CN1981025B - 稳定化的增稠的包含过氧化氢的组合物 - Google Patents
稳定化的增稠的包含过氧化氢的组合物 Download PDFInfo
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Abstract
揭示了稳定化的增稠的包含过氧化氢的组合物。所述组合物包含由以下组分组成的稳定剂体系:锡酸盐稳定剂、含磷稳定剂或含磷稳定剂的混合物;以及芳香族螯合剂或芳香族螯合剂的混合物。所述组合物适合用作消毒剂、清洁剂、以及用于头发护理和牙齿美白之类的各种个人护理应用。
Description
相关申请交叉引用
本申请根据35U.S.C.§119(e)要求2004年7月9日提交的在先美国临时专利申请第60/586,682号和2004年12月28日提交的美国非临时性专利申请第11/023,705号的优先权,这些专利全文参考结合入本文中。
发明领域
本发明涉及包含过氧化氢的组合物的稳定化。具体来说,本发明涉及适用于各种消毒、清洁、个人护理、药物、织物和工业应用的稳定化的增稠的包含过氧化氢的组合物。
发明背景
为避免在清洁组合物中使用次氯酸盐溶液所固有的缺点,这些产品的制造商已经开发出了基于含水过氧化氢的替代组合物。由于过氧化氢的分解产物是氧气和水,因此从毒理学和环境角度来看普遍是可以接受的。另外,这些组合物还具有不会对纤维造成损伤和不会导致褪色的性质。
向清洁组合物中加入聚合物增稠剂以延长它们在非水平表面上的停留时间,以及提高该组合物的美观性,使该组合物便于使用,而且使组合物的其它组分悬浮于其中。由金属离子之类的催化活性物质造成的过氧化氢的分解是很难避免的。另外,许多常规的聚合物增稠剂会加快过氧化氢的分解,而且这些聚合物增稠剂自身在过氧化氢的存在下是不稳定的。因此极难制备具有所需稳定性的组合物。随着过氧化氢的过度分解,所述组合物失去了其清洁能力。另外,聚合物增稠剂的分解会降低所述清洁组合物的粘度,降低其粘附在非水平表面上的能力。
因此已开发出了稳定剂以提高包含过氧化氢的增稠的组合物的稳定性。例如在Ambuter的美国专利第5,997,764号和第6,083,422号中讨论了稳定剂,这些专利的内容参考结合入本文。尽管这些稳定剂能够延长包含过氧化氢的增稠的组合物的储藏寿命,但是这些稳定剂均无法使人完全满意。因此,人们需要具有提高的稳定性的包含过氧化氢的增稠的组合物。
发明简述
本发明是一种包含过氧化氢的增稠的组合物。该组合物包含:
a)约0.5-15重量%的过氧化氢;
b)水;
c)约0.05-10重量%的聚合物增稠剂或者聚合物增稠剂的混合物;
d)包含以下组分的增稠剂体系:
i)约10ppm至大约1%的锡酸盐稳定剂;
ii)约10ppm至大约1%的含磷稳定剂或含磷稳定剂的混合物;
iii)约10ppm至大约1%的芳香族螯合剂或芳香族螯合剂的混合物;
所述组合物的粘度约大于500cP。
包含所述三组分稳定剂体系的包含过氧化氢的增稠的组合物是可稳定储存的。
发明详述
除非另外说明,术语膦酸螯合剂,芳香族螯合剂,锡酸盐稳定剂,表面活性剂,聚合物增稠剂,焦磷酸盐,水性碱,类似的术语还包括这些材料的混合物。除非另外说明,所有的百分数均以重量为基准计(重量%),所有的温度均为摄氏温度(℃)。
本发明是一种稳定化的增稠的包含过氧化氢的组合物。该组合物包含过氧化氢、水、聚合物增稠剂和由三种组分组成的稳定剂体系:含磷稳定剂或含磷稳定剂的混合物、锡酸盐稳定剂、芳香族螯合剂或芳香族螯合剂的混合物。如果所述稳定化的增稠的包含过氧化氢的组合物被用作清洁组合物,则其中包含作为清洁组合物中的常规组分的其它组分,例如表面活性剂或表面活性剂的混合物。
聚合物增稠剂
所述稳定化的增稠的包含过氧化氢的组合物包含聚合物增稠剂或聚合物增稠剂的混合物,所述聚合物增稠剂或聚合物增稠剂的混合物有助于控制组合物的分散,延缓该组合物从施用的非水平表面流下,以及帮助悬浮组合物的其它组分。尽管所述一种或多种聚合物增稠剂的浓度取决于最终组合物所需的粘度、所含一种或多种聚合物增稠剂的性质、以及组合物中所含的其它材料的性质和浓度,但是所述稳定化的增稠的包含过氧化氢的组合物通常包含约0.01-10重量%、优选约0.05-5重量%、较优选约0.05-2.5重量%、更优选约0.25-2.0重量%的一种或多种聚合物增稠剂。所述聚合物增稠剂可分散在水中,并用碱中和,使包含过氧化氢的组合物增稠并形成凝胶。
聚合物增稠剂包括例如合成聚合物、纤维素酯和生物聚合物。合成聚合物包括例如烯键式不饱和羧酸和/或酸酐单体的均聚物和共聚物,所述单体是例如丙烯酸、甲基丙烯酸、马来酸酐、衣康酸酐等。优选的羧酸是丙烯酸。所述共聚物优选是羧酸单体和疏水性单体的共聚物。通常疏水性单体包括长链碳链丙烯酸酯或甲基丙烯酸酯,例如丙烯酸癸酯、丙烯酸月桂酯、丙烯酸硬脂酯、丙烯酸山嵛酯,以及相应的甲基丙烯酸酯,以及芳香族单体,例如苯乙烯和取代苯乙烯。这些聚合物的分子量通常约为10000-900000或更大。所述聚合物还可以是交联的。Ambuter在美国专利第5,997,764号的第6栏第1行至第7栏第29行中揭示了其它有用的聚合物增稠剂,该专利的内容参考结合入本文。
纤维素酯包括例如羧甲基纤维素、甲基纤维素、乙基纤维素、羟丙基纤维素、羟丙基甲基纤维素等。生物聚合物包括例如黄原酸胶、刺槐豆胶、瓜尔胶、角豆胶、魔芋、角叉菜胶、藻朊酸盐、果胶等。例如黄原酸胶是一种通过微生物野油菜黄单胞菌(Xanthomonas campestris)产生的高分子量多糖。
所述增稠的过氧化氢组合物的粘度将取决于组合物中所用的一种或多种聚合物增稠剂、它们的浓度、以及该组合物预期的用途所需的粘度。聚丙烯酸酯增稠剂通常提供约10000-100000cP的粘度。黄原酸胶增稠剂通常提供约500-1500cP的粘度。牙齿增白凝胶的粘度通常约大于10,000cP。必须能够倾倒的液体洗涤剂的粘度通常约为500-2000cP。
稳定剂体系
所述稳定化的增稠的包含过氧化氢的组合物包含三组分稳定剂体系.该稳定剂体系包含(a)约10ppm至约1重量%,优选约15-2500ppm(0.25重量%),较优选约20-1000ppm(0.1重量%),更优选约50-500ppm的锡酸盐稳定剂;(b)约10ppm至约1重量%,优选约15-2500ppm(0.25重量%),较优选约20-1000ppm(0.1重量%),更优选约40-500ppm的含磷稳定剂或含磷稳定剂的混合物(如果使用一种以上的含磷稳定剂的话),以及(c)约10ppm至约1重量%,优选约15-2500ppm(0.25重量%),较优选约20-1000ppm(0.1重量%),更优选约30-600ppm的芳香族螯合剂或芳香族螯合剂的混合物(如果使用一种以上的芳香族螯合剂的话).在一个实施方式中,所述稳定剂体系中这三种组分各自的含量约为30-500ppm,通常为60-300ppm.各组分和整个体系含量的上限是由经济因素和所需的稳定化程度来决定的.
本领域技术人员可以显而易见地看出,在某些pH范围内,这些稳定剂组分中的一种或多种可以以其对应的一种或多种阴离子的形式存在,或者以所述组分与其对应的一种或多种阴离子的平衡混合物的形式存在。这些稳定剂组分的阴离子以及这些稳定剂组分与其对应的一种或多种阴离子的混合物包括在对这些稳定剂组分的各定义中,包括在权利要求书的范围之内。
含磷稳定剂包括焦磷酸盐(例如Na4P2O7、Na3HP2O7、Na2H2P2O7和K2H2P2O7)和膦酸螯合剂。膦酸螯合剂包括例如具有结构通式N(CR1R2PO3H2)3的化合物,式中R1和R2各自独立地为氢或包含1-4个碳原子的烷基,例如氨基三(亚甲基膦酸)(ATMP)(2000,Solutia,St.Louis,MO,USA),其中R1和R2各自为氢;二亚乙基三胺五(亚甲基膦酸)(DTPA)(2066);六亚甲基二胺四(亚甲基膦酸)(2054);双六亚甲基三胺五亚甲基膦酸(2090);以及具有结构通式C(R3)(PO3H2)2OH的化合物,式中R3是氢或包含1-4个碳原子的烷基,例如1-羟基亚乙基-1,1-二膦酸(HEDP)(2010)(C(CH3)(PO3H2)2OH)。优选的磷基螯合剂包括1-羟基亚乙基-1,1-二膦酸、氨基三(亚甲基膦酸)和二亚乙基三胺五(亚甲基膦酸)。
所述锡酸盐稳定剂可通过硫酸锡、锡酸钠(Na2SnO3·3(H2O))、二氯化锡或四氯化锡之类的锡化合物的水解原位形成。尽管人们认为锡酸盐稳定剂是胶体氧化锡,但是通常将其称为胶体锡酸钠或锡酸钠。
增稠的包含过氧化氢的组合物包含芳香族螯合剂或芳香族螯合剂的混合物。尽管不希望被任何说明理论所限制,但是人们认为这种化合物作为自由基清除剂。所述芳香族结构包括碳环芳环,例如苯环或萘环,以及吡啶和喹啉之类的杂芳香环。所述稳定剂还应包含螯合基团,例如羟基、羧基、膦酸根或磺酸根。
所述芳香族螯合剂可以是例如水杨酸;取代水杨酸,例如3-甲基水杨酸、4-甲基水杨酸、5-甲基水杨酸、6-甲基水杨酸、3,5-二甲基水杨酸、3-乙基水杨酸、3-异丙基水杨酸、3-甲氧基水杨酸、4-甲氧基水杨酸、5-甲氧基水杨酸、6-甲氧基水杨酸、4-乙氧基水杨酸、5-乙氧基水杨酸、2-氯水杨酸、3-氯水杨酸、4-氯水杨酸、5-氯水杨酸、3,5-二氯水杨酸、4-氟水杨酸、5-氟水杨酸、6-氟水杨酸;或它们的混合物。所述芳香族螯合剂可以是例如8-羟基-喹啉;取代的8-羟基-喹啉,例如5-甲基-8-羟基-喹啉、5-甲氧基-8-羟基-喹啉,5-氯-8-羟基-喹啉、5,7-二氯-8-羟基-喹啉、8-羟基-喹啉-5-磺酸或它们的混合物。所述芳香族螯合剂可以是例如吡啶-2-羧酸,例如吡啶甲酸(2-吡啶羧酸);二吡啶甲酸(2,6-吡啶二羧酸);6-羟基-吡啶甲酸;取代的6-羟基-吡啶甲酸,例如3-甲基-6-羟基-吡啶甲酸、3-甲氧基-6-羟基-吡啶甲酸、3-氯-6-羟基-吡啶甲酸、3,5-二氯-6-羟基-吡啶甲酸;或它们的混合物。优选的芳香族螯合剂包括水杨酸、6-羟基-吡啶甲酸和8-羟基-喹啉。
水杨酸 6-羟基-吡啶甲酸 8-羟基-喹啉
其它组分
所述稳定化的增稠的包含过氧化氢的组合物可用作例如消毒洗液,或者用于氧化性染发。然而,如果所述稳定化的增稠的包含过氧化氢的组合物将用作清洁组合物,该组合物可包含作为清洁组合物常规组分的其它组分。
该组合物还可包含表面活性剂或表面活性剂的混合物。可用于清洁组合物的大量表面活性剂是众所周知的。例如在McCutcheon′s Detergents and EmulsifiersManufacturing Confectioners Publishing Company,Glen Rock,NJ以及M.and I.Ash,Chemical Publishing Co.,NY编辑的Encyclopedia of Surfactants,Volumes I-III中描述了本领域技术人员众所周知的表面活性剂。例如在Wise,美国专利第5,169,552号;Gosselink,美国专利第4,702,857号,特别是第17栏第27行至第22栏第19行,以及Laughlin,美国专利第3,929,678号,特别是第5栏第65行至第36栏第30行揭示了可用于清洁组合物的表面活性剂。以组合物重量为基准计,所述表面活性剂或表面活性剂混合物的浓度通常约为0.25-25重量%,更优选约为1.0-15重量%。较佳的是,所述一种或多种表面活性剂不含容易被过氧化氢氧化的官能团,例如碳-碳双键、羟基等。
非离子性表面活性剂通常是疏水性有机脂肪族化合物(例如长链脂肪醇)与亲水性环氧乙烷和/或环氧丙烷的缩合产物。可以调节制得的聚醚链的长度,以获得所需的疏水性和亲水性的平衡。非离子性表面活性剂包括例如乙氧基化和丙氧基化的醇,特别是C8-20醇,每摩尔醇用2-100摩尔的环氧乙烷和/或环氧丙烷进行乙氧基化和丙氧基化,具体来说是直链或支链的链结构中包含约8-18个碳原子的伯醇与大约5-30摩尔环氧乙烷的乙氧基化物,例如癸醇、鲸蜡醇、月桂醇或肉豆蔻醇的乙氧基化物;直链或支链的链结构中包含8-18个碳原子的仲脂肪醇与5-30摩尔的环氧乙烷的乙氧基化物;包含约8-20个碳原子的脂肪醇与环氧乙烷和环氧丙烷的缩合物;聚乙二醇和聚环氧乙烷;乙氧基化的氢化蓖麻油;以及山梨聚糖酯的乙氧基化物。
阴离子性表面活性剂包括例如烷基醚磷酸盐、烷基芳基磺酸盐、烷基醚硫酸盐、烷基硫酸盐、芳基磺酸盐、羧基化醇乙氧基化物、烯烃磺酸盐、琥珀酸盐、脂肪酸盐、烷基二苯基二磺酸盐等,以及它们的混合物。阴离子性表面活性剂的例子为:鲸蜡基硫酸钠、月桂基硫酸钠(SLS)、肉豆蔻基硫酸钠、硬脂基硫酸钠、十二烷基苯磺酸钠和聚氧化乙烯月桂基醚硫酸钠。
可包含其它常规的组分,只要各组分与所述增稠的包含过氧化氢的组合物的其它组分相容,而且该组分的存在不会对所述增稠的包含过氧化氢的组合物的性质造成负面影响即可。以常规的形式使用各种另外的组分来改良所述增稠的包含过氧化氢的组合物,所述另外的组分具有有效的含量,即在不会对该组合物的性质造成负面影响的前提下获得所需效果所需的量。
用于例如清洁用途的稳定化的增稠的包含过氧化氢的组合物通常还可包含约0.03-0.5重量%(以组合物为基准计)的芳香剂和香料.还可包含荧光增白剂,其含量通常约为0.1-1.0重量%.可包含抗再沉淀剂,例如聚乙烯基吡咯烷酮、羟乙基纤维素、羧甲基纤维素钠和羟丙基乙基纤维素.可包含硫酸钠或氯化钠之类的填料盐.其它常规组分包括:染料和其它着色剂;织物柔软化组合物;静电控制剂;聚苯乙烯颗粒之类的遮光剂;以及二甲基聚硅氧烷之类的泡沫调节剂.
所述稳定剂体系可以在很宽的pH范围内使用。但是所述稳定化的增稠的包含过氧化氢的组合物的pH值可约小于9,优选约小于8,较优选约为3-7,更优选约为5-7。尽管可以包含磷酸盐缓冲剂之类的缓冲剂,将pH值保持在所需的数值,但是不需要总是如此。
过氧化氢
所述稳定化的增稠的包含过氧化氢的组合物通常包含约0.5-15重量%,优选约1-10重量%,较优选约2重量-8重量%,更优选约3-5重量%的过氧化氢。过氧化氢(H2O2)可以在市场上购得,在大量的专利和出版物中描述了过氧化氢的制备。例如在Riedl的美国专利第2,158,525号中和在Kirk-Othmer Encyclopedia of Chemical Technology,第三版,第13卷,Wiley,New York,1981,第15-22页中描述了蒽醌法(也称为自然氧化法或Riedl-Pfleiderer法)。
可能需要向所述组合物中加入碱,例如氢氧化钠水溶液或氢氧化钾水溶液,直至达到所需的pH值。优选氢氧化钠水溶液。所述碱应当不含能够催化过氧化氢分解的金属离子,例如亚铁离子、三价铁离子、铜离子、亚铜离子、二价锰离子和类似的过渡金属离子。所述碱还应不含能够与过氧化氢反应的有机和无机材料。
在解决了所有的其它组分之后,所述增稠的包含过氧化氢的组合物的余量为水。由于过氧化氢通常是市场上购得的30-70重量%的水溶液,通常需要用水稀释过氧化氢,以获得所需的过氧化氢浓度。所述水应当不含能够催化过氧化氢分解的金属离子,例如亚铁离子、三价铁离子、铜离子、亚铜离子、二价锰离子和类似的过渡金属离子。所述水还应不含能够被过氧化氢氧化的有机材料。所述水还应不含能够与过氧化氢反应的无机材料,例如氯(Cl2)、次氯酸(HOCl)和次氯酸钠(NaOCl)。优选蒸馏水或去离子水。
工业实用性
所述稳定化的增稠的包含过氧化氢的组合物可用于各种消毒、清洁、个人护理、药物、织物和工业应用中。它们对所接触的表面进行消毒,因此可用作消毒溶液或消毒洗液。当包含表面活性剂的时候,它们同时对其接触的表面进行清洁和消毒。它们可通过任何能够在被清洁和/或消毒的对象与所述组合物之间确保良好接触的方法施用,例如喷涂法或擦涂法,然后通过例如用水淋洗和/或擦洗来除去。所述稳定化的增稠的包含过氧化氢的组合物还可用作例如洗涤液和用于口腔护理应用中,例如用于牙齿漂白组合物。
它们还可应用于氧化性染色,氧化性染色广泛用于染发.在氧化性染色过程中,过氧化氢与一种或多种氧化性染发剂(通常是能够扩散入头发中的小分子,包含一种或多种初级中间体和一种或多种成色剂)结合使用.所述过氧化氢使初级中间体的小分子活化,使得它们与成色剂反应,在发干上形成较大尺寸的化合物,以各种色泽和色彩对头发着色.通常的初级中间体包括对苯二胺、对甲苯二胺、对氨基苯酚和4-氨基-3-甲基苯酚.常规的成色剂包括间苯二酚、2-甲基间苯二酚、3-氨基苯酚和5-氨基-2-甲基苯酚.颜色取决于所用的一种或多种初级中间体和成色剂.通常过氧化氢是3-12重量%、优选6重量%的水溶液,该水溶液可以是粘性的液体或凝胶.通常制备包含初级中间体和成色剂的染发组合物,然后在使用的时候,将其与所述稳定化的增稠的包含过氧化氢的组合物混合,直至获得基本均一的组合物.在制备之后,迅速地将制得的组合物用于待染的头发,使其在大约15-50℃与头发接触约2-60分钟,优选约15-45分钟,特别优选约30分钟.用水淋洗头发,然后干燥.如果需要的话,用洗发剂清洗头发,并用例如水或弱酸性溶液、例如柠檬酸溶液或酒石酸溶液淋洗.然后干燥头发.
结合以下实施例可以观察到本发明的有益的性质,这些实施例是说明性的,不会对本发明构成限制。
实施例
术语
(美国宾夕法尼亚州费城罗门哈斯公司)
(美国俄亥俄州,克里夫兰,Noveon)
聚丙烯酸酯聚合物增稠剂
(美国俄亥俄州,克里夫兰,Noveon)
(美国俄亥俄州,克里夫兰,Noveon)
(美国密苏里州,圣路易斯,Solutia)
(美国密苏里州,圣路易斯,Solutia)
黄原酸胶聚合物增稠剂
(美国新泽西州,Cranbury,Rhodia)
锡酸钠 锡酸钠,Na2SnO3·3H2O
焦磷酸盐 Na2H2P2O7
一般步骤
稳定化的50%过氧化氢溶液的制备
将稳定剂与去离子水混合,以制备标准的稳定剂体系溶液。通过将所述稳定剂体系加入70%的过氧化氢中,然后用去离子水将制得的稳定化的过氧化氢稀释到50%,来制备50%的稳定化的过氧化氢溶液。
增稠的包含过氧化氢的组合物的制备
除非另外说明,所述样品包含5-6%的过氧化氢和0.4-3%的聚合物增稠剂。将聚合物增稠剂(0.7克)加入60克去离子水中,然后混合均匀。将稳定剂先于聚合物增稠剂加入所述过氧化氢溶液中。加入氢氧化钠溶液(8%),直至该混合物增稠。加入50%的过氧化氢(7毫升)和水,制备70克的增稠的包含过氧化氢的组合物,该组合物是包含过氧化氢的凝胶。用8%的氢氧化钠水溶液将pH值调节到5-7。所给的各种样品的稳定剂浓度是最终样品中活性组分的浓度。
稳定性评价
除非有另外说明,否则都采用以下的步骤进行稳定性评价。将所述样品置于40-50℃的烘箱中。测量储藏过程中所述组合物的粘度,在一些情况下还测量所述组合物中过氧化氢的浓度。使用Brookfield RVTD数字粘度计和涂敷了Brookfield树脂的转轴#6T测量粘度,粘度单位为cP。通过用高锰酸钾滴定来测量过氧化氢浓度。
实施例1
该实施例显示了包含聚丙烯酸酯聚合物增稠剂和各种稳定剂的样品的粘度以及其中过氧化氢浓度的变化。依照一般步骤所述制备了以下样品,并进行评价。结果列于表1。
所述样品各自包含5重量%的过氧化氢和1重量%的EZ-2聚合物增稠剂。其pH值为6。储存温度为45℃。
样品1-A包含<1ppm的Na2H2P2O7。
样品1-B包含150ppm的水杨酸和<1ppm的Na2H2P2O7。
样品1-C包含150ppm的HEDP和<1ppm的Na2H2P2O7。
样品1-D包含300ppm的锡酸钠和<1ppm的Na2H2P2O7。
样品1-E包含300ppm的锡酸钠,150ppm的HEDP,150ppm的水杨酸和<1ppm的Na2H2P2O7。
表1
aND表示未测定。
样品1-A几乎不含稳定剂,样品1-B至1-D仅含所述稳定剂中的一种。当这些样品在45℃的温度下储存的时候,其粘度和过氧化氢浓度都迅速减小。尽管包含锡酸钠的样品1-D的过氧化氢浓度不像其它样品减小的那样快,但是在测试过程中,该样品的粘度会减小。
样品1-E包含本发明的稳定剂体系。在测试过程中,粘度和过氧化氢都减少得较少。
实施例2
该实施例显示了包含聚丙烯酸聚合物增稠剂和本发明的稳定剂体系的样品的粘度变化。依照一般步骤所述制备了以下样品,并进行评价。结果列于表2。
所述样品各自包含5重量%的过氧化氢和3重量%的聚合物增稠剂。将pH值调节到6。储存温度为45℃。
样品2-A包含小于1ppm的Na2H2P2O7。
样品2-B包含300ppm的锡酸钠、150ppm的HEDP、150ppm的水杨酸和小于1ppm的Na2H2P2O7。
表2
样品2-A几乎不含稳定剂。在45℃下储存的时候,该样品的粘度和过氧化氢浓度都快速减小。
样品2-B包含本发明的稳定剂体系,在六周的测试时间内,粘度和过氧化氢浓度都仅略微降低。
实施例3
该实施例显示了包含聚丙烯酸酯聚合物增稠剂和本发明稳定剂体系的样品的粘度变化。依照一般步骤所述制备了以下样品,并进行表征。以cP为单位的粘度结果列于表3。
样品3-A包含0重量%的过氧化氢。
样品3-B包含5重量%的过氧化氢和<1ppm的Na2H2P2O7。
样品3-C包含5重量%的过氧化氢,40ppm的Na2SnO3·3H2O,200ppm的HEDP,500ppm的6-羟基吡啶甲酸和<1ppm的Na2H2P2O7。
表3
a粘度,单位为cP
样品3-B包含小于1ppm的稳定剂。在1周内,粘度减小超过90%。包含本发明稳定剂体系的样品3-C的粘度减小程度小于不含过氧化氢的样品3-A的粘度减小程度。
实施例4
该实施例显示了包含聚丙烯酸酯聚合物增稠剂和本发明稳定剂体系的样品的粘度变化。依照一般步骤所述制备了以下样品,并进行表征。以cP为单位的粘度结果列于表4。
这些样品各自包含1重量%的EZ 3聚合物增稠剂。将pH值调节到5。储存温度为50℃。
样品4-A包含0%的过氧化氢。
样品4-B包含5%的过氧化氢和<1ppm的Na2H2P2O7。
样品4-C包含5%的过氧化氢,80ppm的Na2SnO3·3H2O,40ppm的Na2H2P2O7,50ppm的8-羟基喹啉和<1ppm的Na2H2P2O7。
表4
a粘度,单位为cP
不使用稳定剂的样品4-B在制备时无法保持粘度。在测试过程中,包含本发明的稳定剂体系的样品4-C的稳定性与不含过氧化氢的样品4-A的稳定性相近。
实施例5
该实施例显示了包含本发明的稳定剂体系、以及作为聚合物增稠剂的黄原酸胶的样品的粘度变化。除非另外说明,否则以下的样品都是依照一般步骤所述制备和评价的。增稠剂是0.4%的T黄原酸胶。用85%的磷酸(2ppm)将pH值调节到5。储存温度为40℃。使用Brookfield DVII粘度计和Brookfield2号转轴测量这些样品的粘度,单位为cP。以cP为单位的粘度结果列于表5。
样品5-A包含0%的过氧化氢。
样品5-C包含6%的过氧化氢,2ppm的Na2H2P2O7,625ppm的2066,和500ppm的水杨酸钠。
表5
a粘度,单位为cP
使用本发明稳定剂体系的样品5-D远比仅含磷基稳定剂的样品5-B和包含膦酸盐和水杨酸盐作为稳定剂的样品5-C稳定。样品5-D似乎甚至比不含过氧化氢的样品5-A更稳定。
在对本发明进行描述之后,下面我们对以下内容及其等同内容作出权利要求。
Claims (23)
1.一种稳定化的增稠的包含过氧化氢的组合物,该组合物包含:
a)0.5-15重量%的过氧化氢;
b)水;
c)0.01-10重量%的一种或多种聚合物增稠剂;
d)包含以下组分的稳定剂体系:
i)10ppm至1%的锡酸盐稳定剂;
ii)10ppm至1%的一种或多种含磷稳定剂;
iii)10ppm至1%的一种或多种芳香族螯合剂;
所述组合物的粘度大于500cP,
所述一种或多种含磷稳定剂选自焦磷酸盐,结构为N(CR1R2PO3H2)3的化合物,其中R1和R2各自独立地为氢或包含1-4个碳原子的烷基,二亚乙基三胺五(亚甲基膦酸),六亚甲基二胺四(亚甲基膦酸),双六亚甲基三胺五亚甲基膦酸,以及具有结构通式C(R3)(PO3H2)2OH的化合物,其中R3是氢或包含1-4个碳原子的烷基;
所述一种或多种芳香族螯合剂选自水杨酸、取代水杨酸、6-羟基-吡啶甲酸、取代的6-羟基-吡啶甲酸、8-羟基-喹啉和取代的8-羟基-喹啉。
2.如权利要求1所述的组合物,其特征在于,所述组合物包含15-2500ppm的锡酸盐稳定剂;15-2500ppm的一种或多种含磷稳定剂;15-2500ppm的一种或多种芳香族螯合剂。
3.如权利要求1所述的组合物,其特征在于,所述一种或多种聚合物增稠剂选自丙烯酸的均聚物和共聚物,所述组合物包含0.05-5重量%的聚合物增稠剂。
4.如权利要求3所述的组合物,其特征在于,所述组合物的pH值为3-7。
5.如权利要求4所述的组合物,其特征在于,所述组合物包含20-1000ppm的锡酸盐稳定剂;20-1000ppm的一种或多种含磷稳定剂;20-1000ppm的一种或多种芳香族螯合剂。
6.如权利要求5所述的组合物,其特征在于,所述组合物包含50-500ppm的锡酸盐稳定剂;40-500ppm的一种或多种含磷稳定剂;以及30-600ppm的一种或多种芳香族螯合剂。
7.如权利要求6所述的组合物,其特征在于,所述一种或多种含磷稳定剂选自焦磷酸盐、氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)、六亚甲基二胺四(亚甲基膦酸)、双六亚甲基三胺五亚甲基膦酸和1-羟基亚乙基-1,1-二膦酸;
所述一种或多种芳香族螯合剂选自水杨酸、6-羟基-吡啶甲酸和8-羟基-喹啉。
8.如权利要求1所述的组合物,其特征在于,所述组合物还包含0.25-25重量%的表面活性剂或表面活性剂的混合物。
9.如权利要求8所述的组合物,其特征在于,所述组合物包含15-2500ppm的锡酸盐稳定剂;15-2500ppm的一种或多种含磷稳定剂;以及15-2500ppm的一种或多种芳香族螯合剂。
10.如权利要求9所述的组合物,其特征在于,所述组合物的pH值为3-7。
11.如权利要求10所述的组合物,其特征在于,所述组合物的粘度为10000-100000cP。
12.如权利要求11所述的组合物,其特征在于,所述增稠剂是聚丙烯酸酯增稠剂。
13.如权利要求10所述的组合物,其特征在于,所述组合物的粘度为500-2,000cP。
14.如权利要求13所述的组合物,其特征在于,所述增稠剂是黄原酸胶。
15.如权利要求10所述的组合物,其特征在于,所述一种或多种含磷稳定剂选自焦磷酸盐,结构为N(CR1R2PO3H2)3的化合物,其中R1和R2各自独立地为氢或包含1-4个碳原子的烷基,二亚乙基三胺五(亚甲基膦酸),六亚甲基二胺四(亚甲基膦酸),双六亚甲基三胺五亚甲基膦酸,以及具有结构通式C(R3)(PO3H2)2OH的化合物,其中R3是氢或包含1-4个碳原子的烷基;
所述一种或多种芳香族螯合剂选自水杨酸、取代水杨酸、6-羟基-吡啶甲酸、取代的6-羟基-吡啶甲酸、8-羟基-喹啉和取代的8-羟基-喹啉。
16.如权利要求15所述的组合物,其特征在于,所述组合物包含20-1000ppm的锡酸盐稳定剂;20-1000ppm的一种或多种含磷稳定剂;20-1000ppm的一种或多种芳香族螯合剂。
17.如权利要求16所述的组合物,其特征在于,所述组合物包含50-500ppm的锡酸盐稳定剂;40-500ppm的一种或多种含磷稳定剂;以及30-600ppm的一种或多种芳香族螯合剂。
18.如权利要求17所述的组合物,其特征在于,所述一种或多种含磷稳定剂选自焦磷酸盐、氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)、六亚甲基二胺四(亚甲基膦酸)、双六亚甲基三胺五亚甲基膦酸和1-羟基亚乙基-1,1-二膦酸;
所述一种或多种芳香族螯合剂选自水杨酸、6-羟基-吡啶甲酸和8-羟基-喹啉。
19.如权利要求18所述的组合物,其特征在于,所述组合物包含0.05-2.5重量%的聚合物增稠剂和2-8重量%的过氧化氢。
20.如权利要求19所述的组合物,其特征在于,所述组合物的粘度为10,000-100,000cP。
21.如权利要求20所述的组合物,其特征在于,所述增稠剂是聚丙烯酸酯增稠剂。
22.如权利要求19所述的组合物,其特征在于,所述组合物的粘度为500-2,000cP。
23.如权利要求22所述的组合物,其特征在于,所述增稠剂是黄原酸胶。
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- 2005-06-22 WO PCT/US2005/022237 patent/WO2006016990A2/en not_active Application Discontinuation
- 2005-06-22 CN CN2005800229715A patent/CN1981025B/zh active Active
- 2005-06-22 BR BRPI0513158A patent/BRPI0513158B1/pt not_active IP Right Cessation
- 2005-06-22 MX MX2007000269A patent/MX2007000269A/es active IP Right Grant
- 2005-06-22 AU AU2005272069A patent/AU2005272069B2/en not_active Ceased
- 2005-06-22 CA CA2572839A patent/CA2572839C/en active Active
- 2005-06-22 EP EP05786814A patent/EP1789524B1/en active Active
- 2005-06-22 JP JP2007520332A patent/JP5410676B2/ja active Active
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BRPI0513158A (pt) | 2008-04-29 |
US20060009371A1 (en) | 2006-01-12 |
US7045493B2 (en) | 2006-05-16 |
EP1789524B1 (en) | 2012-04-11 |
JP5410676B2 (ja) | 2014-02-05 |
AU2005272069A1 (en) | 2006-02-16 |
ES2385656T3 (es) | 2012-07-27 |
AU2005272069B2 (en) | 2010-07-08 |
EP1789524A2 (en) | 2007-05-30 |
US20060063695A1 (en) | 2006-03-23 |
WO2006016990A2 (en) | 2006-02-16 |
JP2008506008A (ja) | 2008-02-28 |
WO2006016990A3 (en) | 2006-07-27 |
EP1789524A4 (en) | 2009-05-06 |
BRPI0513158B1 (pt) | 2018-11-21 |
CA2572839A1 (en) | 2006-02-16 |
MX2007000269A (es) | 2007-04-02 |
CA2572839C (en) | 2011-11-08 |
CN1981025A (zh) | 2007-06-13 |
ATE553176T1 (de) | 2012-04-15 |
US7169743B2 (en) | 2007-01-30 |
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