CN101600785A - 免漂洗织物软化剂 - Google Patents
免漂洗织物软化剂 Download PDFInfo
- Publication number
- CN101600785A CN101600785A CNA2007800484722A CN200780048472A CN101600785A CN 101600785 A CN101600785 A CN 101600785A CN A2007800484722 A CNA2007800484722 A CN A2007800484722A CN 200780048472 A CN200780048472 A CN 200780048472A CN 101600785 A CN101600785 A CN 101600785A
- Authority
- CN
- China
- Prior art keywords
- quaternized
- amine
- composition
- tri
- fabric
- 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.)
- Granted
Links
- 239000002979 fabric softener Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 87
- -1 diester amine Chemical class 0.000 claims abstract description 51
- 239000004744 fabric Substances 0.000 claims abstract description 30
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003599 detergent Substances 0.000 claims abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 239000000194 fatty acid Substances 0.000 claims description 23
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 21
- 229930195729 fatty acid Natural products 0.000 claims description 21
- 150000004665 fatty acids Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 238000005956 quaternization reaction Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000002168 alkylating agent Substances 0.000 claims description 8
- 229940100198 alkylating agent Drugs 0.000 claims description 8
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 6
- 239000011833 salt mixture Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920005628 alkoxylated polyol Polymers 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229960004418 trolamine Drugs 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 10
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- 239000000243 solution Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000007046 ethoxylation reaction Methods 0.000 description 6
- 150000005691 triesters Chemical class 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
- 239000004666 Monoesterquat Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 4
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- 239000004667 Diesterquat Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
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- 239000000843 powder Substances 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229960003168 bronopol Drugs 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- ODGXMRVMAFAHQH-UHFFFAOYSA-M dodecyl(trimethyl)azanium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCCCCCCCCCC[N+](C)(C)C ODGXMRVMAFAHQH-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- OEWKLERKHURFTB-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCCCCCCCCCCCCCC[N+](C)(C)C OEWKLERKHURFTB-UHFFFAOYSA-M 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- SIOLDWZBFABPJU-UHFFFAOYSA-N isotridecanoic acid Chemical compound CC(C)CCCCCCCCCC(O)=O SIOLDWZBFABPJU-UHFFFAOYSA-N 0.000 description 2
- WYTNTFGZBBTWNR-UHFFFAOYSA-M methyl sulfate;trimethyl(octadecyl)azanium Chemical compound COS([O-])(=O)=O.CCCCCCCCCCCCCCCCCC[N+](C)(C)C WYTNTFGZBBTWNR-UHFFFAOYSA-M 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 238000000518 rheometry Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
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- 239000003760 tallow Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
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- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- QTDIEDOANJISNP-UHFFFAOYSA-N 2-dodecoxyethyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOCCOS(O)(=O)=O QTDIEDOANJISNP-UHFFFAOYSA-N 0.000 description 1
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/645—Mixtures of compounds all of which are cationic
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- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
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Abstract
本发明涉及适合作为织物软化剂的组合物,尤其适合于软化已经以高浓缩洗涤剂洗涤过的织物。所述组合物能够通过C6~C22脂肪酸与三乙醇胺的酯化和随后的季铵化而获得,所述组合物包含未季铵化的二酯胺、未季铵化的三酯胺、季铵化的单酯胺、季铵化的二酯胺和季铵化的三酯胺,其中,未季铵化的三酯胺对季铵化的三酯胺的重量比大于1.5。
Description
技术领域
本发明涉及适于作为织物软化剂的组合物,尤其适于软化以高浓缩洗涤剂洗涤过的织物。
背景技术
织物护理组合物在处理时给织物带来了大量所需的特性,包括改善的织物触感和清新的感受。然而,为了确保任何织物护理组合物的较高的消费者接受度,必须提供消费者所需的产品美感,例如不仅有吸引人的洁净的产品气味和令人愉快的产品颜色,还有特别是适宜的产品流变性和令人满意的产品物理稳定性。随着织物软化活性物浓度的降低(即稀释),对织物护理组合物的流变性的控制变得愈加具有挑战性。
通常在洗涤过程和后续的漂洗之后将织物软化剂加入到织物。然而,可能有一些阴离子表面活性剂被带出到添加织物软化剂的步骤,尤其是当洗涤步骤中洗涤剂对水的比例较高时,即例如在手洗条件下的情况下或在上开门式(top loading)非自动洗衣机中处理中洗涤的情况下。阴离子表面活性剂的这种带出可能存在关于后续软化剂处理的问题,这是因为织物软化剂活性物可能与残留的阴离子表面活性剂相互作用。例如,这种相互作用可能导致软化效果下降。
WO-A-02072745描述了用以在漂洗中调理织物的漂洗添加组合物,其中的组合物包含织物软化剂活性物、泡沫(suds)抑制系统和表面活性剂清除剂,其特征在于所述组合物在残留的洗涤剂表面活性剂的存在下使用时具有至少约90%的泡沫减少值并且没有可见的絮凝物。根据WO-A-02072745,优选的是所述织物软化剂活性物和所述表面活性剂清除剂源自相同的起始材料,作为织物软化剂活性物的是二烷基取代的季铵化合物,作为表面活性剂清除剂的是单烷基季铵化合物,因为它们可以在单个化学反应中一起生成,这样,最终的组合物不太可能经历相分离。
根据WO-A-02072745,如果脂肪酸对胺的摩尔比少于2∶1,优选为1.6∶1~0.8∶1,更优选为1.6∶1~1∶1,则可获得单烷基取代化合物和二烷基取代化合物的混合物。
WO-A-02072745的优选织物软化剂活性物是酯季铵盐(esterquat),如氯化N,N-二(硬脂酰-氧-乙基)N,N-二甲基铵、氯化N,N-二(牛脂酰-氧-乙基)N,N-二甲基铵、甲基硫酸N,N-二(硬脂酰-氧-乙基)N-(2-羟乙基)N-甲基铵或氯化1,2-二(硬脂酰-氧)-3-三甲基丙烷铵。
优选的表面活性剂清除剂是织物软化剂活性物的单烷基变体(单烷基酯季铵盐)。
关于将二烷基取代的季铵化合物和单烷基季铵化合物组合,有大量参考书目,其中可以列举的专利或专利申请有EP-A-0018039、EP-A-0369500、US-A-4360437或US-A-4855072等。
描述二烷基取代的酯季铵盐和单烷基酯季铵盐的混合物的参考文献有WO-A-9414935、WO-A-9742279、WO-A-2004044113等。
US-A-6737392描述了含有由高含量单烷基甲基二乙醇胺酯季铵盐和三乙醇胺酯季铵盐组成的混合物的织物软化剂组合物。该织物软化剂组合物包含为全部混合物的15重量%~65重量%的三乙醇胺酯季铵盐和为全部混合物的35重量%~85重量%的所具有的单烷基酯季铵盐水平大于或等于约10%的甲基二乙醇胺酯季铵盐的混合物。根据US-A-6737392,脂肪酸对甲基二乙醇胺的优选摩尔比为1.2∶1~1.7∶1,优选为1.2∶1~1.5∶1,更优选为1.2∶1~1.35∶1,从而增加单烷基酯季铵盐的水平。
最后,根据F,E.Friedli等在AOCS出版的″Upgrading triethanolamineesterquat performance to new levels″,Journal of Surfactants and Detergents,Vol.5,No.3(2002年七月)中的描述,使用2∶1的脂肪酸/三乙醇胺摩尔比,可获得包含单酯季铵盐、二酯季铵盐、三酯季铵盐和三酯胺(tri-esteramine)的最终产物混合物。市售三乙醇胺酯季铵盐的典型重量百分比分析结果为23%的单酯季铵盐、47%的二酯季铵盐、19%的三酯季铵盐和11%的三酯胺。
发明内容
本发明所要解决的问题是提供一种新型组合物和所述组合物的制备方法,该组合物适合用作织物软化剂,尤其是在可能从洗涤过程中带出的阴离子表面活性剂的存在下。
这一问题可通过提供一种包含季铵盐混合物的组合物来解决,所述季铵盐混合物可通过C6~C22脂肪酸与三乙醇胺的酯化和后续的季铵化来获得,所述混合物包含未季铵化的二酯胺、未季铵化的三酯胺、季铵化的单酯胺、季铵化的二酯胺和季铵化的三酯胺,其中,未季铵化的三酯胺对季铵化的三酯胺的重量比大于1.5。
可通过下述方法来制备该组合物,所述方法包括使C6~C22脂肪酸与三乙醇胺缩合以提供包含单酯胺、二酯胺和三酯胺的酯胺混合物,以烷基化试剂将所述混合物季铵化,其中,烷基化试剂对酯胺的摩尔比为0.6~0.9,优选为0.65~0.85。
具体实施方式
酯季铵盐
酯季铵盐一般被理解为经季铵化的脂肪酸烷醇胺酯盐,近年来其已被证明适合作为除了已知的四烷基铵盐之外的另一类阳离子表面活性剂而被用作织物软化剂和化妆品用调节剂。它们通常是通过脂肪酸与烷醇胺的酯化和随后以甲基氯或硫酸二甲酯对烷醇胺酯进行的季铵化而生成。对此可参考WO-A-9101295。本发明的酯季铵盐是通过C6~C22脂肪酸与三乙醇胺的酯化和随后的季铵化而获得,所述混合物包含未季铵化的二酯胺(二酯胺)、未季铵化的三酯胺(三酯胺)、季铵化的单酯胺(单酯季铵盐)、季铵化的二酯胺(二酯季铵盐)和季铵化的三酯胺(三酯季铵盐),其中,未季铵化的三酯胺对季铵化的三酯胺的重量比大于1.5。下文中,将更详细地描述合成酯季铵盐的这两个步骤。
酯化
根据本发明,可通过C6~C22脂肪酸与三乙醇胺(TEA)的缩合来获得烷醇胺酯。
适宜的C6~C22脂肪酸的实例有:最终完全氢化或部分氢化的获得自植物油以及动物油和脂肪的C6~C22脂肪酸,如获得自蓖麻油、椰子油、玉米油、芥子油、橄榄油、棕榈油、花生油、菜子油、向日葵油、豆油、妥尔油、牛脂的C6~C22脂肪酸,以及经纯化的或合成的脂肪酸,如己酸、辛酸、癸酸、异十三烷酸、月桂酸、十四烷酸、十六烷酸、棕榈油酸(palmoleicacid)、硬脂酸、异硬脂酸、2-乙基己酸、油酸、反油酸、伞形花子油酸、亚油酸、亚麻酸、桐酸、蓖麻油酸、花生酸、顺式二十碳-9-烯酸、二十二烷酸、芥酸或它们的工业级(technical-grade)混合物。
所述脂肪酸优选为含有使碘值(″IV″)为0~90、优选为10~90、更优选为15~85、最优选为15~55的不饱和度的C8~C18酸。
同样优选的是本方法中采用的一种或多种脂肪酸所具有的顺式对反式异构体的比率为80∶20~95∶5。更优选的是,所述一种或多种脂肪酸的反式异构体含量小于10%。最佳的反式异构体含量为0.5%~5%。
可以通过已知方法,如WO-A-9101295中所述的方法,来进行C6~C22脂肪酸与三乙醇胺(TEA)的酯化。
优选的是,C6~C22脂肪酸与三乙醇胺的酯化的进行条件为120℃~220℃的温度,2小时~10小时的时间,优选在5mbar~200mbar的降低的压力下,并且优选存在一些已知用于酯化的催化剂,如次磷酸和对甲苯磺酸,还存在一些常用稳定剂和抗氧化剂,如生育酚、BHT、BHA、柠檬酸等。
C6~C22脂肪酸对三乙醇胺的摩尔比通常为1.5∶1~2.5∶1,更通常为1.6∶1~2.0∶1。
该酯化反应的反应产物是脂肪酸的单酯、二酯和三酯的复杂混合物,即除未反应的物种以外的单酯胺、二酯胺和三酯胺的混合物。单酯胺、二酯胺和三酯胺具有下式(II)~(IV):
上式中R代表C5~C21烃基。
季铵化
可以以已知的方式,例如WO-A-9101295中描述的方式,来对酯化反应的反应产物进行季铵化。优选的烷基化试剂包括C1~C3直链或支链烷基的卤化物、磷酸酯、碳酸酯或硫酸酯,C7~C10芳烷基的卤化物、磷酸酯或硫酸酯,和它们的混合物。优选的烷基化试剂的实例包括但不限于甲基氯、苄基氯、硫酸二乙酯、碳酸二甲酯、磷酸三甲酯、硫酸二甲酯或它们的混合物。对所用的烷基化试剂的类型和量的选择是本领域技术人员已知的。根据本发明,烷基化试剂对酯胺的摩尔比通常为0.6~0.9,优选为0.65~0.85,进而更优选为0.7~0.83。
在55℃~120℃的温度下,所述季铵化可以在本体中进行也可以在溶剂中进行。如果使用了溶剂,则起始材料和/或产物必须在所述溶剂中可溶至达到反应所必需的程度。
得到的季铵化的组合物(即酯季铵盐)除了未季铵化的二酯胺、未季铵化的三酯胺和可能未季铵化的单酯胺及其它副产物之外,还含有分别为下式V~VII的单酯季铵盐、二酯季铵盐和三酯季铵盐:
其中
R具有的含义与式II~IV中相同,X代表软化剂相容性阴离子,优选氯离子、溴离子、甲基硫酸根、乙基硫酸根和硝酸根,更优选氯离子或甲基硫酸根,并且Q是C1~C3烷基。
在得到的酯季铵盐中,(未季铵化的)三酯胺对三酯季铵盐的重量比至少为1.5,更优选至少为3,进而更优选至少为5,最优选至少为8。同样优选的是相对于单酯胺、二酯胺、三酯胺、单酯季铵盐、二酯季铵盐和三酯季铵盐的总重量,三酯季铵盐的含量小于3重量%,更优选小于2重量%,最优选小于1重量%。
本文中所述的未季铵化的三酯胺和季铵化的三酯胺的重量百分比(以及其它物种的重量百分比)是通过下述出版物中所述的定量分析法来确定的:″Characterization of quaternized triethanolamine esters(esterquats)by HPLC,HRCGC and NMR″,A.J.Wilkes,C.Jacobs,G.Walraven和J.M:Talbot-4th World Surfactants Congress,Barcelona,1996年6月3日~7日。
在另一个优选的实施方式中,在酯化步骤之后和季铵化之前,向获得的酯胺混合物中加入N-C6~C22烷基,N-二-(C1~C3烷基)胺,即在所述胺的存在下进行季铵化。经季铵化,获得了除(a)上述酯季铵盐之外还含有(b)式(I)的季铵化合物的季铵盐混合物。
其中,
R1代表直链或支链的C6~C22烷基或烯基,
R2、R3和R4独立地代表C1~C3烷基,
X代表软化剂相容性阴离子,优选氯离子、溴离子、甲基硫酸根、乙基硫酸根和硝酸根,更优选氯离子或甲基硫酸根。
化合物(b)优选为氯化N-C6~C22烷基,N-三-甲基铵或甲基硫酸N-C6~C22烷基,N-三-甲基铵。酯季铵盐(a)对化合物(b)的重量比优选为5∶1~60∶1,更优选为8∶1~50∶1,最优选为8∶1~20∶1。
作为选择,还可以在季铵化步骤之后以上述量向酯季铵盐中加入化合物(b)。
如果本发明的组合物中存在有化合物(b),则相对于单酯胺、二酯胺、三酯胺、单酯季铵盐、二酯季铵盐、三酯季铵盐和式(I)的N-C6~C22烷基,N-三-(C1~C3烷基)铵化合物的总重量,化合物(b)的优选存在量为1重量%~20重量%,优选为2重量%~15重量%。
在另一优选的实施方式中,本发明的组合物(单独的酯季铵盐或与化合物(b)组合的酯季铵盐)中还存在非离子表面活性剂,优选为烷氧基化的醇、烷氧基化的多元醇或它们的混合物。
所述烷氧基化的醇优选为:具有直链或支化的烷基链的乙氧基化的C6~C22脂肪醇,所具有的平均乙氧基化度为1~50,优选为1~30,更优选为1~15;或乙氧基化的直链或支链的C7~C15仲醇,优选乙氧基化的直链C11~C15醇,所具有的平均乙氧基化度为1~20,优选为1~15,更优选为5~15。
所述烷氧基化的多元醇优选为乙氧基化的乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、二丙二醇、丙三醇、聚甘油和它们的混合物,所具有的平均乙氧基化度为1~50,优选为1~30,更优选为1~15。优选的是,所述烷氧基化的多元醇是所具有的平均乙氧基化度为1~50、优选为1~30、更优选为1~15的乙氧基化的甘油。
织物软化剂
本发明的主题还包括含有本发明的组合物的织物软化剂。
根据本发明,相对于织物软化剂的总重量,所述织物软化剂中存在的季铵盐混合物(即主要由二酯胺、三酯胺、单酯季铵盐、二酯季铵盐、三酯季铵盐和溶剂以及必要时的未季铵化的单酯胺组成的酯季铵盐(a)和化合物(b))为1重量%~80重量%、优选为1重量%~55重量%、进而更优选为2重量%~40重量%。
在提及其它可任选成份时,不可看作是对所有可能性的穷尽性描述,相反,其它可任选成份是本领域中普通技术人员所公知的,可以列举的有下列:
a)可增强软化组合物的性能的其它产品,例如硅酮,氧化胺,如月桂基醚硫酸盐(lauryl ether sulphate)或月桂基硫酸盐等阴离子表面活性剂,如椰油酰胺丙基甜菜碱或烷基甜菜碱等两性表面活性剂,磺基丁二酸酯(盐)、聚葡糖苷衍生物等。
b)稳定化产品,例如季铵化或未季铵化的具有短链的胺的盐,例如三乙醇胺、N-甲基二乙醇胺等的盐,以及非离子表面活性剂,如乙氧基化的脂肪醇、乙氧基化的脂肪胺、乙氧基化的烷基酚等。
c)改善粘度控制的产品,例如无机盐,如氯化钙、氯化镁、硫酸钙、氯化钠等;可用于减少浓缩组合物中的粘度的产品,例如二醇类的化合物,如乙二醇、二丙二醇、聚乙二醇等;以及用于稀释的组合物的增稠剂,例如由纤维素获得的聚合物、瓜尔胶等。
d)用于调节pH(优选为1.5~4.5)的成分,例如任何类型的无机酸和/或有机酸,例如盐酸、硫酸、磷酸、柠檬酸等。
e)改善污垢释放的试剂,例如已知的基于对苯二甲酸酯的聚合物或共聚物。
f)杀菌性防腐剂,例如甲醛、Kathon GC、溴硝醇(Bronopol)等。
g)其它产品,例如抗氧化剂、着色剂、芳香剂、杀菌剂、杀真菌剂、抗腐蚀剂、抗皱剂、遮光剂、荧光增白剂、珠光光泽剂(pearl lustre agent)等。
本发明的织物软化剂可以采取多种物理形式,包括液体、液体-凝胶、糊状、水性或非水性形式的泡沫、粉末、颗粒和片剂形式。为了更好的分散能力,该组合物的优选形式是液体形式,处于水中的水性分散液的形式。在处于液体形式时,还可以使用如喷雾器或气雾分配器等分配手段来分配该组合物。
当处于液体形式时,在标准(稀释)的织物软化剂的情况中,所述织物软化剂可以含有1重量%~15重量%的织物软化剂(其包含本发明的季铵盐混合物),但在非常浓缩的织物软化剂的情况中,所述织物软化剂可以含有高达30重量%或者甚至40重量%的更高水平的织物软化剂(其包括本发明的季铵盐混合物)。该组合物通常还会含有水和其它添加剂,以提供该组合物的余量。
通常通过将软化成分熔融并在搅拌下将该熔融物加入到热水中以分散水不溶性成分,从而制备液体织物软化剂。
本发明的织物软化剂可以用于所谓的漂洗过程,其中首先将上述的织物软化剂稀释在漂洗池水溶液中。随后,将已经以洗涤剂溶液洗涤过并且必要时已在第一低效率漂洗步骤中(“低效率”的意思是残留的洗涤剂和/或污垢可能随织物带出)漂洗过的洗过织物放置在具有稀释的组合物的漂洗溶液中。当然,一旦将织物浸入到水池中,就可以将该织物软化剂也加入其中。该步骤之后,对漂洗池溶液中的织物施加搅拌从而使泡沫消散,并且去除残留的污垢和表面活性剂。随后必要时可以在干燥前对织物进行绞干。
因此,提供了一种漂洗织物的方法,该方法包括将预先以洗涤剂溶液洗涤过的织物与本发明的织物软化剂接触的步骤。本发明的主题还包括本发明的织物软化剂用于使已经在高泡沫洗涤剂溶液中洗涤过的织物具有织物柔软性并且同时在漂洗中使泡沫或起泡减少而不产生非所需的絮凝物的应用。
这一漂洗过程可以在盆或桶中手工进行,也可以在非自动洗衣机中进行,还可以在自动洗衣机中进行。在进行手洗时,可从洗涤剂溶液中取出洗过的织物并绞干。随后向清水中加入本发明的织物软化剂,之后直接或在可任选的低效率的第一漂洗步骤之后将织物在含有所述组合物的水中按照常规的漂洗习惯进行漂洗。随后使用常规手段来干燥织物。
为了向本领域的技术人员提供充分清楚和完整的本发明的说明,而给出了下述实施例,但就像本说明书的先前部分中所述的,不应该将这些实施例看作是对本发明主题的基本方面的限制。
实施例
1.组合物的合成
-酯化
按照以下通用方法来制备实施例中所用的酯胺:
将786g的牛酯脂肪酸(FA)导入到装配有搅拌器和温度探针的反应器中,并在搅拌下加入261g的三乙醇胺(TEA)、1g的50%次磷酸和0.6g的BHT。在惰性氛围中将该混合物在170℃加热,直到酸值小于5mgKOH/g。当达到这一值时,获得了995g的反应产物,即单酯胺、二酯胺和三酯胺的复杂混合物。
-季铵化
按照以下通用方法,使用表1中所示的试剂和数量制备了表1的组合物(酯季铵盐或混有化合物(b)的酯季铵盐)(所有的数量均以g表示):
在搅拌下和55℃的温度下向上述的酯胺中加入异丙醇(IPA)和N-C6~C22烷基,N,N-二甲基胺(ADMA),用约2小时的时间逐滴加入硫酸二甲酯(DMS)。使混合物保持搅拌和温度条件直到总胺值保持恒定。
表1中还标出了三酯胺/三酯季铵盐的比(EA/EQ)。
表1-季铵化过程
2.织物软化剂组合物的制备
使用下述方案来制备表2和表3中所示的织物软化剂组合物:
将水加热到40℃~45℃。在搅拌条件下,将非离子表面活性剂加入到水中。将软化剂基本成分(实施例1中获得的混合物1.1~1.14)熔融并在搅拌下加入到水中。在均化之后,将配制物冷却至25℃~30℃。在此时加入消泡用硅酮乳液。加入所述乳液之后,加入芳香剂和如染料和防腐剂等其它成分,并混合直至取得均匀的组合物。
对于实施例A1~A7,在加入非离子表面活性剂之后向水中加入酸。
对于实施例C-2b和A-2b,在酯季铵盐添加之前向水中加入单烷基季铵化合物(式(I)的化合物)。
表2-织物软化剂组合物-比较例
1甲基硫酸N-十六烷基-N,N,N-三甲基铵
2甲基硫酸N-月桂基-N,N,N-三甲基铵
3甲基硫酸N-硬脂基-N,N,N-三甲基铵
4平均乙氧基化度为20的鲸蜡硬脂醇(Cetyl Stearyl Alcohol)
表3-织物软化剂组合物-根据本发明
1甲基硫酸N-十六烷基-N,N,N-三甲基铵
2甲基硫酸N-月桂基-N,N,N-三甲基铵
3甲基硫酸N-硬脂基-N,N,N-三甲基铵
4平均乙氧基化度为20的鲸蜡硬脂醇
3.评估方法
3.1白色残余物评估
将60g的市售粉末洗涤剂(ARIEL)加入到8L的水中(水硬度20°HF(法国硬度尺度),水温25℃)。搅拌溶液直至完全溶解。
将棉质厚毛巾(terry towel)(总重300g)浸入洗涤剂溶液中并在保持运动1分钟。
这段时间过后,手工挤压毛巾并将其转移到含有溶于3L水(水硬度20°HF(法国硬度尺度),水温25℃)的45g软化组合物的软化剂漂洗溶液中。
将毛巾保持在软化溶液中30秒,随后取出并手工挤压。
在毛巾取出2分钟后,将软化溶液通过棉织黑色织物过滤。
使黑色织物保持在水平位置直到干燥(室温),随后对比评级量表来目测过滤的残余物。
表4和表5显示了软化剂组合物减少白色残余物形成的效果。
评级由1(较差的状况=所有的黑色织物表面均被白色膜状残余物覆盖)到6(优异的状况=黑色织物表面几乎没有白色残余物)。
3.2柔软性评估
将30g的市售粉末洗涤剂(ARIEL)加入到15L的水中(水硬度20°HF(法国硬度尺度),水温25℃)。搅拌溶液直至完全溶解。
将棉质厚毛巾(总重1Kg)手工洗涤5分钟。
这段时间过后,手工挤压毛巾并将其转移到含有溶于20L水(水硬度20°HF(法国硬度尺度),水温25℃)的25g软化组合物的软化剂漂洗溶液中保持3分钟,之后取出并手工挤压。
在干燥(室内条件,20℃65%RH)后,由20名测试者组成的专家组采用如下标准作为基准通过评级测试来凭感觉评估软化效果:
-空白(评级1),在于毛巾在洗涤剂溶液中处理过、随后在只含有水(水硬度20°HF(法国硬度尺度),水温25℃)的溶液中漂洗,和
-对照(评级5),在于毛巾预先仅在水(水硬度20°HF(法国硬度尺度),水温25℃)中润湿、随后浸入到含有溶于20L水(水硬度20°HF,水温25℃)的25g软化组合物的软化溶液中。
软化效果示于表4和表5中。
表4-织物软化剂组合物的评估-比较例
表5-织物软化剂组合物的评估-根据本发明
从实验结果可以得出,本发明的织物软化剂组合物提供了更好的减少白色残余物(不需要的絮凝物)的效果而不影响柔软性状况。
由织物软化剂组合物A-2a、A2-b和A-3获得了非常良好的结果。
此外,由织物软化剂组合物A-2a(其中,式(I)的化合物是在季铵化过程随酯季铵盐在原位获得的)和织物软化剂组合物A-2b(其中,将式(I)的化合物与酯季铵盐混合)获得了相似的结果。
Claims (14)
1.一种包含酯季铵盐的组合物,所述酯季铵盐能够通过C6~C22脂肪酸与三乙醇胺的酯化和随后的季铵化而获得,所述混合物包含未季铵化的二酯胺、未季铵化的三酯胺、季铵化的单酯胺、季铵化的二酯胺和季铵化的三酯胺,其中,未季铵化的三酯胺对季铵化的三酯胺的重量比大于1.5。
2.如权利要求1所述的组合物,其中,所述未季铵化的三酯胺对季铵化的三酯胺的重量比大于5。
3.如前述权利要求中任一项所述的组合物,其中,相对于未季铵化的单酯胺、未季铵化的二酯胺、未季铵化的三酯胺、季铵化的单酯胺、季铵化的二酯胺和季铵化的三酯胺的总量,季铵化的三酯胺的含量小于3重量%。
5.如权利要求4所述的季铵盐混合物,其中,所述化合物(b)是氯化N-C6~C22烷基,N-三-甲基铵或甲基硫酸N-C6~C22烷基,N-三-甲基铵。
6.如权利要求4或5所述的组合物,其中,所述酯季铵盐对化合物(b)的重量比为5∶1~60∶1。
7.如前述权利要求中任一项所述的组合物,所述组合物进一步包含非离子表面活性剂。
8.如权利要求8所述的组合物,其中,所述非离子表面活性剂是烷氧基化醇、烷氧基化多元醇或它们的混合物。
9.一种组合物的制造方法,所述组合物是前述权利要求中任一项所述的组合物,所述方法包括使C6~C22脂肪酸与三乙醇胺缩合以提供包含单酯胺、二酯胺和三酯胺的酯胺混合物,以烷基化试剂将所述混合物季铵化,其中,烷基化试剂对酯胺的摩尔比为0.6~0.9,优选为0.65~0.85。
10.如权利要求9所述的方法,其中,所述季铵化在N-C6~C22烷基,N,N-二-C1~C3烷基胺的存在下进行。
11.如权利要求9所述的方法,其中,将式(I)的组份(b)与所述酯季铵盐混合。
12.一种织物软化剂,所述织物软化剂包含权利要求1~8中任一项所述的组合物。
13.一种漂洗织物的方法,所述方法包括使预先在洗涤剂溶液中洗涤过的织物与权利要求12所述的织物软化剂接触的步骤。
14.权利要求1~8中任一项所述的组合物使织物具有织物柔软性的应用。
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US6458343B1 (en) * | 1999-05-07 | 2002-10-01 | Goldschmidt Chemical Corporation | Quaternary compounds, compositions containing them, and uses thereof |
JP4024438B2 (ja) * | 1999-11-01 | 2007-12-19 | 花王株式会社 | 第4級アンモニウム塩組成物 |
CN100345953C (zh) * | 2001-03-07 | 2007-10-31 | 宝洁公司 | 适用于对存在有残余洗涤剂的织物进行附加漂洗的调理组合物 |
US20040097396A1 (en) * | 2002-11-14 | 2004-05-20 | Myriam Peeters | Concentrated fabric softening composition containing esterquat with specific ester distribution and an electrolyte |
US20040097395A1 (en) * | 2002-11-14 | 2004-05-20 | Andre Crutzen | Fabric softening composition containing esterquat with specific ester distribution and sequestrant |
US6949500B2 (en) * | 2002-12-16 | 2005-09-27 | Colgate-Palmolive Company | Fabric softener compositions containing a mixture of cationic polymers as rheology modifiers |
DE602006011877D1 (de) * | 2005-04-18 | 2010-03-11 | Procter & Gamble | Verdünnte textilpflegemittel mit verdickern und textilpflegemittel zur verwendung in gegenwart anionischer einschleppungen |
-
2006
- 2006-12-28 EP EP06380339A patent/EP1939273A1/en not_active Withdrawn
-
2007
- 2007-11-09 CN CN2007800484722A patent/CN101600785B/zh not_active Expired - Fee Related
- 2007-11-09 ES ES07822445T patent/ES2363271T3/es active Active
- 2007-11-09 US US12/521,697 patent/US7951769B2/en not_active Expired - Fee Related
- 2007-11-09 AT AT07822445T patent/ATE503821T1/de not_active IP Right Cessation
- 2007-11-09 BR BRPI0720654A patent/BRPI0720654B1/pt not_active IP Right Cessation
- 2007-11-09 DK DK07822445.8T patent/DK2121887T3/da active
- 2007-11-09 PL PL07822445T patent/PL2121887T3/pl unknown
- 2007-11-09 AU AU2007341495A patent/AU2007341495B2/en not_active Ceased
- 2007-11-09 DE DE602007013612T patent/DE602007013612D1/de active Active
- 2007-11-09 MX MX2009007032A patent/MX2009007032A/es active IP Right Grant
- 2007-11-09 WO PCT/EP2007/062156 patent/WO2008080680A1/en active Application Filing
- 2007-11-09 EP EP07822445A patent/EP2121887B1/en not_active Not-in-force
- 2007-11-09 RU RU2009128962/04A patent/RU2423415C2/ru not_active IP Right Cessation
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102230278A (zh) * | 2011-06-07 | 2011-11-02 | 廊坊乐万家联合家化有限公司 | 一种浓缩衣物柔顺剂及其制备方法 |
CN102230278B (zh) * | 2011-06-07 | 2013-02-13 | 廊坊乐万家联合家化有限公司 | 一种浓缩衣物柔顺剂及其制备方法 |
CN104471044A (zh) * | 2012-05-07 | 2015-03-25 | 赢创工业集团股份有限公司 | 织物软化剂活性组合物及其制备方法 |
CN104471044B (zh) * | 2012-05-07 | 2017-07-25 | 赢创德固赛有限公司 | 织物软化剂活性组合物及其制备方法 |
CN105209589A (zh) * | 2013-03-15 | 2015-12-30 | 斯蒂潘公司 | 织物软化剂组合物 |
CN105209589B (zh) * | 2013-03-15 | 2018-02-02 | 斯蒂潘公司 | 织物软化剂组合物 |
CN111684072A (zh) * | 2018-02-13 | 2020-09-18 | 伊士曼化工公司 | 制备可用作酯季铵化合物前体的中间体的酶促方法 |
Also Published As
Publication number | Publication date |
---|---|
PL2121887T3 (pl) | 2011-08-31 |
ES2363271T3 (es) | 2011-07-28 |
US20100331231A1 (en) | 2010-12-30 |
RU2423415C2 (ru) | 2011-07-10 |
DE602007013612D1 (de) | 2011-05-12 |
EP1939273A1 (en) | 2008-07-02 |
ATE503821T1 (de) | 2011-04-15 |
MX2009007032A (es) | 2009-08-18 |
AU2007341495A1 (en) | 2008-07-10 |
BRPI0720654B1 (pt) | 2017-03-28 |
CN101600785B (zh) | 2011-10-26 |
DK2121887T3 (da) | 2011-05-09 |
WO2008080680A1 (en) | 2008-07-10 |
BRPI0720654A2 (pt) | 2014-01-07 |
EP2121887B1 (en) | 2011-03-30 |
AU2007341495B2 (en) | 2010-12-16 |
US7951769B2 (en) | 2011-05-31 |
RU2009128962A (ru) | 2011-02-10 |
EP2121887A1 (en) | 2009-11-25 |
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