CN101243168A - 由在多糖基质中的二酰基过氧化物制得的丸粒 - Google Patents
由在多糖基质中的二酰基过氧化物制得的丸粒 Download PDFInfo
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- CN101243168A CN101243168A CNA2006800302202A CN200680030220A CN101243168A CN 101243168 A CN101243168 A CN 101243168A CN A2006800302202 A CNA2006800302202 A CN A2006800302202A CN 200680030220 A CN200680030220 A CN 200680030220A CN 101243168 A CN101243168 A CN 101243168A
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- pill
- polysaccharide
- diacyl peroxide
- metal ion
- cleaning compositions
- Prior art date
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- 239000012933 diacyl peroxide Substances 0.000 title claims abstract description 51
- 150000004676 glycans Chemical class 0.000 title claims abstract description 37
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 37
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 37
- 239000011159 matrix material Substances 0.000 title claims abstract description 24
- 239000008188 pellet Substances 0.000 title abstract 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 14
- 239000006187 pill Substances 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 63
- 238000004140 cleaning Methods 0.000 claims description 52
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- -1 n-nonyl Chemical group 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
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- 125000000217 alkyl group Chemical group 0.000 claims description 11
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
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- 239000000725 suspension Substances 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
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- 239000012418 sodium perborate tetrahydrate Substances 0.000 claims description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 3
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
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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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- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-compounds
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0034—Fixed on a solid conventional detergent ingredient
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
通过向含有将多糖交联的金属离子的溶液中加入其中悬浮二酰基过氧化物颗粒并且其中溶解至少一种可由金属离子交联的多糖的含水悬浮体的液滴,可以制备含有埋入基质中的二酰基过氧化物颗粒的丸粒。所述丸粒适宜作为清洁组合物中的漂白组分。
Description
本发明涉及含有埋入基质中的二酰基过氧化物颗粒的丸粒、这种丸粒的制备方法和这种丸粒作为清洁组合物中的漂白组分的用途。
在清洁组合物中,特别是在织物洗涤剂中,通常将过酸盐如过硼酸钠或过碳酸钠用作漂白组分,与活化剂如四乙酰基乙二胺组合使用,以提高对可漂白的污点的清洗作用。然而,就亲脂性污点而言,该组合的清洗作用与理想的效果还有一定距离。对这些污点而言用二酰基过氧化物,特别是脂族二酰基过氧化物可以获得较好的漂白作用。
US 4,154,695公开了含有二酰基过氧化物的漂白剂和洗涤剂,二酰基过氧化物与降低撞击敏感度的减敏剂成粒。
WO 93/07086公开了脲与二酰基过氧化物例如过氧化二壬酰的包合物作为洗涤剂中漂白组分的用途。
WO 97/18289公开了粉状或颗粒状洗碗洗涤剂,它制备包括首先将包含二酰基过氧化物的颗粒与液态的分散剂混合,然后与配制品中其它组分混合。所述分散剂包括羧化多糖,特别是淀粉、纤维素和海藻酸盐。
WO 98/11189和WO 00/27990公开了液态酸性织物漂白剂,它包括脂族二酰基过氧化物,例如过氧化二月桂酰,为乳状液或微乳状液。
US 4,515,928公开了二酰基过氧化物的液态含水分散体,它包括表面活性剂作为分散剂并包括多元醇、单糖或碱土金属盐作为防冻剂。所述用于乳化二酰基过氧化物的任选添加剂包括植物胶,例如淀粉、明胶、果胶和海藻酸钠。
US 6,602,837公开了液态碱性洗涤剂配制品,它含有二酰基过氧化物颗粒和螯合络合剂。该配制品还可以含有分散剂,并且所述的多种分散剂也包括羧化多糖,尤其是海藻酸盐。
GB 1390503公开了液态或凝胶洗涤剂,它含有凝胶胶囊,其中核心材料用聚合物凝胶包封。所述凝胶胶囊是用毛细管对核心材料和环状喷嘴对聚合物溶液共挤出制得的;另外描述了具有相同效果的可选方法。合适的聚合物凝胶材料包括多糖,特别是角叉菜聚糖(carrageenans)、瓜尔胶、海藻酸和支链淀粉和果胶,例如低甲氧基化酰胺基果胶和低甲氧基化柑桔果胶。提及的一种可能的核心材料是漂白剂,但是没有具体说明其结构。GB 1 390 503在第3页第76-79行还教导在有钙离子的情况下不应使用海藻酸盐。
现有技术中已知含有二酰基过氧化物的清洁组合物的配制品,实际上当它们含有可以与二酰基过氧化物反应的碱性反应性和/或氧化敏感组分时贮藏稳定性仍然不足。因此需要以可以可靠生产和贮藏的形式配制的二酰基过氧化物并且可用于清洁组合物配制品,与清洁组合物配制品中的组分没有任何不希望的反应。
本发明提供了含至少一种经金属离子交联的多糖的基质和埋入该基质中的二酰基过氧化物颗粒的丸粒。
本发明还提供了这种丸粒的制备方法,包括以下步骤
a)制备一含水悬浮体,其中将二酰基过氧化物颗粒悬浮,并且其中将至少一种可由金属离子交联的多糖溶解,和
b)将悬浮体a)的液滴加入到含有将所述多糖交联的金属离子的溶液中。
本发明还提供了含本发明的丸粒和至少一种阴离子表面活性剂和/或非离子表面活性剂的清洁组合物。
本发明的丸粒包括至少一种经金属离子交联的多糖的基质。术语“基质”是指包围埋入其中的二酰基过氧化物颗粒的固相,并且在含水介质中,在交联金属离子与非交联金属离子部分或完全交换的情况下,所述基质进入溶液,使得埋入基质的二酰基过氧化物颗粒释放。
用于基质的合适多糖包括所有水溶性多糖,它可经金属离子交联得到水不溶性凝胶。优选含羧酸基团的多糖,优选果胶、海藻酸盐和角叉菜聚糖。本领域技术人员从Ullmann’s Encyclopedia ofIndustrial Chemistry Vol.A25、p24-45已知可以经金属离子交联的果胶、海藻酸盐和角叉菜聚糖。
在特别优选的实施方案中,多糖是海藻酸盐或甲氧基化度小于50mol%的果胶,并且交联金属离子是钙离子。
在另一特别优选的实施方案中,多糖是角叉菜聚糖并且交联金属离子是钾离子。
本发明丸粒的基质优选含有大于50重量%的经金属离子交联的多糖,更优选大于80重量%。除了经金属离子交联的多糖之外,本发明丸粒的基质还可以含有其它组分,例如崩解剂。
合适的崩解剂是本领域技术人员已知的所有物质,其中当本发明的丸粒与含水介质接触时,崩解剂促进埋入基质的二酰基过氧化物颗粒释放。合适的崩解剂例如是碳酸氢钠和柠檬酸的混合物。
本发明的丸粒还含有埋入基质中的二酰基过氧化物颗粒。二酰基过氧化物是通式为R1-C(O)OOC(O)-R2的化合物,其中R1和R2各自是有机基团。本发明的丸粒优选含有脂族二酰基过氧化物颗粒,其中R1和R2各自独立地是具有8-20个碳原子的烷基。二酰基过氧化物颗粒优选具有大于40℃的熔点。本发明的丸粒更优选含有过氧化二正癸酰(R=正壬基)、过氧化二正十一烷酰(R=正癸基)或过氧化二月桂酰(R=正十一烷基)的埋入颗粒。
埋入基质中的二酰基过氧化物颗粒优选质量平均粒径d50在5-100μm的范围内,更优选在10-50μm的范围内。通过选择在该范围内的粒径,首先,获得本发明丸粒的良好贮藏稳定性,其次,在从丸粒的基质中释放二酰基过氧化物时确保释放颗粒的大表面积,这样获得快的漂白作用。
在本发明的丸粒中,埋入基质的二酰基过氧化物颗粒的比例优选在30-97重量%的范围内,特别是60-90重量%。在该范围内,首先,保证基质完全包封二酰基过氧化物颗粒并因此保证了良好的贮藏稳定性,其次,获得丸粒中高比例的漂白活性成分。
本发明的丸粒优选为球形。本发明丸粒的尺寸可以在宽范围内选择。为了用于固态颗粒清洁组合物,本发明的丸粒优选质量平均粒径d50在0.4-2mm的范围内,直径小于0.2mm的丸粒的比例更优选小于10重量%。为了用于液态或凝胶清洁组合物,本发明的丸粒优选平均粒径d50在0.1-1.2mm的范围内,更优选0.3-0.8mm。
本发明的丸粒的优点在于它们可以稳定地贮藏,并且在贮藏期间,仅仅缓慢地失去活性氧并且具有低的结块趋势。本发明的丸粒在清洁组合物配制品,特别是在含具有碱性作用的组分的配制品中,也具有高的贮藏稳定性。
制备本发明的丸粒的方法包括至少两步,第一步包括制备含水悬浮体,其中悬浮二酰基过氧化物颗粒并且其中溶解至少一种可由金属离子交联的多糖,并且第二步包括将第一步中形成的悬浮体液滴加入到含将多糖交联的金属离子的溶液中。
为了制备第一步中的含水悬浮体,优选使用如上所述本发明丸粒优选的多糖和二酰基过氧化物颗粒。
多糖在含水悬浮体中的比例优选在0.5-5重量%的范围内,更优选1-2重量%。二酰基过氧化物颗粒在含水悬浮体中的比例优选在1-15重量%的范围内,更优选6-12重量%。
第一步制得的含水悬浮体优选还包含减慢或者防止二酰基过氧化物颗粒沉淀的分散剂。分散剂在含水悬浮体中的比例优选在0.1-5重量%的范围内。用于二酰基过氧化物的合适的分散剂对本领域技术人员为已知,例如可以从US 3,988,261,第10栏第8行至第12栏第53行得知。
在第一步中,含水悬浮体优选通过将二酰基过氧化物的含水悬浮体与可以经金属离子交联的多糖的水溶液混合制得。二酰基过氧化物的含水悬浮体可商购获得,例如以商品名LP-40-SAQ从Degussa获得的过氧化二月桂酰,为40重量%的悬浮体。
在本发明方法的第二步中,将第一步制得的悬浮体的液滴加入到含将多糖交联的金属离子的溶液中。该溶液中金属离子的浓度经过选择,使得得自第一步的悬浮体中溶解的多糖经金属离子交联,得到水不溶性凝胶。第二步所用的溶液中金属离子的浓度优选在0.01-1mol/l的范围内,更优选0.05-0.5mol/l。
在将第一步的悬浮体液滴加入到含交联金属离子的溶液中时,最初围绕加入到的每一液滴形成交联的多糖凝胶的皮层。随着金属离子扩散到液滴内部,由此包封的液滴随后硬化,得到本发明的丸粒。
用于该方法第二步的溶液包含交联金属离子,优选为氯化物盐形式,特别是为氯化钙形式的钙离子,或者为氯化钾形式的钾离子。
将第一步制得的悬浮体的液滴加入到含将多糖交联的金属离子的溶液可以通过本领域技术人员已知的加入液滴的任意方法进行。在该方法的一个优选实施方案中,通过一个或多个振动喷嘴将悬浮体液滴加入到含金属离子的溶液中,选择振动的振幅和频率使得形成均匀大小的液滴。该方法的该实施方案能够制备粒径分布窄的本发明丸粒。
优选在接下来的步骤中将本发明方法第二步获得的丸粒与液相分离,然后干燥。为了从液相中取出丸粒并接着干燥,可以使用本领域技术人员已知的任意固/液分离方法和干燥方法。例如通过过滤、倾析或离心可以从液相中取出丸粒。丸粒可以优选通过如下方式干燥:真空干燥、在气流中流化床干燥、或者通过将颗粒悬浮在除水溶剂,优选甲醇、乙醇或异丙醇中。优选进行干燥使水分含量降低至小于50重量%,更优选小于20重量%。优选在0-50℃范围内的丸粒温度下进行干燥。为了干燥丸粒,还可以使用高于埋入基质中的二酰基过氧化物的熔点的温度,而不会使丸粒有任何结块。
由于二酰基过氧化物不需要加工成纯态,尤其是不在升温下,如在加工二酰基过氧化物熔融物的过程中,因此本发明的方法可以特别可靠地实施。本发明的方法还能够制备粒径分布窄的丸粒,它们在颗粒清洁组合物配制品中不趋向于分聚(segregate)。
本发明的丸粒可以有益地用作清洁组合物中的漂白组分。本发明上下文中的清洁组合物是含有至少一种阴离子表面活性剂和/或非离子表面活性剂并且适合与水组合清洗表面的所有配制品。本发明上下文优选的清洁组合物的形式是适用于在含水清洗液中清洁织物的洗涤剂形式。本发明上下文优选的清洁组合物的另一形式是适用于机洗餐具和刀具的洗碗机洗涤剂形式。
本发明还提供了含本发明丸粒的清洁组合物。本发明的清洁组合物包括本发明的丸粒,以清洗组合物的总量为基础丸粒的量优选为1-40重量%。
本发明的清洁组合物的外形可以是固态,并且除了本发明的丸粒之外,还可以包含粉状或颗粒状的其它组分。它们还可以包括压制成型体,这种情况下本发明的丸粒可以是压制成型体的一部分。这种为挤出物、丸粒、砖状物(briquette)或片剂形式的压制成型体可以通过压制聚集的方法,特别是通过挤出、扭压(strand pressing)、冲压、碾压或压片制得。本发明的清洁组合物还可以包含用于进行压制聚集的粘合剂,其在压制聚集过程中赋予成型体更高硬度。然而,就包含压制成型体的本发明的清洁组合物而言,优选不使用任何附加的粘合剂,并且洗涤活性组分之一,例如非离子表面活性剂,实现粘合剂的功能。
本发明的清洁组合物还可以为液态或凝胶状并含有分散于液相和凝胶相中的本发明的丸粒。除了本发明的丸粒之外,在液相或凝胶相中可以分散其它颗粒。优选调节液相或凝胶相的流变性使得分散其中的颗粒保持悬浮并且在贮藏期间不沉淀出。因此液相的组成优选经过选择使得它具有触变型或假塑性流动性。为了建立这种流动性,可以添加悬浮助剂如膨胀性粘土,特别是蒙脱石、沉淀和热解硅石、植物胶,特别是黄原胶,和聚合胶凝剂如含含羧基的乙烯基聚合物。
液态或凝胶状含大于5重量%的水的本发明的清洁组合物优选另外还含有溶解状态的金属离子,其浓度使得本发明丸粒中存在的多糖交联。金属离子在液态或凝胶清洁组合物中的浓度优选经过选择,使得使用所需清洁组合物的情况下,用水稀释获得足够低的金属离子浓度,从而,由于相对低的交联度,多糖进入溶液并释放埋入的二酰基过氧化物颗粒。
本发明的清洁组合物,除了含有本发明的丸粒和至少一种阴离子表面活性剂和/或非离子表面活性剂之外,还可以含有其它组分如阳离子表面活性剂、助洗剂(builders)、碱性组分、过酸盐、漂白活化剂、酶、螯合络合剂、灰色化抑制剂、抑泡剂、光学增白剂、香料和染料。
合适的阴离子表面活性剂例如有具有磺酸盐基团的表面活性剂,优选烷基苯磺酸盐、烷基磺酸盐、α-烯烃磺酸盐、α-磺基脂肪酸酯或磺基琥珀酸酯。在为烷基苯磺酸盐的情况下,优选具有8-20个碳原子,特别是具有10-16个碳原子的直链或枝化烷基的烷基苯磺酸盐。优选的烷基磺酸盐是具有12-18个碳原子的直链烷基链的那些。在为α-烯烃磺酸盐的情况下,优选使用具有12-18个碳原子的α-烯烃的磺化反应产物。在α-磺基脂肪酸酯中,优选由具有12-18个碳原子的脂肪酸与具有1-3个碳原子的短链醇形成的脂肪酸酯的磺化产物。合适的阴离子表面活性剂也是在分子中具有硫酸盐的表面活性剂,优选烷基硫酸盐和醚硫酸盐。
优选的烷基硫酸盐是具有12-18个碳原子的直链烷基的那些。β-枝化的烷基硫酸盐、和在最长烷基链的中间取代有一个或多个烷基的烷基硫酸盐也适合。优选的醚硫酸盐是烷基醚硫酸盐,它是通过用2-6个环氧乙烷单元乙氧基化具有12-18个碳原子的直链醇,接着硫酸盐化制得的。所用的阴离子表面活性剂最终也可以是皂,例如以下酸的碱金属盐:月桂酸、肉豆蔻酸、棕榈酸、硬脂酸和/或天然脂肪酸混合物,例如椰子脂肪酸、棕榈仁脂肪酸或牛油脂肪酸。
合适的非离子表面活性剂例如有烷氧基化化合物,特别是乙氧基化和丙氧基化化合物。特别合适的化合物是烷基酚或脂肪醇与1-50mol,优选1-10mol的环氧乙烷和/或环氧丙烷的缩合产物。同样合适的有多羟基脂肪酸酰胺,其中具有一个或多个羟基的有机基团(也可以是烷氧基化的)与酰胺氮相连。同样合适的非离子表面活性剂有具有8-22个碳原子,特别是具有12-18个碳原子的直链或枝化烷基、和优选得自葡萄糖的单-或二糖苷基团的烷基糖苷。
合适的阳离子表面活性剂例如有具有与氮相连的C6-至C18-烷基和一个或两个羟基烷基的一烷氧基化季胺和二烷氧基化季胺。
本发明的清洁组合物还可以含有在使用过程中能够粘合溶解于水中的钙离子和镁离子的助洗剂。合适的助洗剂是碱金属磷酸盐和碱金属多磷酸盐,特别是三聚磷酸五钠;水溶性和水不溶性钠硅酸盐,特别是式Na5Si2O5的片状硅酸盐;结构A、X和/或P的沸石;以及柠檬酸三钠。除了助洗剂之外,还可以使用有机共助洗剂(cobuilders),例如聚丙烯酸、聚天冬氨酸、和/或与甲基丙烯酸、丙烯醛或含磺酸的乙烯基单体的丙烯酸共聚物、和它们的碱金属盐。
根据需要,本发明的清洁组合物还可以含有碱性组分,碱性组分使清洁组合物水溶液的pH在8-12的范围内。合适的碱性组分特别是碳酸钠、碳酸氢三钠、偏硅酸钠和其它易溶性碱金属硅酸盐。
本发明的清洁组合物,除了含有本发明的丸粒之外,还可以含有过酸盐,例如碱金属过硼酸盐、碱金属碳酸盐过氧化氢合物、碱金属过硅酸盐、碱金属过硫酸盐、碱金属过磷酸盐和碱金属过焦磷酸盐,由此在含水介质中释放过氧化氢。优选的过酸盐是过硼酸钠四水合物、过硼酸钠一水合物和碳酸钠过氧化氢合物。特别优选碳酸钠过氧化氢合物。用于液体洗涤剂的合适的碳酸钠过氧化氢合物从WO 2004/056955已知。通过将含二酰基过氧化物的本发明的丸粒与释放过氧化氢的过酸盐组合,获得协同漂白作用,它超过单一组分的作用,特别是当清洁组合物含有碱性组分时尤其如此。推测协同作用基于结构R-C(O)OOC(O)-R的二酰基过氧化物与过氧化氢的反应,得到两个结构R-C(O)OOH的过羧酸分子,推测所述反应通过过氧化氢阴离子HOO-攻击二酰基过氧化物进行的。
本发明的清洁组合物的合适的漂白活化剂尤其是具有一个或多个与氮或与氧相连的可过水解(perhydrolyzable)的酰基的化合物,它与清洁组合物水溶液中过碳酸钠颗粒释放的过氧化氢反应得到过氧羧酸。这种化合物的实例有聚酰基化烷撑二胺,例如特别是四乙酰基乙二胺(TAED);酰基化三嗪衍生物,特别是1,5-二乙酰基-2,4-二氧代六氢-1,3,5-三嗪(DADHT);酰基化甘脲,特别是四乙酰基甘脲(TAGU);N-丙烯酰胺类,特别是N-壬酰基琥珀酰胺(NOSI);酰基化苯酚磺酸盐,特别是正-壬酰基-或异壬酰基氧基苯磺酸盐(正-或异-NOBS);羧酸酐例如邻苯二甲酸酐;酰基化多元醇例如乙二醇二乙酸酯、2,5-二乙酰氧基-2,5-二氢呋喃、乙酰基化山梨糖醇和甘露糖醇和乙酰基化糖例如五乙酰基葡萄糖;烯醇酯;和n-酰基化内酰胺,特别是N-酰基己内酰胺和N-酰基戊内酰胺。同样合适作为漂白活化剂的有氨基官能化腈及其盐(nitrile quats),它例如可从杂志TensideSurf.Det.1997,34(6),p 404-409得知。所用漂白活化剂也可以是可以活化过氧化氢用于漂白污点除去的过渡金属络合物。合适的过渡金属络合物例如从以下得知:EP-A 0 544 490第2页第4行-第3页第57行;WO 00/52124第5页第9行至第8页第7行和第8页第19行至第11页第14行;WO 04/039932第2页第25行至第10页第21行;WO 00/12808第6页第29行至第33页第29行;WO 00/60043第6页第9行至第17页第22行;WO 00/27975第2页第1行至第18行和第3页第7行至第4页第6行;WO 01/05925第1页第28行至第3页第14行;WO 99/64156第2页第25行至第9页第18行;和GB-A 2 309 976第3页第1行至第8页第32行。
本发明的清洁组合物还可以含有强化清洁作用的酶,特别是脂肪酶、角质酶(cutinases)、淀粉酶、中性和碱性蛋白酶、酯酶、纤维素酶、果胶酶、乳糖酶和/或过氧化物酶。这些酶可以吸附在载体物质上或者可以埋入涂布材料中以防它们分解。
本发明的清洁组合物还可以含有用于过渡金属的螯合物络合剂,用其可以防止洗涤液或清洁组合物水溶液中活性氧化合物的催化分解,并且通过交联金属离子的络合可以加速本发明丸粒中多糖基质的溶解。合适的有例如膦酸酯如羟基乙烷-1,1-二膦酸酯、次氮基三亚甲基膦酸酯、二亚乙基三胺五(亚甲基膦酸酯)、乙二胺四(亚甲基膦酸酯)、六亚甲基二胺四(亚甲基膦酸酯)和它们的碱金属盐。同样合适的有次氮基三乙酸和聚氨基羧酸,尤其是例如乙二胺四乙酸、二亚乙基三胺五乙酸、乙二胺-N,N’-二琥珀酸、甲基甘氨酸二乙酸和聚天冬氨酸,和它们的碱金属盐和铵盐。最后,多元羧酸,特别是羟基羧酸,例如特别是酒石酸和柠檬酸,也适合作为螯合络合剂。
本发明的清洁组合物还可以含有再沉淀抑制剂,它使分离的污物悬浮并防止该污物再次附着于清洁过的表面。合适的再沉淀抑制剂例如有纤维素醚类如羧甲基纤维素及其碱金属盐、甲基纤维素、羟乙基纤维素和羟丙基纤维素。聚乙烯吡咯烷酮同样适合。
本发明的清洁组合物还可以含有减少清洁水溶液中泡沫形成的抑泡剂。合适的抑泡剂例如有有机聚硅氧烷类如聚二甲基硅氧烷、石蜡和/或蜡、及它们与细粒二氧化硅的混合物。
本发明的清洁组合物可以任选含有增白剂,它附着于纤维上,吸收紫外线范围的光并以蓝色发荧光以弥补纤维发黄。合适的光学增白剂例如有二氨基二苯乙烯二磺酸的衍生物如4,4’-双(2-苯胺基-4-吗啉基-1,3,5-三嗪基-6-氨基)二苯乙烯-2,2’-二磺酸或取代的二苯基苯乙烯基的碱金属盐如4,4’-双(2-磺基苯乙烯基)联苯的碱金属盐。
本发明的清洁组合物最后还可以含有香料和染料。
液态或凝胶状的本发明清洁组合物另外还可以含有不超过30重量%的有机溶剂,例如甲醇、乙醇、正丙醇、异丙醇、正丁醇、乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、甘油、二甘醇、乙二醇甲基醚、乙醇胺、二乙醇胺和/或三乙醇胺。
与含非本发明的二酰基过氧化物颗粒的清洁组合物相比,本发明的清洁组合物呈现更好的贮藏稳定性,贮藏过程中活性氧含量的损失较低,特别是对含有碱性组分的清洁组合物尤其如此。与此同时,对清洁组合物的氧化敏感组分,例如酶、光学增白剂、香料和染料的氧化攻击降低。
本发明的清洁组合物的一个优选实施方案是片状的机洗碗机洗涤剂的清洁组合物,所述片剂也含有银防蚀材料以及本发明的丸粒。本发明中的银防蚀材料是防止或减少非铁金属,特别是银,在用机洗碗机洗涤剂机洗期间锈蚀的试剂。所用银防蚀材料优选是选自***类、苯并***类、双苯并***类、氨基***类和烷基氨基***类的一种或多种化合物。所述这类物质也可以具有取代基,例如具有1-20个碳原子的直链或枝化烷基、以及乙烯基、羟基、硫醇或卤素。在为双苯并***类的情况下,优选其中两个苯并***基团各自在6位经X基团相连的化合物,其中X可以是键、任选取代有一个或多个C1-至C4-烷基并且优选具有1-6个碳原子的直链烷基、具有至少5个碳原子的环烷基、羰基、磺酰基、氧原子或硫原子。特别优选的银腐蚀保护剂是甲苯基***。
本发明的含有银防蚀材料并为片状的机洗碗机洗涤剂,与其中二酰基过氧化物未埋入多糖基质中的机洗碗机洗涤剂相比,在机洗碗机洗涤剂贮藏期间,呈现低得多的片剂变黄。
实施例
实施例1
将25重量份的40重量%过氧化二月桂酰的含水悬浮体与75重量份的的2.5重量%海藻酸钠水溶液混合。将所得悬浮体经直径0.5mm的振动喷嘴以0.21g/s的流速、410Hz的振动频率滴加到搅拌的0.1M氯化钙水溶液中。之后,将所得球形丸粒过滤出并在30℃和减压下干燥48小时。
20℃时所得丸粒几乎不溶于去离子水中并且在4小时内没有明显变化。相反,在0.1M的EDTA溶液中,丸粒在5分钟内溶解,以悬浮体形式释放过氧化物二月桂酰颗粒。
用thermometric AB,Jrflla(瑞典)的TAM Thermal ActivityMonitor经微热量法测定在40℃的贮藏过程中的能量释放,并将48小时后的测量值计为TAM值,由此确定丸粒的贮藏稳定性。所得丸粒呈现2.3μW/g的TAM值。当48小时后能量释放的TAM值不大于10μW/g时,过氧化物足够贮藏稳定。
Claims (11)
1.一种丸粒,其包含:含有至少一种经金属离子交联的多糖的基质,和埋入该基质中的二酰基过氧化物颗粒。
2.如权利要求1所述的丸粒,
其特征在于
所述多糖选自果胶、海藻酸盐和角叉菜聚糖以及它们的混合物。
3.如权利要求2所述的丸粒,
其特征在于
所述金属离子是钙离子,并且所述多糖选自海藻酸盐和甲氧基化度小于15mol%的果胶。
4.如权利要求2所述的丸粒,
其特征在于
所述金属离子是钾离子并且所述多糖是角叉菜聚糖。
5.如权利要求1所述的丸粒,
其特征在于
所述二酰基过氧化物含有酰基R-C(O),其中R是具有8-20个碳原子的烷基,优选正壬基、正癸基或正十一烷基。
6.一种制备如权利要求1所述的丸粒的方法,包括以下步骤:
a)制备含水悬浮体,其中将二酰基过氧化物颗粒悬浮,并且其中将至少一种可由金属离子交联的多糖溶解,和
b)将悬浮体a)的液滴加入到含有将所述多糖交联的金属离子的溶液中。
7.如权利要求6所述的方法,
其特征在于
所述悬浮体还包含分散剂。
8.如权利要求6或7所述的方法,
其特征在于
在步骤a)中,将二酰基过氧化物的含水悬浮体与所述可由金属离子交联的多糖的水溶液混合。
9.如权利要求6-8任一项所述的方法,
其特征在于
将步骤b)中所得的丸粒与液相分离,然后干燥。
10.一种清洁组合物,其包含如权利要求1-5任一项所述的丸粒和至少一种阴离子表面活性剂和/或非离子表面活性剂。
11.如权利要求10所述的清洁组合物,
其特征在于
所述清洁组合物还包含选自下面的过酸盐:过硼酸钠四水合物、过硼酸钠一水合物和碳酸钠过氧化氢合物,优选碳酸钠过氧化氢合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102005044189A DE102005044189A1 (de) | 2005-09-15 | 2005-09-15 | Pellets aus Diacylperoxid in einer Polysaccharidmatrix |
DE102005044189.0 | 2005-09-15 |
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CN101243168A true CN101243168A (zh) | 2008-08-13 |
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US (1) | US20090149368A1 (zh) |
EP (1) | EP1926807A1 (zh) |
JP (1) | JP2009507974A (zh) |
KR (1) | KR100956220B1 (zh) |
CN (1) | CN101243168A (zh) |
CA (1) | CA2621471A1 (zh) |
DE (1) | DE102005044189A1 (zh) |
MX (1) | MX2008001655A (zh) |
RU (1) | RU2398011C2 (zh) |
UA (1) | UA88111C2 (zh) |
WO (1) | WO2007031387A1 (zh) |
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DE102005020552A1 (de) * | 2005-05-03 | 2006-11-09 | Degussa Ag | Verfahren zur chemischen Modifizierung von Polysacchariden |
DE102006023937A1 (de) * | 2006-05-19 | 2007-11-22 | Henkel Kgaa | Verkapselte Bleichmittelteilchen |
DE102007004054A1 (de) * | 2007-01-22 | 2008-07-24 | Henkel Ag & Co. Kgaa | Verfahren zur Herstellung teilchenförmiger Bleichmittelzusammensetzungen |
DE102009001786A1 (de) * | 2009-03-24 | 2010-10-14 | Henkel Ag & Co. Kgaa | Schonendes Bleichmittel |
GB201003892D0 (en) * | 2010-03-09 | 2010-04-21 | Reckitt Benckiser Nv | Detergent composition |
US8440265B2 (en) | 2010-04-15 | 2013-05-14 | Appleton Papers Inc. | Water- and heat-resistant scratch-and-sniff coating |
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US2464081A (en) * | 1946-03-08 | 1949-03-08 | Staley Mfg Co A E | Modification of starch |
GB1538744A (en) * | 1975-05-13 | 1979-01-24 | Interox Chemicals Ltd | Bleaching composition containing diacyl peroxides |
US4389419A (en) * | 1980-11-10 | 1983-06-21 | Damon Corporation | Vitamin encapsulation |
US4515928A (en) * | 1982-07-20 | 1985-05-07 | Ppg Industries, Inc. | Organic peroxide composition containing trihydric alcohol, alkali or alkaline earth metal chloride, or monosaccharide |
US4908233A (en) * | 1985-05-08 | 1990-03-13 | Lion Corporation | Production of microcapsules by simple coacervation |
DE3604795A1 (de) * | 1986-02-15 | 1987-08-20 | Degussa | Verfahren zur trockenkationisierung von galaktomannanen |
DE3604796A1 (de) * | 1986-02-15 | 1987-08-20 | Degussa | Verfahren zur trockenkationisierung von staerke |
DE3804509A1 (de) * | 1988-02-13 | 1989-08-24 | Degussa | Kontinuierliches verfahren zur herstellung von natriumperborat-granulaten |
DE4225761A1 (de) * | 1992-08-04 | 1994-02-10 | Wolff Walsrode Ag | Verfahren zur Herstellung einer lagerstabilen niedrigveresterten alkohol- oder wasserfeuchten Nitrocellulose |
US5597791A (en) | 1994-10-13 | 1997-01-28 | Fmc Corporation | Stable peracid sols, gels and solids |
JPH10510308A (ja) | 1994-12-09 | 1998-10-06 | ザ、プロクター、エンド、ギャンブル、カンパニー | ジアシルペルオキシドの粒子を含む自動食器洗浄組成物 |
EP0717102A1 (en) * | 1994-12-09 | 1996-06-19 | The Procter & Gamble Company | Liquid automatic dishwashing detergent composition containing diacyl peroxides |
CA2215949A1 (en) | 1995-04-17 | 1996-10-24 | The Procter & Gamble Company | Preparation and use of composite particles containing diacyl peroxide |
FR2740357B1 (fr) * | 1995-10-25 | 1997-11-28 | Rhone Poulenc Chimie | Granules redispersables dans l'eau comprenant une matiere active sous forme liquide et un tensio-actif non ionique du type alcoxyles |
US5663133A (en) * | 1995-11-06 | 1997-09-02 | The Procter & Gamble Company | Process for making automatic dishwashing composition containing diacyl peroxide |
US6624136B2 (en) * | 1998-02-02 | 2003-09-23 | Rhodia Chimie | Water-dispersible granules comprising a fragrance in a water-soluble or water-dispersible matrix, and process for their preparation |
ATE227770T1 (de) * | 1999-02-02 | 2002-11-15 | Quest Int | Reinigungsmittelzusammensetzung |
US20100293669A2 (en) * | 1999-05-06 | 2010-11-18 | Jingdong Liu | Nucleic Acid Molecules and Other Molecules Associated with Plants and Uses Thereof for Plant Improvement |
AR037699A1 (es) * | 2001-12-04 | 2004-12-01 | Monsanto Technology Llc | Maiz transgenico con fenotipo mejorado |
DE10164110A1 (de) * | 2001-12-24 | 2003-07-10 | Dragoco Gerberding Co Ag | Mononuklear gefüllte Mikrokapseln |
MXPA04007256A (es) * | 2002-01-29 | 2005-03-31 | Valtion Teknillinen Tutkimusje | Metodo para fabricar carbamato de celulosa. |
US7053034B2 (en) * | 2002-04-10 | 2006-05-30 | Salvona, Llc | Targeted controlled delivery compositions activated by changes in pH or salt concentration |
US6740631B2 (en) * | 2002-04-26 | 2004-05-25 | Adi Shefer | Multi component controlled delivery system for fabric care products |
US6825161B2 (en) * | 2002-04-26 | 2004-11-30 | Salvona Llc | Multi component controlled delivery system for soap bars |
ATE407194T1 (de) * | 2002-08-07 | 2008-09-15 | Procter & Gamble | Waschmittelzusammensetzung |
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2006
- 2006-08-21 MX MX2008001655A patent/MX2008001655A/es unknown
- 2006-08-21 EP EP06778292A patent/EP1926807A1/de not_active Withdrawn
- 2006-08-21 RU RU2008114049/15A patent/RU2398011C2/ru not_active IP Right Cessation
- 2006-08-21 JP JP2008530459A patent/JP2009507974A/ja not_active Withdrawn
- 2006-08-21 KR KR1020087006398A patent/KR100956220B1/ko not_active IP Right Cessation
- 2006-08-21 CN CNA2006800302202A patent/CN101243168A/zh active Pending
- 2006-08-21 CA CA002621471A patent/CA2621471A1/en not_active Abandoned
- 2006-08-21 WO PCT/EP2006/065504 patent/WO2007031387A1/de active Application Filing
- 2006-08-21 US US11/991,776 patent/US20090149368A1/en not_active Abandoned
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KR20080041257A (ko) | 2008-05-09 |
DE102005044189A1 (de) | 2007-03-22 |
US20090149368A1 (en) | 2009-06-11 |
UA88111C2 (ru) | 2009-09-10 |
KR100956220B1 (ko) | 2010-05-04 |
CA2621471A1 (en) | 2007-03-22 |
RU2008114049A (ru) | 2009-10-20 |
WO2007031387A1 (de) | 2007-03-22 |
RU2398011C2 (ru) | 2010-08-27 |
JP2009507974A (ja) | 2009-02-26 |
MX2008001655A (es) | 2008-04-07 |
EP1926807A1 (de) | 2008-06-04 |
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