CN109715773B - 在洗涤液中产生低pH的喷雾干燥的基础洗涤剂颗粒 - Google Patents
在洗涤液中产生低pH的喷雾干燥的基础洗涤剂颗粒 Download PDFInfo
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- CN109715773B CN109715773B CN201780057999.5A CN201780057999A CN109715773B CN 109715773 B CN109715773 B CN 109715773B CN 201780057999 A CN201780057999 A CN 201780057999A CN 109715773 B CN109715773 B CN 109715773B
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- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 108010083879 xyloglucan endo(1-4)-beta-D-glucanase Proteins 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
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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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- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
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- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
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- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0047—Other compounding ingredients characterised by their effect pH regulated compositions
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- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
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- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
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- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
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- C11D3/16—Organic compounds
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- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
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Abstract
本发明涉及一种喷雾干燥的基础洗涤剂颗粒,其中基础洗涤剂颗粒包含(按基础洗涤剂颗粒的重量计):(a)4重量%至35重量%的烷基苯磺酸盐;(b)0重量%至8重量%的沸石助洗剂;(c)0重量%至4重量%的磷酸盐助洗剂;(d)0重量%至8重量%的碳酸钠;(e)0重量%至8重量%的硅酸钠;(f)1重量%至10重量%的有机酸;以及(g)1重量%至10重量%的硫酸镁,其中基础洗涤剂颗粒为喷雾干燥的颗粒,其中在20℃下在去离子水中以1重量%稀释的基础洗涤剂颗粒具有8.5或更低的平衡pH。
Description
技术领域
本发明涉及具有低pH特征的自由流动的固体颗粒状衣物洗涤剂组合物。本发明的组合物提供良好的溶解性特征、良好的清洁特征、良好的稳定性特征和良好的织物护理特征。
背景技术
衣物洗涤剂粉末制造商寻求提供具有良好的溶解性特征、良好的清洁特征、良好的稳定性特征和良好的织物护理特征的自由流动的固体颗粒状衣物洗涤剂组合物。通常,在所选制剂之间需要性能平衡以确保满足这些特征要求。
典型的衣物洗涤剂粉末的pH特征非常高,pH约10.5,并且有时甚至更高。该pH特征确保了历史清洁机制的良好性能:诸如油脂皂化机制和/或织物纤维溶胀机制。然而,这种高pH特征也意味着洗涤剂配方设计师必须利用改善织物护理特征解决问题,并且仍然足够确保织物外观性能和/或织物形状保持性能。
本发明人已经发现,在配制高pH洗涤剂粉末以确保良好的清洁性能同时需要平衡制剂以便也提供良好的织物护理性能的这种历史性二分法的另一种方法是在较低的pH下配制固体洗涤剂粉末,并且然后平衡制剂,以便也提供良好的清洁性能。
为了实现这一点,洗涤剂配方设计师期望从洗衣粉末中去除本体碱性化学物质,诸如碳酸钠和硅酸钠的成分,该碳酸钠和硅酸钠是向洗涤液体提供碱度的主要形式之一。实际上,由于碳酸钠将溶液缓冲至约10.5的pH的缓冲能力,将目前的洗衣粉末通常配制成提供10.5的pH洗涤溶液。为了实现低pH洗衣粉末,这些成分在产品中被配制成非常低的水平或完全去除。去除或显着降低这些本体碱性成分的水平意味着需要将较少的酸包含在洗衣粉末中以实现所需的低pH特征。如果本体碱性成分保持在其通常水平,例如约15重量%至25重量%,则需要将大量的酸包含在洗衣粉末组合物中以实现所需的低pH。掺入如此大量的酸(例如约15重量%至20重量%)是配制低pH粉末的非常低效的方式(酸只是中和产物中存在的碱度),并且还导致在洗涤剂粉末中尤其是喷雾干燥的洗涤剂基础颗粒中掺入此类水平的酸的工艺挑战。一种更好的配制方法是减少或去除制剂中的本体碱度,并且然后将更低和更易处理的酸水平引入产品中。
去除这些成分,同时有助于实现所需的低pH特征,引起洗涤剂制造商必须克服的其它问题。一个此类问题是洗涤剂颗粒的可加工性和物理特性差,这是由于诸如碳酸钠和硅酸钠的成分水平不足或甚至不存在引起的。
用于制备洗衣基础颗粒的常用方法是喷雾干燥,将其它洗涤剂颗粒组合到该洗衣基础颗粒以形成洗衣粉末。向喷雾干燥的基础洗涤剂颗粒中掺入碳酸钠和/或硅酸钠改善了颗粒的可加工性和颗粒特征。喷雾干燥的颗粒中它们的去除或显着减少导致加工不良,诸如粉尘,需要过多的再循环流,并且所得颗粒易碎,在包装过程期间难以处理,流动性差和颗粒强度差以及饼强度差。
具体地,本发明人发现通过仔细控制和组合有机酸和硫酸镁的水平实现良好的加工性能和良好的产品物理特征。将这些成分组合到具有低水平或无水平的碳酸钠和/或硅酸钠的喷雾干燥的颗粒中提供了可加工并且具有良好的颗粒特征诸如良好的饼强度的颗粒。省略这些特征中的一个会降低所得颗粒的性能。
以这种方式,提供了喷雾干燥的基础洗涤剂基础颗粒,其具有良好的可加工性和良好的颗粒强度,尤其是喷雾干燥的洗涤剂基础颗粒的良好的饼强度。
WO03/038028涉及一种衣物洗涤剂组合物,该衣物洗涤剂组合物具有6.5至9.5的pH特征,并且其据称具有低沉降特征,其反过来据称具有降低的洗涤液体泡沫行为。WO03/038028没有教导在喷雾干燥的基础洗涤剂颗粒中将硫酸镁与有机酸以所需水平一起组合以实现具有良好的可加工性和颗粒特征的衣物洗涤剂组合物。此外,WO03/038028的表1中的实施例E和V分别包含高水平的碳酸钠和高水平的沸石,并且此外两个实施例均包含高水平的酸,并且两个实施例均不包含硫酸镁。
发明内容
本发明涉及一种喷雾干燥的基础洗涤剂颗粒,其中基础洗涤剂颗粒包含(按基础洗涤剂颗粒的重量计):
(a)4重量%至35重量%的烷基苯磺酸盐;
(b)0重量%至8重量%的沸石助洗剂;
(c)0重量%至4重量%的磷酸盐助洗剂;
(d)0重量%至8重量%的碳酸钠;
(e)0重量%至8重量%的硅酸钠;
(f)1重量%至10重量%的有机酸;以及
(g)1重量%至10重量%的硫酸镁,
其中基础洗涤剂颗粒为喷雾干燥的颗粒,
其中在20℃下在去离子水中以1重量%稀释的基础洗涤剂颗粒具有8.5或更低的平衡pH。
具体实施方式
本发明涉及一种喷雾干燥的基础洗涤剂颗粒,其中基础洗涤剂颗粒包含(按基础洗涤剂颗粒的重量计):
(a)4重量%至35重量%的烷基苯磺酸盐;
(b)0重量%至8重量%的沸石助洗剂;
(c)0重量%至4重量%的磷酸盐助洗剂;
(d)0重量%至8重量%的碳酸钠;
(e)0重量%至8重量%的硅酸钠;
(f)1重量%至10重量%的有机酸;以及
(g)1重量%至10重量%的硫酸镁,
其中基础洗涤剂颗粒为喷雾干燥的颗粒,
其中在20℃下在去离子水中以1重量%稀释的基础洗涤剂颗粒具有8.5或更低的平衡pH。
基础颗粒优选地具有8.0或更低、或者甚至7.5或更低、或者甚至7.0或更低的pH。优选地,基础洗涤剂颗粒包含0重量%至4重量%的沸石助洗剂。基础洗涤剂颗粒可包含1重量%至8重量%的沸石助洗剂,或1重量%至4重量%的沸石助洗剂。基础颗粒可基本上不含磷酸盐助洗剂。基础颗粒可包含0重量%至4重量%的碳酸钠。基础洗涤剂颗粒可基本上不含碳酸钠。基础洗涤剂颗粒优选地包含1重量%至8重量%的有机酸,或1重量%至6重量%的有机酸。基础洗涤剂颗粒优选地包含1重量%至8重量%的硫酸镁,或1重量%至6重量%的硫酸镁。
基础洗涤剂颗粒可包含其它成分,诸如聚合物、螯合剂、增白剂、调色染料、着色剂和填料盐。这些洗涤剂成分如下所述。
基础洗涤剂颗粒可包含碱性试剂,诸如NaOH。这允许洗涤剂配方设计师根据需要配制基础洗涤剂颗粒pH,例如与洗衣粉末产品的pH特征相容。
基础洗涤剂颗粒可与其它颗粒和成分组合并被配制成衣物洗涤剂粉末组合物。其它颗粒和成分如下所述。合适的颗粒包括干燥加入的颗粒,诸如漂白剂颗粒、酶颗粒、香料颗粒、辅助表面活性剂颗粒和聚合物颗粒。还可将成分直接加入到喷雾干燥的基础颗粒中,或加入到基础颗粒与其它颗粒的混合物中。此类成分通常是液体或软固体,并且可包括例如香料、硅氧烷、非离子表面活性剂和聚合物。
自由流动的固体颗粒状衣物洗涤剂组合物:通常,自由流动的固体颗粒状衣物洗涤剂组合物是全配方衣物洗涤剂组合物,而不是其一部分(诸如仅形成衣物洗涤剂组合物一部分的喷雾干燥的、挤出的或附聚物颗粒)。通常,固体组合物包含多个化学上不同的颗粒,诸如喷雾干燥的基础洗涤剂颗粒和/或附聚的基础洗涤剂颗粒和/或挤出的基础洗涤剂颗粒;组合了一个或多个、通常两个或更多个、或者五个或更多个、或者甚至十个或更多个颗粒,该颗粒选自:表面活性剂颗粒,包括表面活性剂附聚物、表面活性剂挤出物、表面活性剂针状物、表面活性剂面状物、表面活性剂片状物;磷酸盐颗粒;沸石颗粒;聚合物颗粒,诸如羧酸盐聚合物颗粒、纤维素聚合物颗粒、淀粉颗粒、聚酯颗粒、聚胺颗粒、对苯二甲酸聚合物颗粒、聚乙二醇颗粒;美观颗粒,诸如有色条粒、针状物、层状颗粒和环颗粒;酶颗粒,诸如蛋白酶颗粒、淀粉酶颗粒、脂肪酶颗粒、纤维素酶颗粒、甘露聚糖酶颗粒、果胶酸裂解酶颗粒、木葡聚糖酶颗粒、漂白酶颗粒和这些酶中的任一种的共颗粒,优选地这些酶颗粒包含硫酸钠;漂白剂颗粒,诸如过碳酸盐颗粒,尤其是涂覆的过碳酸盐颗粒,诸如涂覆有碳酸盐、硫酸盐、硅酸盐、硼硅酸盐、或它们的任何组合的过碳酸盐,过硼酸盐颗粒,漂白活化剂颗粒诸如四乙酰基乙二胺颗粒和/或烷基氧基苯磺酸盐颗粒,漂白催化剂颗粒诸如过渡金属催化剂颗粒,和/或异喹啉鎓漂白催化剂颗粒,预成形过酸颗粒,尤其是涂覆的预成形过酸颗粒;填料颗粒,诸如硫酸盐颗粒和氯化物颗粒;粘土颗粒,诸如蒙脱石颗粒和粘土与硅氧烷颗粒;絮凝剂颗粒,诸如聚环氧乙烷颗粒;蜡颗粒,诸如蜡质附聚物;硅氧烷颗粒,增白剂颗粒;染料转移抑制剂颗粒;染料固定剂颗粒;香料颗粒,诸如香料微胶囊和淀粉包封的香料谐香剂颗粒,以及前香料颗粒,诸如席夫碱反应产物颗粒;调色染料颗粒;螯合剂颗粒,诸如螯合剂附聚物;以及它们的任何组合。
通常,自由流动的固体颗粒状衣物洗涤剂组合物包含:
(a)阴离子去污表面活性剂;
(b)0重量%至8重量%的沸石助洗剂;
(c)0重量%至4重量%的磷酸盐助洗剂;
(d)0重量%至8重量%的碳酸钠;
(e)0重量%至8重量%的硅酸钠;以及
(f)4重量%至20重量%的有机酸。
通常,在20℃下在去离子水中以1重量%稀释的组合物具有在6.5至9.0,优选地6.5至8.5,更优选地7.0至8.0范围内的平衡pH。
通常,在20℃下在去离子水中以1重量%稀释的组合物具有小于4.0gNaOH/100g,优选地小于3.0gNaOH/100g,或甚至小于2.0gNaOH/100g的至pH 7.0的储备碱度。
如本文所用,术语“储备碱度”是洗涤剂组合物缓冲能力的量度(g/NaOH/100g洗涤剂组合物),其通过用盐酸将1%(w/v)的洗涤剂组合物溶液滴定至pH 7.0来测定,即为了计算如本文所定义的储备碱度:
T=至pH 7.0时的滴定度(ml)
M=HCl的摩尔浓度=0.2
40=NaOH的分子量
Vol=总体积(即1000ml)
W=产品重量(10g)
等分试样=(100ml)
获得10g精确称量至小数点后两位的全配方洗涤剂组合物样品。应在除尘橱中,使用Pascall采样器获得样品。向塑料烧杯中加入10g样品,并加入200ml不含二氧化碳的去离子水。在搅拌台上,使用磁力搅拌器以150rpm搅拌,直至完全溶解,并且搅拌至少15分钟。将烧杯中的内容物转移至1升容量瓶中,并用去离子水补足至1升。充分混合,并且立即使用100ml吸液管,取100ml±1ml的等分试样。使用能够读至±0.01pH单位的pH计测定并记录样品的pH和温度,并且搅拌,以确保温度为21℃+/-2℃。用0.2M的盐酸,在搅拌的同时滴定,直至pH准确测量为7.0。记录所用的盐酸毫升数。取三次相同重复试验的平均滴度。实施上述计算以计算至pH 7.0的储备碱度。
通常,组合物包含30重量%至90重量%的基础洗涤剂颗粒,其中基础洗涤剂颗粒包含(按基础洗涤剂颗粒的重量计):(a)4重量%至35重量%的阴离子去污表面活性剂;(b)任选地,0重量%至8重量%的沸石助洗剂,任选地1重量%至8重量%的沸石助洗剂;(c)0重量%至4重量%的磷酸盐助洗剂;(d)0重量%至8重量%,优选地0重量%至4重量%的碳酸钠;(e)0重量%至8重量%,优选地0重量%至4重量%的硅酸钠;(f)1重量%至10重量%的有机酸;以及(g)任选地,1重量%至10重量%的硫酸镁。基础洗涤剂颗粒为喷雾干燥的颗粒的形式。
通常,有机酸包括柠檬酸,并且基础洗涤剂颗粒包含1重量%至10重量%的柠檬酸。
有机酸可通过水分散性材料至少部分地涂覆或甚至完全涂覆。水分散性材料通常还包括水溶性材料。合适的水分散性材料是蜡。合适的水溶性材料是柠檬酸盐。
通常,阴离子去污表面活性剂包括烷基苯磺酸盐,并且其中基础洗涤剂颗粒包含4重量%至35重量%的烷基苯磺酸盐。
通常,基础洗涤剂颗粒包含0.5重量%至5重量%的羧酸盐共聚物,其中羧酸盐共聚物包含:(i)50重量%至小于98重量%的衍生自一种或多种包含羧基基团的单体的结构单元;(ii)1重量%至小于49重量%的衍生自一种或多种包含磺酸根部分的单体的结构单元;以及(iii)1重量%至49重量%的衍生自一类或多类单体的结构单元,该单体选自由式(I)和(II)表示的含醚键的单体:
式(I):
其中在式(I)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,前提条件是当R为单键时X表示数字1至5,并且R1为氢原子或C1至C20有机基团;
式(II)
其中在式(II)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,并且R1为氢原子或C1至C20有机基团。
通常,基础洗涤剂颗粒包含30重量%至70重量%的硫酸钠。
通常,组合物包含1重量%至20重量%的辅助表面活性剂颗粒,其中辅助表面活性剂颗粒包含:(a)25重量%至60重量%的辅助表面活性剂;(b)10重量%至50重量%的碳酸盐;以及(c)1重量%至30重量%的二氧化硅。通常,辅助表面活性剂颗粒为附聚物的形式。
通常,辅助表面活性剂包含具有0.5至2.5的平均乙氧基化度的烷基乙氧基化硫酸盐,并且其中辅助表面活性剂颗粒包含25重量%至60重量%的具有0.5至2.5的平均乙氧基化度的烷基乙氧基化硫酸盐。
辅助表面活性剂颗粒可包含直链烷基苯磺酸盐和具有0.5至2.5的平均乙氧基化度的烷基乙氧基化硫酸盐。
在20℃下在去离子水中以1重量%稀释的组合物可具有在6.5至8.5范围内的平衡pH。
组合物可具有小于3.0gNaOH/100g的至pH 7.5的储备碱度。
组合物可包含0重量%至6重量%,优选地0重量%至4重量%的碳酸氢钠。
颗粒可包含0重量%至4重量%的碳酸钠。
颗粒可包含0重量%至4重量%的硅酸钠。
颗粒可包含0重量%至4重量%的磷酸盐助洗剂。
颗粒优选地基本上不含磷酸盐助洗剂。
颗粒可基本上不含碳酸钠。
颗粒可基本上不含碳酸氢钠。
颗粒可基本上不含硅酸钠。
“基本上不含”在本文中的通常含义是指:“不包含有意加入的”。
组合物可包含脂肪酶和去垢性聚合物的组合。基础颗粒可包含去垢性聚合物。
优选地,颗粒包含烷基苯磺酸盐,其中烷基苯磺酸盐包含至少25重量%的2-苯基异构体。通过DETAL合成获得具有该特征的合适的烷基苯磺酸盐。
颗粒可包含烷基氧化胺。
颗粒可包含0.5重量%至8重量%的羧酸盐共聚物,其中羧酸盐共聚物包含:(i)50重量%至小于98重量%的衍生自一种或多种包含羧基基团的单体的结构单元;
(ii)1重量%至小于49重量%的衍生自一种或多种包含磺酸根部分的单体的结构单元;以及(iii)1重量%至49重量%的衍生自一类或多类单体的结构单元,该单体选自由式(I)和(II)表示的含醚键的单体:
式(I):
其中在式(I)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,前提条件是当R为单键时X表示数字1至5,并且R1为氢原子或C1至C20有机基团;
式(II)
其中在式(II)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,并且R1为氢原子或C1至C20有机基团。
组合物可包含聚乙二醇聚合物,其中聚乙二醇聚合物包含具有接枝的聚乙酸乙烯酯侧链的聚乙二醇主链。
组合物可包含具有以下结构的聚酯去垢性聚合物:
其中n为1至10;m为1至15;
X为H或SO3Me;
其中Me为H、Na+、Li+、K+、Mg2+、Ca2+、Al3+、铵、单烷基铵、二烷基铵、三烷基铵或四烷基铵;其中烷基基团为C1-C18烷基或C2-C10羟烷基、或它们的任何混合物;
R1独立地选自H或C1-C18正烷基或C1-C18异烷基。
组合物可包含由结构单元(1)至(3)组成的聚酯去垢性聚合物:
其中:
a、b和c为1至10;
x、y为1至10;
z为0.1至10;
Me为H、Na+、Li+、K+、Mg2+、Ca2+、Al3+、铵、单烷基铵、二烷基铵、三烷基铵或四烷基铵,其中烷基基团为C1-C18烷基或C2-C10羟烷基、或它们的任何混合物;
R1独立地选自H或C1-C18正烷基或C1-C18异烷基;
R2为直链或支链的C1-C18烷基,或者直链或支链的C2-C30烯基,或者具有5至9个碳原子的环烷基基团,或者C6-C30芳基基团,或者C6-C30芳烷基基团。
组合物可包含羧甲基纤维素,该羧甲基纤维素具有大于0.65的取代度和大于0.45的嵌段度。
颗粒可包含烷氧基化聚亚烷基亚胺,其中所述烷氧基化聚亚烷基亚胺具有聚亚烷基亚胺核,该聚亚烷基亚胺核具有键合到聚亚烷基亚胺核中的至少一个氮原子的一个或多个侧链,其中所述烷氧基化聚亚烷基亚胺具有经验式(I):(PEI)a-(EO)b-R1,其中a为烷氧基化聚亚烷基亚胺的聚亚烷基亚胺核的平均数均分子量(MWPEI)并且在100道尔顿至100,000道尔顿的范围内,其中b为在烷氧基化聚亚烷基亚胺的所述一个或多个侧链中的平均乙氧基化度并且在5至40的范围内,并且其中R1独立地选自氢、C1-C4烷基、以及它们的组合。
颗粒可包含烷氧基化聚亚烷基亚胺,其中所述烷氧基化聚亚烷基亚胺具有聚亚烷基亚胺核,该聚亚烷基亚胺核具有键合到聚亚烷基亚胺核中的至少一个氮原子的一个或多个侧链,其中烷氧基化聚亚烷基亚胺具有经验式(II):(PEI)o-(EO)m(PO)n-R2或(PEI)o-(PO)n(EO)m-R2,其中o为烷氧基化聚亚烷基亚胺的聚亚烷基亚胺核的平均数均分子量(MWPEI)并且在100道尔顿至100,000道尔顿的范围内,其中m为在烷氧基化聚亚烷基亚胺的所述一个或多个侧链中的平均乙氧基化度,该m在10至50的范围内,其中n为在烷氧基化聚亚烷基亚胺的所述一个或多个侧链中的平均丙氧基化度,该n在1至50的范围内,并且其中R2独立地选自氢、C1-C4烷基、以及它们的组合。
组合物可包含非离子去垢性聚合物和阴离子去垢性聚合物的组合。
非常优选地,组合物基本上不含预形成的过酸。
组合物可包含:
(a)1重量%至20重量%的过碳酸钠;
(b)0.5重量%至5重量%的漂白活化剂;以及
(c)0.5重量%至5重量%的螯合剂。
漂白活化剂可包含四乙酰基乙二胺钠,并且其中组合物可包含0.5重量%至5重量%的四乙酰基乙二胺钠。
螯合剂可包含甲基甘氨酸二乙酸(MGDA)的钠盐,并且其中组合物可包含0.5重量%至5重量%的甲基甘氨酸二乙酸(MGDA)的钠盐。
螯合剂可包含乙二胺二琥珀酸(EDDS),并且其中组合物可包含0.5重量%至5重量%的乙二胺二琥珀酸(EDDS)。
螯合剂可包含4,5-二羟基-1,3-苯二磺酸二钠,并且其中组合物可包含0.5重量%至5重量%的4,5-二羟基-1,3-苯二磺酸二钠。
颗粒可包含4,4'-双-(三嗪基氨基)-二苯乙烯-2,2'-二磺酸增白剂和/或4,4'-二苯乙烯基联苯增白剂。
组合物可包含酰基腙漂白催化剂,其中酰基腙漂白催化剂具有式I:
其中,R1选自CF3、C1-28烷基、C2-28烯基、C2-22炔基、C3-12环烷基、C3-12环烯基、苯基、萘基、C7-9芳烷基、C3-20杂烷基、C3-12环杂烷基、或它们的混合物;
R2和R3独立地选自氢、取代的C1-28烷基、C2-28烯基、C2-22炔基、C3-12环烷基、C3-12环烯基、C7-9芳烷基、C3-28杂烷基、C3-12环杂烷基、C5-16杂芳烷基、苯基、萘基、杂芳基、或它们的混合物;
或者R2和R3连接形成任选地包含杂原子的取代的5元环、6元环、7元环、8元环或9元环;
并且R4选自氢、C1-28烷基、C2-28烯基、C2-22炔基、C3-12环烷基、C3-12环烯基、C7-9芳烷基、C3-20杂烷基、C3-12环杂烷基、C5-16杂芳烷基、取代的苯基、萘基、杂芳基、或它们的混合物。
颗粒可包含具有以下结构的调色剂:
其中:
R1和R2独立地选自:H;烷基;烷氧基;亚烷氧基;烷基封端的亚烷氧基;脲;和酰氨基;
R3为取代的芳基基团;
X为包含磺酰胺部分和任选地烷基和/或芳基部分的取代基,并且其中取代基包含至少一个亚烷氧基链,该至少一个亚烷氧基链包含至少四个亚烷氧基部分的平均摩尔分布(an average molar distribution of at least for alkyleneoxy moieties)。
颗粒可包含具有以下结构的调色剂:
其中指数值x和y独立地选自1至10。
颗粒可包含选自酸性紫50,直接紫9、66和99,溶剂紫13,以及它们的任何组合的调色剂。
组合物可包含与如SEQ ID NO:9所示的解淀粉芽孢杆菌(Bacillusamyloliquefaciens)的氨基酸序列具有至少90%同一性的蛋白酶
组合物可包含与如SEQ ID NO:10所示的解淀粉芽孢杆菌BPN'的氨基酸序列具有至少90%同一性的蛋白酶,并且该蛋白酶包含选自V4I、S9R、A15T、S24G、S33T、S53G、V68A、N76D、S78N、S101M/N、Y167F和Y217Q的一种或多种突变。
组合物可包含与如SEQ ID NO:11所示的嗜热解朊芽孢杆菌(Bacillusthermoproteolyticus)的氨基酸序列具有至少90%同一性的蛋白酶。
组合物可包含与如SEQ IS NO:12所示的迟缓芽孢杆菌(Bacillus lentus)的氨基酸序列具有至少90%同一性的蛋白酶,并且该蛋白酶包含选自S3T、V4I、A194P、V199M、V205I和L217D的一种或突变。
组合物可包含与如SEQ ID NO:13所示的芽孢杆菌属(Bacillus sp.)TY145的氨基酸序列具有至少90%同一性的蛋白酶。
组合物可包含与如SEQ ID NO:14所示的芽孢杆菌属KSM-KP43的氨基酸序列具有至少90%同一性的蛋白酶。
组合物可包含来自芽孢杆菌属的野生型淀粉酶的变体,该变体与氨基酸序列SEQID NO:5具有至少90%的同一性,并且该变体在以下位置处包含一个或多个突变:N195、G477、G304、W140、W189、D134、V206、Y243、E260、F262、W284、W347、W439、W469和/或G476,并且任选地该变体包含D183*和/或G184*的缺失。
组合物可包含来自芽孢杆菌属的野生型淀粉酶的变体,该变体与氨基酸序列SEQID NO:6具有至少90%的同一性,并且该变体在以下位置处包含一个或多个突变:9、26、30、33、82、37、106、118、128、133、149、150、160、178、182、186、193、195、202、214、231、256、257、258、269、270、272、283、295、296、298、299、303、304、305、311、314、315、318、319、320、323、339、345、361、378、383、419、421、437、441、444、445、446、447、450、458、461、471、482和/或484,优选地还含有D183*和G184*的缺失。
组合物可包含来自芽孢杆菌属KSM-K38的野生型淀粉酶的变体,该变体与氨基酸序列SEQ ID NO:7具有至少90%的同一性。
组合物可包含来自噬纤维菌属(Cytophaga sp.)的野生型淀粉酶的变体,该变体与氨基酸序列SEQ ID NO:8具有至少60%的同一性。
组合物可包含来自疏棉状嗜热丝孢菌(Thermomyces lanuginosus)的野生型脂肪酶的变体,该变体与氨基酸序列SEQ ID NO:1具有至少90%的同一性。
组合物可包含来自疏棉状嗜热丝孢菌的野生型脂肪酶的变体,该变体与氨基酸序列SEQ ID NO:1具有至少90%的同一性,并且该变体包含T231R和/或N233R突变。
组合物可包含来自疏棉状嗜热丝孢菌的野生型脂肪酶的变体,该变体与氨基酸序列SEQ ID NO:1具有至少90%的同一性,并且该变体包含G91A、D96G、G225R、T231R和/或N233R突变。
组合物可包含纤维素酶,该纤维素酶为内源于芽孢杆菌属、表现出内切-β-1,4-葡聚糖酶活性(E.C.3.2.1.4)的微生物衍生的内切葡聚糖酶的野生型或变体,该野生型或变体与氨基酸序列SEQ ID NO:2具有至少90%的同一性。
组合物可包含纤维素酶,该纤维素酶为内源于多粘类芽孢杆菌(Paenibacilluspolymyxa)、表现出内切-β-1,4-葡聚糖酶活性(E.C.3.2.1.4)的微生物衍生的内切葡聚糖酶的野生型或变体,该野生型或变体与氨基酸序列SEQ ID NO:3具有至少90%的同一性。
组合物可包含纤维素酶和碳水化合物结合模块,该纤维素酶为杂合融合内切葡聚糖酶,该杂合融合内切葡聚糖酶包含糖基水解酶家族45催化结构域,该结构域为内源于热白丝菌(Melanocarpus albomyces)的微生物衍生的内切葡聚糖酶的野生型或变体,该碳水化合物结合模块为内源于里氏木霉(Trichoderma reesei)的碳水化合物结合模块的野生型或变体,并且该野生型或变体与氨基酸序列SEQ ID NO:4具有至少90%的同一性。
组合物可包含酶,该酶选自甘露聚糖酶、果胶酸裂解酶、漆酶、聚酯酶、半乳聚糖酶、酰基转移酶、以及它们的任何组合。
组合物可包含香料,其中香料包含60重量%至85重量%的具有以下结构的酯香料原料:
其中R1和R2独立地选自C1至C30直链或支链、环状或非环状、芳族或非芳族、饱和或未饱和、取代或未取代的烷基。
组合物可包含:(a)具有0.5至2.0的平均乙氧基化度的烷基乙氧基化硫酸盐;(b)香料,其中香料包含60重量%至85重量%的具有以下结构的酯香料原料:
其中R1和R2独立地选自C1至C30直链或支链、环状或非环状、芳族或非芳族、饱和或未饱和、取代或未取代的烷基。
颗粒可包含聚乙烯基N氧化物聚合物。
组合物可包含:硅酸盐颗粒,尤其是硅酸钠颗粒;和/或碳酸盐颗粒,尤其是碳酸氢钠颗粒。然而,可优选的是,组合物不含硅酸盐颗粒,尤其是不含硅酸钠颗粒。也可优选的是,组合物不含碳酸盐颗粒,尤其是不含碳酸钠颗粒。
优选地,组合物包含1重量%至10重量%的干燥加入的酸性颗粒,优选地2重量%至8重量%的干燥加入的酸性颗粒。合适的干燥加入的酸是有机酸,优选地羧酸,优选地cirtric酸。
基础洗涤剂颗粒:基础洗涤剂颗粒为喷雾干燥的颗粒的形式。通常,组合物包含30重量%至90重量%的基础洗涤剂颗粒,优选地40重量%至80重量%,更优选地50重量%至70重量%的基础洗涤剂颗粒。
基础洗涤剂颗粒通常包含1重量%至10重量%的有机酸,优选地2重量%至8重量%,或3重量%至7重量%的有机酸。优选的有机酸是羧酸,优选地柠檬酸。
其它合适的酸包括甲酸、乙酸、丙酸、丁酸、辛酸和月桂酸、硬脂酸、亚油酸和丙烯酸、甲基丙烯酸、氯乙酸和柠檬酸、乳酸、乙醛酸、乙酰乙酸、草酸、丙二酸、己二酸和苯乙酸、苯甲酸、水杨酸、甘氨酸和丙氨酸、缬氨酸、天冬氨酸、谷氨酸、赖氨酸和苯丙氨酸、烟酸、吡啶甲酸、富马酸、乳酸、苯甲酸、谷氨酸;琥珀酸、乙醇酸。优选地,有机酸选自柠檬酸、苹果酸、琥珀酸、乳酸、乙醇酸、富马酸、酒石酸和甲酸、以及它们的混合物。更优选地,酸是柠檬酸、乳酸和酒石酸。
基础洗涤剂颗粒通常包含1重量%至10重量%的硫酸镁,优选地2重量%至8重量%,或3重量%至6重量%的硫酸镁。
基础洗涤剂颗粒通常包含0重量%至8重量%、或2重量%至6重量%、或2重量%至4重量%的沸石。优选的沸石是沸石A,尤其是沸石4A。
基础洗涤剂颗粒通常包含5重量%至40重量%,优选地10重量%至30重量%的阴离子去污表面活性剂。优选的阴离子去污表面活性剂是烷基苯磺酸盐。
基础洗涤剂颗粒通常包含0.5重量%至5重量%的聚合物,优选地1重量%至3重量%的聚合物。优选的聚合物是羧酸盐聚合物,更优选地共聚物,其包含:(i)50重量%至小于98重量%的衍生自一种或多种包含羧基基团的单体的结构单元;(ii)1重量%至小于49重量%的衍生自一种或多种包含磺酸根部分的单体的结构单元;以及(iii)1重量%至49重量%的衍生自一类或多类单体的结构单元,该单体选自由式(I)和(II)表示的含醚键的单体:
式(I):
其中在式(I)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,前提条件是当R为单键时X表示数字1至5,并且R1为氢原子或C1至C20有机基团;
式(II)
其中在式(II)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,并且R1为氢原子或C1至C20有机基团。
可优选的是,聚合物具有至少30kDa、或至少50kDa、或甚至至少70kDa的重均分子量。
通常,基础洗涤剂颗粒包含30重量%至70重量%、或40重量%至70重量%的硫酸钠。
辅助表面活性剂颗粒:通常,洗涤剂组合物包含辅助表面活性剂颗粒。通常,组合物包含1重量%至20重量%、或2重量%至15重量%、或3重量%至10重量%的辅助表面活性剂颗粒。通常,辅助表面活性剂颗粒为附聚物、挤出物、针状、条粒、薄片、或它们的任何组合的形式。优选地,辅助表面活性剂颗粒为附聚物的形式。
辅助表面活性剂颗粒通常包含25重量%至60重量%的辅助表面活性剂,优选地30重量%至50重量%的辅助表面活性剂。优选的辅助表面活性剂是烷基烷氧基硫酸盐,优选地具有0.5至2.0的平均乙氧基化度的C10-C20烷基乙氧基化硫酸盐。
通常,辅助表面活性剂颗粒包含10重量%至50重量%的碳酸盐。优选的碳酸盐是碳酸钠和/或碳酸氢钠。然而,可优选的是,辅助表面活性剂颗粒不含碳酸盐,尤其是不含碳酸钠。
通常,辅助表面活性剂颗粒包含1重量%至30重量%的二氧化硅,优选地5重量%至20重量%的二氧化硅。
洗涤剂成分:合适的衣物洗涤剂组合物包含选自以下的洗涤剂成分:去污表面活性剂,诸如阴离子去污表面活性剂、非离子去污表面活性剂、阳离子去污表面活性剂、两性离子去污表面活性剂和两性去污表面活性剂;聚合物,诸如羧酸盐聚合物、去垢性聚合物、抗再沉积聚合物、纤维素聚合物和护理聚合物;漂白剂,诸如过氧化氢源、漂白活化剂、漂白催化剂和预形成的过酸;光漂白剂,诸如诸如磺化酞菁锌和/或磺化酞菁铝;酶,诸如蛋白酶、淀粉酶、纤维素酶、脂肪酶;沸石助洗剂;磷酸盐助洗剂;辅助助洗剂,诸如柠檬酸和柠檬酸盐;硫酸盐,诸如硫酸钠;氯化物盐,诸如氯化钠;增白剂;螯合剂;调色剂;染料转移抑制剂;染料固定剂;香料;硅氧烷;织物柔软剂,诸如粘土;絮凝剂,诸如聚环氧乙烷;抑泡剂;以及它们的任何组合。
组合物可包含:硅酸盐,尤其是硅酸钠;和/或碳酸盐,尤其是碳酸氢钠和/或碳酸钠。然而,可优选的是,组合物不含硅酸盐,尤其是不含硅酸钠。也可优选的是,组合物不含碳酸盐,尤其是不含碳酸钠和/或碳酸氢钠。
组合物可具有pH特征,使得在20℃的温度下在去离子水中以1g/L的浓度稀释时,组合物具有在6.5至8.5,优选地7.0至8.0范围内的pH。
合适的衣物洗涤剂组合物可具有低缓冲能力。此类衣物洗涤剂组合物通常具有小于5.0gNaOH/100g,优选地小于3.0gNaOH/100g的至pH 7.5的储备碱度。
组合物优选地基本上不含预形成的过酸。组合物优选地基本上不含邻苯二甲酰亚氨基-过氧己酸。基本上不含是指没有有意加入的。
去污表面活性剂:合适的去污表面活性剂包括阴离子去污表面活性剂、非离子去污表面活性剂、阳离子去污表面活性剂、两性离子去污表面活性剂和两性去污表面活性剂。合适的去污表面活性剂可为直链或支链、取代或未取代的,并且可衍生自石化材料或生物材料。
阴离子去污表面活性剂:合适的阴离子去污表面活性剂包括磺酸盐去污表面活性剂和硫酸盐去污表面活性剂。
合适的磺酸盐去污表面活性剂包括磺酸甲酯、α烯烃磺酸盐、烷基苯磺酸盐,尤其是烷基苯磺酸盐,优选地C10-13烷基苯磺酸盐。合适的烷基苯磺酸盐(LAS)是可获得的,优选地通过使可商购获得的直链烷基苯(LAB)磺化获得;合适的LAB包括低级2-苯基LAB,其它合适的LAB包括高级2-苯基LAB,诸如以商品名由Sasol供应的那些。
合适的硫酸盐去污表面活性剂包括烷基硫酸盐,优选地为C8-18烷基硫酸盐,或主要为C12烷基硫酸盐。
优选的硫酸盐去污表面活性剂为烷基烷氧基化硫酸盐,优选地烷基乙氧基化硫酸盐,优选地C8-18烷基烷氧基化硫酸盐,优选地C8-18烷基乙氧基化硫酸盐,优选地烷基烷氧基化硫酸盐具有0.5至20,优选地0.5至10的平均烷氧基化度,优选地烷基烷氧基化硫酸盐为C8-18烷基乙氧基化硫酸盐,其具有0.5至10,优选地0.5至5,更优选地0.5至3,并且最优选地0.5至1.5的平均乙氧基化度。
烷基硫酸盐、烷基烷氧基化硫酸盐和烷基苯磺酸盐可为直链或支链、取代或未取代的,并且可衍生自石化材料或生物材料。
其它合适的阴离子去污表面活性剂包括烷基醚羧酸盐。
合适的阴离子去污表面活性剂可为盐的形式,合适的抗衡离子包括钠、钙、镁、氨基醇、以及它们的任何组合。优选的抗衡离子为钠。
非离子去污表面活性剂:合适的非离子去污表面活性剂选自:C8-C18烷基乙氧基化物,诸如来自Shell的非离子表面活性剂;C6-C12烷基酚烷氧基化物,其中优选地烷氧基化物单元为乙烯氧基单元、丙烯氧基单元、或它们的混合物;C12-C18醇和C6-C12烷基酚与环氧乙烷/环氧丙烷嵌段聚合物的缩合物,诸如购自BASF的烷基多糖,优选地烷基多苷;甲酯乙氧基化物;多羟基脂肪酸酰胺;醚封端的聚(烷氧基化)醇表面活性剂;以及它们的混合物。
合适的非离子去污表面活性剂为烷基多葡萄糖苷和/或烷基烷氧基化醇。
合适的非离子去污表面活性剂包括烷基烷氧基化醇,优选地C8-18烷基烷氧基化醇,优选地C8-18烷基乙氧基化醇,优选地烷基烷氧基化醇具有1至50,优选地1至30,或1至20,或1至10的平均烷氧基化度,优选地烷基烷氧基化醇为C8-18烷基乙氧基化醇,其具有1至10,优选地1至7,更优选地1至5,并且最优选地3至7的平均乙氧基化度。烷基烷氧基化醇可为直链或支链、以及取代或未取代的。
合适的非离子去污表面活性剂包括基于仲醇的去污表面活性剂。
阳离子去污表面活性剂:合适的阳离子去污表面活性剂包括烷基吡啶鎓化合物、烷基季铵化合物、烷基季鏻化合物、烷基三元锍化合物、以及它们的混合物。
优选的阳离子去污表面活性剂为具有以下通式的季铵化合物:
(R)(R1)(R2)(R3)N+X-
其中,R为直链或支链、取代或未取代的C6-18烷基或烯基部分,R1和R2独立地选自甲基或乙基部分,R3为羟基、羟甲基或羟乙基部分,X为提供电中性的阴离子,优选的阴离子包括:卤离子,优选地氯离子;硫酸根;和磺酸根。
两性离子去污表面活性剂:合适的两性离子去污表面活性剂包括氧化胺和/或甜菜碱。
聚合物:合适的聚合物包括羧酸盐聚合物、去垢性聚合物、抗再沉积聚合物、纤维素聚合物、护理聚合物、以及它们的任何组合。
羧酸盐聚合物:组合物可包含羧酸盐聚合物,诸如马来酸酯/丙烯酸酯无规共聚物或聚丙烯酸酯均聚物。合适的羧酸盐聚合物包括:具有4,000Da至9,000Da的分子量的聚丙烯酸酯均聚物;具有30,000Da至100,000Da、或50,000Da至100,000Da、或60,000Da至80,000Da的分子量的马来酸酯/丙烯酸酯无规共聚物。
另一种合适的羧酸盐聚合物是共聚物,其包含:(i)50重量%至小于98重量%的衍生自一种或多种包含羧基基团的单体的结构单元;(ii)1重量%至小于49重量%的衍生自一种或多种包含磺酸根部分的单体的结构单元;以及(iii)1重量%至49重量%的衍生自一类或多类单体的结构单元,该单体选自由式(I)和(II)表示的含醚键的单体:
式(I):
其中在式(I)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,前提条件是当R为单键时X表示数字1至5,并且R1为氢原子或C1至C20有机基团;
式(II)
其中在式(II)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,并且R1为氢原子或C1至C20有机基团。
可优选的是,聚合物具有至少30kDa、或至少50kDa、或甚至至少70kDa的重均分子量。
去垢性聚合物:组合物可包含去垢性聚合物。合适的去垢性聚合物具有如由以下结构(I)、(II)或(III)中的一种定义的结构:
(I)-[(OCHR1-CHR2)a-O-OC-Ar-CO-]d
(II)-[(OCHR3-CHR4)b-O-OC-sAr-CO-]e
(III)-[(OCHR5-CHR6)c-OR7]f
其中:
a、b和c为1至200;
d、e和f为1至50;
Ar为1,4-取代的亚苯基;
sAr为在5位被SO3Me取代的1,3-取代的亚苯基;
Me为Li、K、Mg/2、Ca/2、Al/3、铵、单烷基铵、二烷基铵、三烷基铵或四烷基铵,其中烷基基团为C1-C18烷基或C2-C10羟烷基、或它们的混合物;
R1、R2、R3、R4、R5和R6独立地选自H或C1-C18正烷基或C1-C18异烷基;并且
R7为直链或支链的C1-C18烷基,或者直链或支链的C2-C30烯基,或者具有5至9个碳原子的环烷基基团,或者C8-C30芳基基团,或者C6-C30芳烷基基团。
抗再沉积聚合物:合适的抗再沉积聚合物包括聚乙二醇聚合物和/或聚乙烯亚胺聚合物。
合适的聚乙二醇聚合物包括无规接枝共聚物,该无规接枝共聚物包含:(i)包含聚乙二醇的亲水性主链;以及(ii)一条或多条疏水性侧链,该一条或多条疏水性侧链选自:C4-C25烷基基团、聚亚丙基、聚亚丁基、饱和C1-C6一元羧酸的乙烯基酯、丙烯酸或甲基丙烯酸的C1-C6烷基酯、以及它们的混合物。合适的聚乙二醇聚合物具有聚乙二醇主链,该聚乙二醇主链具有无规接枝的聚乙酸乙烯酯侧链。聚乙二醇主链的平均分子量可在2,000Da至20,000Da、或4,000Da至8,000Da的范围内。聚乙二醇主链与聚乙酸乙烯酯侧链的分子量比率可在1:1至1:5、或1:1.2至1:2的范围内。每个亚乙基氧单元的平均接枝位点数可小于1、或小于0.8,每个亚乙基氧单元的平均接枝位点数可在0.5至0.9的范围内,或者每个亚乙基氧单元的平均接枝位点数可在0.1至0.5、或0.2至0.4的范围内。合适的聚乙二醇聚合物为Sokalan HP22。合适的聚乙二醇聚合物描述于WO08/007320中。
纤维素聚合物:合适的纤维素聚合物选自烷基纤维素、烷基烷氧基烷基纤维素、羧基烷基纤维素、烷基羧基烷基纤维素、磺酸基烷基纤维素,更优选地选自羧甲基纤维素、甲基纤维素、甲基羟乙基纤维素、甲基羧甲基纤维素、以及它们的混合物。
合适的羧甲基纤维素具有0.5至0.9的羧甲基取代度和100,000Da至300,000Da的分子量。
合适的羧甲基纤维素具有大于0.65的取代度和大于0.45的嵌段度,例如,如描述于WO09/154933中的。
护理聚合物:合适的护理聚合物包括阳离子改性或疏水改性的纤维素聚合物。此类改性的纤维素聚合物在洗涤循环期间可向织物提供抗磨蚀有益效果和染料锁定有益效果。合适的纤维素聚合物包括阳离子改性的羟乙基纤维素。
其它合适的护理聚合物包括氨基-硅氧烷,其可提供织物触感有益效果和织物成形保持有益效果。
漂白剂:合适的漂白剂包括过氧化氢源、漂白活化剂、漂白催化剂、预形成的过酸、以及它们的任何组合。尤其合适的漂白剂包括过氧化氢源与漂白活化剂和/或漂白催化剂的组合。
过氧化氢源:合适的过氧化氢源包括过硼酸钠和/或过碳酸钠。
漂白活化剂:合适的漂白活化剂包括四乙酰基乙二胺和/或烷基苯酚磺酸盐。
漂白催化剂:组合物可包含漂白催化剂。合适的漂白催化剂包括过氧亚胺正离子的漂白催化剂、过渡金属漂白催化剂,尤其是锰和铁漂白催化剂。合适的漂白催化剂具有符合以下通式的结构:
其中R13选自2-乙基己基、2-丙基庚基、2-丁基辛基、2-戊基壬基、2-己基癸基、正十二烷基、正十四烷基、正十六烷基、正十八烷基、异壬基、异癸基、异十三烷基和异十五烷基。
预形成的过酸:合适的预形成的过酸包括邻苯二甲酰亚氨基-过氧己酸。然而,优选的是,组合物基本上不含预形成的过酸。所谓的“基本上不含”是指“没有有意加入的”。
酶:合适的酶包括脂肪酶、蛋白酶、纤维素酶、淀粉酶、以及它们的任何组合。
蛋白酶:合适的蛋白酶包括金属蛋白酶和丝氨酸蛋白酶。合适的中性或碱性蛋白酶的示例包括:枯草杆菌蛋白酶(EC 3.4.21.62);胰蛋白酶型或胰凝乳蛋白酶型蛋白酶;和金属蛋白酶。合适的蛋白酶包括前述合适蛋白酶的经化学修饰或基因修饰的突变体。
合适的可商购获得的蛋白酶包括以商品名 LiquanaseSavinase和由Novozymes A/S(Denmark)出售的那些;以商品名 Preferenz系列蛋白酶,包括P280、P281、P2018-C、P2081-WE、P2082-EE和P2083-A/J、PurafectPurafect和Purafect由DuPont出售的那些;以商品名和由Solvay Enzymes出售的那些;购自Henkel/Kemira的那些,即BLAP(序列示于US 5,352,604的图29中,具有以下突变:S99D+S101 R+S103A+V104I+G159S,下文称为BLAP);均来自Henkel/Kemira的BLAP R(具有S3T+V4I+V199M+V205I+L217D的BLAP)、BLAP X(具有S3T+V4I+V205I的BLAP)和BLAP F49(具有S3T+V4I+A194P+V199M+V205I+L217D的BLAP);以及来自Kao的KAP(具有突变A230V+S256G+S259N的嗜碱芽孢杆菌枯草杆菌蛋白酶)。
合适的蛋白酶描述于WO11/140316和WO11/072117中。
淀粉酶:合适的淀粉酶衍生自内源于芽孢杆菌属DSM 12649的AA560α淀粉酶,优选地具有以下突变:R118K、D183*、G184*、N195F、R320K和/或R458K。合适的可商购获得的淀粉酶包括Plus、Natalase、Ultra、SZ、(均得自Novozymes)和AA、Preferenz系列淀粉酶、和Ox Am、HT Plus(均得自DuPont)。
合适的淀粉酶描述于WO06/002643中。
纤维素酶:合适的纤维素酶包括细菌或真菌来源的那些。化学改性的或蛋白质工程化的突变型也是合适的。合适的纤维素酶包括来自芽孢杆菌属、假单胞菌属(Pseudomonas)、腐质霉属(Humicola)、镰孢属(Fusarium)、草根霉属(Thielavia)、枝顶孢霉属(Acremonium)的纤维素酶,例如由特异腐质霉(Humicola insolens)、嗜热毁丝菌(Myceliophthora thermophila)和尖孢镰孢菌(Fusarium oxysporum)产生的真菌纤维素酶。
可商购获得的纤维素酶包括和Premium、和(Novozymes A/S)、系列酶(DuPont)、以及系列酶(AB Enzymes)。合适的可商购获得的纤维素酶包括Premium、Classic。合适的蛋白酶描述于WO07/144857和WO10/056652中。
脂肪酶:合适的脂肪酶包括细菌、真菌或合成来源、以及它们的变体的那些。化学改性的或蛋白质工程化的突变型也是合适的。合适的脂肪酶的示例包括来自腐质霉属(同义词嗜热霉属(Thermomyces)),例如来自柔毛腐质霉(H.lanuginosa)(疏棉状嗜热丝孢菌(T.lanuginosus))的脂肪酶。
脂肪酶可为“第一循环脂肪酶”,例如,诸如描述于WO06/090335和WO13/116261中的那些。在一个方面,脂肪酶为第一洗涤脂肪酶,优选地为来自包含T231R和/或N233R突变的疏棉状嗜热丝孢菌的野生型脂肪酶的变体。优选的脂肪酶包括以商品名和由Novozymes(Bagsvaerd,Denmark)出售的那些。
其它合适的脂肪酶包括:Lipr1 139,例如如描述于WO2013/171241中的;和TfuLip2,例如如描述于WO2011/084412和WO2013/033318中的。
其它酶:其它合适的酶是漂白酶,诸如过氧化物酶/氧化酶,其包括植物、细菌或真菌来源、以及它们的变体的那些。可商购获得的过氧化物酶包括(NovozymesA/S)。其它合适的酶包括胆碱氧化酶和过水解酶,诸如,用于Gentle Power BleachTM中的那些。
其它合适的酶包括以商品名(来自Novozymes A/S,Bagsvaerd,Denmark)和(DuPont)出售的果胶酸裂解酶和以商品名(Novozymes A/S,Bagsvaerd,Denmark)和(Du Pont)出售的甘露聚糖酶。
同一性:当在本文中使用时,同一性或序列同一性是指两个氨基酸序列之间的相关性。
就本发明的目的而言,两个氨基酸序列之间的序列同一性程度使用Needleman-Wunsch算法(Needleman和Wunsch,1970,J.Mol.Biol.48:443-453)确定,如在EMBOSS程序包的Needle程序中实现(EMBOSS:The European Molecular Biology Open Software Suite,Rice等人,2000,Trends Genet.16:276-277),优选地3.0.0或更新的版本。所用的任选参数是10的空位罚分、0.5的空位延伸罚分和EBLOSUM62(EMBOSS版的BLOSUM62)取代矩阵。使用标记为“最长同一性”的Needle输出(使用-nobrief选项获得)作为百分比同一性,并且如下计算:
(相同残基×100)/(序列长度-序列中的总空位数)
沸石助洗剂:组合物可包含沸石助洗剂。组合物可包含0重量%至5重量%的沸石助洗剂,或3重量%的沸石助洗剂。组合物可甚至基本上不含沸石助洗剂;基本上不含是指“没有有意加入的”。典型的沸石助洗剂包括沸石A、沸石P和沸石MAP。
磷酸盐助洗剂:组合物可包含磷酸盐助洗剂。组合物可包含0重量%至5重量%的磷酸盐助洗剂,或至3重量%的磷酸盐助洗剂。组合物可甚至基本上不含磷酸盐助洗剂;基本上不含是指“没有有意加入的”。典型的磷酸盐助洗剂为三聚磷酸钠。
碳酸盐:组合物可包含碳酸盐。组合物可包含0重量%至5重量%的碳酸盐。组合物可甚至基本上不含碳酸盐;基本上不含是指“没有有意加入的”。合适的碳酸盐包括碳酸钠和碳酸氢钠。
硅酸盐:组合物可包含硅酸盐。组合物可包含0重量%至5重量%的硅酸盐。组合物可甚至基本上不含硅酸盐;基本上不含是指“没有有意加入的”。优选的硅酸盐为硅酸钠,尤其优选的是具有1.0至2.8,优选地1.6至2.0的Na2O:SiO2比率的硅酸钠。
硫酸盐:合适的硫酸盐为硫酸钠。
优选的增白剂为:2(4-苯乙烯基-3-磺苯基)-2H-萘酚[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-吗啉代-1,3,5-三嗪-2-基)]氨基}二苯乙烯-2-2'二磺酸二钠、和4,4'-双(2-磺基苯乙烯基)联苯二钠。合适的荧光增白剂为C.I.荧光增白剂260,该增白剂可以其β或α晶形或这些晶形的混合物形式使用。
螯合剂:组合物还可包含螯合剂,该螯合剂选自:二亚乙基三胺五乙酸盐、二亚乙基三胺五(甲基膦酸)、乙二胺-N’N’-二琥珀酸、乙二胺四乙酸盐、乙二胺四(亚甲基膦酸)、和羟乙烷二(亚甲基膦酸)。优选的螯合剂是乙二胺-N’N’-二琥珀酸(EDDS)和/或羟基乙烷二膦酸(HEDP)。组合物优选地包含乙二胺-N’N’-二琥珀酸或其盐。优选地乙二胺-N’N’-二琥珀酸为S,S对映体形式。优选地,组合物包含4,5-二羟基-间苯二磺酸二钠盐。优选的螯合剂也可充当碳酸钙晶体生长抑制剂,诸如:1-羟基乙烷二磷酸(HEDP)及其盐;N,N-二羧甲基-2-氨基戊烷-1,5-二酸及其盐;2-膦酰基丁烷-1,2,4-三羧酸及其盐;以及它们的组合。
调色剂:合适的调色剂包括小分子染料,通常属于酸性、直接、碱性、活性(包括它们水解的形式)或溶剂或分散染料的颜色索引(C.I.)分类,例如被分类为蓝、紫、红、绿或黑的染料,并且单独地或组合地提供期望色调。优选的此类调色剂包括酸性紫50,直接紫9、66和99,溶剂紫13,以及它们的任何组合。
可适用于本发明的许多调色剂是已知的并且描述于本领域中,诸如描述于WO2014/089386中的调色剂。
合适的调色剂包括酞菁和偶氮染料缀合物,诸如描述于WO2009/069077中的。
合适的调色剂可为烷氧基化的。此类烷氧基化化合物可通过有机合成制备,这可产生具有不同烷氧基化度的分子的混合物。此类混合物可直接用于提供调色剂,或可经历纯化步骤,以增加目标分子的比例。合适的调色剂包括烷氧基化的双偶氮染料,诸如描述于WO2012/054835中的,和/或烷氧基化的噻吩偶氮染料,诸如描述于WO2008/087497和WO2012/166768中的。
调色剂可作为反应混合物的一部分被掺入洗涤剂组合物中,该反应混合物是通过一个或多个任选纯化步骤有机合成染料分子的结果。此类反应混合物一般包含染料分子自身,并且此外还可包含未反应的起始材料和/或有机合成途径的副产物。合适的调色剂可被掺入调色染料颗粒中,诸如描述于WO 2009/069077中的。
染料转移抑制剂:合适的染料转移抑制剂包括聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯基吡咯烷酮、聚乙烯基噁唑烷酮、聚乙烯基咪唑、以及它们的混合物。优选的是聚(乙烯基吡咯烷酮)、聚(乙烯基吡啶甜菜碱)、聚(乙烯基吡啶N-氧化物)、聚(乙烯基吡咯烷酮-乙烯基咪唑)、以及它们的混合物。合适的可商购获得的染料转移抑制剂包括PVP-K15和K30(Ashland),HP165、HP50、HP53、HP59、HP56K、HP56、HP66(BASF),S-400、S403E和S-100(Ashland)。
香料:合适的香料包括选自以下的香料材料:(a)具有小于3.0的ClogP和小于250℃沸点的香料材料(第1象限香料材料);(b)具有小于3.0的ClogP和250℃或更大沸点的香料材料(第2象限香料材料);(c)具有3.0或更大的ClogP和小于250℃沸点的香料材料(第3象限香料材料);和(d)具有3.0或更大的ClogP和250℃或更大沸点的香料材料(第4象限香料材料);以及(e)它们的混合物。
对于香料可优选的是为香料递送技术的形式。此类递送技术还稳定并且增强沉积和香料材料从洗涤过的织物上的释放。此类香料递送技术也可用于进一步增加从洗涤过的织物上释放香料的持久性。合适的香料递送技术包括:香料微胶囊、前香料、聚合物辅助递送、分子辅助递送、纤维辅助递送、胺辅助递送、环糊精、淀粉包封的谐香剂、沸石和其它无机载体、以及它们的任何混合物。合适的香料微胶囊描述于WO2009/101593中。
硅氧烷:合适的硅氧烷包括聚二甲基硅氧烷和氨基-硅氧烷。合适的硅氧烷描述于WO05075616中。
用于制备固体组合物的方法:通常,组合物的颗粒可通过任何适合的方法制备。例如:喷雾干燥、附聚、挤出、以及它们的任何组合。
通常,合适的喷雾干燥方法包括形成含水浆液混合物、通过至少一台泵,优选地两台泵将其转移至压力喷嘴的步骤。雾化含水浆液混合物至喷雾干燥塔中并且干燥含水浆液混合物以形成喷雾干燥的颗粒。优选地,喷雾干燥塔为逆流喷雾干燥塔,尽管顺流喷雾干燥塔也可为合适的。
通常,喷雾干燥的粉末经受冷却,例如气提。通常,喷雾干燥的粉末经受粒度分级,例如筛,以获得期望的粒度分布。优选地,喷雾干燥的粉末具有粒度分布,使得重均粒度在300微米至500微米的范围内,并且小于10重量%的喷雾干燥的颗粒具有大于2360微米的粒度。
可优选的是加热含水浆液混合物以在雾化至喷雾干燥塔中之前升高温度,诸如描述于WO2009/158162中的。
对于阴离子表面活性剂,诸如直链烷基苯磺酸盐可优选的是在形成含水浆液混合物的步骤之后被引入喷雾干燥方法中:例如,在泵送之后,将酸前体引入至含水浆液混合物中,诸如描述于WO 09/158449中的。
对于气体,诸如空气可优选的是在形成含水浆液的步骤之后被引入喷雾干燥方法中,诸如描述于WO2013/181205中的。
对于任何无机成分,诸如硫酸钠和碳酸钠可优选的是如果存在于含水浆液混合物中,被微粉化成小的粒度,诸如描述于WO2012/134969中的。
通常,合适的附聚方法包括在混合器中,使去污成分,诸如去污表面活性剂,例如直链烷基苯磺酸盐(LAS)和/或烷基烷氧基化硫酸盐与无机材料,诸如碳酸钠和/或二氧化硅接触的步骤。附聚方法还可为原位中和附聚方法,其中去污表面活性剂的酸前体诸如LAS与碱性材料,诸如碳酸盐和/或氢氧化钠在混合器中接触,并且其中去污表面活性剂的酸前体在附聚方法期间被碱性材料中和以形成去污表面活性剂。
可附聚的其它合适的洗涤剂成分包括聚合物、螯合剂、漂白活化剂、硅氧烷、以及它们的任何组合。
附聚方法可为高、中、或低剪切附聚方法,其中相应地使用高剪切、中剪切或低剪切混合器。附聚方法可为多步骤附聚方法,其中使用两个或更多个混合器,诸如高剪切混合器与中或低剪切混合器组合。附聚方法可为连续方法或间歇方法。
对于附聚物可优选的是使其经受干燥步骤,例如,经受流化床干燥步骤。对于附聚物也可优选的是使其经受冷却步骤,例如,经受流化床冷却步骤。
通常,附聚物经受粒度分级,例如流化床洗提和/或筛,以获得期望的粒度分布。优选地,附聚物具有粒度分布,使得重均粒度在300微米至800微米的范围内,并且小于10重量%的附聚物具有小于150微米的粒度,并且小于10重量%的附聚物具有大于1200微米的粒度。
对于细小的和过大的附聚物可优选的是再循环返回附聚方法中。通常,过大的颗粒经受粉碎步骤,诸如研磨,并且再循环返回附聚方法中的适当位置,诸如混合器。通常,细粉再循环返回附聚方法中的适当位置,诸如混合器。
对于成分,诸如聚合物和/或非离子去污表面活性剂和/或香料可优选的是喷雾到基底洗涤剂颗粒,诸如喷雾干燥的基底洗涤剂颗粒和/或附聚的基底洗涤剂颗粒上。通常,该喷涂步骤在翻滚式转筒混合器中进行。
洗涤织物的方法:洗涤织物的方法包括使固体组合物与水接触以形成洗涤液体,以及在所述洗涤液体中洗涤织物的步骤。通常,洗涤液体具有高于0℃至90℃、或至60℃、或至40℃、或至30℃、或至20℃的温度。在使固体组合物与水接触之前、之后或同时,织物可与水接触。通常,洗涤液体通过以使得衣物洗涤剂组合物在洗涤液体中的浓度为0.2g/l至20g/l、或0.5g/l至10g/l、或至5.0g/l的此类量使衣物洗涤剂与水接触形成。洗涤织物的方法可在前加载式自动洗衣机,顶部加载式自动洗衣机,包括高效自动洗衣机,或合适的手洗容器中进行。通常,洗涤液体包含90升或更少、或者60升或更少、或者15升或更少、或者10升或更少的水。通常,使200g或更少、或者150g或更少、或者100g或更少、或者50g或更少的衣物洗涤剂组合物与水接触以形成洗涤液体。
自由流动的固体颗粒状衣物洗涤剂组合物例示性实施例:
实施例
实施例1:制备喷雾干燥的颗粒组合物的方法;硫酸镁对加工和粉末质量的影响
在浆液制造容器(搅和器)中制备以下含水洗涤剂浆液,并且随后喷雾干燥。在目标批料浆液温度为80℃下使用直接蒸汽注入(压力为6.0×105Pa的饱和蒸汽被注入搅和器中以提高温度)制备浆液,其具有25%的含水量(不考虑蒸汽冷凝)。然后将浆液泵入低压管线(具有5.0×105Pa的压力),并且然后通过喷雾压力喷嘴随后泵入高压管线(具有8.0×106Pa的压力),进入逆流喷雾干燥塔,该逆流喷雾干燥塔具有280℃的进气口温度。计量压缩空气并以0.0002kg空气/kg浆液直接注入高压管线中以降低喷雾干燥的颗粒的堆积密度。浆液的质量流量为大约1,300kg/小时。
将雾化的浆液干燥,冷却并过筛以去除过大的材料(>1.8mm)以形成喷雾干燥的粉末。细小的材料(<0.15mm)用喷雾干燥塔中的废的废气淘析,然后收集在塔后的密封系统中。喷雾干燥的粉末具有1.5重量%至2.5重量%的含水量。在生产期间监测多种质量和加工测量。这些测量包括(1)堆积密度(2)饼强度(3)平均粒度和粒度分布(4)主要喷雾干燥的粉末流以及由过大材料和过小材料两者的去除产生的再循环流的质量流量。所得喷雾干燥的粉末的组成示于下文中。
喷雾干燥的粉末:
下表呈现了喷雾干燥生产期间获得的粉末特性和工艺两者的结果。
实施例2:制备喷雾干燥的颗粒组合物的方法-柠檬酸对加工和粉末质量的影响
重复实施例1的制备方法,但使用含有较高表面活性剂和较高浆液水分(30%)的配方来比较加入氢氧化钠溶液的效果-参见下面的比较例。
喷雾干燥的粉末:
下表呈现了喷雾干燥生产期间获得的粉末特性和工艺两者的结果。比较例D产生高度易碎的颗粒,没有机械强度。
本文所公开的量纲和值不应理解为严格限于所引用的精确数值。相反,除非另外指明,否则每个此类量纲旨在表示所述值以及围绕该值功能上等同的范围。例如,公开为“40mm”的量纲旨在表示“约40mm”。
Claims (15)
1.一种喷雾干燥的基础洗涤剂颗粒,其中所述基础洗涤剂颗粒包含(按所述基础洗涤剂颗粒的重量计):
4重量%至35重量%的烷基苯磺酸盐;
0重量%至8重量%的沸石助洗剂;
0重量%至4重量%的磷酸盐助洗剂;
0重量%至8重量%的碳酸钠;
0重量%至8重量%的硅酸钠;
3重量%至10重量%的有机酸,所述有机酸为柠檬酸;
3重量%至10重量%的硫酸镁;
0.5重量%至8重量%的羧酸盐共聚物;以及
30重量%至70重量%的硫酸钠,
其中所述基础洗涤剂颗粒为喷雾干燥的颗粒,
其中在20℃下在去离子水中以1重量%稀释的所述基础洗涤剂颗粒具有8.5或更低的平衡pH。
2.根据权利要求1所述的颗粒,其中在20℃下在去离子水中以1重量%稀释的所述基础洗涤剂颗粒具有7.5或更低的平衡pH。
3.根据权利要求1或2所述的颗粒,其中所述颗粒不含碳酸钠,并且其中所述颗粒不含硅酸钠。
4.根据权利要求1所述的颗粒,其中所述基础洗涤剂颗粒包含3重量%至7重量%的柠檬酸。
5.根据权利要求1所述的颗粒,其中:
(a)阴离子去污表面活性剂包括烷基苯磺酸盐,并且其中所述基础洗涤剂颗粒包含4重量%至35重量%的烷基苯磺酸盐;并且/或者
(b)所述基础洗涤剂颗粒包含0.5重量%至5重量%的羧酸盐共聚物,其中所述羧酸盐共聚物包含:
(i)50重量%至小于98重量%的衍生自一种或多种包含羧基基团的单体的结构单元;
(ii)1重量%至小于49重量%的衍生自一种或多种包含磺酸根部分的单体的结构单元;以及
(iii)1重量%至49重量%的衍生自一种或多种类型的单体的结构单元,所述单体选自由式(I)和(II)表示的含醚键的单体:
式(I):
其中在式(I)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,前提条件是当R为单键时X表示数字1至5,并且R1为氢原子或C1至C20有机基团;
式(II)
其中在式(II)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,并且R1为氢原子或C1至C20有机基团。
6.根据权利要求1所述的颗粒,其中所述颗粒包含:
(a)0重量%至6重量%的碳酸氢钠;
(b)0重量%至4重量%的碳酸钠;
(c)0重量%至4重量%的硅酸钠;以及
(d)0重量%至4重量%的磷酸盐助洗剂,
并且任选地,其中所述颗粒不含磷酸盐助洗剂,
并且任选地,其中所述颗粒不含碳酸钠,
并且任选地,其中所述颗粒不含碳酸氢钠,
并且任选地,其中所述颗粒不含硅酸钠。
7.根据权利要求1所述的颗粒,其中所述颗粒包含去垢性聚合物。
8.根据权利要求1所述的颗粒,其中所述颗粒包含烷基氧化胺。
9.根据权利要求1所述的颗粒,其中所述颗粒包含:
(a)0.5重量%至8重量%的羧酸盐共聚物,其中所述羧酸盐共聚物包含:
(i)50重量%至小于98重量%的衍生自一种或多种包含羧基基团的单体的结构单元;
(ii)1重量%至小于49重量%的衍生自一种或多种包含磺酸根部分的单体的结构单元;以及
(iii)1重量%至49重量%的衍生自一种或多种类型的单体的结构单元,所述单体选自由式(I)和(II)表示的含醚键的单体:
式(I):
其中在式(I)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,前提条件是当R为单键时X表示数字1至5,并且R1为氢原子或C1至C20有机基团;
式(II)
其中在式(II)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0至5,并且R1为氢原子或C1至C20有机基团;和/或
(b)聚乙二醇聚合物,其中所述聚乙二醇聚合物包含具有接枝的聚乙酸乙烯酯侧链的聚乙二醇主链;和/或
(c)具有以下结构的聚酯去垢性聚合物:
其中n为1至10;m为1至15;
X为H或SO3Me;
其中Me为H、Na+、Li+、K+、Mg2+、Ca2+、Al3+、铵、单烷基铵、二烷基铵、三烷基铵或四烷基铵;其中烷基基团为C1-C18烷基或C2-C10羟烷基、或它们的任何混合物;
R1独立地选自H或C1-C18正烷基或C1-C18异烷基;和/或
(d)由结构单元(1)至(3)组成的聚酯去垢性聚合物:
其中:
a、b和c为1至10;
x、y为1至10;
z为0.1至10;
Me为H、Na+、Li+、K+、Mg2+、Ca2+、Al3+、铵、单烷基铵、二烷基铵、三烷基铵或四烷基铵,其中烷基基团为C1-C18烷基或C2-C10羟烷基、或它们的任何混合物;
R1独立地选自H或C1-C18正烷基或C1-C18异烷基;
R2为直链或支链的C1-C18烷基,或者直链或支链的C2-C30烯基,或者具有5至9个碳原子的环烷基基团,或者C6-C30芳基基团,或者C6-C30芳烷基基团;和/或
(e)羧甲基纤维素,所述羧甲基纤维素具有大于0.65的取代度和大于0.45的嵌段度;和/或
(f)烷氧基化聚亚烷基亚胺,其中所述烷氧基化聚亚烷基亚胺具有聚亚烷基亚胺核,所述聚亚烷基亚胺核具有键合到所述聚亚烷基亚胺核中的至少一个氮原子的一个或多个侧链,其中所述烷氧基化聚亚烷基亚胺具有经验式(I):(PEI)a-(EO)b-R1,其中a为所述烷氧基化聚亚烷基亚胺的所述聚亚烷基亚胺核的平均数均分子量(MWPEI)并且在100道尔顿至100,000道尔顿的范围内,其中b为在所述烷氧基化聚亚烷基亚胺的所述一个或多个侧链中的平均乙氧基化度并且在5至40的范围内,并且其中R1独立地选自氢、C1-C4烷基、以及它们的组合;和/或
(g)烷氧基化聚亚烷基亚胺,其中所述烷氧基化聚亚烷基亚胺具有聚亚烷基亚胺核,所述聚亚烷基亚胺核具有键合到所述聚亚烷基亚胺核中的至少一个氮原子的一个或多个侧链,其中所述烷氧基化聚亚烷基亚胺具有经验式(II):(PEI)o-(EO)m(PO)n-R2或(PEI)o-(PO)n(EO)m-R2,其中o为所述烷氧基化聚亚烷基亚胺的所述聚亚烷基亚胺核的平均数均分子量(MWPEI)并且在100道尔顿至100,000道尔顿的范围内,其中m为在所述烷氧基化聚亚烷基亚胺的所述一个或多个侧链中的平均乙氧基化度,所述m在10至50的范围内,其中n为在所述烷氧基化聚亚烷基亚胺的所述一个或多个侧链中的平均丙氧基化度,所述n在1至50的范围内,并且其中R2独立地选自氢、C1-C4烷基、以及它们的组合;和/或
(h)非离子去垢性聚合物和阴离子去垢性聚合物的组合。
10.根据权利要求1所述的颗粒,其中所述颗粒包含0.5重量%至5重量%的四乙酰基乙二胺钠。
11.根据权利要求1所述的颗粒,其中所述颗粒包含:
(a)0.5重量%至5重量%的甲基甘氨酸二乙酸的三钠盐(MGDA);和/或
(b)0.5重量%至5重量%的乙二胺二琥珀酸(EDDS)。
12.根据权利要求1所述的颗粒,其中所述颗粒包含4,4'-双-(三嗪基氨基)-二苯乙烯-2,2'-二磺酸增白剂和/或4,4'-二苯乙烯基联苯增白剂。
13.根据权利要求1所述的颗粒,其中所述颗粒包含0.5重量%至4重量%的4,5-二羟基-1,3-苯二磺酸二钠。
15.根据权利要求1所述的颗粒,其中所述颗粒包含聚乙烯基N氧化物聚合物。
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EP17177079.5A EP3301152B1 (en) | 2016-10-03 | 2017-06-21 | Spray-dried base detergent particle giving rise to a low ph in the wash |
EP17177076.1 | 2017-06-21 | ||
EP17177079.5 | 2017-06-21 | ||
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CN117940542A (zh) * | 2021-09-15 | 2024-04-26 | 联合利华知识产权控股有限公司 | 制备喷雾干燥的洗涤剂颗粒的方法 |
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WO2018067489A1 (en) | 2018-04-12 |
CN109790489B (zh) | 2021-06-01 |
EP3301151A1 (en) | 2018-04-04 |
CN109790489A (zh) | 2019-05-21 |
WO2018067494A1 (en) | 2018-04-12 |
RU2716255C1 (ru) | 2020-03-11 |
US20180094225A1 (en) | 2018-04-05 |
MX2019003842A (es) | 2019-06-24 |
EP3301152A1 (en) | 2018-04-04 |
EP3301153B1 (en) | 2019-09-11 |
ES2758226T3 (es) | 2020-05-04 |
ES2915331T3 (es) | 2022-06-21 |
US20180094227A1 (en) | 2018-04-05 |
CN109715773A (zh) | 2019-05-03 |
PL3301152T3 (pl) | 2022-06-13 |
HUE046263T2 (hu) | 2020-02-28 |
EP3301153A1 (en) | 2018-04-04 |
WO2018067493A1 (en) | 2018-04-12 |
MX2019003847A (es) | 2019-06-24 |
US20180094210A1 (en) | 2018-04-05 |
MX2019003846A (es) | 2019-06-24 |
PL3301153T3 (pl) | 2020-03-31 |
CN109790488A (zh) | 2019-05-21 |
EP3301152B1 (en) | 2022-05-04 |
US10676703B2 (en) | 2020-06-09 |
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