CN105793289A - 用于洗衣洗涤剂中和用作抗泛灰剂的改性多糖 - Google Patents
用于洗衣洗涤剂中和用作抗泛灰剂的改性多糖 Download PDFInfo
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- CN105793289A CN105793289A CN201480065856.5A CN201480065856A CN105793289A CN 105793289 A CN105793289 A CN 105793289A CN 201480065856 A CN201480065856 A CN 201480065856A CN 105793289 A CN105793289 A CN 105793289A
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- polysaccharides
- modification
- acid
- laundry detergent
- polysaccharide
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
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- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L3/10—Oxidised starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Abstract
本发明涉及一种可通过包括用气态或液态SO2处理多糖的步骤的方法获得的改性多糖、一种包含所述改性多糖的洗衣洗涤剂组合物、所述改性多糖用于提高洗涤织物的白度的用途、所述改性多糖作为抗泛灰剂用于水洗衣方法中的用途、所述改性多糖作为流变调节剂用于家庭护理应用的用途以及所述改性多糖用于生产液体洗衣组合物的用途。本发明的其他方面为一种制备包含所述改性多糖的洗衣洗涤剂组合物的方法。
Description
本发明涉及一种可通过包括用气态或液态SO2处理多糖的步骤的方法获得的改性多糖、一种包含所述改性多糖的洗衣洗涤剂组合物、所述改性多糖用于提高洗涤织物的白度的用途、所述改性多糖作为抗泛灰剂用于水洗衣方法中的用途、所述改性多糖作为流变调节剂用于家庭护理应用的用途以及所述改性多糖用于生产液体洗衣组合物的用途。本发明的其他方面为一种制备包含所述改性多糖的洗衣洗涤剂组合物的方法。
在衣物的洗涤过程中,可能发生污垢的重新沉积,这通常导致纺织品泛灰。为了减少污垢的重新沉积,可在洗衣洗涤剂组合物中添加天然或改性多糖如羧甲基多糖(CMC)(例如参见EP2135933A1)。然而,本领域可得的天然或改性多糖的应用受到限制,这是因为它们中的大多数在水中通常具有高粘度,因此当配制于液体洗衣洗涤剂组合物中时会形成凝胶。因此,它们中的大多数仅可用于粉末洗涤剂组合物中。尽管本领域已知许多不同类型的多糖,然而仅有限数量的多糖适于用于液体洗衣洗涤剂组合物中,例如重均分子量为250,000或更小的改性多糖(参见例如WO00/40684)。
因此,本发明的目的是提供可用于液体洗衣洗涤剂组合物中的抗泛灰剂。
现已令人惊讶地发现,所述目的可在很大程度上通过提供可通过包括用气态或液态SO2处理多糖的步骤的方法获得的改性多糖实现。该改性多糖具有优异的抗泛灰性质,且可成功地配制于液体洗衣洗涤剂组合物中。
本发明的一个方面为一种可通过包括用气态或液态SO2处理多糖的步骤的方法获得的改性多糖。
在优选的实施方案中,所述多糖为木葡聚糖、甘露聚糖、木聚糖、淀粉或其混合物。
在更优选的实施方案中,所述多糖为木葡聚糖。
木葡聚糖广泛分布于自然界中。它们属于通常称为半纤维素的多糖类,且可见于不同植物,例如属于双子叶植物类别的植物和属于非禾本科单子叶植物子类别的植物的初生细胞壁中。根据本发明,任何木葡聚糖均可用于制备改性木葡聚糖。
这些植物中的数种(全部为双子叶植物)还利用木葡聚糖作为碳水化合物储备,而非最常见的碳水化合物储备淀粉。这些植物的种子具有包含大量木葡聚糖的厚细胞壁。该类植物的实例为豆瓣菜属(Nasturtium)的开花植物,例如Nasturtiumafricanum、Nasturtiumfiondanum、Nasturtiumgambe/ii、西洋菜(Nasturtiummicrophyllum)、Onerowyellowcress和豆瓣菜(Nasturtiumofficinale);凤仙花属(lmpatiens)的开花植物,例如lmpatiensbalfouni、凤仙花(lmpatiensbalsamina)、卡佩风仙花(lmpatienscapensis)、lmpatiensedgeworthli、喜马拉雅凤仙花(lmpatiensgandullfera)、lmpatienshians、Impatiensmarianae、刚果凤仙花(lmpatiensniamniamensis)、水金凤(lmpatiensnoli-tangere)、小花凤仙花(Impatiensparvifiora)、lmpatiensplatypetala、蔓性凤仙花(lmpatiensrepens);番荔枝(Annonas)属的开花植物,例如Annonaamambayensis、Annonaacuminata、Annonaambotay、Annonaasplundiana、Annonaatabapensis、泡状番蒸枝(Annonabullata)、Annonabifiora、Annonabicolor、Annonabrasi/i/ensis、Annonacacans、Annonacalophylla、Annonacampestris、秘鲁番荔枝(Annonacherimola)、Annonachrysophylla、Annonapubescens、Annonatripetala、Annonaconica、Annonacoriacea、Annonacormfolia、Annonacrassifiora、Annonacristalensis、Annonacrotomfolia、Annonadeceptrix、Annonademinuta、Annonadioica、异叶番荔枝(Annonadiverstfolia)、Annonadolabripetala、Annonadolichophylla、Annonaechinata、Annonaecuadorensis、Annonaekmami、Annonaexcellens、圆滑番荔枝(Annonaglabra)、比丽巴番荔枝(Annonapalustris)、Annonaglaucohylla、Annonahaematantha、Annonahayesti、Annonahypoglauca、Annonahystricotdes、Annonajahnli、Annonajamaicensis、Annonalongifiora、Annonalutescens、Annonamacrocalyx、Annonamalmeana、Annonamanabiensis、Annonamicrocarpa、山刺番荔枝(Annonamontana)、Annonamarcgravli、Annonamonticola、刺果番荔枝(Annonamuricata)、Annonamacrocarpa、Annonanittda、Annonanutans、Annonaoligocarpa、Annonapaludosa、Annonaparaguayensis、Annonaphaeoclados、Annonapraetermissa、Annonapurpurea、Annonapygmaea、牛心番荔枝(Annonareticulata)、Annonasalzmanmi、Annonascleroderma、Annonasenegalensis、绢毛叶番荔枝(Annonasericea)、Annonaspinescens、Annonaspraguet、释迦(Annonasquamosa)、Annonatestudinea、毛叶番荔枝(Annonatomentosa)、Annonatruncifiora,和罗望子属(Tamarindus)的树如罗望子(Tamarindusindica)。
关于木葡聚糖结构及其结构确定方法的更多细节可参见S.F.Fry.J.Expt.Botany1989,40,1-11;A.Mishra等,J.Mater.Chem.2009,19,8528-8536;W.York等,Carbohydr.Res.1990,200,9-31;Hoffman等,Carbohydr.Res.2005,340,1826-1840;W.York等,Carbohydr.Res.1996,25285,98-128;和其中所引用的文献。
在优选的实施方案中,本发明的改性多糖为罗望子木葡聚糖。
罗望子木葡聚糖可商购获得。罗望子片和粉末的一些供应商为Vishnugumandchemicals(印度)、TCIGermanyGmbH(德国)、AltrafineGums(印度)、Balasanka(印度)、RamachandraPulverisers&lndustries(印度)、TheAndhrastarch(印度)、MYSORE(印度)、DainipponSumitomoPharma(日本)、VishnuEngeneeringWorks(印度)、ShreeVinayakCorporation(印度)、Megazyme(爱尔兰)。
在另一优选实施方案中,所述多糖为甘露聚糖,优选为葡甘露聚糖。关于甘露聚糖结构及其结构确定方法的更多细节可参见McGraw-Hill:Hemicellulose,EncyclopediaofScienceandTechnology,第5版,2005;MoreiraLR,FilhoEX.,ApplMicrobiolBiotechnol.,2008年5月,79(2):165-78;和KanameKatsuraya,KohsakuOkuyamab,KenichiHatanakab,RyuichiOshimab,TakayaSatoc和KeiMatsuzakic(2003),“Constitutionofkonjacglucomannan:chemicalanalysisand13CNMRspectroscopy”,CarbohydratePolymers53(2):183-189以及其中引用的文献中。
在另一优选实施方案中,所述多糖为木聚糖,优选为同木聚糖或阿糖基木聚糖。关于木聚糖结构及其结构确定方法的更多细节可参见F.L.Motta,C.C.P.Andrade和M.H.A.Santana,AReviewofXylanaseProductionbytheFermentationofXylan:Classification,CharacterizationandApplications,SustainableDegradationofLignocellulosicBiomass-Techniques,ApplicationsandCommercialization,2013年5月15日;PellerinP,GosselinM,LepoutreJP,SamainE,DebeireP.,Enzymaticproductionofoligosaccharidesfromcorncobxylan,EnzymeandMicrobialTechnology(1991)13:617-621;和VermaD,SatyanarayanaT.,Molecularapproachesforamelioratingmicrobialxylanases,BioresourceTechnology(2012)17:360-367中。
本发明的改性多糖可通过包括用气态或液态SO2处理多糖的步骤的方法获得。因此,所述多糖可用气态SO2处理,例如使SO2喷射通过包含所述多糖的水溶液。或者,可将包含所述多糖的水溶液与液态SO2混合,所述液态SO2可例如通过将气态SO2溶于水中而获得。
用气态或液态SO2处理多糖可在搅拌釜或高压釜中进行。
待用气态或液态SO2处理的多糖可呈粉末形式,或者呈水溶液形式。优选地,将呈粉末形式的多糖添加至SO2水溶液中。
在优选的实施方案中,所述方法使用0.1:1-5:1,优选0.2:1-1:1,更优选0.2:1-0.5:1的SO2:多糖工艺质量比进行(在大气压下)。所述SO2:多糖工艺质量比为重量比。在加压方法(1-10巴)中,所述质量比可降至0.01:1-5:1,优选0.01:1-1:1,更优选0.02:1-0.5:1。
当在25℃下以2%溶于水中时,本发明的改性多糖优选显示出小于100mPas的粘度。当在25℃下以5%溶于水中时,所述多糖优选具有20-1500mPas的粘度。当在25℃下以10%溶于水中时,所述多糖优选具有小于15,000mPas的粘度。当在25℃下以15%溶于水中时,所述多糖优选具有小于100,000mPas的粘度。所述粘度可使用Brookfield根据DINISO2555:2000-01(LVT转子,RT)测定。
在另一优选实施方案中,所述方法在0-150℃,优选40-150℃,更优选70-120℃,甚至更优选70-95℃的温度下实施。
在另一优选实施方案中,当所述方法在95-150℃的温度下实施时,所述方法在0(大气压)-10巴,优选1-3巴的压力下进行。
在又一优选实施方案中,所述方法实施1分钟至10小时,优选5分钟至8小时,更优选1-6小时,甚至更优选30分钟至5小时。在甚至更优选的实施方案中,所述方法实施1-90分钟,更优选5-30分钟。
在优选的实施方案中,所述方法在0.1-10巴的压力下在110-150℃的温度下实施1-90分钟,优选5-30分钟。
在另一优选实施方案中,所述方法在大气压下在1-95℃,优选75-93℃的温度下实施30分钟至10小时,优选1-8小时。
在另一优选实施方案中,所述方法进一步包括将pH调节至3-7,优选4-6,更优选5-6的步骤。
本发明的另一方面为一种包含本发明改性多糖的洗衣洗涤剂组合物。
在优选的实施方案中,所述洗衣洗涤剂为液体或凝胶状。根据本发明,液体意指在室温下小于500mPas的粘度;根据本发明,凝胶状意指为粘稠但仍可倾倒的,即在室温下的粘度小于10,000mPas,优选在室温下的粘度为500-10,000mPas。所述粘度可使用Brookfield根据DINISO2555:2000-01(LVT转子,RT)测定。
在本发明的一个实施方案中,本发明的改性多糖(A)是洗衣洗涤剂组合物的组分,所述组合物额外包含至少一种表面活性剂(B)和至少一种助洗剂(C)。
所述表面活性剂优选选自阴离子、非离子、阳离子、两性和/或两性离子表面活性剂。
合适的非离子表面活性剂特别为:
-烷氧基化的C8-C22醇,例如脂肪醇烷氧基化物、羰基合成醇烷氧基化物和格尔伯特(Guerbet)醇烷氧基化物:所述烷氧基化可使用C2-C20氧化烯,优选氧化乙烯、氧化丙烯和/或氧化丁烯进行。可存在嵌段共聚物或无规共聚物。它们基于每摩尔醇通常包含2-50摩尔,优选3-20摩尔至少一种氧化烯。优选的氧化烯为氧化乙烯。所述醇优选具有10-18个碳原子。
-烷基酚烷氧基化物,尤其是包含C6-C14烷基链和5-30摩尔氧化烯/摩尔的烷基酚乙氧基化物。
-包含C8-C22烷基,优选C10-C18烷基链和通常为1-20个,优选1.1-5个葡糖苷单元的烷基聚葡糖苷。
-N-烷基葡糖酰胺、脂肪酸酰胺烷氧基化物、脂肪酸链烷醇酰胺烷氧基化物,以及氧化乙烯、氧化丙烯和/或氧化丁烯的嵌段共聚物。
合适的阴离子表面活性剂例如为:
-具有8-22个,优选10-18个碳原子的(脂肪族)醇的硫酸酯盐,尤其是C9C11醇硫酸酯盐、C12C14醇硫酸酯盐、C12-C18醇硫酸酯盐、月桂基硫酸酯盐、鲸蜡基硫酸酯盐、肉豆蔻基硫酸酯盐、棕榈基硫酸酯盐、硬脂基硫酸酯盐和牛脂醇硫酸酯盐。
-硫酸化的烷氧基化C8-C22醇(烷基醚硫酸盐):该类化合物例如通过首先将C8-C22醇,优选C10-C18醇,例如脂肪醇烷氧基化,然后将所述烷氧基化产物硫酸化而制备。对烷氧基化而言,优选使用氧化乙烯。
-直链C8-C20烷基苯磺酸盐(LAS),优选直链C9-C13-烷基苯磺酸盐和-烷基甲苯磺酸盐。
-链烷磺酸盐,尤其是C8-C24链烷磺酸盐,优选C10-C18链烷磺酸盐。
-式R1CH(SO3M)CO2R2的脂肪酸酯磺酸盐,其中R1为C6-C20烷基,优选为C8-C16烷基,且R2为C1-C4烷基,优选为甲基或乙基,且M为氢、水溶性阳离子,例如碱金属阳离子或铵离子。
-具有8-22个,优选12-18个碳原子的烯烃磺酸盐。
-羟乙基磺酸盐,尤其是酰基羟乙基磺酸盐和N-酰基牛磺酸盐。
-N-酰基肌氨酸盐。
-磺基琥珀酸酯盐(磺基琥珀酸的单或二酯)和烷基琥珀酸酯盐。
-有机磷酸酯盐,尤其是羟基封端的烷氧基化物缩合物的磷酸单酯和二酯及其盐的混合物。这些包括聚氧烷基化的烷基芳基磷酸酯盐,例如基于烷氧基化C8-C22醇或烷氧基化酚衍生物。
-皂类,例如C8-C24羧酸的钠和钾盐。
所述阴离子表面活性剂优选以盐形式添加至所述洗涤剂中。合适的盐例如为碱金属盐如钠、钾和锂盐,和铵盐如羟乙基铵盐、二(羟乙基)铵盐和三(羟乙基)铵盐。
特别合适的阳离子表面活性剂包括:
-C7-C25烷基胺;
-N,N-二甲基-N-(C7-C25-羟基烷基)铵盐;
-用烷基化试剂季化的单-和二-(C7-C25烷基)二甲基铵化合物;
-酯季化物,尤其是季酯化的单-、二-、和三-链烷醇胺,其用C8-C22羧酸酯化;
-咪唑啉季化物。
合适的两性表面活性剂为脂族或杂环族仲胺和叔胺的衍生物,其中脂族基团优选具有8-18个碳原子,且至少一个基团包含一个或多个阴离子水溶性基团,例如一个或多个羧酸根、磺酸根、硫酸根、磷酸根或膦酸根。
合适的两性表面活性剂的实例为:
-3-(烷基氨基)丙酸酯、(烷基氨基)乙酸酯、3-(二烷基氨基)丙酸酯和(二烷基氨基)乙酸酯,其中优选地,至少一个烷基包含8-18个碳原子;
-3-[(3-烷基氨基丙基)氨基]丙酸酯和[(3-烷基氨基丙基)氨基]乙酸酯,其中烷基优选包含8-18个碳原子;
-[(2-酰基氨基乙基)(2-羟基乙基)氨基]乙酸酯,其中酰基优选包含8-18个碳原子;
-(烷基氨基)丙磺酸酯,其中烷基优选包含8-18个碳原子。
合适的两性离子表面活性剂例如为:
-氧化胺,尤其是烷基二甲基胺氧化物和烷基二乙基胺氧化物,其中烷基优选包含8-18个碳原子;
-甜菜碱类,尤其是羰基甜菜碱类(carbobetaines)、磺基甜菜碱和膦酸酯甜菜碱(phosphobetaine),例如:
R6(R7)2N+(CH2)nCOO-,其具有如下的各变量优选定义:R6:C8-C18烷基;R7:C1-C3烷基;n:1-5;
R6CONH(CH2)m(R7)2N+(CH2)nCOO-,其具有如下的各变量优选定义:
R6:C7-C17烷基;R7:C1-C3烷基;n,m:各自独立地为1-5;
R6(R7)2N+(CH2)nSO3 -,其具有如下的各变量优选定义:R6:C8-C18烷基;
R7:C1-C3烷基;n:1-5;
-椰油酰胺基丙基甜菜碱。
两性和两性离子表面活性剂的详细描述还可参见EP-A-851023以及DieTenside[表面活性剂],CarlHanserVerlag,1993。
助洗剂(C)的实例为配位剂(下文也称为配位剂(C))、离子交换化合物和沉淀剂(C)。助洗剂(C)的实例为柠檬酸化物、磷酸盐、硅酸盐、碳酸盐、膦酸盐、氨基羧酸盐和多羧酸化物。
配位剂(C)(“螯合剂”)的实例选自诸如但不限于如下的配位剂:柠檬酸化物、磷酸盐、膦酸盐、硅酸盐以及选自乙二胺四乙酸盐、二亚乙基五胺五乙酸盐、甲基甘氨酸二乙酸盐和谷氨酰胺二乙酸盐的亚乙基胺衍生物。下文将更详细地描述配位剂(C)。
沉淀剂(C)的实例为碳酸钠和碳酸钾。
在本发明的一个实施方案中,本发明的用途包括将本发明的改性多糖(A)与至少一种酶(D)一起使用。可用的酶例如为如下中的一种或多种:脂肪酶、水解酶、淀粉酶、蛋白酶、纤维素酶、半纤维素酶、磷脂酶、酯酶、果胶酶、乳糖酶、过氧化物酶,以及前述类型中至少两种的组合。
本发明的用途可处理任何类型的衣物以及任何类型的纤维。纤维可为天然或合成来源的,或者其可为天然和合成纤维的混合物。天然来源的纤维的实例为棉和羊毛。合成来源的纤维的实例为聚氨酯纤维,如或聚酯纤维或聚酰胺纤维。纤维可为单独的纤维或者为纺织品如针织物、纺织物或无纺布的一部分。
本发明的用途可通过将本发明的改性多糖(A)作为液体,例如作为溶液或凝胶,作为泡沫或作为固体施加至纤维上而实施。优选将本发明的改性多糖(A)用于洗液中。在施加前,可将其储存在可为固体或液体,优选为液体的配制剂中。
优选地,可实施本发明的用途以清洁,例如除垢、脱脂或者洗衣等。待移除的污垢或污物可为蛋白、油脂、脂肪、油、皮脂、非极性污垢如烟灰和碳氢化合物不完全燃烧的副产物,颗粒状污迹如颜料和粘土,或者前述至少两种的混合物。特别优选的是用于移除油脂(脱脂)和移除粘土污垢/抗再沉积的本发明用途。
本发明的改性多糖(A)优选在15-90℃,优选20-60℃的温度下使用。
本发明的用途可手动实施,但优选以机械方式,例如在洗衣机中使用本发明的改性多糖(A)。
本发明的另一方面为洗衣洗涤剂组合物,就本发明而言,其还称为本发明的组合物。本发明的洗衣洗涤剂组合物可为液体、凝胶或固体组合物,固体实施方案涵盖例如粉末和片剂。液体洗衣洗涤剂组合物可包装成单位剂量的形式。
本发明的洗衣洗涤剂组合物包含本发明的改性多糖。在优选的实施方案中,所述改性多糖可以以0.1-40重量%的量,优选0.2-30重量%的量,更优选0.5-10重量%的量存在。
在优选的实施方案中,本发明的洗衣洗涤剂组合物包含:
(A)至少一种本发明的改性多糖,
(B)至少一种表面活性剂,
(C)至少一种选自柠檬酸化物、磷酸盐、硅酸盐、碳酸盐、膦酸盐、氨基羧酸盐和多羧酸化物的助洗剂。
本发明的改性多糖(A)和表面活性剂(B)已在上文定义。
本发明的洗衣洗涤剂组合物可包含至少一种助洗剂(C)。就本发明而言,不对助洗剂和别处也称为“共助洗剂”的该类组分加以区分。助洗剂(C)的实例为配位剂(下文也称为配位剂(C))、离子交换化合物和沉淀剂(C)。助洗剂选自柠檬酸化物、磷酸盐、硅酸盐、碳酸盐、膦酸盐、氨基羧酸盐和多羧酸化物。
就本发明而言,术语“柠檬酸化物”包括柠檬酸的单-和二-碱金属盐,特别是单-和优选三-钠盐、柠檬酸的铵盐或取代铵盐,以及柠檬酸。柠檬酸化物可以以无水化合物或水合物,例如柠檬酸三钠二水合物的形式使用。柠檬酸化物的量相对于无水柠檬酸三钠计算。
术语“磷酸盐”包括偏磷酸钠、正磷酸钠、磷酸氢钠、焦磷酸钠和聚磷酸盐如三聚磷酸钠。然而,优选本发明的组合物不含磷酸盐和聚磷酸盐(包括磷酸氢盐),例如不含磷酸三钠、三聚磷酸五钠和偏磷酸六钠(“不含磷酸盐”)。就磷酸盐和聚磷酸盐而言,“不含”在本发明的上下文中应理解为意指磷酸盐和聚磷酸盐的含量总计占相应组合物的10ppm至0.2重量%(通过重量分析法测定)。
术语“碳酸盐”包括碱金属碳酸盐和碱金属碳酸氢盐,优选钠盐。特别优选Na2CO3。
膦酸盐的实例为羟基链烷膦酸盐和氨基链烷膦酸盐。在羟基链烷膦酸盐中,特别重要的是使用1-羟基乙烷-1,1-二膦酸盐(HEDP)作为助洗剂。其优选以钠盐形式使用,其中二钠盐是中性的,四钠盐是碱性的(pH9)。合适的氨基链烷膦酸盐优选为乙二胺四亚甲基膦酸盐(EDTMP)、二亚乙基三胺五亚甲基膦酸盐(DTPMP)及其高级同系物。它们优选以中性反应性钠盐的形式使用,例如EDTMP的六钠盐或DTPMP的七和八钠盐。
氨基羧酸盐和多羧酸化物的实例为次氮基三乙酸盐、乙二胺四乙酸盐、二亚乙基三胺五乙酸盐、三亚乙基四胺六乙酸盐、丙二胺四乙酸、乙醇-二甘氨酸、甲基甘氨酸二乙酸盐和谷氨酰胺二乙酸盐。术语“氨基羧酸盐和多羧酸化物”还包括其相应的未取代或取代铵盐和碱金属盐,如钠盐,特别是相应的完全中和的化合物。
就本发明而言,硅酸盐特别包括二硅酸钠和偏硅酸钠,硅铝酸盐如沸石和层状硅酸盐,特别是式α-Na2Si2O5、β-Na2Si2O5和δ-Na2Si2O5的那些。
本发明的洗衣洗涤剂组合物可包含一种或多种选自不为上文所述物质的助洗剂。助洗剂的实例为α-羟基丙酸和氧化淀粉。
在本发明的一个实施方案中,助洗剂(C)选自多羧酸化物。术语“多羧酸化物”包括非聚合物的多羧酸化物,例如琥珀酸、C2-C16烷基二琥珀酸盐、C2-C16链烯基二琥珀酸盐、乙二胺N,N’-二琥珀酸、酒石酸二乙酸盐、碱金属丙二酸盐、酒石酸单乙酸盐、丙烷三甲酸、丁烷四甲酸和环戊烷四甲酸。
低聚或聚合多羧酸化物例如为聚天冬氨酸、聚丙烯酸和聚甲基丙烯酸及其碱金属盐。
合适的聚合物尤其为聚丙烯酸(或其碱金属盐),其优选具有1,000-40,000g/mol,更优选1,000-10,000g/mol,特别是1,000-8,000g/mol的平均分子量MW。合适的还有丙烯酸与甲基丙烯酸的共聚物,以及丙烯酸和/或甲基丙烯酸与至少一种选自单烯属不饱和C4-C10二羧酸或其酸酐,例如马来酸、马来酸酐、富马酸、衣康酸和柠康酸的单体的共聚物。
还可使用至少一种选自单烯属不饱和C3-C8单羧酸和单烯属不饱和C4-C10二羧酸或其酸酐,例如丙烯酸、甲基丙烯酸、马来酸、马来酸酐、富马酸、衣康酸和柠康酸的单体与至少一种下文所列的亲水性或疏水性单体的共聚物。
合适的疏水性单体例如为异丁烯、二异丁烯、丁烯、戊烯、己烯和苯乙烯、具有10个或更多碳原子的烯烃或其混合物,例如1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯、1-二十二碳烯、1-二十四碳烯和1-二十六碳烯、C22-α-烯烃、C20-C24-α-烯烃的混合物,和每分子平均具有12-100个碳原子的聚异丁烯。
合适的亲水性单体为具有磺酸根或膦酸根的单体,以及具有羟基官能团或氧化烯基团的非离子单体。下述单体用作实例:烯丙基醇及其烷氧基化物、异戊二烯醇及其烷氧基化物、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、甲氧基聚丁二醇(甲基)丙烯酸酯、甲氧基聚(氧化丙烯-共聚-氧化乙烯)(甲基)丙烯酸酯、乙氧基聚乙二醇(甲基)丙烯酸酯、乙氧基聚丙二醇(甲基)丙烯酸酯、乙氧基聚丁二醇(甲基)丙烯酸酯和乙氧基聚(氧化丙烯-共聚-氧化乙烯)(甲基)丙烯酸酯。此处,聚亚烷基二醇每分子可包含3-50个,特别是5-40个,尤其是10-30个氧化烯单元。
此处,特别优选的含磺酸基的单体为1-丙烯酰胺基-1-丙磺酸、2-丙烯酰胺基-2-丙磺酸、2-丙烯酰胺基-2-甲基丙磺酸、2-甲基丙烯酰胺基-2-甲基丙磺酸、3-甲基丙烯酰胺基-2-羟基丙磺酸、烯丙基磺酸、甲基烯丙基磺酸、烯丙氧基苯磺酸、甲基烯丙氧基苯磺酸、2-羟基-3-(2-丙烯氧基)丙磺酸、2-甲基-2-丙烯-1-磺酸、苯乙烯磺酸、乙烯基磺酸、丙烯酸3-磺基丙酯、甲基丙烯酸2-磺基乙酯、甲基丙烯酸3-磺基丙酯、磺基甲基丙烯酰胺、磺基甲基甲基丙烯酰胺,所述酸的盐,例如其钠、钾或铵盐。
特别优选的含磷酸根的单体为乙烯基膦酸及其盐。
此外,还可使用两性聚合物作为助洗剂。
本发明的洗衣洗涤剂组合物可包含例如0.1-70重量%,优选10-50重量%,优选至多20重量%的助洗剂(C),尤其是在固体配制剂的情况下。本发明的液体配制剂优选包含0.1-8重量%的助洗剂(C)。
本发明的洗衣洗涤剂组合物可包含一种或多种碱性载体。如果希望碱性pH,则碱性载体确保例如至少为9的pH。合适的有例如碱金属碳酸盐、碱金属碳酸氢盐和上文所述的碱金属偏硅酸盐,额外还有碱金属氢氧化物。在每种情况下,优选的碱金属为钾,特别优选为钠。
可用的酶(D)的实例为如下中的一种多种:脂肪酶、水解酶、淀粉酶、蛋白酶、纤维素酶、半纤维素酶、磷脂酶、酯酶、果胶酶、乳糖酶、过氧化物酶,以及前述类型中至少两种的组合。
酶(D)可以以足以提供清洁有效量的水平掺入。优选的量为0.001-5重量%活性酶,基于本发明洗涤剂组合物的重量。还可与酶一起使用酶稳定体系,例如钙离子、硼酸(boricacid)、硼酸(boronicacid)、丙二醇和短链羧酸。就本发明而言,短链羧酸选自每分子具有1-3个碳原子的单羧酸,和每分子具有2-6个碳原子的二羧酸。优选的实例为甲酸、乙酸、丙酸、草酸、琥珀酸、HOOC(CH2)3COOH、己二酸和前述至少两种的混合物,以及相应的钠和钾盐。
本发明的洗衣洗涤剂组合物可包含一种或多种漂白剂(E)(漂白试剂)。
优选的漂白剂(E)选自呈例如无水或一水合物或四水合物或所谓的二水合物形式的过硼酸钠、呈例如无水或一水合物形式的过碳酸钠,和过硫酸钠,其中术语“过硫酸盐”在每种情况下包括过酸H2SO5的盐以及过氧二硫酸盐。
就此而言,所述碱金属盐在每种情况下也可为碱金属碳酸氢盐、碱金属过硼酸氢盐和碱金属过硫酸氢盐。然而,在每种情况下优选二碱金属盐。
本发明的洗衣洗涤剂组合物可包含一种或多种漂白催化剂。漂白催化剂可选自氧氮丙啶(oxaziridinium)基漂白催化剂、漂白促进性过渡金属盐或过渡金属配合物,例如锰-、铁-、钴-、钌-或钼-salen配合物或羰基配合物。还可将锰、铁、钴、钌、钼、钛、钒和铜与含氮三足配体的配合物以及钴-、铁-、铜-和钌-胺配合物用作漂白催化剂。
本发明的洗衣洗涤剂组合物可包含一种或多种漂白活化剂,例如四乙酰基乙二胺,四乙酰基亚甲基二胺,四乙酰基甘脲,四乙酰基亚己基二胺,酰化的苯酚磺酸盐如正壬酰基-或异壬酰氧基苯磺酸盐,N-甲基吗啉-乙腈盐(“MMA盐”),三甲铵乙腈盐、N-酰基酰亚胺如N-壬酰基琥珀酰亚胺、1,5-二乙酰基-2,2-二氧代六氢-1,3,5-三嗪(“DADHT”)或腈季化物(三甲铵乙腈盐)。
本发明的洗衣洗涤剂组合物可包含一种或多种腐蚀抑制剂。在本情况下,这应理解为包括抑制金属腐蚀的那些化合物。合适的腐蚀抑制剂的实例为三唑类,特别是苯并三唑类、双苯并三唑类、氨基三唑类、烷基氨基三唑类,以及苯酚衍生物如氢醌、焦儿茶酚、羟基氢醌、棓酸、均苯三酚或焦棓酚。
在本发明的一个实施方案中,本发明的洗衣洗涤剂组合物包含总计为0.1-1.5重量%的腐蚀抑制剂。
本发明的洗衣洗涤剂组合物可包含一种或多种助洗剂,例如硫酸钠。
本发明的洗衣洗涤剂组合物可包含至少一种选自上文所定义的非离子、阴离子、阳离子、两性离子和/或两性表面活性剂的额外表面活性剂。
其他任选的成分可为但不限于粘度调节剂、阳离子表面活性剂、泡沫促进剂或减泡剂、香料、染料、荧光增白剂、染料转移抑制剂和防腐剂。
本发明的液体洗衣洗涤剂组合物可包含其量优选为至多约80重量%,特别是40-70重量%的水(基于全部组合物),其中希望的话,这也可被水溶性溶剂组分成比例地替代。可用于所述液体洗衣洗涤剂组合物中的非水溶剂来自例如一元或多元醇,链烷醇胺或二醇醚,条件是它们与水在所述浓度范围内混溶。溶剂优选选自乙醇,正丙醇或异丙醇,丁醇,乙二醇,丁二醇,甘油,二甘醇,丁基二甘醇,己二醇,乙二醇甲基醚,乙二醇乙基醚,乙二醇丙基醚,乙二醇单正丁基醚,二甘醇甲基醚,二甘醇乙基醚,丙二醇甲基醚、乙基醚或丙基醚,二丙二醇单甲基醚或乙基醚,二异丙二醇单甲基或乙基醚,甲氧基、乙氧基或丁氧基三甘醇,1-丁氧基乙氧基-2-丙醇,3-甲基-3-甲氧基丁醇,丙二醇叔丁基醚及其混合物。非水水溶性溶剂组分的量优选为至多15重量%,特别是0.5-10重量%,基于所述组合物的总量。
希望的话,可存在的本发明液体洗衣洗涤剂组合物的另一组分为水溶助长剂。优选的水溶助长剂包括磺酸化的水溶助长剂,例如烷基芳基磺酸盐或烷基芳基磺酸。优选的水溶助长剂选自二甲苯-、甲苯-、异丙基苯-、萘-磺酸盐或-磺酸及其混合物。抗衡离子优选选自钠、钙和铵。需要的话,本发明的液体洗衣洗涤剂组合物可包含至多20重量%,特别是0.05-10重量%的水溶助长剂。
本发明的液体洗衣洗涤剂组合物可进一步包含烷氧基化的聚亚烷基聚胺,其可通过使氧化烯与聚亚烷基聚胺反应而获得。优选地,所述液体洗衣洗涤剂组合物包含0.1-10重量%的烷氧基化聚亚烷基聚胺。在优选的实施方案中,所述烷氧基化聚亚烷基聚胺为烷氧基化聚乙烯亚胺。
聚乙烯亚胺目前通过乙烯亚胺的均聚而获得。乙烯亚胺是高反应性的、腐蚀性和毒性中间体,其可以以不同方式合成(吖丙啶类,UlrichSteuerle,RobertFeuerhake;Ullmann’sEncyclopediaofIndustrialChemistry,2006,Wiley-VCH,Weinheim)。烷氧基化聚亚烷基聚胺可如WO2013/076024所述制备。
洗涤剂成分是公知常识。详细描述可参见例如WO99/06524、WO99/04313、US2008/0248987和LiquidDetergents,编辑:Kuo-YannLai,SurfactantSci.Ser.,第67卷,MarcelDecker,NewYork,1997,第272-304页。
本发明的另一方面是本发明改性多糖用于提高洗涤织物的白度的用途、本发明改性多糖用作抗泛灰剂在水洗衣方法中的用途、本发明改性多糖用作流变调节剂在家庭护理应用中的用途,以及本发明改性多糖用于生产液体洗衣洗涤剂组合物的用途。
本发明的另一方面是一种提高洗涤织物的白度的方法,包括将本发明的改性多糖以有效量添加剂至液体洗衣洗涤剂组合物中,并将所述组合物用于水洗衣方法中的步骤。本发明进一步涉及一种降低水洗衣方法中的泛灰的方法,包括将本发明的改性多糖以有效量添加至液体洗衣洗涤剂组合物,并将所述组合物用于水洗衣方法中。本发明进一步涉及一种改变家庭护理组合物的流变性的方法,包括将本发明的改性多糖以有效量添加至家庭护理组合物中,并将所述组合物用于家庭护理应用如自动洗碗或I&I(机构和工业)应用中。本发明还涉及一种生产液体洗衣洗涤剂组合物的方法,包括将本发明的改性木葡聚糖以有效量与上文所定义的组分(B)和(C)以及任选的其他组分在水存在下一起混合。各种成分的添加顺序并不重要,然而优选首先添加洗涤剂,且希望的话,酶作为最后组分添加。混合可例如通过搅动或搅拌进行。可实施所述搅动或搅拌,直至形成澄清溶液或均一外观的分散体。
如果希望获得固体洗涤剂组合物,则可全部或部分移除水,例如通过喷雾干燥,例如借助喷嘴。
术语“有效量”意指足以提高洗涤织物的白度、足以降低水洗衣方法中的泛灰或足以改变家庭护理组合物的流变性的改性多糖的量。
实施例
实施例1:作为多糖5制备表1所示的改性多糖
在具有搅拌器和热敏元件/控制器的2L四颈玻璃釜中装入900g水。在室温(20℃)下,使14.7LSO2(40g)通过多孔玻璃过滤器达50分钟。添加100g木葡聚糖(DSPGokyoFood&ChemicalCo.,Ltd.或DainipponSumitomoPharmaCo.Ltd,Osaka,CAS39386-78-2),并在剧烈搅拌下将温度逐步加热至80℃(约30分钟),将所述混合物再在80℃下连续搅拌1.5小时,随后第二次添加在80℃下通过的20gSO2(约20分钟)。添加最后量的50g木葡聚糖,将全部混合物再在80℃下保持2.5小时。然后将分散体骤冷,用10%苛性钠溶液中和,从而获得5.5-6.5的最终pH。
所得溶液为15%,其显示出16,400mPas的粘度。用水稀释得到表1所示的10%、5%和2%粘度。粘度在RT℃下借助BrookfieldDV-II+根据DINENISO2555:2000-01(LVT转子)测定。
实施例2:改性多糖的一般制备
在3L带颈釜(具有搅拌器和冷却器)中,在室温下将10-20g气态SO2溶于425g水中。添加(300-500RPM,叶片搅拌器)50g多糖(参见表1),将温度升至80℃,并在该温度下保持90分钟。取决于具体配方(如果多糖(A)/SO2的质量比<3.5:1;参见表1),添加10-20g气态SO2,随后为额外量的25g多糖(如果制备15%溶液)。再次将温度保持在80℃达另外2-5小时。使用20%NaOH将pH设定为pH5.5(+/-0.25)。粘度在RT℃下借助BrookfieldDV-II+根据DINENISO2555:2000-01(LVT转子)测定。
表1显示了2%、5%、10%和15%溶液的粘度。2%、5%和10%溶液通过用水稀释15%溶液而获得。
表1:不同多糖的粘度
实施例3:测定本发明改性多糖的抗泛灰性质
所述多糖的泛灰抑制作用通过使用14°dH硬度的水(2.5mmol/L;Ca:Mg:HCO34:1:8)制备包含5g/L测试洗涤剂T(参见表2)和1.0-1.5%本发明改性多糖(参见表1,1-11)制备洗涤溶液而测试,作为对比,使用相对于洗涤剂剂量为1.0-1.5%的相当多糖(参见表1,C1和C2)。
表2:洗涤剂T
测试织物为不同棉(wfk10A作为标准棉,wfK12A作为毛圈棉布,wfk80A作为棉针织物,EMPA221作为棉布,大花帘布,经漂白的,不具有荧光增白剂,获自Brantic,Kapart品牌的T恤)和合成织物(wfk20A,wfk30A,EMPA406)的10cm×10cm正方形。测试在具有1L尺寸烧杯的耐洗牢度试验仪(型号LP2,获自SDLAtlas,Inc.)中进行。污垢为两种2.5gEMPA101(棉上的橄榄油/炭黑,购自EMPATestmaterials,Stgallen,瑞士)的混合物,以及两种2,5gSBL2004织物(污垢压载(ballast)织物“Formula2004”,其模拟皮脂油脂污迹,购自wfkTestgewebeGmbH,Brüggen,德国)的混合物。
第一次循环使用含测试洗涤溶液(0.25L)加测试织物和压载污垢的耐洗牢度试验仪烧杯在40℃下实施20分钟(织物与液体比1:10)。在洗涤后,将测试织物和压载污垢分离。使用经洗涤的测试织物重复该过程,且总计实施3次循环。对每次循环使用新的压载污垢。在3次循环后,将测试织物在水中漂洗,随后在环境室温下干燥过夜。
棉和合成测试织物的泛灰通过在洗涤后使用具有460nmUV截止滤光器的球反射率分光光度计(型号SF500,获自美国Datacolor,波长范围360-700nm,光学几何d/8°)测定白度(反射率值)而测定。
然后,在添加1.0-1.5%相应多糖(参见表1)后,定量测量测试洗涤剂的抗泛灰性质。反射率值随着织物的可见泛灰而降低,反射率值越高,则洗涤剂的抗泛灰性能越好。简单起见,棉Δ反射率值(ΔR)示于表3中。棉ΔR值显示了总计5种不同棉织物在含相应多糖的测试洗涤剂T洗涤之后的反射率(R1)与在不含多糖的测试洗涤剂洗涤之后的反射率之差。ΔR值>14意味着多糖对配制剂T的棉抗泛灰性质的明显可见贡献。合成Δ反射率并未显示在表3中,因为所述改性多糖对合成织物的二次洗涤性能不具有影响。
为了测定储存稳定性和在液体洗涤剂配制剂中的相容性,将本发明的改性多糖(参见表3中的1-11)和未改性多糖(参见表3中的C1和C2)二者添加至所述洗涤剂配制剂中并在37℃下储存4周。在储存期间,对市售液体洗衣洗涤剂而言重要的是粘度不急剧增大(不发生胶凝),且洗涤剂具有稍微浑浊至澄清的外观,且没有沉淀和/或相分离的迹象。如表3所示,当使用未改性多糖(参见表3中的C1和C2)时,或者当使用改性的纤维素(参见表3中的C3,即羧甲基纤维素(CMC);将CMC直接添加至烧杯中)时,不溶性是主要问题。换言之,在使用对比多糖(参见表3中的C1-C3)时,获得了沉淀(非澄清溶液)。
表3:耐洗牢度试验仪洗涤测试和储存稳定性测试的结果
液体测试洗涤剂配制剂的pH为约8.5。
棉Δ反射率以2次重复的平均值表示。
**CMC,羧甲基纤维素,获自Dow(WalocelCRT2,000PA)
++:澄清/几乎澄清,可溶,无相分离,对粘度无影响
+:稍微浑浊,可溶,无相分离,对粘度无影响
-:浑浊,不溶性部分,粘度稍微增大
--:浑浊,可溶,相分离,粘度急剧增大(胶凝化)
如表3所示,改性多糖(1-8)对二次洗涤作用具有有利影响,其防止了移除的污垢由洗液再次沉积至织物上。表3的改性多糖9-11还显示出与对比的未改性多糖类似的性能。此外,当与未改性多糖和CMC(C1-C3)相比时,它们全部显示出良好的可配制性。
总之,就抗泛灰性质而言,本发明改性多糖的性能与未改性多糖和CMC一样好或者更好。所述结果还表明,就溶解性和配制剂行为(液体配制剂)而言,本发明改性多糖的性能优于未改性多糖和CMC。
Claims (12)
1.一种改性多糖,其可通过包括用气态或液态SO2处理多糖的步骤的方法获得。
2.根据权利要求1的改性多糖,其中所述多糖为木葡聚糖、甘露聚糖、木聚糖、淀粉或其混合物。
3.根据权利要求1或2的改性多糖,其中所述方法使用0.1:1-5:1的SO2:多糖工艺质量比进行。
4.根据权利要求1-3中任一项的改性多糖,其中所述改性多糖在25℃下以2%溶于水中时显示出小于100mPas的粘度。
5.根据权利要求1-4中任一项的改性多糖,其中所述方法在0-150℃的温度下实施。
6.根据权利要求1-5中任一项的改性多糖,其中所述方法在0-10巴的压力下实施。
7.一种洗衣洗涤剂组合物,其包含根据权利要求1-6中任一项所定义的改性多糖。
8.根据权利要求7的洗衣洗涤剂组合物,其中所述洗衣洗涤剂为液体或凝胶状。
9.如权利要求1-6中任一项所定义的改性多糖用于提高洗涤织物的白度的用途。
10.如权利要求1-6中任一项所定义的改性多糖用作抗泛灰剂在水洗衣方法中的用途。
11.如权利要求1-6中任一项所定义的改性多糖用作流变调节剂在家庭护理应用中的用途。
12.如权利要求1-6中任一项所定义的改性多糖用于生产液体洗衣洗涤剂组合物的用途。
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CN110382553B (zh) | 2016-12-16 | 2022-06-14 | 营养与生物科学美国4公司 | 两亲多糖衍生物和包含其的组合物 |
WO2018172503A2 (en) | 2017-03-24 | 2018-09-27 | Basf Se | Liquid laundry detergent comprising modified saccharide or polysaccharide |
CN115362248A (zh) | 2020-04-07 | 2022-11-18 | 巴斯夫欧洲公司 | 适合作为洗涤剂制剂中的抗灰化剂的聚合物组合物 |
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