CN113056550A - 洗涤剂组合物 - Google Patents
洗涤剂组合物 Download PDFInfo
- Publication number
- CN113056550A CN113056550A CN201980076352.6A CN201980076352A CN113056550A CN 113056550 A CN113056550 A CN 113056550A CN 201980076352 A CN201980076352 A CN 201980076352A CN 113056550 A CN113056550 A CN 113056550A
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- detergent composition
- surfactant
- seq
- sterol esterase
- soil release
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
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Abstract
本发明提供一种洗涤剂组合物,其包含:(i)1至60重量%的表面活性剂;和(ii)0.0005至5重量%的甾醇酯酶;以及使用所述酶的方法和所述酶用于改善织物上的皮脂污渍的清洁的用途;其中所述甾醇酯酶具有与SEQ ID NO:1或2.10中任一项至少60%、优选至少70%、更优选至少75%、更优选至少80%、更优选至少85%、甚至更优选至少90%、甚至更优选至少95%、最优选至少97%、至少98%或甚至至少99%、最优选100%的序列同一性。
Description
技术领域
本发明涉及洗涤剂组合物,更具体地涉及洗衣洗涤剂组合物,所述组合物包含新型甾醇酯酶。
背景技术
皮脂是保持为难以从穿着的衣服上除去的污渍的油性污垢。在鼓励用户在较低温度下洗涤的驱动下,对于有效去除皮脂的挑战仍然难以满足。皮脂由大量脂肪和酯组成,包括蜡酯、胆固醇酯、角鲨烯和许多游离脂肪酸/醇。皮脂在体温下是液体,但在环境温度下是固体。
这些性质对于衣领/袖口的污垢去除特别重要,因为从衣服上去除液体身体油比去除固体更容易。目前的洗衣酶不能降解皮脂的所有组分,这使得难以从织物上去除。
皮脂去除的问题在于,包括目前商业酶的洗涤剂不充分去除皮脂。
发明内容
我们发现,在洗涤剂组合物中加入新型甾醇酯酶改善了从织物去除皮脂。
在一个方面,本发明提供一种液体洗涤剂组合物,其包含:
(i)1至60重量%,优选2至50重量%,更优选3至45重量%,甚至更优选5至40重量%,最优选6至40重量%的表面活性剂;和
(ii)0.0005至5重量%,优选0.005至2.5重量%,更优选0.01至1重量%的甾醇酯酶,
其中所述甾醇酯酶具有与SEQ ID NO:1或2中任一项至少60%、优选至少70%、更优选至少75%、更优选至少80%、更优选至少85%的序列同一性。
优选地,所述甾醇酯酶具有与SEQ ID NO:1或2中任一项至少90%、甚至更优选至少95%、最优选至少97%、至少98%或甚至至少99%的序列同一性。
最优选地,所述甾醇酯酶具有与SEQ ID NO:1或2中任一项100%的序列同一性。
优选地,洗涤剂组合物包含0.1至10重量%,优选0.2至9重量%,更优选0.25至8,甚至更优选0.5至6重量%,最优选1至5重量%的污物释放聚合物,更优选基于聚酯的污物释放聚合物。
优选地,聚酯污物释放聚合物是基于聚对苯二甲酸乙二酯和/或聚对苯二甲酸丙二酯的污物释放聚合物,优选基于聚对苯二甲酸丙二酯的污物释放聚合物。优选地,洗涤剂组合物包含烷氧基化聚胺,优选地,其含量为0.1至8重量%,更优选0.2至6重量%,最优选0.5至5重量%。
优选地,洗涤剂组合物是洗衣洗涤剂组合物。
优选地,洗涤剂组合物中的表面活性剂包含阴离子表面活性剂和/或非离子表面活性剂,在一种情况下,包含阴离子表面活性剂和非离子表面活性剂两者。
优选的洗涤剂组合物,特别是洗衣洗涤剂组合物,还包含选自以下的另外的酶:脂肪酶、蛋白酶、纤维素酶、α-淀粉酶、过氧化物酶/氧化酶、果胶酸裂解酶和/或甘露聚糖酶。
优选的洗涤剂组合物,特别是洗衣洗涤剂组合物,还包含选自荧光剂、香料、调色染料和聚合物及其混合物的另外的成分。
在另一个方面,本发明提供一种处理具有皮脂污渍的织物基材的方法,所述方法包括将具有与SEQ ID NO:1或2中任一项至少60%,优选至少70%,更优选至少75%,更优选至少80%,更优选至少85%,甚至更优选至少90%,甚至更优选至少95%,最优选至少97%,至少98%或甚至至少99%,最优选100%的序列同一性的甾醇酯酶加入到包含1至60重量%的表面活性剂的洗涤剂组合物中;和随后用所述组合物处理具有皮脂污渍的织物基材。
在另一个方面,本发明提供甾醇酯酶用于改善织物上的皮脂污渍的清洁的用途,其中所述甾醇酯酶具有与SEQ ID NO:1或2中任一项至少60%、优选至少70%、更优选至少75%、更优选至少80%、更优选至少85%、甚至更优选至少90%、甚至更优选至少95%、最优选至少97%、至少98%、或甚至至少99%、最优选100%的序列同一性。
具体实施方式
除非另有规定,否则本文所用不定冠词“一个/种(‘a’或‘an’)”及其相应的定冠词“所述/该(the)”是指至少一个/种,或一个/种或多个/种。
除非另有规定,否则本文所列组合物(制剂)中成分的所有含量%为基于总体制剂的重量%计。
应理解,任何对洗涤剂组合物的优选成分的提及都被预期为是可与本文公开的洗涤剂组合物的任何其它优选成分组合的主题内容。
洗涤剂组合物为液体。
洗涤剂组合物可以施用于任何合适的基材。特别优选的基材是织物。特别优选的洗涤剂组合物是洗衣洗涤剂组合物。
序列信息
本文公开的序列为SEQ ID NO 1或2。
SEQ ID 1是衍生自SEQ ID 2的截短序列且来自Corynebacterium(棒状杆菌属)。
序列为:
MNLALSGTFFNVNIRHLEGDGFSLFVDSDKKGEEDVPTARLKMEHAVASDLCLYVTTDLPAVGESTLALKAKGDNSVEATGLLVGASNIEGSLVMQDANVGIDASQLSQSADPGTWGLYAKQVSLTADDVRATSLGAKTLSAKNVGVSVERGRGNVC
SEQ ID 2来自Corynebacterium。
序列为:
MGRINVPKAAVGLVAGFAAFGVAGVAVAQGGLTANLALSGTFFNVNIRHLEGDGFSLFVDSDKKGEEDVPTARLKMEHAVASDLCLYVTTDLPAVGESTLALKAKGDNSVEATGLLVGASNIEGSLVMQDANVGIDASQLSQSADPGTWGLYAKQVSLTADDVRATSLGAKTLSAKNVGVSVERGRGNVC
甾醇酯酶
甾醇酯酶具有与SEQ ID NO:1或2中任一项至少60%的序列同一性。
优选地,甾醇酯酶具有与SEQ ID NO:1或2中任一项至少70%、更优选至少75%、更优选至少80%、更优选至少85%、甚至更优选至少90%、甚至更优选至少95%、最优选至少97%、至少98%、或甚至至少99%的序列同一性。
最优选地,甾醇酯酶具有与SEQ ID NO:1或2中任一项100%的序列同一性。
甾醇酯酶可以被描述为属于酶类EC 3.1.1.13。
优选的甾醇酯酶来自Corynebacterium。
表面活性剂
洗涤剂组合物包含表面活性剂(其可包括单一表面活性剂或两种或更多种表面活性剂的混合物)。组合物包含1至60重量%,优选2至50重量%,更优选3至45重量%,甚至更优选5至40重量%,最优选6至40重量%的表面活性剂。
洗涤剂组合物(优选地,洗衣洗涤剂组合物)包含阴离子表面活性剂和/或非离子表面活性剂,优选地包含阴离子表面活性剂和非离子表面活性剂两者。
可以使用的合适的阴离子洗涤剂化合物通常是具有含约8至约22个碳原子的烷基的有机硫酸和磺酸的水溶性碱金属盐,术语烷基用于包括较高级烷基的烷基部分。
合适的合成阴离子洗涤剂化合物的实例是烷基硫酸钠和烷基硫酸钾,特别是通过使例如由牛油或椰油制得的较高级C8至C18醇硫酸盐化而获得的那些,烷基C9至C20苯磺酸钠和钾,特别是直链仲烷基C10至C15苯磺酸钠;以及烷基甘油醚硫酸钠,特别是衍生自牛油或椰油的较高级醇和衍生自石油的合成醇的那些醚。
阴离子表面活性剂优选选自:直链烷基苯磺酸盐;烷基硫酸盐;烷基醚硫酸盐;皂;烷基(优选甲基)酯磺酸盐及其混合物。
最优选的阴离子表面活性剂选自:直链烷基苯磺酸盐;烷基硫酸盐;烷基醚硫酸盐及其混合物。优选地,烷基醚硫酸盐是具有平均1至3个EO(乙氧基化物)单元的C12-C14正烷基醚硫酸盐。
月桂基醚硫酸钠(SLES)是特别优选的。优选地,直链烷基苯磺酸盐是C11至C15烷基苯磺酸钠。优选地,烷基硫酸盐是直链或支链C12至C18烷基硫酸钠。十二烷基硫酸钠是特别优选的(SDS,也称为伯烷基硫酸盐)。
在液体制剂中,优选地存在两种或更多种阴离子表面活性剂,例如直链烷基苯磺酸盐连同烷基醚硫酸盐。
在液体制剂中,优选地,除了阴离子表面活性剂之外,洗衣组合物还包含烷基乙氧基化非离子表面活性剂,优选2至8重量%的烷基乙氧基化非离子表面活性剂。
可以使用的合适的非离子洗涤剂化合物包括,特别是,具有脂肪族疏水基团和反应性氢原子的化合物(例如,脂肪醇、酸或酰胺)与尤其是环氧乙烷(单独或与环氧丙烷一起)的反应产物。优选的非离子洗涤剂化合物是脂肪族C8至C18直链或支链伯或仲醇与环氧乙烷的缩合产物。
最优选地,非离子洗涤剂化合物为烷基乙氧基化非离子表面活剂,其为具有7EO至9EO单元的平均乙氧基化的C8至C18伯醇。
优选地,使用的表面活性剂是饱和的。
污物释放聚合物
污物释放聚合物优选以0.1至10重量%的水平存在。污物释放聚合物的优选的包含水平优选为0.2至9重量%,更优选0.25至8重量%,甚至更优选0.5至6重量%,最优选1至5重量%。优选地,污物释放聚合物是基于聚酯的污物释放聚合物。更优选地,聚酯污物释放聚合物是基于聚对苯二甲酸乙二酯和/或聚对苯二甲酸丙二酯的污物释放聚合物聚合物,最优选基于聚对苯二甲酸丙二酯的污物释放聚合物。
合适的基于聚酯的污物释放聚合物描述在WO 2014/029479和WO 2016/005338中。
烷氧基化聚胺
洗涤剂组合物优选包含烷氧基化聚胺。尤其当洗涤剂组合物是洗衣组合物的形式时,优选的是包含烷氧基化聚胺。
烷氧基化聚胺的优选的含量为0.1至8重量%,优选0.2至6重量%,更优选0.5至5重量%。另一个优选的含量为1至4重量%。
烷氧基化聚胺可以是直链或支链的。其可以支化至其是树枝状大分子的程度。烷氧基化通常可以是乙氧基化或丙氧基化,或两者的混合物。当氮原子被烷氧基化时,优选的平均烷氧基化度为10-30,优选15-25。
优选的材料是烷氧基化聚乙烯亚胺,最优选乙氧基化聚乙烯亚胺,其平均乙氧基化度为10-30,优选15-25,其中氮原子被乙氧基化。
另外的酶
除了所指定的脂肪酶之外,另外的酶可以存在于洗涤剂组合物中。优选的是另外的酶存在于优选的洗衣洗涤剂组合物中。
如果存在,则每种酶在本发明的洗衣组合物中的含量为0.0001重量%至0.1重量%。
在该组合物中存在的酶的含量优选与作为纯蛋白的酶的含量有关。
优选的另外的酶包括以下的那些:脂肪酶、蛋白酶、纤维素酶、α-淀粉酶、过氧化物酶/氧化酶、果胶酸裂解酶和/或甘露聚糖酶。所述优选的另外的酶包括这些酶中的两种或更多种的混合物。
优选地,所述另外的酶选自:脂肪酶、蛋白酶、纤维素酶和/或α-淀粉酶。合适的脂肪酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的脂肪酶的实例包括来自以下的脂肪酶:腐质霉(Humicola)(同义词嗜热真菌(Thermomyces)),例如来自EP 258 068和EP 305 216中所述的H.lanuginosa(T.lanuginosus)或来自WO 96/13580中所述的H.insolens;假单胞菌脂肪酶,例如来自产碱假单胞菌(P.alcaligenes)或假产碱假单胞菌(P.pseudoalcaligenes)(EP 218 272)、洋葱假单胞菌(P.cepacia)(EP 331 376)、施氏假单胞菌(P.stutzeri)(GB 1,372,034)、荧光假单胞菌(P.fluorescens),假单胞菌菌株SD 705(WO 95/06720和WO 96/27002)、P.wisconsinensis(WO 96/12012);芽孢杆菌脂肪酶,例如来自枯草芽孢杆菌(B.subtilis)(Dartois等(1993),Biochemica et Biophysica Acta,1131,253-360)、嗜热脂肪芽孢杆菌(B.stearothermophilus)(JP 64/744992)或短小芽孢杆菌(B.pumilus)(WO 91/16422)。
其他实例是脂肪酶变体,例如在WO 92/05249、WO 94/01541、EP 407225、EP 260105、WO 95/35381、WO 96/00292、WO 95/30744、WO 94/25578、WO 95/14783、WO 95/22615、WO 97/04079和WO 97/07202、WO 00/60063中描述的那些。
优选的可商购脂肪酶包括LipolaseTM和Lipolase UltraTM、LipexTM和LipocleanTM(Novozymes A/S)。
本发明的方法可以在分类为EC 3.1.1.4和/或EC 3.1.1.32的磷脂酶存在下进行。如在本文中所使用的,术语磷脂酶是对磷脂具有活性的酶。
磷脂,例如卵磷脂或磷脂酰胆碱,由在外部(sn-1)和中间(sn-2)位置被两个脂肪酸酯化,并在第三位置被磷酸酯化的甘油组成;磷酸反过来可以被酯化成氨基醇。磷脂酶是参与磷脂水解的酶。可以区分磷脂酶活性的多种类型,包括磷脂酶A1和A2,其水解一个脂肪酰基(分别在sn-1和sn-2位置)以形成溶血磷脂;和溶血磷脂酶(或磷脂酶B),其可以水解溶血磷脂中剩余的脂肪酰基。磷脂酶C和磷脂酶D(磷酸二酯酶)分别释放二酰基甘油或磷脂酸。
蛋白酶水解肽和蛋白质内的键,在洗衣环境中,这导致对含有蛋白质或肽的污渍的去除增强。合适的蛋白酶家族的实例包括天冬氨酸蛋白酶;半胱氨酸蛋白酶;谷氨酸蛋白酶;天冬酰胺(aspargine)肽裂解酶;丝氨酸蛋白酶和苏氨酸蛋白酶。这样的蛋白酶家族在MEROPS肽酶数据库(http://merops.sanger.ac.uk/)中描述。丝氨酸蛋白酶是优选的。枯草杆菌酶(subtilase)型丝氨酸蛋白酶是更优选的。根据Siezen等,Protein Engng.4(1991)719-737和Siezen等,Protein Science 6(1997)501-523,术语“枯草杆菌酶”指丝氨酸蛋白酶的亚组。丝氨酸蛋白酶是特征在于在活性位点具有丝氨酸的蛋白酶的亚组,该丝氨酸与底物形成共价加合物。枯草杆菌酶可以分为6个亚分类,即枯草杆菌蛋白酶(Subtilisin)家族、嗜热蛋白酶(Thermitase)家族、蛋白酶K(Proteinase K)家族、羊毛硫氨酸抗生素(Lantibiotic)肽酶家族、Kexin家族和Pyrolysin家族。
枯草杆菌酶的实例是源自芽孢杆菌例如在US7262042和WO09/021867中描述的迟缓芽孢杆菌,嗜碱芽孢杆菌,枯草芽孢杆菌,解淀粉芽孢杆菌,短小芽孢杆菌和吉氏芽孢杆菌的那些,以及在WO89/06279中描述的迟缓枯草杆菌蛋白酶(subtilisin lentus),枯草杆菌蛋白酶Novo,枯草杆菌蛋白酶Carlsberg,地衣芽孢杆菌,枯草杆菌蛋白酶BPN’,枯草杆菌蛋白酶309,枯草杆菌蛋白酶147和枯草杆菌蛋白酶168,以及在WO93/18140中描述的蛋白酶PD138。其它有用的蛋白酶可以是WO92/175177,WO01/016285,WO02/026024和WO02/016547中描述的那些。胰蛋白酶样蛋白酶的实例是WO89/06270,WO94/25583和WO05/040372中描述的胰蛋白酶(例如,猪或牛来源的)和镰刀菌蛋白酶,以及在WO05/052161和WO05/052146中描述的源自纤维单胞菌属(Cellumonas)的糜蛋白酶。
最优选地,蛋白酶是枯草杆菌蛋白酶(EC 3.4.21.62)。
枯草杆菌酶的实例是源自芽孢杆菌例如在US7262042和WO09/021867中描述的迟缓芽孢杆菌,嗜碱芽孢杆菌,枯草芽孢杆菌,解淀粉芽孢杆菌,短小芽孢杆菌和吉氏芽孢杆菌的那些,以及在WO89/06279中描述的迟缓枯草杆菌蛋白酶,枯草杆菌蛋白酶Novo,枯草杆菌蛋白酶Carlsberg,地衣芽孢杆菌,枯草杆菌蛋白酶BPN’,枯草杆菌蛋白酶309,枯草杆菌蛋白酶147和枯草杆菌蛋白酶168,以及在WO93/18140中描述的蛋白酶PD138。优选地,枯草杆菌蛋白酶源自芽孢杆菌,优选迟缓芽孢杆菌,嗜碱芽孢杆菌,枯草芽孢杆菌,解淀粉芽孢杆菌,短小芽孢杆菌和吉氏芽孢杆菌,如US 6,312,936 B1,US 5,679,630,US 4,760,025,US7,262,042和WO09/021867所述。最优选地,枯草杆菌蛋白酶源自吉氏芽孢杆菌或迟缓芽孢杆菌。
组合物可以使用分类在EC 3.1.1.74中的角质酶(cutinase)。根据本发明使用的角质酶可以是任何来源。优选地,角质酶具有微生物来源,特别是细菌、真菌或酵母来源。
合适的淀粉酶(α和/或β)包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。淀粉酶包括例如获自芽孢杆菌,例如在GB 1,296,839中更详细描述的地衣芽孢杆菌的特殊菌株,或在WO 95/026397或WO 00/060060中公开的芽孢杆菌菌株的α-淀粉酶。可商购的淀粉酶是DuramylTM、TermamylTM、Termamyl UltraTM、NatalaseTM、StainzymeTM、AmplifyTM、FungamylTMand BANTM(Novozymes A/S)、RapidaseTM和PurastarTM(来自Genencor International Inc.)。
合适的纤维素酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。合适的纤维素酶包括来自以下的纤维素酶:芽孢杆菌属、假单胞菌属、腐质霉属、镰刀菌属、梭孢壳属、支顶孢属,例如从公开于US 4,435,307、US 5,648,263、US 5,691,178、US 5,776,757、WO 89/09259、WO 96/029397和WO 98/012307的特异腐质霉、太瑞斯梭孢壳霉、嗜热毁丝霉和尖孢镰刀菌产生的真菌纤维素酶。可商购的纤维素酶包括CelluzymeTM、CarezymeTM、Celluclean TM、EndolaseTM、RenozymeTM(Novozymes A/S)、ClazinaseTMand Puradax HATM(Genencor International Inc.)和KAC-500(B)TM(KaoCorporation)。CellucleanTM是优选的。
合适的过氧化物酶/氧化酶包括具有植物、细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的过氧化物酶的实例包括来自鬼伞属,例如来自灰盖鬼伞的过氧化物酶,及其变体,如在WO93/24618、WO 95/10602和WO 98/15257中描述的那些。可商购过氧化物酶包括GuardzymeTM和NovozymTM51004(Novozymes A/S)。
另外的适用的酶在WO2009/087524、WO2009/090576、WO2009/107091、WO2009/111258和WO2009/148983中讨论。
该方法中使用的水性溶液优选地具有存在的酶。酶优选地在该方法中使用的水性溶液中以0.01至10ppm,优选0.05至1ppm范围的浓度存在。
酶稳定剂
存在于组合物中的任何酶可以使用常规稳定剂来稳定化,例如多元醇,如丙二醇或甘油;糖或糖醇;乳酸;硼酸或硼酸衍生物,例如芳族硼酸酯,或苯基硼酸衍生物,如4-甲酰基苯基硼酸,并且组合物可以如例如WO 92/19709和WO 92/19708中所述配制。
另外的材料
可以包含在洗涤剂组合物(优选地,洗衣洗涤剂组合物)中的另外的任选但优选的材料包括荧光剂、香料、调色染料、聚合物和螯合剂。
荧光剂
组合物优选包含荧光剂(光学增亮剂)。荧光剂是众所周知的,并且许多这样的荧光剂是可商购的。通常,这些荧光剂以其碱金属盐例如钠盐的形式供应和使用。
组合物中使用的一种或多种荧光剂的总量通常为0.0001至0.5重量%,优选0.005至2重量%,更优选0.01至0.1重量%。
优选的荧光剂类别是:二苯乙烯基联苯基化合物,例如Tinopal(商标)CBS-X,二胺二苯乙烯二磺酸化合物,例如Tinopal DMS pure Xtra和Blankophor(商标)HRH,以及吡唑啉化合物,例如Blankophor SN。
优选的荧光剂是具有CAS-No 3426-43-5;CAS-No 35632-99-6;CAS-No 24565-13-7;CAS-No 12224-16-7;CAS-No 13863-31-5;CAS-No 4193-55-9;CAS-No 16090-02-1;CAS-No 133-66-4;CAS-No 68444-86-0;CAS-No 27344-41-8的荧光剂。
最优选的荧光剂是:2-(4-苯乙烯基-3-磺基苯基)-2H-萘并(napthol)[1,2-d]三唑钠、4,4'-双{[(4-苯胺基-6-(N-甲基-N-2-羟乙基)氨基-1,3,5-三嗪-2-基)]氨基}二苯乙烯-2-2'-二磺酸二钠、4,4'-双{[(4-苯胺基-6-吗啉基-1,3,5-三嗪-2-基)]氨基}二苯乙烯-2-2'-二磺酸二钠及4,4'-双(2-磺基苯乙烯基)联苯二钠。
该方法中使用的水性溶液具有荧光剂存在。荧光剂优选地在该方法中使用的水性溶液中的存在范围为0.0001g/L至0.1g/L,更优选0.001至0.02g/L。
香料
组合物优选包含香料。在由CFTA Publications出版的CTFA(Cosmetic,Toiletryand Fragrance Association)1992 International Buyers Guide和由SchnellPublishing Co.出版的OPD 1993 Chemicals Buyers Directory 80th Annual Edition中提供了香料的许多合适实例。
优选地,香料包含以下的至少一种香型(note)(化合物):α-异甲基紫罗酮,水杨酸苄酯;香茅醇;香豆素;己基肉桂醛;芳樟醇;2-甲基戊酸乙基酯;辛醛;乙酸苄酯;3,7-二甲基-1,6-辛二烯-3-醇3-乙酸酯;2-(1,1-二甲基乙基)-环己醇1-乙酸酯;δ-大马酮(damascone);β-紫罗酮;乙酸三环癸烯酯(verdyl acetate);十二醛;己基肉桂醛(hexylcinnamic aldehyde);环十五内酯;苯乙酸2-苯基乙基酯;水杨酸戊酯;β-石竹烯;十一碳烯酸乙酯;邻氨基苯甲酸香叶酯;α-鸢尾酮;β-苯基乙基苯甲酸酯;α-檀香醇;雪松醇;乙酸柏木酯;甲酸柏木酯(cedry formate);水杨酸环己酯;γ-十二内酯,和β-苯乙基苯基乙酸酯。
香料的有用组分包括天然和合成来源的材料两者。它们包括单一化合物和混合物。这样的组分的具体实例可见于现有文献中,例如,Fenaroli's Handbook of FlavorIngredients,1975,CRC Press;M.B.Jacobs,Synthetic Food Adjuncts,1947,VanNostrand编辑;或S.Arctander,Perfume and Flavor Chemicals,1969,Montclair,N.J.(USA)。
在制剂中存在多种香料组分是常见的。在本发明的组合物中,设想将存在四种或更多种、优选五种或更多种、更优选六种或更多种、或甚至七种或更多种不同的香料组分。
在香料混合物中,优选15至25重量%是头香。头香是由Poucher(Journal of theSociety of Cosmetic Chemists 6(2):80[1955])所定义的。优选的头香选自柑桔油、芳樟醇、乙酸芳樟酯、薰衣草、二氢月桂烯醇、玫瑰醚(rose oxide)和顺-3-己醇。
国际日用香精香料协会已在2011年发布了香氛成分(香料)的列表。(http:// www.ifraorg.org/en-us/ingredients#.U7Z4hPldWzk)
国际日用香料研究所提供了具有安全性信息的香料(香氛)数据库。
香料头香可用于提示本发明的白度和亮度益处。
一些或所有香料可以被包封,有利于包封的典型香料组分包括具有相对低的沸点的那些,优选沸点小于300℃,优选为100-250℃的那些。包封具有低Clog P(即,将具有更高的被分配到水中的倾向的那些),优选具有小于3.0的CLog P的香料组分也是有利的。具有相对低沸点和相对低CLog P的材料已经被称为“延迟释香(delayed blooming)”的香料成分,并且包含以下材料中的一种或多种:己酸烯丙酯、乙酸戊酯、丙酸戊酯、茴香醛、苯甲醚、苯甲醛、乙酸苄酯、苄基丙酮、苯甲醇、甲酸苄酯、异戊酸苄酯、丙酸苄酯、β-γ己烯醇、樟脑胶、左旋-香芹酮、d-香芹酮、肉桂醇、甲酸肉桂酯(cinamyl formate)、顺-茉莉酮、顺-3-己烯基乙酸酯、枯茗醇、cyclal c、二甲基苄基甲醇、二甲基苄基甲醇乙酸酯、乙酸乙酯、乙酰乙酸乙酯、乙基戊基酮、苯甲酸乙酯、丁酸乙酯、乙基己基酮、乙基苯基乙酸酯、桉树脑、丁香酚、乙酸葑酯(fenchyl acetate)、flor acetate(三环癸烯基乙酸酯)、frutene(三环癸烯基丙酸酯)、香叶醇、己烯醇、乙酸己烯酯、乙酸己酯、甲酸己酯、龙葵醇(hydratropicalcohol)、羟基香茅醛、茚酮、异戊醇、异薄荷酮、乙酸异胡薄荷酯(isopulegyl acetate)、异喹啉酮、女贞醛、芳樟醇、芳樟醇氧化物、甲酸芳樟酯、薄荷酮、薄荷基苯乙酮(menthylacetphenone)、甲基戊基酮、邻氨基苯甲酸甲酯、苯甲酸甲酯、甲基苄基乙酸酯(methylbenyl acetate)、甲基丁香酚、甲基庚烯酮、甲基庚炔碳酸酯(methyl heptinecarbonate)、甲基庚基酮、甲基己基酮、甲基苯基甲基乙酸酯、水杨酸甲酯、甲基-n-甲基邻氨基苯甲酸酯、橙花醇、辛内酯、辛醇、对甲酚、对甲酚甲基醚、对甲氧基苯乙酮、对甲基苯乙酮、苯氧乙醇、苯基乙醛、苯基乙基乙酸酯、苯基乙基醇、苯基乙基二甲基甲醇、乙酸异戊二烯酯、硼酸丙酯(propyl bornate)、胡薄荷酮、玫瑰醚(rose oxide)、黄樟素、4-萜品烯醇(4-terpinenol)、α-萜品烯醇和/或苯乙醛二甲醇缩醛(viridine)。多种香料组分存在于制剂中是常见的。在本发明的组合物中,设想将有来自上文给出的延迟释香香料的给定列表的四种或更多种,优选五种或更多种,更优选六种或更多种,或甚至七种或更多种不同的香料组分存在于香料中。
可以与本发明一起应用的另一组香料是所谓的“芳香疗法”材料。这些包括也用于香水中的许多组分,包括精油的组分如鼠尾草、桉树、天竺葵、薰衣草、肉豆蔻干皮(Mace)提取物、橙花油、肉豆蔻、留兰香、甜紫罗兰叶和缬草。
优选的是洗衣处理组合物不含过氧漂白剂,例如过碳酸钠,过硼酸钠和过酸。
调色染料
优选地,当组合物是洗衣洗涤剂组合物时,则其包含调色染料。优选地,调色染料以组合物的0.0001至0.1重量%存在。
染料在Color Chemistry Synthesis,Properties and Applications ofOrganic Dyes and Pigments,(H Zollinger,Wiley VCH,Zürich,2003)and,IndustrialDyes Chemistry,Properties Applications.(K Hunger(ed),Wiley-VCH Weinheim 2003)中描述。
用于洗衣组合物的调色染料优选在可见光范围(400-700nm)中的最大吸收处具有大于5000L mol-1cm-1,优选大于10000L mol-1cm-1的消光系数。染料的颜色是蓝色或紫色。
优选的调色染料发色团是偶氮、吖嗪、蒽醌和三苯甲烷。
偶氮、蒽醌、酞菁和三苯甲烷染料优选带有净阴离子电荷或不带电荷。吖嗪优选带有净阴离子或阳离子电荷。在洗涤过程的洗涤或漂洗步骤期间,蓝色或紫色调色染料沉积到织物上,从而为织物提供可见的色调。在这方面,染料对白色布料赋予蓝色或紫色,色调角为240至345、更优选250至320、最优选250至280。该测试中使用的白色布料是经漂白的、非丝光处理的编织棉片。
调色染料在WO 2005/003274,WO 2006/032327(Unilever)、WO 2006/032397(Unilever)、WO 2006/045275(Unilever)、WO 2006/027086(Unilever)、WO 2008/017570(Unilever)、WO 2008/141880(Unilever)、WO 2009/132870(Unilever)、WO 2009/141173(Unilever)、WO 2010/099997(Unilever)、WO 2010/102861(Unilever)、WO 2010/148624(Unilever)、WO 2008/087497(P&G)、WO 2011/011799(P&G)、WO 2012/054820(P&G)、WO2013/142495(P&G)和WO 2013/151970(P&G)中讨论。
单偶氮染料优选含有杂环,并且最优选是噻吩染料。单偶氮染料优选是烷氧基化的,并且优选在pH=7时不带电荷或带阴离子电荷。烷氧基化噻吩染料在WO/2013/142495和WO/2008/087497中讨论。噻吩染料的优选实例如下所示:
双偶氮染料优选为磺化双偶氮染料。磺化双偶氮化合物的优选实例是直接紫7,直接紫9,直接紫11,直接紫26,直接紫31,直接紫35,直接紫40,直接紫41,直接紫51,直接紫66,直接紫99及其烷氧基化形式。烷氧基化双偶氮染料在WO2012/054058和WO2010/151906中讨论。
烷氧基化双偶氮染料的实例是:
噻吩染料可从Milliken以商品名Liquitint Violet DD和Liquitint Violet ION获得。
吖嗪染料优选选自磺化吩嗪染料和阳离子吩嗪染料。优选的实例是酸性蓝98,酸性紫50,CAS号为72749-80-5的染料,酸性蓝59,以及选自以下的吩嗪染料:
其中:
X3选自:-H;-F;-CH3;-C2H5;-OCH3;和–OC2H5;
X4选自:-H;-CH3;-C2H5;-OCH3;和–OC2H5;
Y2选自:-OH;-OCH2CH2OH;-CH(OH)CH2OH;-OC(O)CH3;和C(O)OCH3。
调色染料以0.0001至0.5重量%、优选0.001至0.1重量%的范围存在于组合物中。取决于调色染料的性质,存在取决于调色染料的效力的优选范围,所述调色染料的效力取决于类别和任何特定类别内的具体效力。如上所述,调色染料是蓝色或紫色调色染料。
可以使用调色染料的混合物。
调色染料最优选是与烷氧基化聚乙烯亚胺共价连接的活性蓝色蒽醌染料。烷氧基化优选选自乙氧基化和丙氧基化,最优选丙氧基化。优选地,通过丙氧基化将聚乙烯亚胺中80至95摩尔%的N-H基团替换为异丙醇基团。优选地,在与染料反应和丙氧基化之前,聚乙烯亚胺具有的分子量为600至1800。
共价连接到丙氧基化聚乙烯亚胺的优选活性蒽醌的实例结构是:
聚合物
组合物可包含一种或多种另外的聚合物。实例为羧甲基纤维素、聚(乙二醇)、聚(乙烯醇)、聚羧酸酯如聚丙烯酸酯、马来酸/丙烯酸共聚物和甲基丙烯酸月桂酯/丙烯酸共聚物。
螯合剂
螯合剂可以存在或不存在于洗涤剂组合物中。如果存在,则螯合剂的存在量为0.01至5重量%。
膦酸(或其盐)螯合剂的实例为:1-羟基亚乙基-1,1-二膦酸(HEDP);二亚乙基三胺五(亚甲基膦酸)(DTPMP);六亚甲基二胺四(亚甲基膦酸)(HDTMP);氨基三(亚甲基膦酸)(ATMP);乙二胺四(亚甲基膦酸)(EDTMP);四亚甲基二胺四(亚甲基膦酸)(TDTMP);和膦丁烷三羧酸(PBTC)。
实施例
将通过以下非限制性实施例阐述本发明。
实施例
包括序列信息的克隆&表达在NCBI数据库中鉴定编码具有推定的胆固醇酯酶活性的蛋白质的DNA序列,并采用针对大肠杆菌的密码子优化来合成。使用用于C-末端His6-标签的aLICator LIC克隆和表达试剂盒(pLATE31)进行克隆。为了更好的蛋白质溶解度,在克隆过程中,截短了含有跨膜螺旋的蛋白质的N-末端位点。使用大肠杆菌XL2 Blue作为克隆菌株,并使用热激方法转化。在质粒分离之后,对质粒测序,证实克隆成功。转化(热激)含有共表达伴侣蛋白(chaperons)的质粒pKJE7的大肠杆菌BL21(DE3),并用作蛋白质生产的表达菌株。
截短的蛋白质的序列(SEQ ID 1):
MNLALSGTFFNVNIRHLEGDGFSLFVDSDKKGEEDVPTARLKMEHAVASDLCLYVTTDLPAVGESTLALKAKGDNSVEATGLLVGASNIEGSLVMQDANVGIDASQLSQSADPGTWGLYAKQVSLTADDVRATSLGAKTLSAKNVGVSVERGRGNVC
全长蛋白质(SEQ ID 2):
胆固醇酯酶[Corynebacterium]
MGRINVPKAAVGLVAGFAAFGVAGVAVAQGGLTANLALSGTFFNVNIRHLEGDGFSLFVDSDKKGEEDVPTARLKMEHAVASDLCLYVTTDLPAVGESTLALKAKGDNSVEATGLLVGASNIEGSLVMQDANVGIDASQLSQSADPGTWGLYAKQVSLTADDVRATSLGAKTLSAKNVGVSVERGRGNVC
发酵(收获)和纯化
在2L锥形瓶中用1L LB培养基和用于质粒选择的合适抗生素(氨苄青霉素,100μg/mL;氯霉素,35μg/mL)进行蛋白质生产。用1-3%(v/v)的预培养物接种LB-培养基,并在37℃和180rpm下温育,直到达到OD600=0.6。用20mg/mL L-阿拉伯糖酶诱导伴侣蛋白的表达,并在20℃使培养物培养30分钟,通过加入IPTG至终浓度1mM来诱导基因表达并在20℃和180rpm下进行3h。通过离心(4750×g,20min,4℃)收获细胞并在-80℃保存。
通过将细胞糊重悬于平衡缓冲液(对于1g细胞湿重为25mM Tris-HCl,pH 8.0,500mM NaCl,20mM咪唑,10mL缓冲液)中并在冰上超声破碎细胞来进行细胞裂解。使用1mLHisTrap FF柱和用于通过多组氨酸-标签进行亲和层析的AKTA纯化系统进行蛋白质纯化。使用咪唑浓度递增的缓冲液(25mM Tris-HCl,pH 8.0,500mM NaCl,500mM咪唑),经由线性梯度进行30分钟的蛋白质洗脱。通过吸光度(280nm)鉴定洗脱级分并施加至SDS-PAGE。合并含有感兴趣的蛋白质的级分,并用5L不含咪唑的缓冲液(25mM Tris-HCl,pH 8.0,500mMNaCl)透析过夜。透析的蛋白补充有0.005%(v/v)的叠氮化钠和10%(v/v)的甘油用于冷冻并储存在-80℃。
生物分析
蛋白质浓度的测定
通过使用Sigma-Aldrich(二辛可宁酸)BCA测定试剂盒来估计酶样品的蛋白质总量,并且按照使用者手册中的指示制备工作试剂。通过以50:1(v/v)比率混合溶液A[1%(w/v)的钠盐形式的二辛可宁酸、2%(w/v)的碳酸钠、0.16%(w/v)的酒石酸钠、0.4%(w/v)的氢氧化钠、0.95%(w/v)的碳酸氢钠,pH11.5]与溶液B[4%(w/v)的硫酸铜]制备BCA试剂。在去离子水中进行牛血清白蛋白的连续稀释(2mg/mL),以产生7个点的标准曲线。为了进行该测定,将BCA试剂(200μL)加入96孔板的孔中,随后进行样品蛋白稀释(20μL)。将微量滴定板(MTP)密封并在37℃下孵育30分钟。在孵育之后,在分光光度计上测量540nm处的吸光度。
酶纯度的测定用SDS-PAGE加样缓冲液制备含酯酶的蛋白质样品(20μL),并在70℃加热10分钟,然后在170V下,在含MOPS缓冲液的4-12%NuPage Bis-Tris凝胶上跑胶。PageRulerPlus分子量标记物与样品一起跑胶以测定分子质量。然后按照生产商的方案,使用GelCode Blue Safe Protein Stain对每个凝胶进行染色。
甾醇酯酶活性的生化测定
通过比色法,使用4-硝基苯基戊酸酯(C5)和4-硝基苯基十二烷酸酯(C12)作为底物,测定甾醇酯酶活性。将4-硝基苯基十二烷酸酯(25mg)或4-硝基苯基戊酸酯(18mg)溶于10mL溶剂(甲醇)中以制备8mM储备溶液。在进行测定之前,将1mL储备溶液加入7mL酸化水(pH4.5)中以得到1mM的终浓度。在96孔微量滴定板中,加入60μL dH2O、115μL Tris-HCl缓冲液(pH8.5,50mM)、5μL稀释的酶溶液和20μL底物(在结束处的多通道)。对于空白,用dH2O代替酶溶液。在加入试剂之后,在环境温度下,在405nm处监测产物(4-硝基苯酚)的释放15分钟。
施用测试
模型类人皮脂的组成和施用于织物表1A显示了待用于洗涤研究的类人皮脂的组成,其与文献中分析的人皮脂(表1B)相当。将Macrolex紫色染料(0.4%w/w)加入到模型皮脂中,然后将100μL施用到预热至60℃的10×10cm的聚棉样品上。通过使污渍在60℃下干燥过夜来促进污渍的芯吸(wicking),通过比色测定整个样品上的SRI值来确认染渍的均匀性,随后将其切成更小的30mm直径的圆形,使得能够装配在6孔微量滴定板中用于随后的洗涤试验。
表1:(A)测试的类人皮脂的组成。在比较(B)中显示了Nikkari1974,In Ro2005,Stefaniak 2010提出的人皮脂的组成。设计了模型类人皮脂以模拟文献描述。
针对类人皮脂的酶清洁性能的洗涤研究
对30mm直径皮脂污渍进行洗涤前读数,以测量污渍强度。在5mL体积(在6孔板中,在40℃下,以100rpm进行1小时)或100mL(在玻璃瓶中,在40℃下,以100rpm进行1小时)中进行洗涤研究。酶以25mg/L存在于2g/L的7.5%表面活性制剂中。然后,在洗涤后漂洗污渍三次,以完全除去洗涤液和任何残留的酶。在干燥之后,对污渍板进行数字扫描,并测量它们的ΔE。该值用于表示清洁效果,并定义为白色布和洗涤后的染污布之间的色差。
在数学上,ΔE的定义是:
ΔE=[(ΔL)2+(Δa)2+(Δb)2]1/2
其中ΔL是洗涤布和白色布之间的暗度的差异的量度;Δa和Δb分别是两种布料之间的红色和黄色的差异的量度。从这个等式中明显看出,ΔE值越低,布料越白。关于这种颜色测量技术,参考Commission International de l'Eclairage(CIE);Recommendationon Uniform Colour Spaces,colour difference equations,psychometric colourterms,supplement no.2to CIE Publication,no.15,Colormetry,Bureau Central de IaCIE,Paris1978。
本文中,清洁效果以去污指数(SRI)的形式表示:
SRI=100-ΔE
SRI越高,布越清洁,SRI=100(白色)。
针对类人皮脂的酶清洁性能
5mL洗涤体积的洗涤研究确定,甾醇酯酶显示出比对照制剂改善的去除类人皮脂的性能。实验酶甾醇酯酶的SRI增加显示出比包括洗衣酯酶基准(Cutinase)和洗衣脂肪酶基准(Lipase Evity)的对照样品改善的去除类人皮脂的性能。对于所示实验酶为4-6个单位的SRI增加是超过对照酶(Cutinase)和洗衣脂肪酶基准(Lipase Evity)的明显可见的清洁改善。在40℃下,一式三份进行测试1小时。所使用的制剂含有7.5%的总表面活性剂。
与Cutinase和Lipex Evity相比,对于本发明的甾醇酯酶,>4个单位的SRI增加是明显可见的清洁改善(表2)。
表2:在水或制剂+基准商业酯酶(Cutinase)或制剂+基准商业洗衣脂肪酶(LipexEvity)中与洗涤对照相比显示的SEQ ID1的甾醇酯酶(针对模型类人皮脂)的清洁性能。
测量指示洗涤性能的去污指数(SRI)。±统计涉及95%置信水平。该试验表明,SEQID1的甾醇酯酶具有比商业酯酶(Cutinase)和脂肪酶(Lipex Evity)好得多的抗皮脂性能。
针对类人皮脂的酶清洁性能
100ml体积的洗涤研究证实,与包括目前商业酯酶(Cutinase)和脂肪酶(LipexEvity)的对照样品相比,SEQ ID 1的甾醇酯酶显示出对于去除类人皮脂的改善的性能(表3)。该测试在40℃下一式三份进行1小时。使用的制剂含有7.5%的总表面活性剂。
表3:在水或制剂+基准商业酯酶(Cutinase)或制剂+基准商业洗衣脂肪酶(LipexEvity)中与洗涤对照相比显示的SEQ ID 1的甾醇酯酶(针对模型类人皮脂)的清洁性能。
Claims (11)
1.一种液体洗涤剂组合物,其包含:
(i)1至60重量%,优选2至50重量%,更优选3至45重量%,甚至更优选5至40重量%,最优选6至40重量%的表面活性剂;和
(ii)0.0005至5重量%,优选0.005至2.5重量%,更优选0.01至1重量%的甾醇酯酶;
其中所述甾醇酯酶具有与SEQ ID NO:1或2中任一项至少60%、优选至少70%、更优选至少75%、更优选至少80%、更优选至少85%的序列同一性。
2.根据权利要求1所述的洗涤剂组合物,其中所述甾醇酯酶具有与SEQ ID NO:1或2中任一项至少90%、甚至更优选至少95%、最优选至少97%、至少98%、或甚至至少99%的序列同一性。
3.根据权利要求1或权利要求2所述的洗涤剂组合物,其中所述甾醇酯酶具有与SEQ IDNO:1或2中任一项100%的序列同一性。
4.根据前述权利要求中任一项所述的洗涤剂组合物,其包含0.1至10重量%,优选0.2至9重量%,更优选0.25至8,甚至更优选0.5至6重量%,最优选1至5重量%的污物释放聚合物,更优选基于聚酯的污物释放聚合物。
5.根据权利要求4所述的洗涤剂组合物,其中所述聚酯污物释放聚合物为基于聚对苯二甲酸乙二酯和/或聚对苯二甲酸丙二酯的污物释放聚合物,优选基于聚对苯二甲酸丙二酯的污物释放聚合物。
6.根据前述权利要求中任一项所述的洗涤剂组合物,其中所述洗涤剂组合物包含烷氧基化聚胺,优选含量为0.1至8重量%,更优选0.2至6重量%,最优选0.5至5重量%。
7.根据前述权利要求中任一项所述的洗衣洗涤剂组合物,其中所述表面活性剂包含阴离子表面活性剂和/或非离子表面活性剂,优选包含阴离子表面活性剂和非离子表面活性剂两者。
8.根据前述权利要求中任一项所述的洗涤剂组合物,优选洗衣洗涤剂组合物,其还包含选自以下的另外的酶:脂肪酶、蛋白酶、纤维素酶、α-淀粉酶、过氧化物酶/氧化酶、果胶酸裂解酶和/或甘露聚糖酶。
9.根据前述权利要求中任一项所述的洗涤剂组合物,优选洗衣洗涤剂组合物,其还包含选自以下的另外的成分:荧光剂、香料、调色染料和聚合物、及其混合物。
10.一种处理具有皮脂污渍的织物基材的方法,所述方法包括将具有与SEQ ID NO:1或2中任一项至少60%,优选至少70%,更优选至少75%,更优选至少80%,更优选至少85%,甚至更优选至少90%,甚至更优选至少95%,最优选至少97%,至少98%或甚至至少99%,最优选100%的序列同一性的甾醇酯酶加入到包含1至60重量%的表面活性剂的液体洗涤剂组合物中;和随后用所述组合物处理具有皮脂污渍的织物基材。
11.甾醇酯酶用于改善织物上的皮脂污渍的清洁的用途,其中所述甾醇酯酶具有与SEQID NO:1或2中任一项至少60%、优选至少70%、更优选至少75%、更优选至少80%、更优选至少85%、甚至更优选至少90%、甚至更优选至少95%、最优选至少97%、至少98%、或甚至至少99%、最优选100%的序列同一性。
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CN113056550B (zh) | 2022-10-28 |
EP3884024A1 (en) | 2021-09-29 |
ZA202102582B (en) | 2023-03-29 |
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