composition.
The adhesive compositions will further comprise an appropriate adhesive polymer.
[00014] WO 2007092250 pubished August 16, 2007, and US Publication 20070179277 pubished August 2, 2007, both to Anthony Dallavia, disclosed a rosin ester with low color and process for preparing same. The process for producing light color rosins ester resin, preferably based on tall rosin is conducted in the presence of less than 10 weight % of an acid functional organic compound and avoids the need for use of a stoichiometric excess of rosin acid, or a stoichiometric excess of polyol hydroxy groups. The process allows for the use of lower colored or darker tall oil rosin in the production of low color rosin esters.
[00015] All of the patents, applications and publications cited in this specification, are herein incorporated by reference.
[00016] However, in spite of the above advancements, there exists a need in the art for rosin esters, for products there from, and for methods of making and using such resin esters and products.
[00017] There is another need for alternative adhesives to the hydrogenated hydrocarbon resin based tackifiers that have been found acceptable in non-woven applications.
[00018] There is even another need in the art for rosin esters with suitable color, color stability and./or odor, for example for non-woven applications.
[00019] There is still another need in the art for tackifiers.
[00020] There is yet another need in the art for tackifiers for EVA
packaging adhesives that give increased viscosity stability to the adhesive.
[00021] There is even still another need in the art for new tackifiers for pressure sensitive adhesives (PSA) with a low color at a lower cost than with the use of hydrogenated hydrocarbon resin based tackifiers.
[00022] There is even still a need in the art for new tackifiers for bookbinding adhesives that offer a low color and improved viscosity stability at a low cost.
[00023] These and other needs in the art will become apparent to those of skill in the art upon review of this specification, including its drawings and claims.
SUMMARY OF THE INVENTION
5 [00024] Various embodiments of the present invention may fulfill none, one or more of the following objects.
[00025] It is an object of the present invention to provide for rosin esters, for products there from, and for methods of making and using such resin esters and products.
[00026] It is another object of the present invention to provide for alternative adhesives to the hydrogenated hydrocarbon resin based tackifiers that have been found acceptable in non-woven applications.
[00027] It is even another object of the present invention to provide for rosin esters with suitable color, color stability and/or odor.
[00028] 11 is still another object of the present invention to provide for tackifiers.
[00029] It is yet another object of the present invention to provide for tackifiers for EVA packaging adhesives that give increased viscosity stability to the adhesive.
[00030] It is even still another object of the present invention to provide for tackifiers for pressure sensitive adhesives (PSA) with a low color at a lower cost than with the use of hydrogenated hydrocarbon resin based tackifiers.
[00031] It is even yet another object of the present invention to provide for tackifiers for bookbinding adhesives that offer a low color and improved viscosity stability at a low cost.
[00032] These and other objects of the present invention will become apparent to those of skill in the art upon review of this specification, including its drawings and claims.
[00033] According to one embodiment of the present invention, there is provided method of producing a rosin ester. The method may include any one or more of the following steps in any order: contacting a rosin having PAN isomers with disproportionation agent to provide a rosin having a PAN number less than 45 providing a disproportionated rosin; contacting the disproportionated rosin with an adduction agent to further reduce the PAN number to provide an adducted rosin; and/or contacting the adducted rosin with a polyhydric polyol to form a rosin ester.
[00034] According to another embodiment of the present invention, there is also provided a method of producing a rosin ester. The method may include one or more of the following steps in any order: contacting rosin having a PAN number less than 45 with an adduction agent to further reduce the PAN number to provide an adducted rosin;
contacting the adducted rosin with a polyhydric polyol to form a rosin ester.
[00035] According to even another embodiment of the present invention, there is provided a rosin ester composition having an odor intensity of less than 80%
relative to comparison rosin ester made from 100% pentaerythritol.
[00036] According to still another embodiment of the present invention, there is provided an adhesive comprising a rosin ester composition having an odor intensity of less than 80% relative to comparison rosin ester made from 100% pentaerythritol.
[00037] According to yet another embodiment of the present invention, there is provided a non-woven product comprising an adhesive comprising a rosin ester composition having an odor intensity of less than 80% relative to comparison rosin ester made from 100%
pentaerythritol.
DETAILED DESCRIPTION OF THE INVENTION
[00038] In the practice of certain non-limiting embodiments of the present invention, a process has been developed to synthesize rosin esters with lower odor, lighter color, and/or improved color stability compared to prior art technology. Certain embodiments of the rosin ester compositions of the present invention have substantially improved color stability at temperatures up to 150C and/or these compositions impart excellent thermal stability to a hot melt adhesive upon aging at temperatures up to 150C. These certain resulting rosin esters are suitable for use in conventional packaging and pressure sensitive adhesives, and unlike conventional rosin esters it can also be used for odor and color sensitive applications such as non-woven adhesives (diaper construction adhesives) or other high-end packaging adhesives.
[00039] In the practice of the present invention, possible approaches for providing a low odor RE adhesive included using a polyol other than pentaerythritol (PE), using a mixture of polyols, or to significantly reduce the PE content in rosin ester forrnulations by replacement of part or all of the PE with one or more other types of polyols.
[00040] Specifically one non-limiting embodiment of the present invention provides fumaric-modified esters based upon a polyol component that may be a blend of polyols, a non-limiting example of which includes glycerol and PE. Some of the embodiments may provide lighter color and lower odor as compared to cotnmercial SYLVALITETm Rosin Ester and !nay also provide superior color stability and viscosity stability upon aging or storage at elevated temperatures simulating warehouse conditions.
[00041] Some of the embodiments of the present invention will provide an adhesive with the lower initial color and lower aged color as compared to commercial adhesives.
Some of the embodiments of the present invention provide smaller viscosity change on aging as compared to commercial adhesives. As a non-limiting example, the viscosity change of adhesives made from some embodiments of the rosin esters of the present invention may be less than 5%, 4%, 3%, 2% or 1%, after aging for 96 hours at 350F.
[00042] Some embodiments of the present invention may utilize a partial disproportion step. It was also noticed that the rosin color may decreases during this step, although the final ester may not necessarily be unusually light in color.
[00043] It should be appreciated, methods and agents for rosin disproportionation are well known, and that any suitable disproportionation method(s) and agent(s) may be utilized, and the present invention is not to be limited to any 'particular method or agent. Certainly one or more disproportionation methods and agents may be utilized. Non-limiting examples of suitable disproportionation methods and agents are provided in US 3,423,389, US 4,302,371 and US 4,657,703 all herein incorporated by reference.
[00044]
Disproportionation agents may fall into several classes. Some embodiments of the present invention utilize phenol sulfide type of agents. As specific non-limiting examples, ROSINOXTM (poly-t-butylphenoldisulfide available from Arkema, Inc.), LOWINOXTm TBM-6 (4,41-thiobis(2-t-butyl-5-methylphenol available from Chemtura), ETHANOXTm 323 (nonylphenol disulfide oligomer available from Albemarle Corp.), and/or VULTACTm 2 (amylphenol disulfide polymer available from Sovereign Chemical Co.).
[00045] Other non-limiting examples of suitable disproportionation agents include thiobisnaphthols in general. Suitable non-limiting examples include but are not limited to 2,2'-thiobis phenols, 3,3'-thiobisphenols, 4,4'-thiobis(resorcinol) and t,V-thiobis(pyrogallol), 4,4'-thiobis(6-t-butyl-m-cresol) and 4/4'-thiobis(6-t-buty1-o-creso1) thiobisnaphthols, 2,2'-thio-bis phenols, 3,3'-thio-bis phenols, and the like.
[00046] Other non-limiting examples of suitable disproportionation agents include metals (non-limiting examples of which include but are not limited to palladium, nickel, platinum ) or iodine or iodides (a non limiting example of which includes but is not limited to iron iodide) or sulfides (a non limiting example of which includes but is not limited to like iron sulfide).
[00047] In some embodiments, the rosin prior to disproportionation may have a PAN
number on the order of about 50. As used herein, the PAN number is the sum of the percentage of rosin acids in the rosin that are Palustrie Acid, Abietic Acid, and Neoabietic Acid. In some embodiments of the present invention disproportionation will result in a final PAN number from about 20 - 25. In other embodiments of the present invention disproportionation will result in a final PAN number from 15 - 30. In even other embodiments of the present invention disproportionation will result in a final PAN number from 10 - 40. Disproportionation may result in a final PAN number that is 0.1, 1, 2, 5, 10, 15, 20, 25, 35, 35, 40, or 45, or in any range from/to or between any two of the foregoing numbers.
[00048] Some embodiments of the present invention exhibit color improvement in disproportionated rosin and improved oxidation resistance of esters made from such rosin combined with the discovery that a fumaric acid adducted glycerol/pentaerythritol ester may exhibit improved odor and color stability. Certain embodiments of the present invention may provide a suitable low odor light color rosin ester that may be suitable for use in non-woven adhesives by implementing a proper combination of process and synthetic conditions.
[00049] As is well known in the prior art, rosin esters may be prepared from rosin, catalyst(s), bleaching agent(s), polyhydric alcohol(s) also as known as a polyols, and a stabilizer and/or antioxidant. Such catalyst, stabilizers and/or bleaching agents are known is the art as described, for example, in U.S. Pat. Nos. 2729660, 3310575, 3423389, 3780013, 4172070, 4548746, 4690783, 4693847, 4725384, 4744925, 4788009, 5021548 and 5049652.
[00050] In general, the process for making the rosin esters of the present invention may include contacting a rosin, preferably a molten rosin, with a polyhydric alcohol.
[00051] Suitable examples of rosins useful in the process of the invention may include but are not limited to gum rosin, wood rosin or tall oil rosin or any subsets or mixtures thereof. The preferred rosin is tall oil rosin. In some embodiments, the tall oil rosin may be an isomeric mixture primarily composed of C20 fused-ring, monocarboxylic acid hydrocarbons and may be typified by levopimaric acid, abietic acid, pimaric acid and dehydroabietic acid. In the present invention, the amount of rosin used will vary depending on the end use application.
[00052] The gum, wood, tall oil and other rosins may be employed in the processes of the present invention as is, or alternatively may be subjected to other treannents prior to use in the present esterification process. For example, the rosin material may be subjected to distillation, disproportionation, hydrogenation or polymerization, or some combination of these and/or other treatments, prior to use in the subject processes.
[00053] Polyhydric alcohols, also sometimes referred to as polyols, the other reactant employed in the subject process, are also well known. Exemplary of such compounds are ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, glycerol, pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, Erimethylolpropane, mannitol and sorbitol. Some embodiments of the present invention may utilize combinations of 2 or more of the above. As a non limiting example, some embodiments may utilize combinations of two or more of glycerol, pentaerythritol, and trimethylolpropane.
[00054] Some embodiments of the present invention will utilize a polyol combination of pentaerythritol and at least 1, 2, 3, 4, 5 or more other polyols, a non-limiting example of which includes pentaerythritol and at least one of glycerol or trimethylolpropane (TMP). The combination may be added as a mixture of the pentraeythritol and the other polyol(s), or !nay the combination may be added as a sequential additional of the pentraeythritol followed by the other polyol(s), or the one or more of the polyol(s) followed by the pentraeythritol. Thus, some embodiments of the present invention may utilize a sequential addition of pentaerythritol followed by at least 1, 2, 3, 4, 5 or more other polyols, non-limiting example of which include pentaerythritol followed by glycerol, pentaerythritol followed by trimethylolpropane, pentraeythriol followed by glycerol then trimethylolpropane, pentraeythriol followed by trimethylolpropane then glycerol, or pentraeythriol followed by a mixture of glycerol and trimethylolpropane. Some embodiments of the present invention may utilize the addition of a mixture of pentaerythritol and glycerol, a mixture of pentraeythriol and trimethylolpropane, or a mixture of pentraeythriol, glycerol and trimethylolpropane.
[00055] Some embodiments of the present invention will utilize a combination of a glycerol and/or trimethylolpropane and at least 1, 2, 3, 4, or 5 other polyols. The combination may- be added as a mixture of the glycerol and/or trimethylolpropane and the other polyol(s), or may the combination may be added as a sequential additional of the glycerol and/or trimethylolpropane followed by the other polyol(s), or the one or more of the polyol(s) followed by the glycerol. Thus, some emboditnents of the present invention may utilize a sequential addition of glycerol and/or trimethylolpropane at least 1, 2, 3, 4, 5 or more other polyols followed by the glycerol, a non-limiting example of which includes glycerol followed by pentaerythritol, trimethylolpropane followed by pentaerythritol, or glycerol and trimethylolpropane (together or in either order) followed by pentaerythritol.
[00056] The polyol combinations described above may comprise weight percent pentaerythritol (based on the total weight of the polyols in the combination) at or below 0, 0.001, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 17.5, 20, or in any range from/to or between any two of the foregoing numbers.
[00057] The amount of the alcohol employed in the esterification process may be varied widely. Generally, however, at least about an equivalent amount of polyhydric 5 alcohol, based on the amount of rosin, is employed, with the upper limit generally being about 50% excess over the equivalent.
[00058] In some embodiments of the present invention, the rosin inay be subjected to an adduction step prior to contracting the alcohol. In some embodiments, the adduction agents may be selected to react most readily with the PAN isomers of the rosin through a 10 Diels-Alder reaction or an Ene reaction. Non-limiting examples of suitable adduction agents include, but is not limited to, unsaturated acids or their equivalents like anhydrides.
[00059] In some embodiments of the present invention, a sufficient amount of PAN
isomers may be present in the rosin after the disproportionation step to allow reaction with the adduction agent. In some embodiments a sufficiently low PAN isomers may be required as too many unreacted PAN acid isomers (either free acids or esterified acids) present in the final rosin ester may in some circumstances lead to poor oxidation stability upon storage which may result in poor color stability and poor odor. Non-limiting examples of suitable PAN numbers for rosin to be subjected to adduction (i.e., pre-adduction PAN
number) include 0.1, 1, 2, 5, 10, 15, 20, 25, 35, 35, 40, or 45, or in any range from/to or between any two of the foregoing numbers. Non-limiting examples of suitable ranges includes but is not limited to, 20 -- 25, 15 - 30, and 10 - 40.
[00060] Non-limiting examples of suitable adducting agents include but are not limited to fumaric acid, maleic anhydride, acrylic acid, and other unsaturated acids or their equivalents like anhydrides.
[00061] In some embodiments, the adduction step is may be utilized to further reduce the level of the PAN rosin isomers left after the disproportionation. In some embodiments, the adduction step may increase the molecular weight and the softening point of the rosin ester. In some embodiments, this may allow replacetnent of pentaerythritol (PE) with other polyoIs like glycerol or l'MP that may provide lower odor esters but may also have lower softening points than PE esters. As a non-limiting example, a fumaric acid adducted glycerol ester may have a similar softening point to a PE ester and may be used for similar applications but may possess greater oxidation resistance and a lower odor. In some embodiments, a partial disproportionation step may further increase the oxidation resistance and may lower the odor of the final rosin ester. For some embodiments, as shown by Examples below, the higher levels of furnaric acid provide lower odor rosin esters as judged by our odor panel when compared to a standard commercial PE rosin ester.
[00062] In some embodiments, the adduction agent may be utilized at or above 0.1, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 10, 20, 30 weight percent of the formulation, or in any range from/to or between any two of the foregoing numbers. As a non-limiting example, the fumaric acid levels of about 2 - 2.8% of the formulation raises the weight average molecular weight Mw of the resultant rosin ester to about 1200 - 1600 Daltons as compared to about 900 - 1000 Daltons for a PE rosin ester. For some embodiments, 2.4 - 2.8%
fiimaric acid may be desired.
[00063] Some embodiments of the rosin ester may exhibit reduced odor intensity when compared to PE rosin esters. As non-limiting examples, the odor intensity of certain embodiments of rosin esters (which utilize less then 100% PE), will have relative intensities (relative to rosin esters utilizing 100% PE) that are at or below 80%, 75%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30% of rosin esters utilizing 100% PE, or in any range front/to or between any two of the foregoing numbers. The odor intensity is determined as shown below in the Examples.
[00064] Some embodiments of the rosin esters of the present invention may find use as tackifier resins in hot melt adhesives and as binding resins in low color, overprint varnishes used in the printing, for example, high gloss magazines, advertising and corporate annual reports.
EXAMPLES
[00065] The following Examples, with results shown in Tables 1-6 below, illustrate the advantages of the present invention by means of the results of the various types of tests and evaluations conducted on the rosin ester of this invention.
[00066] The Examples were conducted generally as follows:
600 g. of light colored (3.2 neat Gardner color) tall oil rosin (SYLVAROS1 m R
Type S) was melted under nitrogen at I80 C in a 2-liter 3-neck flask.
To this was added 3.53 g. of ROS1NOXTm disproportionation agent, with the resultant mixture heated to 275 C for 2 hours with a slow nitrogen flow through the reactor along with the addition of 3.9 ml/hr of distilled water to the flask using a syringe pump.
Next the flask was cooled to 180 C and 19.77 g. (2.8% of total charge) of fumaric acid was added, with the resultant mixture heated to 220 C. for 1 hr followed by cooling to 180'C.
Some of the embodiments of the present invention provide smaller viscosity change on aging as compared to commercial adhesives. As a non-limiting example, the viscosity change of adhesives made from some embodiments of the rosin esters of the present invention may be less than 5%, 4%, 3%, 2% or 1%, after aging for 96 hours at 350F.
[00042] Some embodiments of the present invention may utilize a partial disproportion step. It was also noticed that the rosin color may decreases during this step, although the final ester may not necessarily be unusually light in color.
[00043] It should be appreciated, methods and agents for rosin disproportionation are well known, and that any suitable disproportionation method(s) and agent(s) may be utilized, and the present invention is not to be limited to any 'particular method or agent. Certainly one or more disproportionation methods and agents may be utilized. Non-limiting examples of suitable disproportionation methods and agents are provided in US 3,423,389, US 4,302,371 and US 4,657,703 all herein incorporated by reference.
[00044]
Disproportionation agents may fall into several classes. Some embodiments of the present invention utilize phenol sulfide type of agents. As specific non-limiting examples, ROSINOXTM (poly-t-butylphenoldisulfide available from Arkema, Inc.), LOWINOXTm TBM-6 (4,41-thiobis(2-t-butyl-5-methylphenol available from Chemtura), ETHANOXTm 323 (nonylphenol disulfide oligomer available from Albemarle Corp.), and/or VULTACTm 2 (amylphenol disulfide polymer available from Sovereign Chemical Co.).
[00045] Other non-limiting examples of suitable disproportionation agents include thiobisnaphthols in general. Suitable non-limiting examples include but are not limited to 2,2'-thiobis phenols, 3,3'-thiobisphenols, 4,4'-thiobis(resorcinol) and t,V-thiobis(pyrogallol), 4,4'-thiobis(6-t-butyl-m-cresol) and 4/4'-thiobis(6-t-buty1-o-creso1) thiobisnaphthols, 2,2'-thio-bis phenols, 3,3'-thio-bis phenols, and the like.
[00046] Other non-limiting examples of suitable disproportionation agents include metals (non-limiting examples of which include but are not limited to palladium, nickel, platinum ) or iodine or iodides (a non limiting example of which includes but is not limited to iron iodide) or sulfides (a non limiting example of which includes but is not limited to like iron sulfide).
[00047] In some embodiments, the rosin prior to disproportionation may have a PAN
number on the order of about 50. As used herein, the PAN number is the sum of the percentage of rosin acids in the rosin that are Palustrie Acid, Abietic Acid, and Neoabietic Acid. In some embodiments of the present invention disproportionation will result in a final PAN number from about 20 - 25. In other embodiments of the present invention disproportionation will result in a final PAN number from 15 - 30. In even other embodiments of the present invention disproportionation will result in a final PAN number from 10 - 40. Disproportionation may result in a final PAN number that is 0.1, 1, 2, 5, 10, 15, 20, 25, 35, 35, 40, or 45, or in any range from/to or between any two of the foregoing numbers.
[00048] Some embodiments of the present invention exhibit color improvement in disproportionated rosin and improved oxidation resistance of esters made from such rosin combined with the discovery that a fumaric acid adducted glycerol/pentaerythritol ester may exhibit improved odor and color stability. Certain embodiments of the present invention may provide a suitable low odor light color rosin ester that may be suitable for use in non-woven adhesives by implementing a proper combination of process and synthetic conditions.
[00049] As is well known in the prior art, rosin esters may be prepared from rosin, catalyst(s), bleaching agent(s), polyhydric alcohol(s) also as known as a polyols, and a stabilizer and/or antioxidant. Such catalyst, stabilizers and/or bleaching agents are known is the art as described, for example, in U.S. Pat. Nos. 2729660, 3310575, 3423389, 3780013, 4172070, 4548746, 4690783, 4693847, 4725384, 4744925, 4788009, 5021548 and 5049652.
[00050] In general, the process for making the rosin esters of the present invention may include contacting a rosin, preferably a molten rosin, with a polyhydric alcohol.
[00051] Suitable examples of rosins useful in the process of the invention may include but are not limited to gum rosin, wood rosin or tall oil rosin or any subsets or mixtures thereof. The preferred rosin is tall oil rosin. In some embodiments, the tall oil rosin may be an isomeric mixture primarily composed of C20 fused-ring, monocarboxylic acid hydrocarbons and may be typified by levopimaric acid, abietic acid, pimaric acid and dehydroabietic acid. In the present invention, the amount of rosin used will vary depending on the end use application.
[00052] The gum, wood, tall oil and other rosins may be employed in the processes of the present invention as is, or alternatively may be subjected to other treannents prior to use in the present esterification process. For example, the rosin material may be subjected to distillation, disproportionation, hydrogenation or polymerization, or some combination of these and/or other treatments, prior to use in the subject processes.
[00053] Polyhydric alcohols, also sometimes referred to as polyols, the other reactant employed in the subject process, are also well known. Exemplary of such compounds are ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, glycerol, pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, Erimethylolpropane, mannitol and sorbitol. Some embodiments of the present invention may utilize combinations of 2 or more of the above. As a non limiting example, some embodiments may utilize combinations of two or more of glycerol, pentaerythritol, and trimethylolpropane.
[00054] Some embodiments of the present invention will utilize a polyol combination of pentaerythritol and at least 1, 2, 3, 4, 5 or more other polyols, a non-limiting example of which includes pentaerythritol and at least one of glycerol or trimethylolpropane (TMP). The combination may be added as a mixture of the pentraeythritol and the other polyol(s), or !nay the combination may be added as a sequential additional of the pentraeythritol followed by the other polyol(s), or the one or more of the polyol(s) followed by the pentraeythritol. Thus, some embodiments of the present invention may utilize a sequential addition of pentaerythritol followed by at least 1, 2, 3, 4, 5 or more other polyols, non-limiting example of which include pentaerythritol followed by glycerol, pentaerythritol followed by trimethylolpropane, pentraeythriol followed by glycerol then trimethylolpropane, pentraeythriol followed by trimethylolpropane then glycerol, or pentraeythriol followed by a mixture of glycerol and trimethylolpropane. Some embodiments of the present invention may utilize the addition of a mixture of pentaerythritol and glycerol, a mixture of pentraeythriol and trimethylolpropane, or a mixture of pentraeythriol, glycerol and trimethylolpropane.
[00055] Some embodiments of the present invention will utilize a combination of a glycerol and/or trimethylolpropane and at least 1, 2, 3, 4, or 5 other polyols. The combination may- be added as a mixture of the glycerol and/or trimethylolpropane and the other polyol(s), or may the combination may be added as a sequential additional of the glycerol and/or trimethylolpropane followed by the other polyol(s), or the one or more of the polyol(s) followed by the glycerol. Thus, some emboditnents of the present invention may utilize a sequential addition of glycerol and/or trimethylolpropane at least 1, 2, 3, 4, 5 or more other polyols followed by the glycerol, a non-limiting example of which includes glycerol followed by pentaerythritol, trimethylolpropane followed by pentaerythritol, or glycerol and trimethylolpropane (together or in either order) followed by pentaerythritol.
[00056] The polyol combinations described above may comprise weight percent pentaerythritol (based on the total weight of the polyols in the combination) at or below 0, 0.001, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 17.5, 20, or in any range from/to or between any two of the foregoing numbers.
[00057] The amount of the alcohol employed in the esterification process may be varied widely. Generally, however, at least about an equivalent amount of polyhydric 5 alcohol, based on the amount of rosin, is employed, with the upper limit generally being about 50% excess over the equivalent.
[00058] In some embodiments of the present invention, the rosin inay be subjected to an adduction step prior to contracting the alcohol. In some embodiments, the adduction agents may be selected to react most readily with the PAN isomers of the rosin through a 10 Diels-Alder reaction or an Ene reaction. Non-limiting examples of suitable adduction agents include, but is not limited to, unsaturated acids or their equivalents like anhydrides.
[00059] In some embodiments of the present invention, a sufficient amount of PAN
isomers may be present in the rosin after the disproportionation step to allow reaction with the adduction agent. In some embodiments a sufficiently low PAN isomers may be required as too many unreacted PAN acid isomers (either free acids or esterified acids) present in the final rosin ester may in some circumstances lead to poor oxidation stability upon storage which may result in poor color stability and poor odor. Non-limiting examples of suitable PAN numbers for rosin to be subjected to adduction (i.e., pre-adduction PAN
number) include 0.1, 1, 2, 5, 10, 15, 20, 25, 35, 35, 40, or 45, or in any range from/to or between any two of the foregoing numbers. Non-limiting examples of suitable ranges includes but is not limited to, 20 -- 25, 15 - 30, and 10 - 40.
[00060] Non-limiting examples of suitable adducting agents include but are not limited to fumaric acid, maleic anhydride, acrylic acid, and other unsaturated acids or their equivalents like anhydrides.
[00061] In some embodiments, the adduction step is may be utilized to further reduce the level of the PAN rosin isomers left after the disproportionation. In some embodiments, the adduction step may increase the molecular weight and the softening point of the rosin ester. In some embodiments, this may allow replacetnent of pentaerythritol (PE) with other polyoIs like glycerol or l'MP that may provide lower odor esters but may also have lower softening points than PE esters. As a non-limiting example, a fumaric acid adducted glycerol ester may have a similar softening point to a PE ester and may be used for similar applications but may possess greater oxidation resistance and a lower odor. In some embodiments, a partial disproportionation step may further increase the oxidation resistance and may lower the odor of the final rosin ester. For some embodiments, as shown by Examples below, the higher levels of furnaric acid provide lower odor rosin esters as judged by our odor panel when compared to a standard commercial PE rosin ester.
[00062] In some embodiments, the adduction agent may be utilized at or above 0.1, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 10, 20, 30 weight percent of the formulation, or in any range from/to or between any two of the foregoing numbers. As a non-limiting example, the fumaric acid levels of about 2 - 2.8% of the formulation raises the weight average molecular weight Mw of the resultant rosin ester to about 1200 - 1600 Daltons as compared to about 900 - 1000 Daltons for a PE rosin ester. For some embodiments, 2.4 - 2.8%
fiimaric acid may be desired.
[00063] Some embodiments of the rosin ester may exhibit reduced odor intensity when compared to PE rosin esters. As non-limiting examples, the odor intensity of certain embodiments of rosin esters (which utilize less then 100% PE), will have relative intensities (relative to rosin esters utilizing 100% PE) that are at or below 80%, 75%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30% of rosin esters utilizing 100% PE, or in any range front/to or between any two of the foregoing numbers. The odor intensity is determined as shown below in the Examples.
[00064] Some embodiments of the rosin esters of the present invention may find use as tackifier resins in hot melt adhesives and as binding resins in low color, overprint varnishes used in the printing, for example, high gloss magazines, advertising and corporate annual reports.
EXAMPLES
[00065] The following Examples, with results shown in Tables 1-6 below, illustrate the advantages of the present invention by means of the results of the various types of tests and evaluations conducted on the rosin ester of this invention.
[00066] The Examples were conducted generally as follows:
600 g. of light colored (3.2 neat Gardner color) tall oil rosin (SYLVAROS1 m R
Type S) was melted under nitrogen at I80 C in a 2-liter 3-neck flask.
To this was added 3.53 g. of ROS1NOXTm disproportionation agent, with the resultant mixture heated to 275 C for 2 hours with a slow nitrogen flow through the reactor along with the addition of 3.9 ml/hr of distilled water to the flask using a syringe pump.
Next the flask was cooled to 180 C and 19.77 g. (2.8% of total charge) of fumaric acid was added, with the resultant mixture heated to 220 C. for 1 hr followed by cooling to 180'C.
At this point the pentaerythritol was added followed by the glycerol and the temperature was raised to 250 C.
Upon reaching 250 C, l .06 g of tris-(nonylphenyl) phosphite (TNPP) was added.
After 1 hour the temperature was dropped to 180 C overnight (13 hrs).
The next morning it was heated to 250 C for 2 hours.
A reactor sample had an 85.2 C softening point, a 24.5 acid number, and a 2 neat Gardner color.
The reaction was heated to 275 C and sparged with nitrogen for 4 hours.
The reaction was next cooled and 0.14 g. of 50% aq. KOH, 0.99 g. of lrganoxTm 1010, and 0.35 g of lrganox-rm 565 were added. The 200 C resin was poured into pans to cool.
Final analysis: softening point 98.3 C, acid number 4.9, and a 2+ neat Gardner color.
[00067] Odor panel evaluations of five non-limiting embodiments of the present rosin ester at 50 C were compared to a commercial rosin ester, SYLVALITETm Rosin Ester with low numbers representing low odor intensity.
Example 1 [00068] Significant odor reduction was seen in some inventive embodiments as illustrated in Table 1.
[00069] A summary of the test tnethod for odor intensity is as follows:
[00070] 1. 25 g of each resin are weighed into 8 oz jars. Two of the jars contain experimental test resins and the third contains a standard.
[00071] 2. The resins are crushed to a coarse powder to expose a fresh surface area.
[00072] 3, The three capped jars are placed in random order in an oven that has been preheated to (49 -I- 2 oC ).
[000'73] 4. The jars are marked with a code so test subjects do not know the identity of each sample.
[00074] 5. The samples are allowed to equilibrate in the oven for 2 hours.
[00075] 6. At least 5 testers on our odor panel, who are experienced in smelling rosin ester samples, evaluate the set of samples as follows:
[00076] 7. Each panelist briefly smells the jars and assigns each resin a number from 0 to 10 based on the intensity of the odor, 0 means no odor and 10 means an enormously intense odor. The panelist may also write down a description of the odor, but their number only reflects the intensity and not the character of the odor.
Upon reaching 250 C, l .06 g of tris-(nonylphenyl) phosphite (TNPP) was added.
After 1 hour the temperature was dropped to 180 C overnight (13 hrs).
The next morning it was heated to 250 C for 2 hours.
A reactor sample had an 85.2 C softening point, a 24.5 acid number, and a 2 neat Gardner color.
The reaction was heated to 275 C and sparged with nitrogen for 4 hours.
The reaction was next cooled and 0.14 g. of 50% aq. KOH, 0.99 g. of lrganoxTm 1010, and 0.35 g of lrganox-rm 565 were added. The 200 C resin was poured into pans to cool.
Final analysis: softening point 98.3 C, acid number 4.9, and a 2+ neat Gardner color.
[00067] Odor panel evaluations of five non-limiting embodiments of the present rosin ester at 50 C were compared to a commercial rosin ester, SYLVALITETm Rosin Ester with low numbers representing low odor intensity.
Example 1 [00068] Significant odor reduction was seen in some inventive embodiments as illustrated in Table 1.
[00069] A summary of the test tnethod for odor intensity is as follows:
[00070] 1. 25 g of each resin are weighed into 8 oz jars. Two of the jars contain experimental test resins and the third contains a standard.
[00071] 2. The resins are crushed to a coarse powder to expose a fresh surface area.
[00072] 3, The three capped jars are placed in random order in an oven that has been preheated to (49 -I- 2 oC ).
[000'73] 4. The jars are marked with a code so test subjects do not know the identity of each sample.
[00074] 5. The samples are allowed to equilibrate in the oven for 2 hours.
[00075] 6. At least 5 testers on our odor panel, who are experienced in smelling rosin ester samples, evaluate the set of samples as follows:
[00076] 7. Each panelist briefly smells the jars and assigns each resin a number from 0 to 10 based on the intensity of the odor, 0 means no odor and 10 means an enormously intense odor. The panelist may also write down a description of the odor, but their number only reflects the intensity and not the character of the odor.
[00077] 8. The set of capped samples is shaken lightly and placed back in the oven for a minimum of 30 minutes between odor evaluations.
[00078] 9. After evaluation by 5 to 8 odor panelists, the odor intensity values for each sample are averaged. The ratio of each sample's intensity to the standard is calculated and reported along with the raw data. (The standard = 1.0).
[00079] Specifically, samples D and E had the highest fumaric acid content, (SYLVAL1TETm Rosin Ester has none). Without being limited by theory, applicants postulate that this surprisingly may be one of the factors related to the odor reduction. One non-limiting hypothesis is that the fumaric acid preferentially reacts with the most reactive rosin isomers, which might also be related to odor generation.
Table 1. Odor Intensity vs. Fumaric Adduction Level (Odor Intensity Relative to SYLVAL1TETm Rosin Ester) Fumaric Acid Resin Relative Intensity Adduction 0.45 2.8%
0.55 /.4%
A 0.55 /.2%
0.56 2.2%
0.59 2.0%
SYINALITETm I .00 0%
Rosin Ester Example 2 [00080] Table 2 shows odor panel data on test resin formulations made with a constant 2% fumaric acid (FA) adduction and consistent process conditions but with varying levels of pentaerythritol replacing some of the glycerol. These results are consistent with earlier speculations that pentaerythritol impurities or decomposition products produced during the high temperature esterification process contribute to the unpleasant odors in the final ester.
This would therefore suggest that for some embodiments, if PE is used, that it be kept to a low level in order to minimize odor of resulting rosin ester.
Table 2. Odor Intensityys. Pentaegthritol Level Odor intensity Relative PE as to SYLVALITEmi 9/0 of Resin Rosin Ester Total Formulation Polyol %FA
8. 0.59 2 2.0 24 0.69 2 2,0 19 0,70 10 2.0 18 0.75 17.5 2.0 16 0.81 17.5 2.0 17 1.11 25.0 2.0 Example 3 [00081] Table 3 shows the high oxidation resistance of certain embodiments of the present inventive with the disproportionation step included in the process. At 150 C
in air for 24 hours, the inventive tackifier resins, especially favored formulations C and D, showed much less color darkening than the control. While not necessarily true for all embodiments, at least for the embodiment of this Example, disproportionation provides a resin ester having properties more desirable in some circumstances. Thus, depending upon the desired end use, in certain circumstances, it may be desired to require a disproportionation step. Similarly in an EVA based adhesive formulation, certain embodiment of the present inventive tackifier resins showed better color than in the control.
Table 3. Oxidation Stability and Color Improvements from this Invention NEAT RE COLOR EVA ADHESIVE COLOR
Sample Oxid. Initial 24 24 h EVA
EVA/72h DSC Hours Color Gain Stability Adhesive At (min) Color 150C 150C Initial 130C
Gain color SYLVALITETt'T (Control RE) 13.2 2.5 4.1 1.6 2.8 3.1 Rosin Ester 43 New process 7.9 2.7 7.0 4.3 Without ______________ disproportionation 413 New process 37.6 2.2 3.5 1,3 1,2 1.5 420 New process 65.2 2,5 3.7 1.2 1.5 2.9 42.1 New process 45.7 2.9 3.5 __ 0.6 2.0 2.7 ................................................................
A New process 55.7 1.2 2.3 New process 53.4 22 2.4 = 0.2 New process 49.1 2.1 23 0.2 1.2 2.1 DSC
differential Scanning Calorimetry. In oxidative DSC the sample s heated under 550 psi oxygen pressure at 128 C until the sample oxidizes as shown by its heat emission, EVA = ethylene vinyl acetate copolymer, 5 Example 4 [00082] Table 4 shows an odor comparison made between a commercial SIS /
hydrogenated hydrocarbon resin tackified adhesive and SIS adhesives made with rosin ester tackifiers. For these embodiments, adhesives made with a top grade of commercially available (Arizona Chemical) pentaerythritol rosin ester and adhesives made certain 10 embodiments of the present inventive ester without the disproportionation step showed similar or stronger odors than the commercial adhesive. However, adhesives made with sample resins from certain embodiments of the present invention were judged by an odor panel to have a significantly lower odor than the commercial SIS adhesive.
Table 4. Odor comparison of SIS Adhesives using New Rosin Ester Tackifiers to a Commercial SIS / Hydrocarbon Resin Adhesive Odor SIS Adhesive relative to Formulation Commercial SIS
Made Hydrocarbon Comments Adhesive Commercial PE
Ester Control IMO
New Resin without #1 Disproportionation LOO
New Resin without #3 Disproportionation 1.25 #9 New Resin 0.75 #10 New resin 0.87 SIS = Styrene-isoprene-styrene block copolymer Low numbers indicate a lower odor intensity Example 5 [00083] Rosin ester C from certain embodiments of the present invention was also evaluated in a standard pressure-sensitive adhesive formulation based on Styrene-Isoprene-Styrene (SIS) for label applications. The results were compared to those obtained for a standard commercial rosin ester, SYLVALITETh4Rosin Ester. The results are shown in 'Table 5, Although the rosin ester of the invention exhibited a lower loop tack, overall it performed comparably or better than the commercial rosin ester; and therefore would be expected to be an acceptable tacki.fier for such adhesives.
Table 5. Adhesive performance of SIS-based IIMPSA Label formulations using Rosin Ester C and Commercial SYLVALITETm Rosin Ester G'/G" Tg SAFT Loop tack Peel Temp. (stainless (stainless Steel.) Steel) ..
Rosin Ester C 81 C 11 C 139 F 7.5 1 SYLVALITE-rg-7.-69 C 7 C 133 F 9.2 7.1 Rosin Ester Example 6 [00084] Rosin ester C from the present invention was also evaluated in a standard hot melt packaging adhesive formulation based on EVA. The results of the thermal stability (Color and viscosity stability) were compared to those obtained for a standard commercial rosin ester, SYLVAL1TETm Rosin Ester. The results are shown in Table 6. The adhesive made with the rosin ester of the invention exhibited comparable stability to the commercial product; and therefore the rosin ester of this invention would be expected to be an acceptable tackifier for such adhesives.
Table 6. Adhesive Stability of EVA-based Hot Melt Packaging Adhesive formulation Using Rosin Ester C and Commercial SYLVALITErm Rosin Ester Initial Color Initial Viscosity % Change Color 96h/350 F Viscosity 96h/350 F
Viscosity 96h/350 F
Rosin Ester C 1.6 7.2 1010 1028 1.8 SYLVAL1TETh4 1.8 6.7 993 1045 5.2 Rosin Ester [00085] The present disclosure is to be taken as illustrative rather than as limiting the scope or nature of the claims below. Numerous modifications and variations will become apparent to those skilled in the art after studying the disclosure, including use of equivalent functional andlor structural substitutes for elements described herein, use of equivalent functional couplings for couplings described herein, and/or use of equivalent functional actions for actions described herein. Any insubstantial variations are to be considered within the scope of the claims below.
[00078] 9. After evaluation by 5 to 8 odor panelists, the odor intensity values for each sample are averaged. The ratio of each sample's intensity to the standard is calculated and reported along with the raw data. (The standard = 1.0).
[00079] Specifically, samples D and E had the highest fumaric acid content, (SYLVAL1TETm Rosin Ester has none). Without being limited by theory, applicants postulate that this surprisingly may be one of the factors related to the odor reduction. One non-limiting hypothesis is that the fumaric acid preferentially reacts with the most reactive rosin isomers, which might also be related to odor generation.
Table 1. Odor Intensity vs. Fumaric Adduction Level (Odor Intensity Relative to SYLVAL1TETm Rosin Ester) Fumaric Acid Resin Relative Intensity Adduction 0.45 2.8%
0.55 /.4%
A 0.55 /.2%
0.56 2.2%
0.59 2.0%
SYINALITETm I .00 0%
Rosin Ester Example 2 [00080] Table 2 shows odor panel data on test resin formulations made with a constant 2% fumaric acid (FA) adduction and consistent process conditions but with varying levels of pentaerythritol replacing some of the glycerol. These results are consistent with earlier speculations that pentaerythritol impurities or decomposition products produced during the high temperature esterification process contribute to the unpleasant odors in the final ester.
This would therefore suggest that for some embodiments, if PE is used, that it be kept to a low level in order to minimize odor of resulting rosin ester.
Table 2. Odor Intensityys. Pentaegthritol Level Odor intensity Relative PE as to SYLVALITEmi 9/0 of Resin Rosin Ester Total Formulation Polyol %FA
8. 0.59 2 2.0 24 0.69 2 2,0 19 0,70 10 2.0 18 0.75 17.5 2.0 16 0.81 17.5 2.0 17 1.11 25.0 2.0 Example 3 [00081] Table 3 shows the high oxidation resistance of certain embodiments of the present inventive with the disproportionation step included in the process. At 150 C
in air for 24 hours, the inventive tackifier resins, especially favored formulations C and D, showed much less color darkening than the control. While not necessarily true for all embodiments, at least for the embodiment of this Example, disproportionation provides a resin ester having properties more desirable in some circumstances. Thus, depending upon the desired end use, in certain circumstances, it may be desired to require a disproportionation step. Similarly in an EVA based adhesive formulation, certain embodiment of the present inventive tackifier resins showed better color than in the control.
Table 3. Oxidation Stability and Color Improvements from this Invention NEAT RE COLOR EVA ADHESIVE COLOR
Sample Oxid. Initial 24 24 h EVA
EVA/72h DSC Hours Color Gain Stability Adhesive At (min) Color 150C 150C Initial 130C
Gain color SYLVALITETt'T (Control RE) 13.2 2.5 4.1 1.6 2.8 3.1 Rosin Ester 43 New process 7.9 2.7 7.0 4.3 Without ______________ disproportionation 413 New process 37.6 2.2 3.5 1,3 1,2 1.5 420 New process 65.2 2,5 3.7 1.2 1.5 2.9 42.1 New process 45.7 2.9 3.5 __ 0.6 2.0 2.7 ................................................................
A New process 55.7 1.2 2.3 New process 53.4 22 2.4 = 0.2 New process 49.1 2.1 23 0.2 1.2 2.1 DSC
differential Scanning Calorimetry. In oxidative DSC the sample s heated under 550 psi oxygen pressure at 128 C until the sample oxidizes as shown by its heat emission, EVA = ethylene vinyl acetate copolymer, 5 Example 4 [00082] Table 4 shows an odor comparison made between a commercial SIS /
hydrogenated hydrocarbon resin tackified adhesive and SIS adhesives made with rosin ester tackifiers. For these embodiments, adhesives made with a top grade of commercially available (Arizona Chemical) pentaerythritol rosin ester and adhesives made certain 10 embodiments of the present inventive ester without the disproportionation step showed similar or stronger odors than the commercial adhesive. However, adhesives made with sample resins from certain embodiments of the present invention were judged by an odor panel to have a significantly lower odor than the commercial SIS adhesive.
Table 4. Odor comparison of SIS Adhesives using New Rosin Ester Tackifiers to a Commercial SIS / Hydrocarbon Resin Adhesive Odor SIS Adhesive relative to Formulation Commercial SIS
Made Hydrocarbon Comments Adhesive Commercial PE
Ester Control IMO
New Resin without #1 Disproportionation LOO
New Resin without #3 Disproportionation 1.25 #9 New Resin 0.75 #10 New resin 0.87 SIS = Styrene-isoprene-styrene block copolymer Low numbers indicate a lower odor intensity Example 5 [00083] Rosin ester C from certain embodiments of the present invention was also evaluated in a standard pressure-sensitive adhesive formulation based on Styrene-Isoprene-Styrene (SIS) for label applications. The results were compared to those obtained for a standard commercial rosin ester, SYLVALITETh4Rosin Ester. The results are shown in 'Table 5, Although the rosin ester of the invention exhibited a lower loop tack, overall it performed comparably or better than the commercial rosin ester; and therefore would be expected to be an acceptable tacki.fier for such adhesives.
Table 5. Adhesive performance of SIS-based IIMPSA Label formulations using Rosin Ester C and Commercial SYLVALITETm Rosin Ester G'/G" Tg SAFT Loop tack Peel Temp. (stainless (stainless Steel.) Steel) ..
Rosin Ester C 81 C 11 C 139 F 7.5 1 SYLVALITE-rg-7.-69 C 7 C 133 F 9.2 7.1 Rosin Ester Example 6 [00084] Rosin ester C from the present invention was also evaluated in a standard hot melt packaging adhesive formulation based on EVA. The results of the thermal stability (Color and viscosity stability) were compared to those obtained for a standard commercial rosin ester, SYLVAL1TETm Rosin Ester. The results are shown in Table 6. The adhesive made with the rosin ester of the invention exhibited comparable stability to the commercial product; and therefore the rosin ester of this invention would be expected to be an acceptable tackifier for such adhesives.
Table 6. Adhesive Stability of EVA-based Hot Melt Packaging Adhesive formulation Using Rosin Ester C and Commercial SYLVALITErm Rosin Ester Initial Color Initial Viscosity % Change Color 96h/350 F Viscosity 96h/350 F
Viscosity 96h/350 F
Rosin Ester C 1.6 7.2 1010 1028 1.8 SYLVAL1TETh4 1.8 6.7 993 1045 5.2 Rosin Ester [00085] The present disclosure is to be taken as illustrative rather than as limiting the scope or nature of the claims below. Numerous modifications and variations will become apparent to those skilled in the art after studying the disclosure, including use of equivalent functional andlor structural substitutes for elements described herein, use of equivalent functional couplings for couplings described herein, and/or use of equivalent functional actions for actions described herein. Any insubstantial variations are to be considered within the scope of the claims below.
Claims (23)
1. A method of producing a rosin ester, the method comprising:
(A) Contacting a rosin having PAN isomers with disproportionation agent to provide a rosin having a PAN number less than 45 providing a disproportionated rosin;
(8) Contacting the disproportionated rosin with an adduction agent to further reduce the PAN
number to provide an adducted rosin;
(C) Contacting the adducted rosin with a polyhydric polyol, wherein the polyhydric polyol comprises at or below 20 percent by weight of pentaerythritol, based on total weight of the polyhydric polyol;
to form a rosin ester, wherein the rosin ester has an odor intensity of less than 80% relative to comparison rosin ester made from 100% pentaerythritol.
(A) Contacting a rosin having PAN isomers with disproportionation agent to provide a rosin having a PAN number less than 45 providing a disproportionated rosin;
(8) Contacting the disproportionated rosin with an adduction agent to further reduce the PAN
number to provide an adducted rosin;
(C) Contacting the adducted rosin with a polyhydric polyol, wherein the polyhydric polyol comprises at or below 20 percent by weight of pentaerythritol, based on total weight of the polyhydric polyol;
to form a rosin ester, wherein the rosin ester has an odor intensity of less than 80% relative to comparison rosin ester made from 100% pentaerythritol.
2. The method of claim 1, wherein the disproportionation agent comprises at least one selected from among phenol sulfides, metals, iodine, iodides, and sulfides, and the adduction agent is selected to react with the PAN isomers of the rosin through a Diels-Alder reaction or an Ene reaction.
3. The method of claim 1 wherein the disproportionation agent comprises at least one selected from 2,2'-thiobis phenols, 3,3'-thiobisphenols, 4,4'-thiobis(resorcinol) and t,t'-thiobis(pyrogallol),
4,4'-thiobis(6-t-butyl-m-cresol) and 4/4'-thiobis(6-t-butyl-o-cresol) thiobisnaphthols, 2,2'-thio-bis phenols, 3,3'-thio-bis phenols, palladium, nickel, platinum, iodine, iron iodide, iron sulfide.
4. The method of claim 1, wherein the adduction agent comprises at least one selected from fumaric acid, maleic anhydride, acrylic acid, unsaturated acids and anhydrides.
4. The method of claim 1, wherein the adduction agent comprises at least one selected from fumaric acid, maleic anhydride, acrylic acid, unsaturated acids and anhydrides.
5. The method of claim 1, wherein the polyhydric polyol comprises at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, glycerol, dipentaerythritol, tripentaerythritol, trimethylolethane, trimethylolpropane, mannitol and sorbitol.
6. The method of claim 1, wherein the polyhydric polyol comprises at least one selected from the group consisting of glycerol and trimethylolpropane.
7. A method of producing a rosin ester, the method comprising:
(A) Contacting rosin having a PAN number less than 45 with an adduction agent to further reduce the PAN number to provide an adducted rosin;
(B) Contacting the adducted rosin with a polyhydric polyol, wherein the polyhydric polyol comprises at or below 20 percent by weight of pentaerythritol, based on total weight of the polyhydric polyol;
to form a rosin ester, wherein the rosin ester has an odor intensity of less than 80% relative to comparison rosin ester made from 100% pentaerythritol.
(A) Contacting rosin having a PAN number less than 45 with an adduction agent to further reduce the PAN number to provide an adducted rosin;
(B) Contacting the adducted rosin with a polyhydric polyol, wherein the polyhydric polyol comprises at or below 20 percent by weight of pentaerythritol, based on total weight of the polyhydric polyol;
to form a rosin ester, wherein the rosin ester has an odor intensity of less than 80% relative to comparison rosin ester made from 100% pentaerythritol.
8. The method of claim 7, wherein the adduction agent is selected to react with the PAN isomers of the rosin through a DieIs-Alder reaction or an Ene reaction.
9. The method of claim 7, wherein the adduction agent comprises at least one selected from fumaric acid, maleic anhydride, acrylic acid, unsaturated acids and anhydrides.
10. The method of claim 7, wherein the polyhydric polyol comprises at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, glycerol, dipentaerythritol, tripentaerythritol, trimethylolethane, trimethylolpropane, mannitol and sorbitol.
11. The method of claim 7, wherein the polyhydric polyol comprises at least one selected from the group consisting of glycerol and trimethylolpropane.
12. A rosin ester composition having an odor intensity of less than 80%
relative to comparison rosin ester made from 100% pentaerythritol, wherein the composition is made from a polyhydric polyol comprising at or below 20 percent by weight of pentaerythritol, based on total weight of the polyhydric polyol.
relative to comparison rosin ester made from 100% pentaerythritol, wherein the composition is made from a polyhydric polyol comprising at or below 20 percent by weight of pentaerythritol, based on total weight of the polyhydric polyol.
13. The composition of claim 12 having an odor intensity of less than 60%
relative to comparison rosin ester made from 100% pentaerythritol.
relative to comparison rosin ester made from 100% pentaerythritol.
14. The composition of claim 12 having an odor intensity of less than 55%
relative to comparison rosin ester made from 100% pentaerythritol.
relative to comparison rosin ester made from 100% pentaerythritol.
15. The composition of claim 12 having an odor intensity of less than 50%
relative to comparison rosin ester made from 100% pentaerythritol.
relative to comparison rosin ester made from 100% pentaerythritol.
16. An adhesive comprising a rosin ester composition having an odor intensity of less than 80%
relative to comparison rosin ester made from 100% pentaerythritol, wherein the composition is made from a polyhydric polyol comprising at or below 20 percent by weight of pentaerythritol, based on total weight of the polyhydric polyol.
relative to comparison rosin ester made from 100% pentaerythritol, wherein the composition is made from a polyhydric polyol comprising at or below 20 percent by weight of pentaerythritol, based on total weight of the polyhydric polyol.
17. The adhesive of claim 16 wherein the composition comprises an odor intensity of less than 60%
relative to comparison rosin ester made from 100% pentaerythritol.
relative to comparison rosin ester made from 100% pentaerythritol.
18. The adhesive of claim 16 wherein the composition comprises an odor intensity of less than 55%
relative to comparison rosin ester made from 100% pentaerythritol.
relative to comparison rosin ester made from 100% pentaerythritol.
19. The adhesive of claim 16 wherein the composition comprises an odor intensity of less than 50%
relative to comparison rosin ester made from 100% pentaerythritol.
relative to comparison rosin ester made from 100% pentaerythritol.
20. A non-woven product comprising an adhesive comprising a rosin ester composition having an odor intensity of less than 80% relative to comparison rosin ester made from 100% pentaerythritol, wherein the composition is made from a polyhydric polyol comprising at or below 20 percent by weight of pentaerythritol, based on total weight of the polyhydric polyol.
21. The product of claim 20 wherein the odor intensity is less than 60%
relative to comparison rosin ester made from 100% pentaerythritol.
relative to comparison rosin ester made from 100% pentaerythritol.
22. The product of claim 20 wherein the odor intensity is less than 55%
relative to comparison rosin ester made from 100% pentaerythritol.
relative to comparison rosin ester made from 100% pentaerythritol.
23. The product of claim 20 wherein the odor intensity is less than 50%
relative to comparison rosin ester made from 100% pentaerythritol.
relative to comparison rosin ester made from 100% pentaerythritol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2011/031884 WO2012141675A1 (en) | 2011-04-11 | 2011-04-11 | Rosin esters for non-wovens |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2833114A1 true CA2833114A1 (en) | 2012-10-18 |
Family
ID=47009591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CA2833114A Abandoned CA2833114A1 (en) | 2011-04-11 | 2011-04-11 | Rosin esters for non-woven applications, methods of making and using and products therefrom |
Country Status (9)
| Country | Link |
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| EP (1) | EP2697322A4 (en) |
| JP (1) | JP2014517091A (en) |
| KR (1) | KR20140022059A (en) |
| CN (1) | CN103517957B (en) |
| AU (1) | AU2011365712A1 (en) |
| BR (1) | BR112013026297A2 (en) |
| CA (1) | CA2833114A1 (en) |
| RU (1) | RU2569081C2 (en) |
| WO (1) | WO2012141675A1 (en) |
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| JP6040686B2 (en) * | 2012-09-28 | 2016-12-07 | 星光Pmc株式会社 | Rosin polyhydric alcohol ester resin, ink emulsification suitability improver, varnish for offset printing ink and ink composition for offset printing |
| CN103436174B (en) * | 2013-08-27 | 2015-03-18 | 广西梧州松脂股份有限公司 | Preparation method of rosin glycerin ester |
| EP3049475B1 (en) | 2013-09-27 | 2018-01-10 | Arizona Chemical Company, LLC | Compositions containing ethylene polymers |
| CN105916949A (en) * | 2013-09-27 | 2016-08-31 | 阿利桑那化学公司 | Rosin esters and compositions thereof |
| CN104559794B (en) * | 2013-12-16 | 2017-05-10 | 广西梧州日成林产化工股份有限公司 | Preparation method of alcohol soluble acrylic rosin resin |
| US10253215B2 (en) | 2014-03-12 | 2019-04-09 | Arakawa Chemical Industries, Ltd. | Pressure-sensitive adhesive composition and acrylic pressure-sensitive adhesive composition |
| JP6477689B2 (en) * | 2014-03-28 | 2019-03-06 | 荒川化学工業株式会社 | Tackifying resin, adhesive composition containing the same, tackifying resin for hot melt adhesive, hot melt adhesive composition, styrene-conjugated diene block copolymer adhesive composition And styrene-conjugated diene block copolymer system hot-melt adhesive composition |
| KR101582952B1 (en) * | 2014-04-16 | 2016-01-06 | 주식회사 아이티엠반도체 | Package of battery protection circuits and battery pack |
| WO2016109206A2 (en) * | 2014-12-31 | 2016-07-07 | Arizona Chemical Company, Llc | Rosin-containing materials and methods of making thereof |
| CN104694015B (en) * | 2015-03-18 | 2017-01-11 | 桂林兴松林化有限责任公司 | Preparation method of light-color glycerol ester of rosin |
| KR102464692B1 (en) * | 2015-03-26 | 2022-11-09 | 크라톤 케미칼, 엘엘씨 | Compositions comprising rosin esters and ethylene polymers |
| KR102040268B1 (en) * | 2015-07-10 | 2019-11-04 | 재단법인 한국화학융합시험연구원 | Anti-cutting and anti-chipping agent for rubber and preparation method thereof |
| JP6996077B2 (en) * | 2015-12-28 | 2022-01-17 | 荒川化学工業株式会社 | Adhesive-imparting resin, adhesive / adhesive, hot melt adhesive |
| TWI731094B (en) * | 2016-06-16 | 2021-06-21 | 日商荒川化學工業股份有限公司 | Tackifying resin, tackifying resin emulsion, water-based adhesive composition, polychloroprene latex-based adhesive composition |
| WO2019210036A1 (en) * | 2018-04-26 | 2019-10-31 | Ingevity South Carolina, Llc | Carboxylic acid adducted rosin polyol ester with fatty acid functionality and methods of producing the same |
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| US2980629A (en) * | 1957-09-13 | 1961-04-18 | Hercules Powder Co Ltd | Gel-free rosin soap and method of preparing same |
| US3377334A (en) * | 1966-09-16 | 1968-04-09 | Arizona Chem | Disproportionation of rosin |
| JPS559605A (en) * | 1978-06-23 | 1980-01-23 | Arakawa Chem Ind Co Ltd | Preparation of rosin ester having high softening point and improved stability |
| US4447354A (en) * | 1983-03-21 | 1984-05-08 | Arizona Chemical Company | Method for making oxidation-stable, light-colored glycerol ester of modified rosin |
| US4842691A (en) * | 1986-03-19 | 1989-06-27 | Arakawa Chemical Industries, Ltd. | Sizing agents in neutral range and sizing methods using the same |
| JPH064954B2 (en) * | 1986-04-21 | 1994-01-19 | 荒川化学工業株式会社 | Neutral papermaking sizing method |
| JP2548033B2 (en) * | 1989-03-22 | 1996-10-30 | ハリマ化成株式会社 | Rosin derivative, production method thereof, hot melt adhesive composition and production method thereof |
| EP0572680B1 (en) * | 1991-12-21 | 1997-05-28 | Arakawa Kagaku Kogyo Kabushiki Kaisha | Process for producing rosin ester and colorless rosin |
| SE9203499L (en) * | 1992-11-20 | 1994-05-21 | Eka Nobel Ab | Rosin derivative as surfactant |
| US5541246A (en) * | 1994-10-24 | 1996-07-30 | Arizona Chemical Company | Repulpable hot melt adhesives |
| FI112247B (en) * | 1997-04-18 | 2003-11-14 | Arizona Chemical Oy | Preparation of a low odor level tall oil resin ester |
| US5969071A (en) * | 1998-05-08 | 1999-10-19 | Westvaco Corporation | Method for preparing phenolic rosin resins |
| US6562888B1 (en) * | 1998-07-27 | 2003-05-13 | Arizona Chemical Company | Light-colored rosin esters and adhesive compositions |
| JP2003119230A (en) * | 2001-10-09 | 2003-04-23 | Toyo Ink Mfg Co Ltd | Curable composition, curable ink, method of printing by using it, and printed matter obtained by using it |
| US20050113499A1 (en) * | 2002-02-13 | 2005-05-26 | Thomas Tamcke | Low-emission aqueous dispersion adhesive |
| WO2007092250A2 (en) * | 2006-02-02 | 2007-08-16 | Hexion Specialty Chemicals Inc. | Rosin ester with low color and process for preparing same |
| US7910794B2 (en) * | 2007-03-05 | 2011-03-22 | Adherent Laboratories, Inc. | Disposable diaper construction and adhesive |
| CN101264454B (en) * | 2008-03-21 | 2012-03-21 | 广州英科新材料有限公司 | Composite catalyst and its application in preparing light-colored rosin esters |
-
2011
- 2011-04-11 BR BR112013026297A patent/BR112013026297A2/en not_active IP Right Cessation
- 2011-04-11 AU AU2011365712A patent/AU2011365712A1/en not_active Abandoned
- 2011-04-11 KR KR1020137029360A patent/KR20140022059A/en not_active Application Discontinuation
- 2011-04-11 JP JP2014505109A patent/JP2014517091A/en active Pending
- 2011-04-11 RU RU2013145603/05A patent/RU2569081C2/en not_active IP Right Cessation
- 2011-04-11 CN CN201180070558.1A patent/CN103517957B/en not_active Expired - Fee Related
- 2011-04-11 CA CA2833114A patent/CA2833114A1/en not_active Abandoned
- 2011-04-11 WO PCT/US2011/031884 patent/WO2012141675A1/en active Application Filing
- 2011-04-11 EP EP11863683.6A patent/EP2697322A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140022059A (en) | 2014-02-21 |
| CN103517957B (en) | 2015-06-10 |
| BR112013026297A2 (en) | 2017-06-06 |
| JP2014517091A (en) | 2014-07-17 |
| AU2011365712A1 (en) | 2013-10-31 |
| CN103517957A (en) | 2014-01-15 |
| RU2569081C2 (en) | 2015-11-20 |
| RU2013145603A (en) | 2015-05-20 |
| WO2012141675A1 (en) | 2012-10-18 |
| EP2697322A4 (en) | 2015-08-05 |
| EP2697322A1 (en) | 2014-02-19 |
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