CN103168096B - 洗衣洗涤剂颗粒 - Google Patents
洗衣洗涤剂颗粒 Download PDFInfo
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- CN103168096B CN103168096B CN201180049310.7A CN201180049310A CN103168096B CN 103168096 B CN103168096 B CN 103168096B CN 201180049310 A CN201180049310 A CN 201180049310A CN 103168096 B CN103168096 B CN 103168096B
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- Prior art keywords
- pigment
- coated detergent
- detergent particle
- weight
- red
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 13
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Classifications
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
本发明提供了小扁豆状或盘状的涂覆洗涤剂颗粒,其具有正交尺寸x、y和z,其中x为1-2mm,y为2-8mm,且z为2-8mm,其中该颗粒包含:(i)40-90重量%的选自阴离子型表面活性剂和非离子型表面活性剂的表面活性剂;(ii)1-40重量%水溶性无机盐;和(iii)0.0001-0.1重量%的颜料,其中该颜料选自有机和无机颜料,其中所述无机盐作为涂层存在于所述洗涤剂颗粒上,而所述表面活性剂和所述颜料作为核存在。
Description
发明领域
本发明涉及大的洗涤剂颗粒。
发明背景
对有色的固体洗涤剂产品存在需求,但不幸地,发现这样的产品引起不可接受的染色。
WO9932599描述了制造洗衣洗涤剂颗粒的方法,其为挤出方法,其中将增效剂和表面活性剂(该表面活性剂包含硫酸化或磺酸化的阴离子表面活性剂作为主要组分)进料到挤出机内,在至少40℃,优选至少60℃的温度下机械加工,并通过具有多个挤出孔的挤出头挤出。在大部分实施例中,将表面活性剂与增效剂以超过1份增效剂比2份表面活性剂的重量比一起进料到所述挤出机中。所述挤出物显然需要进一步干燥。在实施例6中,将PAS糊状物干燥并挤出。这样的PAS条状物质(noodle)是现有技术中熟知的。如实施例2所述的,条状物质通常是圆柱形的,并且它们的长度超过它们的直径。
US7022660公开了制备具有涂层的洗涤剂颗粒的方法。
发明概述
令人惊讶地,我们发现了在核中用颜料着色的大的涂覆洗衣洗涤剂颗粒产生低水平的染色。
在一个方面中,本发明提供了涂覆洗涤剂颗粒,具有正交尺寸x、y和z,其中x为1-2mm,y为2-8mm(优选3-8mm),而z为2-8mm(优选3-8mm),其中所述颗粒包含:
(i)40-90重量%,优选50-90重量%的表面活性剂,其选自:阴离子型表面活性剂和非离子型表面活性剂;
(ii)1-40重量%,优选20-40重量%的水溶性无机盐;和
(iii)0.0001-0.1重量%的颜料,优选0.001-0.01重量%的颜料,其中所述颜料选自有机和无机颜料,
其中所述无机盐作为涂层存在于所述洗衣洗涤剂颗粒上,而所述表面活性剂和所述颜料作为核存在。
除非另外指出,所有重量%指的是颗粒中以干重计的总百分比。
在另一个方面,本发明提供了一种涂覆的洗涤剂颗粒,它是表面活性剂多于无机固体的浓缩制剂。只有通过使涂层包覆柔软的表面活性剂才能产生这种洗涤所需的单位用量减少的颗粒状浓缩物。向所述核添加溶剂会使所述颗粒转变为液态制剂。另一方面,具有更高的无机固体量会产生较低浓缩的制剂;无机物含量高将返回到常规的低表面活性剂浓度的粒状粉末。本发明的涂覆洗涤剂颗粒介于这两种常规(液体和粒状)形式之间。
发明详述
形状
优选地,所述涂覆的洗衣用洗涤剂颗粒是曲面的。
涂覆的洗衣用洗涤剂颗粒可以是扁豆形的(形状像完整的干的小扁豆)、即扁椭球体,其中z和y是赤道直径,且x是极直径;优选y=z。
所述涂覆的洗衣用洗涤剂颗粒可以是圆盘形状。
优选地,涂覆的洗衣用洗涤剂颗粒没有孔;也就是说,所述涂覆的洗衣用洗涤剂颗粒没有贯穿过核的贯通通道,即所述涂覆的洗涤剂颗粒具有的拓扑亏格(topologic genus)为零。
核
表面活性剂
涂覆的洗衣用洗涤剂颗粒包含40至90重量%、优选50至90重量%的表面活性剂,最优选70至90重量%。一般而言,表面活性剂体系的非离子型和阴离子型表面活性剂可以选自下列文献描述的表面活性剂:″表面活性剂(Surface Active Agents)″,Schwartz&Perry第一卷, Interscience,1949年,和Schwartz、Perry&Berch第二卷,Interscience,1958年;在Manufacturing Confectioners Company出版的现行版″McCutcheon的乳化剂和洗涤剂(McCutcheon′s Emulsifiers andDetergents)″中或在H.Stache的第二版,Carl Hauser Verlag,1981年的″Tenside-Taschenbuch″中。优选地,所使用的表面活性剂是饱和的。
阴离子型表面活性剂
可以使用的合适的阴离子型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,所用的术语烷基包括较高级酰基的烷基部分。合适的合成的阴离子型洗涤剂化合物的例子是烷基硫酸钠和烷基硫酸钾,尤其是通过将从例如牛脂或椰子油产生的C8至C18的高级醇硫酸化而得到的那些;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;和烷基甘油基醚硫酸钠,尤其是从牛脂或椰子油衍生的较高级醇和从石油衍生的合成醇的那些醚。最优选的阴离子型表面活性剂是月桂基醚硫酸钠(SLES),特别优选具有1至3个乙氧基,C10至C15的烷基苯磺酸钠和C12至C18的烷基硫酸钠。适用的表面活性剂还有例如EP-A-328177(Unilever)中描述的那些(其显示出耐盐析性),EP-A-070074中描述的烷基多聚糖苷,和烷基单糖苷。所述表面活性剂的链可以是支链的或直链的。
皂也可以存在。使用的脂肪酸皂优选含有约16至约22个碳原子,优选为直链构型。皂的阴离子贡献优选是总阴离子的0至30重量%。
优选地,至少50重量%的阴离子型表面活性剂选自:C11至C15的烷基苯磺酸钠;和C12至C18的烷基硫酸钠。甚至更优选地,所述阴离子型表面活性剂是C11至C15的烷基苯磺酸钠。
优选地,所述涂覆的洗衣用洗涤剂颗粒中存在的阴离子型表面活性剂的水平是总表面活性剂的15至85重量%,更优选50至80重量%。
非离子型表面活性剂
可以使用的合适的非离子型洗涤剂化合物特别包括,具有疏水基和 反应性氢原子的化合物(例如脂族醇、酸、酰胺或烷基酚)与环氧烷(尤其是单独的环氧乙烷或其与环氧丙烷一起)的反应产物。优选的非离子型洗涤剂化合物是C6至C22的烷基酚-环氧乙烷缩合物,通常为5-25EO、即每分子中含5至25个环氧乙烷单元,以及直链或支链的脂族C8至C18伯或仲醇与环氧乙烷的缩合产物,通常5-50EO。优选地,所述非离子型化合物是10-50EO,更优选20-35EO。特别优选烷基乙氧基化物。
优选非离子型表面活性剂在所述涂覆的洗衣用洗涤剂颗粒中存在的水平是总表面活性剂的5至75重量%,更优选为总表面活性剂的10至40重量%。
阳离子型表面活性剂可以作为次要成分存在,其水平优选是总表面活性剂的0至5重量%。
优选地,在干燥之前将所有表面活性剂混合在一起。可以使用常规的混合设备。可以通过挤出或碾压形成洗衣用洗涤剂颗粒的表面活性剂核,随后用无机盐涂覆。
耐钙的表面活性剂体系
在另一个方面,所使用的表面活性剂体系是耐钙的,因为这减少了对增效剂的需要,所以是优选的方案。
优选不需要存在增效剂就能在硬水中有效洗涤的表面活性剂混合物。如果它们通过了下文中提出的测试的话,这样的混合物就被称为耐钙的表面活性剂混合物。然而,本发明也可以用于软水洗涤,所述软水是天然存在的或利用软水剂制成的。在这种情况下,耐钙性不再重要,并且可以使用并非耐钙的那些混合物。
如下测试表面活性剂混合物的耐钙性:
所讨论的表面活性剂混合物制成每升水0.7g表面活性剂固体的浓度,所述水含有足够的钙离子以产生40的French硬度(4x10-3摩尔Ca2+)。向所述溶液添加其他不含硬度离子的电解质,例如氯化钠、硫酸钠和氢氧化钠,以将离子强度调节到0.05M和将pH调节到10。在样品制备之后15分钟测量波长540nm的光通过4mm样品的吸收。做十次测量并计算平均值。给出小于0.08的吸收值的样品被认为是耐钙的。
满足上述耐钙性测试的表面活性剂混合物的例子包括下述的那些:其具有LAS表面活性剂(本身不是耐钙的)作为主要部分与一种或多种耐钙的其他表面活性剂(助表面活性剂)混合,产生充分耐钙以致可在很少或没有增效剂下使用并通过所给定的测试的混合物。合适的耐钙的助表面活性剂包括SLES 1-7EO,和烷基-乙氧基化物非离子型表面活性剂,特别是熔点低于40℃的那些。
LAS/SLES表面活性剂混合物具有优于LAS非离子型表面活性剂混合物的泡沫特性,因此是需要高水平泡沫的手洗制剂中优选的。SLES可以使用的水平最多为表面活性剂混合物的30重量%。
水溶性无机盐
水溶性无机盐优选选自碳酸钠、氯化钠、硅酸钠和硫酸钠、或其混合物,最优选总水溶性无机盐的70至100重量%是碳酸钠。水溶性无机盐在颗粒上作为涂层存在。水溶性无机盐优选以将所述洗衣用洗涤剂颗粒的粘度降低至一个值的水平存在,在该值下所述颗粒是自由流动的。
本领域技术人员将理解,虽然可以施加具有相同或不同涂层材料的多个涂层,但为操作简单和使涂覆的厚度最大化,优选单层涂覆。为了使洗涤剂颗粒的抗结块性能的结果最好,涂覆的量应该是所述颗粒的1至40重量%、优选20至40重量%、更优选25至35重量%。
所述涂层优选通过从水溶性无机盐的水溶液沉积而施加于表面活性剂核的表面上。或者,可以使用浆料进行涂覆。所述水溶液优选含有大于50g/L、更优选200g/L的所述盐。已经发现,所述涂覆溶液在流化床中的水性喷雾给出良好的结果,并还可以在所述流化过程期间对洗涤剂颗粒产生轻微的圆滑作用。可能需要干燥和/或冷却来完成所述过程。
优选的耐钙的涂覆洗衣用洗涤剂颗粒中的表面活性剂包含15至100重量%的阴离子型表面活性剂,所述阴离子型表面活性剂的20至30重量%是月桂基醚硫酸钠。
颜料
将颜料加入表面活性剂中并搅拌,之后形成颗粒的核。
颜料可以选自无机和有机颜料,最优选颜料是有机颜料。
颜料描述于G.Buxbaum和G.Pfaff编辑的Industrial InorganicPigments(第3版,Wiley-VCH 2005)中。合适的有机颜料描述于W.Herbst和K.Hunger编辑的Industrial Organic Pigments(第3版,Wiley-VCH2004)中。颜料列举在国际染色家协会和美国纺织品染化师协会2002(internationalSociety of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002)的染料索引中。
颜料是几乎不溶的有色颗粒,优选它们具有0.02-10μm的初级颗粒大小,其中该距离表示初级颗粒的最长尺寸。通过扫描电子显微镜来测量初级颗粒大小。最优选,有机颜料具有0.02-0.2μm的初级颗粒大小。
几乎不溶的意思是在20℃下,使用10重量%的表面活性剂溶液,水中的溶解度小于万亿分之500(ppt),优选10ppt。
有机颜料优选选自单偶氮颜料、β-萘酚颜料、萘酚AS颜料、苯并咪唑酮颜料、金属络合物颜料、异吲哚酮和异二氢吲哚颜料、酞菁颜料、喹吖啶酮颜料、二萘嵌苯和芘酮颜料、二酮吡咯-吡咯颜料、硫靛颜料、蒽醌颜料、蒽嘧啶(anthrapyrmidine)颜料、黄烷士酮(flavanthrone)颜料、蒽嵌蒽醌颜料、二噁嗪颜料和喹酞酮颜料。
偶氮和酞菁颜料是最优选的颜料类别。
优选的颜料是颜料绿8、颜料蓝28、颜料黄1、颜料黄3、颜料橙1、颜料红4、颜料红3、颜料红22、颜料红112、颜料红7、颜料棕1、颜料红5、颜料红68、颜料红51、颜料53、颜料红53:1、颜料红49、颜料红49:1、颜料红49:2、颜料红49:3、颜料红64:1、颜料红57、颜料红57:1、颜料红48、颜料红63:1、颜料黄16、颜料黄12、颜料黄13、颜料黄83、颜料橙13、颜料紫23、颜料红83、颜料蓝60、颜料蓝64、颜料橙43、颜料蓝66、颜料蓝63、颜料紫36、颜料紫19、颜料红122、颜料蓝16、颜料蓝15、颜料蓝15:1、颜料蓝15:2、颜料蓝15:3、颜料蓝15:4、颜料蓝15:6、颜料绿7、颜料绿36、颜料蓝29、颜料绿24、 颜料红101:1、颜料绿17、颜料绿18、颜料绿14、颜料棕6、颜料蓝27和颜料紫16。
颜料可以是任何颜色的,优选颜料是蓝色、紫色、绿色或红色。最优选,颜料是蓝色或紫色。
如果将颜料加入到溶液/浆料中的核前体中(这降低了该核前体的粘度),使得该核的形成不是最佳的,则例如通过白色薄膜蒸发器除去过量的溶液,例如水。
涂覆洗衣洗涤剂颗粒
优选地,涂覆洗衣洗涤剂颗粒构成包装中10-100重量%,更优选50-100重量%,甚至更优选80-100重量%,最优选90-100重量%的洗衣洗涤剂制剂。
包装是用于销售给公众的商业制剂,并且优选为0.01kg至5kg的范围,优选0.02kg至2kg,最优选0.5kg至2kg。
优选地,涂覆洗衣洗涤剂颗粒使得至少90%至100%的涂覆洗衣洗涤剂颗粒中,最大与最小的涂覆洗衣洗涤剂颗粒在x、y和z尺寸上的变化在20%、优选10%以内。
含水量
在293K和50%相对湿度下,颗粒优选包含0-15重量%的水,更优选0-10重量%,最优选1-5重量%的水。这有助于颗粒的储存稳定性及其机械性能。
其他助剂
所述涂层或核中可以存在如下所述的助剂。它们可以存在于核或涂层中。
荧光剂
涂覆的洗衣用洗涤剂颗粒优选包含荧光剂(荧光增白剂)。荧光剂是公知的,并且许多这样的荧光剂是市售的。通常,这些荧光剂以它们的碱金属盐例如钠盐的形式供应和使用。所述组合物中使用的一种或多种荧光剂的总量通常为0.005到2重量%。更优选0.01到0.1重量%。适合 用于本发明的荧光剂描述在K.Hunger编著的《工业颜料》(IndustrialPigments)第7章(2003年,Wiley-VCH ISBN 3-527-30426-6)中。
优选的荧光剂选自以下类别:二苯乙烯联苯、三嗪基氨基均二苯代乙烯、二(1,2,3-***-2-基)均二苯代乙烯、二(苯并[b]呋喃-2-基)联苯、1,3-二苯基-2-吡唑啉和香豆素。所述荧光剂优选是磺化的。
优选的荧光剂类别是:二-苯乙烯联苯化合物,例如Tinopal(商标)CBS-X,二-胺均二苯代乙烯二磺酸化合物,例如Tinopal DMS pureXtra和Blankophor(商标)HRH,和吡唑啉化合物,例如Blankophor SN。优选的荧光剂是:2(4-苯乙烯基-3-磺苯基)-2H-萘酚[1,2-d]***钠,4,4′-二{[4-苯胺基-6-(N-甲基-N-2-羟乙基)氨基-1,3,5-三嗪-2-基)]氨基}均二苯代乙烯-2-2′二磺酸二钠,4,4′-二{[4-苯胺基-6-吗啉基-1,3,5-三嗪-2-基)]氨基}均二苯代乙烯-2-2′二磺酸二钠,和4,4′-二(2-磺基苯乙烯基)联苯二钠。
TinopalDMS是4,4′-二{[4-苯胺基-6-吗啉基-1,3,5-三嗪-2-基)]氨基}均二苯代乙烯-2-2′二磺酸二钠的二钠盐。TinopalCBS是4,4′-二(2-磺基苯乙烯基)联苯二钠的二钠盐。
香料
优选所述组合物包含香料。所述香料优选为0.001到3重量%、最优选0.1到1重量%。许多合适的香料实例提供在CFTA Publications出版的CTFA(化妆品及盥洗用品、香水协会(Cosmetic,Toiletry and Fragrance Association))1992年国际买家指南(1992 International Buyers Guide),和Schnell Publishing Co.出版的OPD 1993年化学品买家目录80周年版(Chemicals Buyers Directory 80th Annual Edition)中。
制剂中存在多种香料组份是很寻常的。在本发明的组合物中,可有四种或更多种、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份。
在香料混合物中,优选15到25重量%是头香。头香由Poucher定义(Journal of the Society of Cosmetic Chemists 6(2):80[1955])。优选的头香选自柑橘油、里哪醇、乙酸里哪酯、熏衣草、二氢月桂烯醇、玫瑰醚 和顺式-3-己醇。
优选所述涂覆的洗衣用洗涤剂颗粒不含过氧漂白剂,例如过碳酸钠、过硼酸钠和过酸。
聚合物
所述组合物可以包含一种或多种其它的聚合物。实例是羧甲基纤维素、聚(乙二醇)、聚(乙烯醇)、聚乙烯亚胺、乙氧基化聚乙烯亚胺、水溶性聚酯聚合物、聚羧酸酯例如聚丙烯酸酯、马来酸/丙烯酸共聚物和甲基丙烯酸月桂酯/丙烯酸共聚物。
酶
本发明的组合物中优选存在一种或多种酶。
优选每种酶的水平是基于产品计0.0001重量%至0.5重量%蛋白质。
特别可使用的酶包括蛋白酶、α-淀粉酶、纤维素酶、脂肪酶、过氧化物酶/氧化酶、果胶酸裂解酶、和甘露聚糖酶,或其混合物。
适合的脂肪酶包括细菌或真菌来源的那些脂肪酶。包括化学修饰或蛋白质工程的突变体。有用的脂肪酶的实例包括源自腐质霉属(Humicola)(同义词嗜热真菌属(Thermomyces))的脂肪酶,例如源自EP258068和EP 305216中所述的疏棉状腐质霉(H.lanuginosa)(细毛嗜热霉(T.lanuginosus))或出自WO 96/13580中所述的特异腐质霉(H.insolens);假单胞菌属(Pseudomonas)脂肪酶,例如源自产碱假单胞菌属(P.alcaligenes)或类产碱假单胞菌(P.pseudoalcaligenes)(EP 218 272)、洋葱假单胞菌(P.cepacia)(EP 331 376)、斯氏假单胞菌(P.stutzeri)(GB 1,372,034)、荧光假单胞菌(P.fluorescens)、假单胞菌属菌株SD 705(WO 95/06720和WO 96/27002),威斯康星假单胞菌(P.wisconsinensis)(WO 96/12012);芽孢杆菌属(Bacillus)脂肪酶,例如源自枯草芽孢杆菌(B.subtilis)(Dartois等(1993),Biochemica et Biophysica Acta,1131,253-360)、嗜热脂肪芽胞杆菌(B.stearothermophilus)(JP 64/744992)或短小芽孢杆菌(B.pumilus)(WO 91/16422)。
其他实例有脂肪酶变体,例如下列文献中描述的那些:WO 92/05249、WO 94/01541、EP 407225、EP 260105、WO 95/35381、WO96/00292、WO 95/30744、WO 94/25578、WO 95/14783、WO 95/22615、WO 97/04079、WO 97/07202、WO 00/60063、WO 09/107091和WO09/111258。
优选的可商购的脂肪酶包括LipolaseTM和Lipolase UltraTM,LipexTM(Novozymes A/S)和LipocleanTM。
本发明的方法可以在归类为EC 3.1.1.4和/或EC 3.1.1.32的磷脂酶存在下进行。在本文中使用时,术语磷脂酶是指对磷脂有活性的酶。
磷脂,例如卵磷脂或磷脂酰胆碱,由甘油的外部(sn-1)和中部(sn-2)位置被两个脂肪酸酯化并且其第三个位置被磷酸酯化而构成;所述磷酸进而可以被酯化为氨基醇。磷脂酶是参与磷脂水解的酶。可以区别几种类型的磷脂酶活性,包括水解一个脂酰基(分别在sn-1和sn-2位置)形成溶血磷脂的磷脂酶A1和A2;和可以水解溶血磷脂中剩余脂肪酰基的溶血磷脂酶(或磷脂酶B)。磷脂酶C和磷脂酶D(磷酸二脂酶)分别释放二酰基甘油或磷脂酸。
合适的蛋白酶包括动物、植物或微生物来源的蛋白酶。优选微生物来源的。包括化学修饰或蛋白质工程的突变体。所述蛋白酶可以是丝氨酸蛋白酶或金属基蛋白酶,优选碱性微生物蛋白酶或类胰蛋白酶。优选的市售蛋白酶包括AlcalaseTM、SavinaseTM、PrimaseTM、DuralaseTM、DyrazymTM、EsperaseTM、EverlaseTM、PolarzymeTM和KannaseTM(Novozymes A/S)、MaxataseTM、MaxacalTM、MaxapemTM、ProperaseTM、PurafectTM、Purafect OxPTM、FN2TM、和FN3TM(GenencorInternational Inc.)。
本发明的方法可以在归类为EC 3.1.1.74的角质酶存在下进行。本发明使用的角质酶可以是任何来源的。优选的角质酶是微生物来源的,特别是细菌、真菌或酵母来源的。
合适的淀粉酶(α和/或β)包括细菌或真菌来源的淀粉酶。包括化学修饰或蛋白质工程的突变体。淀粉酶包括例如如下来源的α-淀粉酶:芽孢杆菌属、例如在GB 1,296,839中有更详细描述的地衣形芽胞杆菌(B. licheniformis)特殊菌株、或WO 95/026397或WO 00/060060中公开的芽孢杆菌菌株。市售的淀粉酶是DuramylTM、TermamylTM、Termamyl UltraTM、NatalaseTM、StainzymeTM、FungamylTM和BANTM(Novozymes A/S)、RapidaseTM和PurastarTM(来自Genencor International Inc.)。
合适的纤维素酶包括细菌或真菌来源的那些纤维素酶。包括化学修饰或蛋白质工程的突变体。合适的纤维素酶包括源自芽孢杆菌属、假单胞菌属、腐质霉菌属、镰刀菌属(Fusarium)、梭孢壳属(Thielavia)、枝顶孢属(Acremonium)的纤维素酶,例如US 4,435,307、US 5,648,263、US 5,691,178、US 5,776,757、WO 89/09259、WO 96/029397和WO98/012307中公开的由特异腐质霉(Humicola insolens)、土生梭孢霉(Thielavia terrestris)、嗜热毁丝霉(Myceliophthora thermophila)和尖孢镰刀菌(Fusarium oxysporum)产生的真菌纤维素酶。可商购的纤维素酶包括CelluzymeTM、CarezymeTM、EndolaseTM、RenozymeTM(Novozymes A/S)、ClazinaseTM和Puradax HATM(Genencor International Inc.)、和KAC-500(B)TM(Kao Corporation)。
合适的过氧化物酶/氧化酶包括植物、细菌或真菌来源的那些。包括化学修饰或蛋白质工程的突变体。有用的过氧化物酶的例子包括出自鬼伞属(Coprinus)、例如出自灰盖鬼伞(C.cinereus)的过氧化物酶,及其变体,如WO 93/24618、WO 95/10602和WO 98/15257中描述的那些。市售的过氧化物酶包括GuardzymeTM和NovozymTM 51004(Novozymes A/S)。
适用的其它酶公开在WO2009/087524,WO2009/090576、WO2009/148983和WO2008/007318中。
酶稳定剂
组合物中存在的任何酶可以利用常规的稳定剂稳定,所述稳定剂例如,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、或苯基硼酸衍生物例如4-甲酰基苯基硼酸,并且所述组合物可以按照例如WO 92/19709和WO 92/19708中的描述配制。
在烷基长得足以形成分支链或环状链时,所述烷基包含支链、环状和直链的烷基链。烷基优选是直链或支链的,最优选直链的。
除非另有说明,“一”或“一个”和相应的“所述”在本文中使用时是指至少一个、或一个或多个。除非另作说明,该单数形式包括复数。
所述涂覆的洗衣用洗涤剂颗粒中可以存在螯合剂。
优选所述涂覆的洗涤剂颗粒的核壳比为3至1∶1,最优选2.5至1.5∶1;最佳核壳比是2∶1。
实验
实施例1:(颗粒制造)
如下制造用颜料蓝15:1(来自BASF的Pigmosol蓝6900)着色的洗衣洗涤剂颗粒。颗粒1在核中具有颜料,而颗粒2是在含有聚乙烯醇(PVOH)的涂层中具有颜料的参照颗粒。颗粒是扁椭球,其具有以下近似尺寸x=1.1mm,y=4.0mm,z=5.0mm。
核的制造
将表面活性剂原料混合在一起,以获得67重量%的活性糊状物,其包含85份阴离子型表面活性剂直链烷基苯磺酸盐(来自Unger的Ufasan65)LAS和15份非离子型表面活性剂(来自BASF的Lutensol AO 30,通式为RO(CH2CH2O)30H,其中R是C13和C15的羰基合成醇)。将糊状物预热至进料温度,并且进料到刮膜蒸发器的顶部以降低含水量并且产生固体紧密的表面活性剂混合物,其通过了耐钙性测试。表中给出了用于产生这种LAS/NI混合物的条件。
离开冷却辊后,使用锤式研磨机将冷却的干燥表面活性剂混合物颗粒碾碎,还将2%Alusill(来自Ineos)作为研磨助剂加入锤式研磨机中。所得到的碾碎材料是吸湿的,因此将其储存于密封的容器中。将冷 却的干燥碾碎组合物进料到配置有成型孔板和切割刀片的双螺杆共转(corotating)挤出机中。还将如下表所示的多种其他成分定量进料到挤出机中:
然后如下所示,涂覆所得到的核颗粒:
涂覆
通过喷雾使核颗粒涂覆碳酸钠(颗粒1)或聚乙烯醇(颗粒2参照)。将上述挤出物装载到Strea 1实验室流化床干燥器(Aeromatic-FielderAG)的流化室中,并且使用涂覆溶液,使用顶部喷雾构造进行喷雾涂覆。将涂覆溶液通过蠕动泵(Watson-Marlow型号101U/R)进料到Strea 1的喷嘴中。下表中给出了用于涂覆的条件:
实施例2:染色特性
将每种25个颗粒分散在平放于桌上的20×20cm的潮湿白色棉织布 块上。将潮湿的白色棉织布浸没在500ml的去矿物质水中2分钟,取出拧干并且用于实验。将颗粒在室温下静置15小时,然后清洗、漂洗和干燥布。计数每块布上的蓝色染色数量,并且计算染色%。染色%是产生蓝色染色的颗粒分数:
染色%=100×(染色数量)/(颗粒数量)
下表中给出了结果:
染色% | |
颗粒1染料在核中 | 8 |
颗粒2染料涂层中(参照) | 56 |
颗粒1产生了比颗粒2低的染色。
Claims (18)
1.涂覆洗涤剂颗粒,其具有正交尺寸x、y和z,其中x为1-2mm,y为2-8mm,且z为2-8mm,其中所述颗粒包含:
(i)40-90重量%表面活性剂,其选自:阴离子型表面活性剂和非离子型表面活性剂;
(ii)1-40重量%水溶性无机盐,所述水溶性无机盐为碳酸钠;和
(iii)0.0001-0.1重量%颜料,其中所述颜料选自:有机和无机颜料,
其中所述无机盐作为涂层存在于所述洗涤剂颗粒上,而所述表面活性剂和所述颜料作为核存在。
2.根据权利要求1的涂覆洗涤剂颗粒,其中所述颜料选自有机颜料。
3.根据权利要求1或2的涂覆洗涤剂颗粒,其中所述颜料选自单偶氮颜料、β-萘酚颜料、偶氮色淀颜料、苯并咪唑酮颜料、金属络合物颜料、异吲哚啉酮和异吲哚啉颜料、酞菁颜料、喹吖啶酮颜料、二萘嵌苯颜料、芘酮颜料、二酮吡咯并吡咯颜料、硫靛颜料、蒽醌颜料、蒽嘧啶颜料、黄烷士酮颜料、蒽嵌蒽醌颜料、二噁嗪颜料和喹酞酮颜料。
4.根据权利要求1或2的涂覆洗涤剂颗粒,其中所述颜料为萘酚AS颜料。
5.根据权利要求3的涂覆洗涤剂颗粒,其中所述颜料选自颜料绿8;颜料蓝28;颜料黄1;颜料黄3;颜料橙1;颜料红4;颜料红3;颜料红22;颜料红112;颜料红7;颜料棕1;颜料红5;颜料红68;颜料红51;颜料53;颜料红53:1;颜料红49;颜料红49:1;颜料红49:2;颜料红49:3;颜料红64:1;颜料红57;颜料红57:1;颜料红48;颜料红63:1;颜料黄16;颜料黄12;颜料黄13;颜料黄83;颜料橙13;颜料紫23;颜料红83;颜料蓝60;颜料蓝64;颜料橙43;颜料蓝66;颜料蓝63;颜料紫36;颜料紫19;颜料红122;颜料蓝16;颜料蓝15;颜料蓝15:1;颜料蓝15:2;颜料蓝15:3;颜料蓝15:4;颜料蓝15:6;颜料绿7;颜料绿36;颜料蓝29;颜料绿24;颜料红101:1;颜料绿17;颜料绿18;颜料绿14;颜料棕6;颜料蓝27;和,颜料紫16。
6.根据权利要求1的涂覆洗涤剂颗粒,其中所述颜料的初级颗粒大小为0.02-10μm。
7.根据权利要求1或2的涂覆洗涤剂颗粒,其中所述无机盐作为增效剂。
8.根据权利要求1或2的涂覆洗涤剂颗粒,其中所述涂覆洗涤剂颗粒包含基于表面活性剂15-85重量%的阴离子型表面活性剂和基于表面活性剂5-75重量%的非离子型表面活性剂,并且阴离子型表面活性剂和非离子型表面活性剂的总重量百分数等于100%。
9.根据权利要求1或2的涂覆洗涤剂颗粒,其中所述涂覆洗涤剂颗粒包含基于表面活性剂15-100重量%的阴离子型表面活性剂,其中所述阴离子型表面活性剂的20-30重量%是月桂基醚硫酸钠。
10.根据权利要求1或2的涂覆洗涤剂颗粒,其中所述阴离子型表面活性剂选自烷基苯磺酸盐、烷基醚硫酸盐、烷基硫酸盐。
11.根据权利要求10的涂覆洗涤剂颗粒,其中所述阴离子型表面活性剂选自具有1-3个乙氧基的月桂基醚硫酸钠、C10-C15烷基苯磺酸钠和C12-C18烷基硫酸钠。
12.根据权利要求1或2的涂覆洗涤剂颗粒,其中所述非离子型表面活性剂是10-50EO非离子型表面活性剂。
13.根据权利要求12的涂覆洗涤剂颗粒,其中所述非离子型表面活性剂是直链或支链的脂族C8-C18伯或仲醇与20-35个环氧乙烷基团的缩合产物。
14.根据权利要求1或2的涂覆洗涤剂颗粒,其中所述涂覆洗涤剂颗粒包含20-40重量%无机盐增效剂作为涂层。
15.根据权利要求14的涂覆洗涤剂颗粒,其中所述涂覆洗涤剂颗粒包含25-35重量%无机盐增效剂作为涂层。
16.根据权利要求1或2的涂覆洗涤剂颗粒,其中所述颗粒包含0-15重量%的水。
17.根据权利要求16的涂覆洗涤剂颗粒,其中所述颗粒包含1-5重量%的水。
18.根据权利要求1或2的涂覆洗涤剂颗粒,其中90%至100%的所述涂覆洗涤剂颗粒中最大与最小的涂覆洗涤剂颗粒在x、y和z尺寸的变化在20%以内。
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- 2011-09-01 US US13/878,448 patent/US9284517B2/en active Active
- 2011-09-01 IN IN621MUN2013 patent/IN2013MN00621A/en unknown
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- 2011-09-01 AU AU2011315792A patent/AU2011315792B2/en not_active Ceased
- 2011-09-01 WO PCT/EP2011/065152 patent/WO2012048949A1/en active Application Filing
- 2011-09-01 CN CN201180049310.7A patent/CN103168096B/zh active Active
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Also Published As
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CL2013001024A1 (es) | 2013-12-20 |
BR112013009132A2 (pt) | 2016-07-19 |
BR112013009132B1 (pt) | 2021-12-14 |
MX340440B (es) | 2016-07-08 |
EP2627753A1 (en) | 2013-08-21 |
US20130288943A1 (en) | 2013-10-31 |
AU2011315792A1 (en) | 2013-05-02 |
ZA201302298B (en) | 2014-06-25 |
US9284517B2 (en) | 2016-03-15 |
CN103168096A (zh) | 2013-06-19 |
ES2614083T3 (es) | 2017-05-29 |
AR083406A1 (es) | 2013-02-21 |
CA2814019A1 (en) | 2012-04-19 |
PL2627753T3 (pl) | 2017-05-31 |
AU2011315792B2 (en) | 2014-03-13 |
CA2814019C (en) | 2018-08-28 |
WO2012048949A1 (en) | 2012-04-19 |
IN2013MN00621A (zh) | 2015-06-12 |
MX2013003962A (es) | 2013-06-28 |
EP2627753B1 (en) | 2016-11-02 |
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