CN1234819A - 经活化的液体漂白组合物 - Google Patents
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Abstract
描述了一种包含过氧化氢或过氧化氢源,以及一种漂白活化剂的液体漂白组合物。这种液体漂白活化剂是憎水性的,并且这种组合物被配制成所说的漂白活化剂在一种包括水和一种含有阴离子和非离子表面活性剂的表面活性剂体系的亲水性基质中的微乳状液。
Description
技术领域
本发明涉及基于过氧漂白剂的液体漂白组合物,它在纺织品的漂白中特别有用。
发明背景
本领域已广泛地描述了漂白和洗涤组合物。由于种种原因希望使用过氧漂白剂而不用氯漂白剂也是众所周知的。特别是,过氧漂白剂一般被认为对织物比氯漂白剂更温和。然而过氧漂白剂具有这样的缺点,即它们一般在低温下效果较差。针对这一缺点,已描述过还含有漂白活化剂的过氧漂白组合物。漂白活化剂与过羟基离子反应产生一种过酸,它是“经活化的”漂白物种。
但是活化的漂白组合物具有这样的缺点,即活化剂和漂白剂在它们被配制成的组合物中有起反应的趋势。因此这类组合物化学上不稳定。
这个问题的一种解决办法被描述于EP598170中,其中把一种憎水性的漂白活化剂与一种亲水性的漂白剂配制在一种组合物中。这种在′170专利中的组合物被配制成含有一个亲水相和一个憎水相的乳液。亲水相包含一种亲水的非离子性表面活性剂和漂白剂,而憎水相包含一种憎水的非离子性表面活性剂和憎水的液体漂白活化剂。
在稳定性方面这些组合物是很令人满意的,但是在配方的灵活性方面则有严格的限制。例如,很难把较大量的阴离子表面活性剂掺入这些组合物中,而它可能需要一些这样的表面活性剂来使它在白度和去污方面做得更好,特别对颗粒和酶污渍,尤其是泥土和血迹。还有,憎水性非离子性表面活性剂的存在在某些特定条件下可能是一个缺点。例如,在低温、高度稀释以及短的洗涤循环下,憎水性非离子表面活性剂对于除去全部污渍只能提供有限的帮助。
这样,本发明的一个目的是配制一种能避免上述问题的活化的漂白组合物。
现已发现,这样一种组合物可被配制为将所说的憎水性液体漂白活化剂加在一种基质中形成的微乳状液,该基质包含水和一种含有阴离子和非离子表面活性剂的亲水性表面活性剂体系。
在EP598170中,组合物仅被具体描述为乳液。在专利′170中未推荐阴离子的存在。在EP92932中,描述了一种活化的漂白组合物,它是以乳液的形式存在,并且所说的漂白活化剂需要一种乳化剂。在WO93900847中叙述了活化的液体漂白组合物,它含有憎水的液体漂白活化剂,即乙酰基柠檬酸三乙酯(ATC)。含有ATC的液体组合物被一般地描述于专利′847中,它不是以微乳状液的形式存在。
发明概述
根据本发明的组合物是含有过氧化氢或过氧化氢源以及一种液体憎水性漂白活化剂的液体漂白组合物。本发明的组合物被配制成所说的憎水性液体漂白活化剂在一种基质中的微乳状液,该基质含有水、所说的过氧化氢或过氧化氢源以及一种含有阴离子和非离子表面活性剂的亲水性表面活性剂体系。
发明详述
根据本发明的组合物是液体含水漂白组合物。这样,它们含有水和漂白剂。
这里使用的合适的漂白剂包括过氧化氢或水溶性的过氧化氢源。实际上,为了保证漂白剂和漂白活化剂不过早地发生反应,主要的是这里的漂白剂要和漂白活化剂分开。因此,漂白剂应当是水溶性的。除过氧化氢以外,合适的水溶性过氧化氢源还包括过硼酸盐、过碳酸盐、过苯甲酸和烷基过苯甲酸、过硅酸盐和过硫酸盐等。这里最方便使用的是过氧化氢。按总组合物重量计,本发明的组合物应含有0.5%至20%,优选2%至15%,最优选3%至10%的过氧化氢或所说的过氧化氢源。
本发明的第二种主要成分是一种液体憎水性漂白活化剂。这里的漂白活化剂是指这样一种化合物,它和过氧化氢反应可形成一种过酸。这样形成的过酸构成了活化的漂白剂。为本发明的目的,必要的是这种漂白活化剂应是憎水性的,以保证它与亲水性的漂白剂分开,从而避免两种化合物之间的过早反应。因此,这里的憎水性漂白活化剂是指这样一种活化剂,它不能大量地和稳定地与水混溶。一般地,这样的憎水性漂白活化剂具有低于11的HLB值。这类合适的液体憎水性漂白活化剂一般属于酯类、酰胺类、酰亚胺类或酸酐类。具体地一类令人关注的漂白活化剂被公开于EP624154中,该类活化剂中特别优选的是乙酰基柠檬酸三乙酯(ATC)。ATC具有的另一个优点是它对环境无害,因为它最终被降解为柠檬酸和醇。还有,ATC在这里的组合物中具有良好的水解稳定性,并且它是一种有效的漂白活化剂。最后,它对组合物还提供良好的增效作用。在此也可能使用液体憎水性漂白活化剂的混合物。按总组合物的重量计,这里的组合物应含有0.5%至20%、优选1%至10%、最优选2%至7%的所说的漂白活化剂。
作为第三种主要成分,这里的组合物中还含有一种包含阴离子表面活性剂和非离子表面活性剂的亲水性表面活性剂体系。为了稳定地把憎水性活化剂掺入的一个关键因素是所说的表面活性剂中至少有一种必须具有与憎水性活化剂大不相同的HLB值。实际上,如果所有所说的表面活性剂都具有与憎水性活化剂相同的HLB值,则可能形成连续的单相从而降低漂白剂/漂白活化剂体系的化学稳定性。优选地,所说的表面活性剂中至少一种具有与所说的漂白活化剂相差至少1.0个HLB单位、优选2.0个HLB单位的HLB值。
这里合适的阴离子表面活性剂包括通式为ROSO3M的水溶性盐或酸类,其中R优选是一个C10-C24烃基,优选具有C10-C20烷基部分的烷基或羟基烷基,更优选具有C12-C18烷基部分的烷基或羟基烷基,和M是H或一个阳离子,例如一种碱金属阳离子(例如钠、钾、锂)或铵或取代的铵(例如甲基-、二甲基-和三甲基铵阳离子和季铵盐阳离子,诸如四甲基铵和二甲基基啶鎓(piperdinium)阳离子以及由烷基胺诸如乙胺、二乙胺、三乙胺以及它们的混合物所衍生的季铵阳离子等)。一般地,对于较低的洗涤温度(例如低于大约50℃)优选C12-C16烷基链,而对于较高的洗涤温度(例如高于大约50℃),则优选C16-18烷基链。
这里使用的其它合适的阴离子表面活性剂有通式为RO(A)mSO3M的水溶性盐类或酸类,其中R是一个具有C10-C24烷基部分的未取代的C10-C24烷基或羟基烷基基团、优选C12-C20烷基或羟基烷基、更优选C12-C18烷基或羟基烷基,A是一个乙氧基或丙氧基单元,m值大于零,一般在大约0.5和大约6之间,更优选在大约0.5和大约3之间,M是H或一个阳离子,它可以是,例如,一种金属阳离子(例如钠、钾、锂、钙、镁等),铵或取代的铵阳离子。这里也可考虑用烷基乙氧基化的硫酸盐和烷基丙氧基化的硫酸盐。取代的铵阳离子的具体实例包括甲基-、二甲基-、三甲基铵和季铵阳离子,诸如四甲基铵、二甲基基啶鎓以及由链烷醇胺类所衍生的阳离子诸如乙胺、二乙胺、三乙胺以及它们的混合物等。典型的表面活性剂有C12-C18烷基聚乙氧基化的(1.0)硫酸盐、C12-C18E(1.0)M、C12-C18烷基聚乙氧基化的(2.25)硫酸盐、C12-C18E(2.25)M、C12-C18烷基聚乙氧基化的(3.0)硫酸盐C12-C18E(3.0)M和C12-C18烷基聚乙氧基化的(4.0)硫酸盐C12-C18E(4.0)M,其中M可方便地选自钠和钾。
在此也可使用其它可用于洗涤目的的阴离子表面活性剂。这些可包括肥皂、C9-C20直链烷基苯磺酸盐、C8-C22伯或仲烷基磺酸盐、C8-C24烯烃磺酸盐、通过把碱土金属柠檬酸盐的热解产物进行磺化制得的磺化聚羧酸的盐类(包括,例如,钠、钾、铵和取代的铵盐诸如一、二和三乙醇胺盐),如在英国专利说明书No.1,082,179中所描述的;C8-C24烷基聚乙二醇醚硫酸盐(含有多至10摩尔环氧乙烷);烷基酯磺酸盐诸如C14-16甲酯磺酸盐;酰基甘油磺酸盐,脂肪油基甘油硫酸盐,烷基酚环氧乙烷醚硫酸盐,链烷烃磺酸盐,烷基磷酸盐,羟乙磺酸盐诸如酰基羟乙磺酸盐,N-酰基氨基乙磺酸盐,烷基琥珀酰胺酸盐和磺基丁二酸盐,磺基丁二酸盐的单酯(特别是饱和及不饱和的C12-C18单酯),磺基丁二酸盐二酯(特别是饱和及不饱和的C6-C14二酯),酰基肌氨酸盐,烷基多糖的硫酸盐诸如烷基多苷的硫酸盐(被描述于下文的非离子性的非硫酸化的化合物),带支链的伯烷基硫酸盐,烷基聚乙氧基羧酸盐诸如那些式子为RO(CH2CH2O)kCH2COO-M+的盐,其中R是C8-C22烷基,k是一个0至10的整数,M是可溶性的成盐阳离子。树脂酸和氢化的树脂酸也是合适的,诸如松香、氢化的松香,以及存在于妥尔油中或由它衍生的树脂酸和氢化的树脂酸。进一步的实例可见于“表面活性剂和洗涤剂(Surface Active Agents and Detergents)”(卷Ⅰ和卷Ⅱ,Schwartz、Perry和Berch著)。许多这类表面活性剂也一般地被公开于1975年12月30日授权给Laughlin等人的美国专利3,929,678中的第23栏第58行至29栏第23行(在此引入作为参考)。
用于这里的组合物中的优选的表面活性剂有烷基苯磺酸盐、烷基硫酸盐、烷基烷氧基化的硫酸盐以及它们的混合物。如前所述,阴离子表面活性剂可提供改进的洗涤性能。此外,这里的阴离子表面活性剂,即使是在低浓度和较高的温度(可达50℃)下,也显示出能改善本发明组合物的物理稳定性。
这里使用的适宜非离子表面活性剂包括烷氧基化的脂肪醇。实际上,有多种这类烷氧基化的脂肪醇可从市场上买到,它们的HLB值具有很大差异。这类烷氧基化的非离子表面活性剂的HLB值主要依赖于脂肪醇的链长、烷氧基化的性质和烷氧基化度。亲水性的非离子表面活性剂趋向于具有高的烷氧基化度和短链脂肪醇,而憎水性的表面活性剂则趋向于具有低的烷氧基化度和长链脂肪醇。可买到表面活性剂的目录,其中列举了许多包括非离子表面活性剂在内的表面活性剂,以及它们各自的HLB值。
本组合物优选的制法包括把表面活性剂和水预混合,然后加入包括过氧化氢在内的其它组分,最后加入憎水性的漂白活化剂。不考虑这一优选的加料顺序,重要的是在组分的混合过程中,组合物要经常保持在相对高搅拌能量的搅拌之下,优选在750rpm搅拌30分钟,最优选在1000rpm搅拌30分钟。
本发明的组合物进一步的特征在于它们在没有遮光剂和染料存在时宏观上是透明的,并且组合物可进一步被显微镜检验和离心法鉴定。在离心时,可观察到本发明的组合物在6000RPM转速下离心15分钟后仍不会发生析相作用。在显微镜下,组合物呈现为珠滴在基质中的分散物。基质即前述亲水性基质,珠滴则由液体憎水性漂白活化剂所构成。我们已经观察到颗粒的大小一般具有大约3微米或更小的直径。相信这里的组合物是微乳状液。
作为一种任选但优选的特性,这里的组合物应在酸性pH范围内配制,最好是在2和6之间,更优选在3和5之间。
作为另一种任选但优选的特性,这里的组合物还可包含一种通式为R1R2R3NO的氧化胺表面活性剂,其中每个R1、R2和R3独立地是一个C6-C30、优选C10-C30、最优选C12-C16的烃链。实际上,我们已经观察到通过加入这样一类氧化胺可改进化学稳定性,即可降低漂白剂和漂白活化剂的分解。相信这样的稳定性是由于氧化胺具有限制漂白剂和漂白活化剂之间的相互作用的能力,这可能是通过乳化作用达到的。相信这种稳定效果与基质无关。这样,另一方面,本发明提供了一种含有过氧化氢或过氧化氢源、一种漂白活化剂和一种氧化胺的液体含水组合物。
这里的组合物作为洗衣预处理剂特别有用,即在一种方法中,在把所说的织物进行单独的典型洗衣操作之前,把纯态的所述组合物施用到织物被弄脏的部分上。最好是,在把织物用所说的洗衣操作进行洗涤之前,让所说的组合物以纯态保留在所说的被弄脏的部分上作用一段时间。但最好是所说的纯净形式的组合物在所说的部份不致留到干燥。优选地,所说的这段作用时间在1分钟至24小时之间,更优选1分钟至1小时之间,最优选1分钟至30分钟之间。供选择地,当所说的织物被层层污渍和赃物弄脏时,所说的预处理过程还可包括搓擦和刷洗。已经观察到在这样一种预处理方法中,所述氧化胺的存在可以进一步增强对颗粒和油脂污渍的洗涤性能。相信这种在洗涤性能上的改进与基质无关。这样本发明的另一方面是提供了一种预处理织物的方法,其中织物用含有前面定义的氧化胺的组合物进行预处理。
为了获得这两种益处,这里的氧化胺存在的量按总组合物的重量计应在0.1%至10%范围内,优选1.5%至3%之间。
作为另一任选但优选的特性,这里的组合物可包含按总组合物的重量计为0.5%至5%、优选2%至4%的一种通式为HO-CR′R″-OH的醇,其中R′和R″独立地是H或C2-C10烃链和/或环。优选的具有该化学式的醇是丙二醇。实际上,我们已经发现这些醇一般地,尤其是丙二醇,也改进了组合物的化学稳定性,即也像上述氧化胺那样降低了漂白剂和漂白活化剂的分解。此外,所说的醇类还降低了产物的表面张力,从而防止了表面膜或凝胶的形成。这样,所说的醇类改进了这里的组合物的审美外观。相信所说的醇类的化学稳定化作用是双重的。首先它们可作为游离基清除剂而起作用,其次它们可与过氧化氢相互作用,防止或限制水解作用,从而降低了过氧化物分解的速率。相信通过所说的醇类获得的在化学稳定性方面的改进与基质无关。这样,本发明的另一方面是提供了一种含有过氧化氢或过氧化氢源,以及稳定量的所说的醇或它们的混合物的含水组合物。
作为另一种任选的特性,本发明的组合物还可含有具有下式的醇:其中n是一个0至10之间的整数,其中R、R′、R″、R和RⅣ可以是H或C1-C10直链或支化的烷基链,或C1-C10直链或支化的链烯基或炔基链,优选的具有这一式子的醇是苄醇。实际上,我们已经观察到这类化合物在想把本发明的微乳状液配制成低粘度,即具有5cps至2000cps的粘度、优选10cps至500cps的粘度、更优选20cps至200cps的粘度的微乳状液时具有特别的好处,上述粘度是用Brookfield主轴3在20℃、50rpm的速率下测量的。
因此,本发明的组合物可含有按总组合物的重量计多至20%,优选0.1%至10%,更优选0.5%至5%的具有上式的醇类或它们的混合物。
本发明的组合物可进一步含有多种其它供选择的组分,诸如助洗剂、螯合剂、游离基清除剂、酶、增白剂、染料、香料等。
本发明的组合物适合于多种应用,典型地有织物洗涤,特别是在预处理操作中;清洗地毯和硬表面以及盘碟等。
本发明将通过以下实施例作进一步的说明。
实施例
下面的组合物是通过按列出的比例将列出的组份混合而制得的。
列出的比例是基于总的组合物计算的重量%。
实施例1 实施例2 实施例3 实施例4漂白剂 6%H2O2 6%H2O2 6%H2O2 6%H2O2漂白活化剂 3.5%ATC 3.5%ATC 3.5%ATC 3.5%ATC非离子表面 6%Dob45-7 12%Dob45-7 12%Dob23-6.5 6%Dob.45-7活性剂 6%Dob23-6.5 6%Dob.23-6.5阴离子表面 12%C25AE3S 12%C25AE2.5S 12%NaAS 12%NaAS活性剂氧化胺 1.5% 0.5% 1.5% 3%丙二醇 3% 3% 3% 5%水和少量 加至平衡 加至平衡 加至平衡 加至平衡成份
实施例5 实施例6 实施例7 实施例8漂白剂 3%H2O2 4%H2O2 7%H2O2 6.0%H2O2漂白 3.5%OCL 3.0%NVL 3.5%OCL 3.0%活化剂 (辛酰己内酰胺)(壬酰戊内酰胺)+3.5%ATC 三乙酸甘油酯非离子 5%Dob.91-10 5%Dob91-8+ 9%Dob45-7+ 6%Dob45-7表面 +2%Dob.23-3活性剂阴离子 - 10%HLAS 6%AES 6%AS表面活性剂氧化胺 - 1.0% - 1%丙二醇 - - 3% 3%水和少 加至平衡 加至平衡 加至平衡 加至平衡量组分
实施例9 实施例10漂白剂 4%H2O2 4%H2O2漂白活化剂 2%ATC 2%ATC非离子表面活性剂 6%Neodol 45-7 6%Neodol 45-7
+3.5%Neodol 23-3 +3.5%Neodol 23-3阴离子表面活性剂 6%NaAS 6%C25AE2.5S苄醇 3% 3%水和少量组分 加至平衡 加至平衡
在上述实施例中,“Dob”代表Dobanol,是一系列可从市场上买到的非离子表面活性剂。
评估了组合物的化学稳定性并测出了下面的结果:
-过氧化氢损失:在40℃四星期后小于2%
-粘度(在20℃下的cps)实施例1-8为200-400,
实施例9和10为50-80
-相稳定性:在6000rpm下离心15分钟后未发生析相作用
-漂白活化剂活性:理论AvO值的60-80%(在洗涤条件下有效
地与过氧化氢反应的活化剂%)
Claims (15)
1.一种含有过氧化氢或过氧化氢源以及一种液体憎水性漂白活化剂的液体漂白组合物,所说的组合物被配制成所说的憎水性液体漂白活化剂在一种基质中的微乳状液,所述基质包括水、所说的过氧化氢或过氧化氢源、以及一种含有阴离子和非离子表面活性剂的亲水表面活性剂体系。
2.一种根据权利要求1的组合物,其中至少一种在所说的体系中的所述表面活性剂具有与所说的漂白活化剂相差至少1个HLB单位,优选相差2个HLB单位的HLB值。
3.一种根据前面权利要求的组合物,它含有按总的组合物重量计1%至10%的过氧化氢或所述过氧化氢源。
4.一种根据前面权利要求的组合物,它含有按总的组合物重量计0.5%至20%,优选2%至7%的所说的液体憎水性漂白活化剂。
5.一种根据前面权利要求的组合物,其中所说的液体憎水性漂白活化剂是乙酰基柠檬酸三乙酯。
6.一种根据前面任意一项权利要求的组合物,其中还含有按总的组合物重量计0.5%至5%,优选1%至3%的式R1R2R3NO的氧化胺,其中每个R1、R2和R3独立地是C6-C30,优选C10-C30,最优选C12-C16烃链。
7.-种根据前面任意一项权利要求的组合物,其中还含有按总的组合物的重量计1%至10%,优选2%至4%的式HO-CR′R″-OH的醇,其中R′和R″独立地是H或C2-C10烃链,和/或环,或者它们的混合物。
8.一种根据权利要求7的组合物,其中所说的醇是丙二醇。
9.一种根据前面权利要求的组合物,它的pH值为2至6,优选是3至5。
11.一种含有过氧化氢或过氧化氢源、一种漂白活化剂和一种式R1R2R3NO的氧化胺的液体含水组合物,其中每个R1、R2和R3独立地是C6-C30,优选C10-C30,最优选C12-C16的烃链。
12.一种预处理织物的方法,其中在把所说的织物进行单独的、典型洗衣操作之前,在织物被弄脏的部分上先施用纯态的组合物,所说的组合物含有一种式R1R2R3NO的氧化胺,其中每个R1、R2和R3独立地是C6-C30,优选C10-C30,最优选C12-C16的烃链。
13.一种预处理织物的方法,其中在把所说的织物进行单独的、典型的洗衣操作之前,在织物被弄脏的部分先施用纯态的组合物,所说的组合物是根据权利要求1-10的组合物。
14.一种含有过氧化氢或过氧化氢源以及稳定量的式HO-CR′R″-OH的醇的含水组合物,其中R′和R″独立地是H或C2-C10烃链和/或环,或它们的混合物。
15.一种根据权利要求14的组合物,其中所说的醇是丙二醇。
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US5409632A (en) * | 1992-11-16 | 1995-04-25 | The Procter & Gamble Company | Cleaning and bleaching composition with amidoperoxyacid |
ATE163037T1 (de) * | 1992-11-16 | 1998-02-15 | Procter & Gamble | Reinigungs- und bleichmittelzusammensetzungen |
GB9302015D0 (en) * | 1993-02-02 | 1993-03-17 | Unilever Plc | Improvements to hygiene compositions |
US5713962A (en) * | 1993-06-09 | 1998-02-03 | The Procter & Gamble Company | Process for the bleaching of fabrics |
US5405413A (en) * | 1993-06-24 | 1995-04-11 | The Procter & Gamble Co. | Bleaching compounds comprising acyl valerolactam bleach activators |
US5759989A (en) * | 1993-07-12 | 1998-06-02 | The Procter & Gamble Company | Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent |
JPH0734094A (ja) * | 1993-07-19 | 1995-02-03 | Kao Corp | 液体漂白剤組成物 |
ES2143538T3 (es) * | 1994-06-17 | 2000-05-16 | Procter & Gamble | Composiciones blanqueantes. |
US5880079A (en) * | 1994-06-17 | 1999-03-09 | The Procter & Gamble Company | Bleaching compositions |
US5879584A (en) * | 1994-09-10 | 1999-03-09 | The Procter & Gamble Company | Process for manufacturing aqueous compositions comprising peracids |
US5929012A (en) * | 1995-02-28 | 1999-07-27 | Procter & Gamble Company | Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage |
US5681805A (en) * | 1995-05-25 | 1997-10-28 | The Clorox Company | Liquid peracid precursor colloidal dispersions: microemulsions |
US5792385A (en) * | 1995-05-25 | 1998-08-11 | The Clorox Company | Liquid peracid precursor colloidal dispersions: liquid crystals |
US5759439A (en) * | 1996-06-14 | 1998-06-02 | The Procter & Gamble Company | Peroxygen bleaching compositions comprising peroxygen bleach and a fabric protection agent suitable for use as a pretreater for fabrics |
EP0751210A1 (en) * | 1995-06-27 | 1997-01-02 | The Procter & Gamble Company | Bleaching compositions |
US5908707A (en) * | 1996-12-05 | 1999-06-01 | The Procter & Gamble Company | Cleaning articles comprising a high internal phase inverse emulsion and a carrier with controlled absorbency |
-
1995
- 1995-12-02 DE DE69525526T patent/DE69525526T2/de not_active Expired - Fee Related
- 1995-12-02 ES ES95203330T patent/ES2173151T3/es not_active Expired - Lifetime
- 1995-12-02 ES ES00102577T patent/ES2258948T3/es not_active Expired - Lifetime
- 1995-12-02 EP EP95203330A patent/EP0735133B1/en not_active Expired - Lifetime
- 1995-12-02 EP EP00102577A patent/EP1010749B1/en not_active Expired - Lifetime
- 1995-12-02 DE DE69534793T patent/DE69534793T2/de not_active Expired - Fee Related
- 1995-12-02 AT AT00102577T patent/ATE318298T1/de not_active IP Right Cessation
-
1996
- 1996-03-04 BR BR9607962A patent/BR9607962A/pt not_active IP Right Cessation
- 1996-03-04 CN CN96194174A patent/CN1234819A/zh active Pending
- 1996-03-04 JP JP8529370A patent/JPH11502883A/ja not_active Withdrawn
- 1996-03-04 RU RU97117884/04A patent/RU2154702C2/ru active
- 1996-03-04 PL PL96322451A patent/PL181648B1/pl unknown
- 1996-03-04 AU AU51713/96A patent/AU711628B2/en not_active Ceased
- 1996-03-04 KR KR1019970706746A patent/KR19980703341A/ko active IP Right Grant
- 1996-03-04 US US08/913,376 patent/US5900187A/en not_active Expired - Fee Related
- 1996-03-04 CA CA002215709A patent/CA2215709A1/en not_active Abandoned
- 1996-03-04 WO PCT/US1996/002308 patent/WO1996030456A1/en not_active Application Discontinuation
- 1996-03-04 MX MX9707355A patent/MX9707355A/es not_active IP Right Cessation
- 1996-03-04 SK SK1313-97A patent/SK131397A3/sk unknown
- 1996-03-04 HU HU9801425A patent/HUP9801425A3/hu unknown
- 1996-03-04 CZ CZ973039A patent/CZ303997A3/cs unknown
- 1996-03-27 AR AR33592096A patent/AR001434A1/es unknown
-
1997
- 1997-09-12 NO NO974212A patent/NO974212D0/no unknown
- 1997-09-26 FI FI973808A patent/FI973808A/fi unknown
-
1998
- 1998-12-15 US US09/211,380 patent/US5997585A/en not_active Expired - Fee Related
-
1999
- 1999-09-01 AU AU45878/99A patent/AU4587899A/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1302095C (zh) * | 2001-06-29 | 2007-02-28 | 宝洁公司 | 用于纺织品应用的稳定性增强的过酸漂白体系 |
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