CN102167960A - 用于施用在卫浴用品上的粘附剂 - Google Patents
用于施用在卫浴用品上的粘附剂 Download PDFInfo
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- CN102167960A CN102167960A CN2011100326360A CN201110032636A CN102167960A CN 102167960 A CN102167960 A CN 102167960A CN 2011100326360 A CN2011100326360 A CN 2011100326360A CN 201110032636 A CN201110032636 A CN 201110032636A CN 102167960 A CN102167960 A CN 102167960A
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Abstract
本发明涉及一种应用于卫浴领域的制剂,该制剂可直接施加于卫浴用品上,粘附于此,只有经相对多次数的冲洗操作后才会被冲掉,其中,该制剂含有填充剂及粘合促进剂,其中,该粘合促进剂选自聚亚烷基衍生物、氢化的聚苯乙烯衍生物、硅氧烷体系、选自聚(甲基乙烯基醚/羧酸酐的单烷基酯的共聚物、烯烃均聚物及两种或更多种烯烃的共聚物,其中,烯烃均聚物及烯烃共聚物也可被部分氢化、部分氧化或通过接枝分子进一步官能团化,及聚亚烷基亚胺(其也为烷氧基化的形式)、聚醚胺(烷氧基化胺)及聚甘油聚醚烷基羧酸或含有所述聚合物种类的聚合物或衍生物,该制剂的粘度至少为30Pa s,其使用Haake粘度计测量,板/板***,板直径为10mm,剪切率为2.62s-1,20℃,该制剂所具有的粘性可将块状制剂固定在坐便器上,本发明此外还涉及所述制剂的应用及一种制备此制剂的方法。
Description
本申请是2010年8月30日进入中国国家阶段的PCT申请(其中国国家申请号为200980107059.8)的分案申请。
技术领域
本发明涉及一种用于卫浴领域,特别是施用于卫浴用品上的制剂,例如施用于坐便器水槽。
现有技术
所述制剂具有粘性,通常为糊状,其例如由适当的容器直接施用于卫浴用品表面,粘附于此,只有经相对多次数的冲洗后才会被冲掉。
WO 99/66017公开一种用于清洁及芳香的卫浴制剂,其含有表面活性剂、水、芳香剂、制剂。将该卫浴制剂直接施用于卫浴用品上后,只有经相对多次数的冲洗后才能被冲刷掉。
EP 1325103B1公开此种卫浴制剂的改进方案,其因添加有多元醇而表面更为光滑。
EP 1318191B1公开其它卫浴制剂,这些制剂基于含寡聚亚烷基氧化物或聚亚烷基基氧化物的嵌段共聚物或基于芳基乙氧基化物或烷基芳基乙氧基化物,DE 102004056554A1则公开含漂白剂的卫浴制剂。
所述公知的卫浴制剂可通过恰当的设备以简单且卫生的方式进行施加,其粘着于卫浴用品表面,保持其形状不变,水无法将其完全冲刷,只有经相对多次数的冲洗后才会逐渐分解。
近年来涌现了多种使用在坐便器的厕所小筐中的传统块状厕所清洁剂及芳香剂的多相产品:
例如WO 00/23558所公开的含附加漂白剂的卫浴制剂,EP 1418225A1所公开的含清洁剂型体相及凝胶相的卫浴制剂,以及WO 00/58434所公开的清洁剂型体,其包括含水溶性盐类及非水溶性盐类的相。
所述多相制剂可通过将厕所清洁剂及芳香剂划分为需完成各种功能的多个相,举例而言,专门相用于强效芳香,专门相用于清洁,从而可更佳地满足用户要求。
本发明的目的在于提供一种可以简单且卫生的方式施用的卫浴制剂,其可多方面应用,且在强效芳香及有效清洁方面可满足用户需求。
此目的通过如权利要求1的特征而达成。
本发明出人意料地发现,粘度至少为30Pa s(其使用Haake粘度计测量,板/板***,板直径为10mm,剪切率为2.62s-1,20℃)且含填充剂及粘合促进剂的卫浴制剂不仅可直接施加于卫浴用品上,粘附于此,只有经相对多次数的冲洗操作后才会被冲掉,也可通过其粘性将块状卫浴制剂固定在坐便器上,其中,该粘合促进剂选自聚亚烷基衍生物、氢化的聚苯乙烯衍生物、硅氧烷体系、选自聚(甲基乙烯基醚/羧酸酐的单烷基酯的共聚物、烯烃均聚物及两种或更多种烯烃的共聚物,其中,烯烃均聚物及烯烃共聚物也可被部分氢化、部分氧化或通过接枝分子(Pfropfmolekül)进一步官能团化,及聚亚烷基亚胺(其也为烷氧基化的形式)、聚醚胺(烷氧基化胺)及聚甘油聚醚烷基羧酸(烷氧基化聚甘油的酯)或含有所述聚合物种类的聚合物或所述化合物的衍生物。
专用粘合促进剂用于使卫浴制剂粘附于卫浴用品表面上,以及将其它材料(如含有具清洁及芳香作用的有效成分的块状卫浴制剂)粘着于制剂表面。这些粘合促进剂的另一特点在于,含有此粘合促进剂的卫浴制剂可无残余地被冲刷掉,含有该粘合促进剂的卫浴制剂中粘合促进剂与填充剂的混合比的变化对卫浴制剂无明显影响。
通过添加适当的填充剂可对卫浴制剂的粘度和/或可冲刷性进行调节,以及使卫浴制剂达到预期的芳香及染色效果。
本发明的卫浴制剂具有广泛用途:
在使用水溶性粘合促进剂的情况下,该卫浴制剂可用作暂时起粘着作用的水溶性粘附剂,将块状清洁剂(例如连续挤压型体形式清洁剂)固定在坐便器中,这些清洁剂从而不再需要专门的固定装置。
在将该卫浴制剂作为“纯粘附剂”而施用时,卫浴制剂成为了被用户认为是不卫生的厕所小筐的替代品。施用于坐便器表面的制剂上可固定含有效成分且具自有功能的块状制剂,如具有一个或多个相的传统清洁块、具有芳香相的清洁块、芳香片、含有漂白剂的清洁块等,其中,制剂卫生地取代厕所小筐,反复冲洗后与粘着于其上的块状制剂一起被冲掉。当然也可将用粉末或颗粒压制而成的片剂或含有效成分的水溶性或非水溶性塑料固定于制剂上。
在此种应用中,该卫浴制剂含有至少一种本发明的粘合促进剂及增稠剂。由于本发明的粘合促进剂通常为粘性液体,故必须添加增稠剂作为填充剂,才能使该卫浴制剂的粘度达到至少为30Pa s的预期值。由于本发明的粘合促进剂为水溶性,故在该实施形式中无需添加用于提高冲洗性能的表面活性剂。
当然也可在该由粘合促进剂及增稠剂组成的基础配方中添加其它成分,例如染料、芳香剂、任选地表面活性剂及起泡剂等。
根据第一实施方式的一种改进方案,该卫浴制剂除粘合促进剂及增稠剂外还含有香料,故该卫浴制剂可同时起到粘着及芳香两种作用。
在第二应用方式中,该制剂含有本发明的粘合促进剂及作为填充剂的表面活性剂,因而通过对表面活性剂及可能的其它添加剂的类型及浓度进行适当选择,可使该制剂自身即具有清洁功能。利用粘附作用可在坐便器中施加其它期望的有效制剂,例如将芳香剂、漂白片剂、去垢片剂及广告载体等。
通过具清洁作用的制剂,用户可例如依据自身意愿选择相应的香味以及将相应的芳香片压至已施用的具清洁作用的制剂上,芳香片从而可粘附于制剂上,此做法可使厕所持续芳香一或两周。
本发明的制剂甚至可与一系列的芳香片或芳香凝胶、漂白片剂、去垢片剂及强效清洁片剂等整套配合使用,用户从而可为其制剂进行个性化配备。
若用户期望进行额外漂白,则可将漂白片剂粘着于制剂表面。
若用户期望对厕所进行强效清洁,则可在已具清洁作用的制剂上另粘附清洁片剂。也可构建由粘附剂-功能制剂-粘附剂-功能制剂等若干层构成的多层制剂。
开篇所述的公知制剂虽可良好而持久地粘附于卫浴用品上,但这些卫浴制剂上无法“粘附”其它制剂。
除用于厕所卫生外,该制剂也可用作冷粘附剂,其由于添加有表面活性剂而可被水冲掉。该制剂可在卫浴范围内作为冷粘附剂用于固定小便池中的物品,也可使用在冲淋装置中的盥洗水槽或瓷砖上,或使用在厨房、餐厅、屠宰间或其它可用水冲刷的地方。
若将该冷粘附剂使用在可用水冲刷的地方,则可在冲刷掉制剂的同时也通过制剂所含的表面活性剂进行清洁。
也可将本发明的制剂使用于机动车的清洗装置中或施用于下水道或排水沟之上或之中,从而实现暂时芳香。
本发明的制剂也可作为用于容纳防治害虫的饵料的可洗刷掉的软膏使用,或将其连续使用而用于固定易淋雨的窗玻璃或房屋正面。
本发明的制剂的各成分为:
选自聚亚烷基衍生物的非水溶性粘合促进剂的优选类别含有聚亚烷基链,所述聚亚烷基链具有无规分布官能团。所述聚亚烷基链优选为聚丁二烯、聚异丙基及聚丙烯链。
无规分布于聚亚烷基链上的官能团优选为反应性基团,特别而言选自酐、硫醇、环氧化物或伯胺。
特别优选者为含有无规键合在聚丁二烯链上的顺丁烯二酸酐基的聚合物。1,4-顺-聚丁二烯上的特别优选顺丁烯二酸酐加合物由Degussa公司以“Polyvest”的名称销售。选自聚苯乙烯衍生物的粘合促进剂特别优选为溶于矿物油的交联聚苯乙烯衍生物,特别而言为亚烷基苯乙烯共聚物,例如氢化的丁烯/乙烯/苯乙烯共聚物及氢化的乙烯/丙烯/苯乙烯共聚物,这些共聚物例如由Penreco公司以商业名“Versagel M750”或“Versagel M1600”进行销售。
此外可将硅氧烷体系用作非水溶性粘合促进剂,例如选自解离出乙酸的结构硅氧烷(Bausilikon)、(醋酸酯体系)的硅氧烷体系。
这些也被称作“冷固化单成分硅氧烷橡胶”的有机硅氧烷烷混合物通常会在室温下在从周围环境吸水的情况下交联成橡胶弹性聚合物。将双官能及优选更多官能的乙酰氧基硅烷化合物用作增链剂及交联剂,这些乙酰氧基硅烷化合物通过与聚硅氧烷反应或通过水解作用解离乙酸,从而引起大分子网络的形成。
原则上也可将基于胺/胺氧基体系、肟体系、苯甲酰胺体系及烷氧基体系的硅氧烷体系用作粘合促进剂,仅需这些体系可被此处所说明的附加体系成分稳定成均匀、稳定的混合物。
此外可将非水溶性烯烃均聚物以及两种或更多种烯烃的共聚物用作粘合促进剂。举例而言,聚丁二烯橡胶、苯乙烯-丁二烯嵌段共聚物及聚异丙烯属于此类化合物。也可使用“无规(嵌段)聚合物”(通过在苯乙烯或α-甲基苯乙烯上1,3-加成丁二烯或异戊二烯而制成)、乙烯及丙烯的均聚物或共聚物(如乙烯-丙烯二烯-三元共聚物、乙烯-环氧乙烷-共聚物)、天然橡胶及降冰片烯聚合物(如聚双环戊二烯)。选自烯烃均聚物及共聚物的化合物也可部分氢化、部分氧化或通过接枝分子(Pfropfmolekül)进一步官能团化。
也可将选自聚(甲基乙烯基醚/羧酸酐的单烷基酯的共聚物用作水溶性粘合促进剂,这些共聚物由(例如)ISP公司以商标名“Gantrez”销售。
该水溶性粘合促进剂的另一优选类别为聚亚烷基亚胺,即聚合胺或含聚亚胺基团的聚合物。聚亚胺的类别特别而言含有通式-(R-NH)n-(其中R=烷基或烷基衍生物,n=10-105)及通过氮官能团实现的二维或三维交联(取决于氮上的烷化程度或芳基化程度)的均聚聚亚烷基亚胺。
聚亚烷基亚胺的一种优选类别为聚合球形聚亚烷基亚胺,其基础特别而言为伯、仲及叔胺官能团之间存在特定比例的均聚聚乙烯。该聚乙烯亚胺可与水或酸发生季铵化,即产生聚阳离子。
当然,该聚乙烯亚胺作为亚烷基除亚乙基外也可含有亚甲基、亚丙基、亚丁基或更高级的亚烷基。
聚亚烷基亚胺由BASF公司以商标“Lupasol”及不同的摩尔质量及交联度供应。
聚亚烷基亚胺原则上也可以衍生物和/或阳离子聚合物的形式存在。
聚亚烷基亚胺溶于水及其它极性溶剂。
也可以烷氧基化、乙氧基化或丙氧基化形式使用该聚亚胺。
同样可溶于水的聚醚胺(烷氧基化胺)也可用作粘合促进剂。
所涉及者特别而言为乙氧基化或丙氧基化的伯和/或仲和/或叔烷基胺或芳基胺。烷基或芳基可分枝,从而(形式上)产生二-、三-、寡-或聚(EO/PO)-胺。烷氧基化聚胺与其它官能团发生典型的胺反应(酰胺形成、脲类似物、带羰基的亚胺形成等)。
该烷氧基化聚胺优选选自聚醚胺。这些聚醚胺可含有三官能、双官能和/或单官能伯胺,作为聚醚基可含有聚环氧乙烷基、混合聚(环氧乙烷/环氧丙烷)基或聚环氧丙烷基,其中,这些聚醚胺的亲水性按此顺序减小。该烷氧基化胺当然也可含有其它聚醚基,例如聚氧化丁烯基。
也可使用含二胺的聚醚胺或含仲胺的聚醚胺。
聚醚胺的摩尔质量可在较大范围内发生变化。本发明范围内使用摩尔质量为500-5000的聚醚胺。
鉴于烷氧基化胺粘度较小,故本发明的制剂内须以填充剂的形式添加增粘物质,例如粉末表面活性剂、多糖(木粉、淀粉、麦粉)、木质素等。
此外也可将符合以下化学式的乙氧基化聚胺(即通过聚胺的乙氧基化而获得的体系)用作聚胺衍生物:
其中,R1=烷基或烷基衍生物,R2,R3=(-CH2-CH2-O)n-R4或(-(CH2)3-O)n-R4,R4=H、烷基、芳基,n=1-100。
也可将通过在氮官能团上发生反应而获得的化合物用作聚胺衍生物,例如聚胺酯衍生物等,也就是说,R2,R3=C(O)-N-X,其中X=共聚物,例如聚胺酯,也就是说,侧基(Seitenrest)再度接在上述化学式(1)中的聚合链(亚胺可视为嵌段聚合物的准共聚物)上。
根据本发明,此外也可将聚甘油聚醚烷基羧酸用作水溶性粘合促进剂。聚甘油聚醚烷基羧酸为通过甘油发生酯化的聚烷基醚羧酸,例如聚乙二醇-150-聚甘油基-2-三硬脂酸酯或PEG-150-二甘油基-三硬脂酸酯或PEG-150-四甘油基-二硬脂酸酯,其中,PEG-150-聚甘油基-2-三硬脂酸酯为优选的。
该聚合物由聚甘油基-骨架(Rückgrad)构成,该骨架上通过挠性链固定有脂肪酸基。
增稠效果的基础可能在于PEG-150-聚甘油基-2-三硬脂酸酯的脂肪酸基与该配方内的表面活性剂微胞之间的联合相互作用。通过物理相互作用可形成三维网络,此网络在水性表面活性剂体系(例如在厕所内实施冲刷过程)中具提高粘度的作用。该聚合物的结构(即该脂肪酸基的极性(碳链长))、该挠性间隔链的长度(该PEG的乙氧基化程度)及该骨架的结构(甘油单元数量)均会对增稠特性产生影响。
当然也可将上述粘合促进剂的组合应用于本发明的制剂。
选择粘合促进剂时也须对其反应性加以考虑。在本发明范围内不应将反应性特强的聚合主导化合物(例如硅氧烷物质)用作粘合促进剂,因为这些聚合初始化合物会一直发生聚合反应,从而愈变愈粘稠。基于聚胺酯的体系或包括含环氧化物的初始化合物的体系反应速度也过快,混合时即变得粘塑。这些体系仅具极小的粘着作用或完全不具有粘着作用。
该粘合促进剂使该制剂粘附于卫浴用品表面。本发明的制剂既可粘附于干燥表面,也可粘附于潮湿表面。
此外,该专用粘合促进剂也可使所施用的制剂的表面具有粘性,由此可在该制剂的表面粘着其它有效制剂。
该粘合促进剂通常也会产生网络状结构,此结构使该制剂即便在受到冲洗用水的极大作用力的情况下也能具有必要的形状稳定性。
该粘合促进剂的所用浓度取决于该粘合促进剂的材料类别及网络形成能力,通常为2wt%-60wt%,优选7wt%-50wt%,特别优选8wt%-40wt%。
此外,本发明的制剂所含的填充剂可选自下列:表面活性剂、增稠剂、芳香剂、染料、盐类、泡沫稳定剂、增泡剂、起泡剂及聚合的天然材料。
原则上可使用所有公知的阴离子表面活性剂和/或阳离子表面活性剂和/或非离子性表面活性剂和/或两性表面活性剂,其中,粉末状至硬糊状表面活性剂为优选的。该制剂内的表面活性剂含量应为0wt%-80wt%,优选为10wt%-60wt%,特别优选为25wt%-45wt%。
阴离子表面活性剂在本发明中具有多种作用;其一,当聚合物基质为非水溶性时,阴离子表面活性剂在不破坏粘性的情况下将该聚合物基质乳化。其次,阴离子表面活性剂作为增粘剂(增稠剂)也具有将该初始聚合物(粘合促进剂)塑化的作用。阴离子表面活性剂优选也应具有强效起泡作用,以便在坐便器中产生视觉上的清洁效果。最后,此类表面活性剂也应具有由良好的润湿特性支持的良好的清洁效用。
优选将选自羧酸盐、硫酸半酯及磺酸,优选选自脂肪酸、脂族烷基硫酸及烷基芳基磺酸的一种或多种物质用作阴离子表面活性剂。这些阴离子表面活性剂的碳链分布范围为6至40个碳原子,优选为8至30个碳原子,特别而言为12至22个碳原子。
金属盐类(优选碱金属盐)及天然或合成混合物形式的羧酸(C6-C22)以及硫酸半酯及长链醇类的碱金属盐也可用作阴离子表面活性剂。
可用于本发明的另一类别的阴离子表面活性剂是烷基醚硫酸的碱金属盐。烷基醚硫酸与烷基硫酸一样是用脂肪醇合成,脂肪醇与环氧乙烷反应生成相应的脂肪醇的乙氧基化物。也可用环氧丙烷代替环氧乙烷。随后由相应的烷基醚硫酸提供磺化作用。
在本发明范围内,也可将烷磺酸及烯烃磺酸的碱金属盐用作阴离子表面活性剂。烷磺酸可以末端键合(伯烷磺酸)或沿碳链(仲烷磺酸)的方式含有磺酸基。具代表性的典型者为烷基苯磺酸盐,特别优选为直链烷基苯磺酸盐(LAS)。
上述的阴离子表面活性剂可以其中性形式单独使用,或彼此混合使用。
在本发明范围内,若以重量为基准,该表面活性剂相优选含有10wt%至90wt%的月桂基硫酸盐,特别优选含有40wt%至85wt%的月桂基硫酸盐。
在含有基于丁二烯衍生物的低粘粘合促进剂的制剂中,阴离子表面活性剂同时也具有增稠剂的作用。
可将烷氧基化的,优选乙氧基化的,特别而言含有优选8至18个C原子、每摩尔醇平均1至12摩尔亚乙基氧(EO)的伯醇用作非离子性表面活性剂,在这些醇中,醇基可为直链或优选为2位甲基支链,或者含有如含氧醇基中的混合状态的直链基及甲基支链基。但含有C原子数为12至18的天然醇类(例如椰油醇、棕榈油醇、动物脂醇或油醇)直链基、每摩尔醇平均2至8摩尔EO的醇乙氧基化物为优选的。除这些非离子性表面活性剂外,也可使用12EO以上的脂肪醇。例如14EO、25EO、30EO或40EO的动物脂醇。
此外也可将通式为烷基-O(G)的烷基糖苷用作非离子性表面活性剂,其中,“烷基”代表含有8至22个、优选12至18个C原子的伯直链脂族基或甲基支链(特别而言为2-甲基支链)脂族基,G代表含有5或6个C原子的糖苷单元,优选代表葡萄糖。
可用于本发明的另一优选类别的非离子性表面活性剂是烷基链中优选含1至4个碳原子的烷氧基化脂肪酸烷基酯,优选乙氧基化脂肪酸烷基酯或乙氧基化及丙氧基化脂肪酸烷基酯,特别而言脂肪酸甲酯,这些非离子性表面活性剂既可单独使用,也可与其它非离子性表面活性剂结合使用。也可将氧化胺用作非离子性表面活性剂,例如N-椰油烷基-N,N-二甲胺基氧化物及N-牛脂烷基-N,N-二羟乙基氧化胺或链烷醇酰胺。
该或所述非离子性表面活性剂在整个表面活性剂相上的含量至多50%,优选至多30%,特别优选至多25%。
若需要,也可为该表面活性剂相配备阳离子表面活性剂或两性表面活性剂或两性离子表面活性剂。举例而言,可为两性表面活性剂配备具有C5-C12脂肪酸含量的脂肪酸酰胺丙基甜菜碱,当然也可配备两性二乙酸酯。
阳离子表面活性剂优选在酸性配方中与杀菌物质结合使用。两性离子表面活性剂可示范性地描述成季铵成分、鏻成分或锍成分,其通过脂族桥键与其它阴离子基团(例如羧基、磺酸盐、硫酸盐、磷酸盐或膦酸盐)相连。
该制剂内可继续添加用作起泡剂的烯基磺酸盐、醚硫酸酯或酸甲基牛磺酸()。若需使用强效起泡剂,则可将该表面活性剂的优选1%至50%,特别而言1-25%替换成一种或多种选自(例如)甜菜碱、烷氧基化烷基醚硫酸酯或乳糖酸衍生物的起泡剂。此类起泡剂可在具有C5-C21脂肪酸含量的脂肪酸酰胺丙基甜菜碱(例如椰油酰胺丙基甜菜碱)、具有1至5EO的月桂基醚硫酸酯的碱金属盐或铵盐、乳糖椰油酰胺(Lactobionococoylamid)、乳糖油酰胺、乳糖动物脂酰胺等等及其混合物中选择。这些起泡剂可良好地进入该制剂内。优选使用以固态、优选粉末状或高粘的形式存在的助表面活性剂。
除本发明的成分外,该制剂可含有其它常用成分,例如盐类、杀菌剂(例如氧或氯气释放剂)、防腐剂(例如异噻唑啉酮衍生物)、泡沫稳定剂(例如链烷醇酰胺)、疏水剂(例如矿物油或(部分)甲基化的硅氧烷及硅烷)、钙分散剂(如多元羧酸的钠盐)或染料。
通过香料油或芳香剂的添加,该制剂也可用于室内空气除臭。
可将各种芳香物质化合物(例如醛、醇、酯、醚、酮及烃的合成产物)用作香料油或芳香剂。酯类芳香物质化合物例如有乙酸苄酯或甲酸苄酯。醚类有苄基乙基醚,醛类有香茅醛,酮类有α-异甲基紫罗兰酮,醇类有香茅醇、丁香油酚、香叶醇及沉香醇。烃类主要有萜类,如柠檬油精及蒎烯。但优选使用不同芳香物质的混合物,以便产生所期望的香味。其中包括含有草本天然芳香物质混合物的香料油,例如松油、柑橘油、熏衣草油、薄荷油或橘皮油。
芳香剂以0.25wt%-20wt%,优选3wt%-15wt%,特别优选5wt%-10wt%的浓度直接加入该配方。
若需要,也可在此配方内添加盐类填充剂,例如硫酸钠,以便提高溶解速度。最高为90wt%的盐类含量可极大地降低产物成本。盐类含量通常最高为10wt%,优选最高为5wt%。强酸的碱金属盐(如硫酸钠、氯化钠或聚磷酸钠)为适用的盐类。也可使用单羧酸、二羧酸及多元羧酸的碱金属盐及强酸的碱土金属盐(如硫酸钙)或碳酸的盐类。
使用钙盐可提高该制剂的耐久性,因为钙盐在聚丁二烯衍生物的基础上与该粘合促进剂的顺丁烯二酸酐共同形成聚皂,该聚皂具疏水作用,且在形成钙皂网络的情况下将整个体系稳定于表面,从而对抗可冲刷性。
当该制剂由于钙聚皂(Calciumpolyseifen)的形成而受到过度强烈的疏水作用时,可在该制剂内添加钙皂分散剂以提高可冲刷性,例如两性二丙酸酯(Lonza KL型)或顺丁烯二酸/丙烯酸-共聚物-钠盐(BASF公司Sokalan系列,如Sokalan CP5或CP45)。
该制剂内可添加任何一种对需用染料加以处理的表面无明显直接性的染料填充剂。若在该配方中使用水溶性染料,再使该配方作为成品与水接触(例如用水冲洗坐便器),则可获得也与营销主张(Marketing-Argumenten)相关的有利色彩标示。举例而言,可使缓慢的染蓝过程(淡蓝向深蓝的变化过程)指示出有效成分逐渐发生作用直至达其最佳活性该过程。
也可将该制剂调节为酸性,使其含有可溶解石灰石或尿碱的物质(酸)作为填充剂。
此外,本发明的制剂内也可添加(助)增稠剂,以便提高该制剂的塑性。举例而言,可将膨润土、粉末表面活性剂、黄原胶、聚丁二烯橡胶、聚异丙烯、嵌段共聚物(含有由寡-或聚环氧乙烷和/或寡-或环氧丙烷和/或寡-或聚氧化丁烯构成的交联寡聚物)及芳基乙氧基化物或烷基芳基乙氧基化物用作(助)增稠剂。聚合的天然物质,例如木质素或其碱金属盐或碱土金属盐,也可用作(助)增稠剂。
亲水性黄原胶为(助)增稠剂的优选类别。使用亲水性黄原胶可在该制剂内产生亲水性极强的化合物,将该制剂粘着于潮湿表面时,该化合物会“吸收”周围水分。
此外也可在该制剂内添加疏水剂形式的填充剂,例如高分散硅胶(Aerosil),特别是完全甲基化的高分散硅胶(Carbot Carbon)。
若想加快粘附速度,则可在该制剂内添加增粘剂形式的填充剂,特别是烃树脂类、天然树脂(如妥尔油松香或香树脂)类或聚萜烯树脂类的增粘剂。
为了除去异味,该制剂可含有除臭剂,这些除臭剂优选添加在芳香剂中。(例如)US 7,288,507B2公开过此类除臭剂。
施用及更换本发明的制剂时不会接触到与厕所水槽相连的不洁净设备,故施用方式十分卫生。
本发明的制剂的一大优点在于,该制剂可按用户需求加以分配使用和/或用各种不同的份额包装进行提供。该制剂的施用可通过注射器完成,或者通过恰当的设备以经预分配的用量进行施用。这些施用设备可为“夹具***”、夹钳或膜撕型薄片、带有预拉伸组件的施用***,这些设备可将相应份额的制剂安置于陶瓷表面。
本发明的制剂也可以简单的方式同时施加在卫浴用品的不同位置上,以便使多种有效制剂(例如芳香片剂与漂白片剂)可就近发挥其效用。
该制剂在卫浴用品的垂直表面上也可达到极佳的粘附效果,即便受到冲洗用水的附加作用力,该制剂也不会脱落。
本发明的粘附剂只有经相对多次数的冲洗操作后才会被冲掉。冲洗次数取决于所用制剂的组成、施用量及所用制剂的几何形状,在施用厚度为2mm至5mm的情况下,可将该制剂冲掉的冲洗次数通常为50次至150次,特别而言在超过120次。
若将该制剂作为粘附剂使用在坐便器中,则该制剂的耐久性主要取决于所施用的其它制剂(块状制剂)的耐冲洗时间。若以传统厕所清洁块为例,则可实现的耐久性为100次至200次冲洗,部分情况下大于250次,在此过程中,该制剂逐渐随粘着材料一起被冲掉。施用量占被粘着制剂的质量的3wt%至15wt%,特别而言为5wt%至10wt%。
本发明的制剂优选为白色,呈膏状、糊状和/或乳状,形状稳定,故该制剂不会“下落”或“下滴”。
该制剂即便在受到冲水过程所引起的较大力(摩擦、变形、剪切效应)的作用时也会保持其粘附状态及形状。
该制剂主要为结构粘度,也就是说,粘度随剪力增大而变小。但若剪切率较低,则可观察到极强的限流效应;此外,粘度曲线在2.5s-1-30s-1的剪切率减速阶段会出现局部最大值。显然,该制剂具有不同粘度范围,或者该制剂会在较短的测量时间(100秒的减速时间)内改变其结构。
此制剂在Haake粘度计(板/板***,板直径10mm,剪切率2.62s-1,20℃)上所测定的粘度应为至少30Pa s,优选应为至少45Pa s,特别优选应为至少100Pa s。所述粘度优选应为150Pa s或300Pa s至6000Pa s,特别优选应为200Pa s至1000Pa s或1000Pa s至4000Pa s。
本发明的含有表面活性剂的制剂优选会产生细泡状泡沫,通过恰当的添加剂(增泡剂)可对该泡沫的容积进行调节。本发明的制剂的泡数应超过40ml。特别优选的泡数应>60ml,更优选的泡数应为140ml或超过200ml。
该制剂的表面张力可为50mN/m-65mN/m。优选的制剂的表面张力应<=60mN/m。特别优选的制剂的表面张力应小于或等于40mN/m。表面张力为一种用于量度表面的可润湿性的标准。表面张力愈小,则该表面愈容易润湿。良好的润湿效果是该制剂具备有效的清洁能力的前提条件。
本发明的制剂的制备方式是在室温下同时对上述的成分进行搅拌。
下文将通过不同的实施例及试验对本发明进行说明。
发明说明部分末尾所附的表1集中给出了本发明的制剂的各种配方。
表1中的冲洗次数是在2-5g的施用量上测定的。
发明说明部分末尾所附的表2给出了制备本发明如表1所列的制剂所用的原料。
本发明如配方V13至V38的全部制剂均具有极佳的粘附效果,其外表面所具的粘性可视具体的粘附剂用量粘住质量至多50g的传统型厕所清洁剂。其中,块状制剂的粘附质量与粘附剂质量之比最大为100∶1,优选最大为50∶1,特别优选最大为10∶1。当然,若增大粘附面积,则可改进该制剂的粘附效果。常用的粘附面积为1000mm2至800mm2(完全接触)。若成环带状涂覆粘附剂,则粘附面积也可小于400mm2。
在所有将所述制剂成功冲掉的试验中,所用的表面活性剂均为阴离子表面活性剂。这些制剂所能经受的冲洗次数表明这些制剂具有从较高到高的耐久性。
V20为用于制备酸性制剂的配方。该制剂所能经受的冲洗次数较少,其原因可能在于pH值较小而无法形成可增加冲洗次数的钙皂。
V23a、V24、V29及V30仅含有(阴离子)表面活性剂及粘合促进剂。所述仅由两种成分构成的制剂也具有符合预期的粘附能力、必要的粘性及大于100次的冲洗次数。
与的相比,纯粘合促进剂Polyvest 800S(1,4-顺丁二烯顺丁烯二酸酐加合物)——一种低粘产品——施用在坐便器上后会立即向下流动,无粘附效果。无法在此种纯粘合促进剂Polyvest上粘附质量为50g、30g、10g、5g的传统厕所清洁块。该块状制剂即刻便会脱落;观察不到任何粘着效果。
与的相反,纯粘合促进剂Versagel M1600(氢化丁烯/乙烯/苯乙烯共聚物)施用在坐便器上后会牢固地粘附在坐便器上,经许多次冲洗后也不会被冲掉。这些粘合促进剂上也可粘附厕所清洁块,但厕所清洁块会随粘附剂Versagel一起逐渐下滑。
发明说明部分末尾所附的表3集中给出了用本发明如表1所列的制剂所实施的各种粘着试验的结果。
实施这些粘着试验时,或将给定量的制剂(粘附剂)涂抹于试样背面,或用刮刀在该试样的表面区域内施加厚度约为2-4mm的该粘附剂。
随后将该试样直接粘附于陶瓷坐便器中。一般以较小压力将试样粘附在坐便器潮湿的前部内表面。粘附剂及试样即刻便处于备用状态,可对其直接冲洗。
表3所列的试验表明,本发明含有粘合促进剂Polyvest(1,4-顺聚丁二烯-顺丁烯二酸酐加合物)的制剂不仅可粘着于卫浴用品上,其所具有的粘性也可使厕所清洁块、去垢片剂、透明皂体系等等粘附在卫浴用品上。
若将本申请的体系的粘着性能与WO 99/66017所公开的体系相比较,则可发现,后者不会对表3所列的试样产生任何粘着作用。
将常用的厕所清洁块固定在WO 99/66017所公开的凝胶的表面后,此厕所清洁块即刻间即会在重力作用下发生下滑。也就是说,该凝胶不具有持久的粘着作用。
据本申请人猜测,本发明的基于Polyvert的制剂的所以具有良好的粘着特性,其原因一方面在于存在无规分布的顺丁烯二酸酐基,这些顺丁烯二酸酐基可于载体表面以化学方式对官能团产生粘着作用(反应性粘附剂);另一方面,该效应也可能会向内延续,这些顺丁烯二酸酐基可能会与结构中的官能团(例如相关表面活性剂及助增稠剂的亲核性基团)发生反应(内聚效应),从而形成膨胀程度有强有弱的类甘酞树脂结构。
初始物质在纯形式上即已是粘附剂,在很长时间内(直至反应性基团硬化为止)持续保持粘性。但若无表面活性成分,则无法或很难从陶瓷表面移除此种纯粘附剂。
顺丁烯二酸酐官能团的内聚效应应该在该配方所包含的长链脂肪纯或长链PEG体系(Polyox WSR 303)中得到增强。
结合使用V2块剂所进行的试验V22首先说明了上述的相互作用(表3)。在试样极小的情况下,V2块剂的配方可达到超过460次的冲洗次数。
除交联过程外,钙离子形成聚皂的事实在本配方中也具重要作用,此点会增强整个体系的疏水性,从而加大该体系溶于水的难度。
此外,所用的黄原胶也具有增大粘着力的作用。在与厕所***内的水性表面发生接触时,水胶体的迅速形成会使该表面迅速脱水。由此可使该粘附剂与假干燥的陶瓷表面迅速发生其它类型的相互作用(例如粘着性相互作用)。
作为上述的全部相互作用的结果,这些粘着化合物即使受到水流冲刷也将较长时间地粘附于陶瓷表面上。此点令人惊讶的原因更在于,冲洗用水本应在冲洗过程中使含表面活性剂的制剂(具有良好的润湿率)发生位移,从而使其从陶瓷上脱落。
在本体系内,甚至会发生该粘附剂或粘附在该粘附剂上的第二成分被自外向内腐蚀的情况。
发明说明部分末尾所附的表4示范性地给出了本发明如表1所列的部分制剂的泡数及表面张力。
表4表明,本发明的制剂明显不同于EP 1325103B1所公开的公知制剂。换言之,本制剂为明显更佳的起泡剂。
测定泡数时,将100ml被调温至20℃的母液导入250ml容量瓶内,用PTFE塞子封闭该容量瓶。随后将容量瓶来回翻转二十次(颠倒20次)。分别于30sec/5min/30min后读取并记录所产生的泡沫容积(ml)。
用Krüss公司的BP2气泡压力测量仪测定表面张力。
按如下方式检验空白试验值:用Ufaryl DL 90C制备0.1%溶液,在20℃下通过预先测定的毛细管直径记录三次测量曲线,求其平均值。与平均值之间的允许偏差至多为1mN/m。
将初次试验作为初始值,并将所有逐次试验与该初始值比较(50/100/500ms)。当偏差大于±2mN/m时,更换毛细管。
测量时,测定0.1%溶液(20℃)与其表面年龄(age)相关的表面张力。分别于100ms、500ms、1000ms后观察表面张力。
表5所列为本发明的制剂以聚亚烷基亚胺为粘合促进剂的各种配方,表6所列为本发明的制剂以烷氧基化胺及聚甘油聚醚烷基羧酸为粘合促进剂的各种配方。
表5
*用具有矩形窄口的施加器施加,涂抹成宽度约为2cm、厚度约为3mm的带状。
**将该制剂施加于厕所清洁块上,施用量约占该厕所清洁块的重量的约10%。随后通过该制剂将该厕所清洁块粘附于卫浴用品表面。
Tensopol USP 94为表面活性剂(C12-C16月桂基硫酸盐),由Manro公司提供。
Marlinat 242/90T由C12-C14-醇-聚乙二醇及丙烯醚-(2EO)-硫酸酯,乙二醇三异丙醇铵盐(Sasol)构成。
Orange Fun为香料,由Givaudan公司提供。
Kelzan AS为黄原胶(增稠剂/助增稠剂),由Kelco公司提供。
Genapol DAT为PEG-150聚甘油基-2-三硬脂酸酯及PEG-6-癸酰基/癸酸甘油酯。
Lupasol SK为一种由BASF公司提供的液态聚乙烯亚胺,摩尔质量约为2000000,Lupasol P为一种由BASF公司提供的液态聚乙烯亚胺,摩尔质量约为750000。
表6
Emanon XLF为甘油聚醚-7辛酸酯/癸酸酯,由Kao Corporation,S.A.提供。
Jeffamine T 5000为一种聚醚胺,由美国Huntsman公司提供,摩尔质量约为5000(三胺,由环氧丙烷与三醇类起始剂反应,随后将末端羟基胺化而制成)。
Jeffamine ST-404为一种聚醚胺衍生物,摩尔质量约为565,由美国Huntsman公司提供(仲胺变型,仲三胺。胺端基与酮(例如丙酮)发生反应,并被还原)。
Cab-Osil为高分散硅石。
Arboform(水溶性)由德国Ilsfeld(伊尔斯费尔特)Tecnaro公司提供,为一种粒料,由木质素聚合物或木质素衍生物、生物可降解聚酯、木质纤维素或木化纤维及天然树脂(即,脂族或芳族酮、醇、羧酸、内酯及单体、寡聚物及聚合物形式的多环物)构成。
本发明经试验的全部制剂均既可极佳地粘着/粘附在干燥表面,也可极佳地粘着/粘附在湿润表面。
这些制剂的外表面所具的粘性可视具体的粘附剂用量粘住质量至多50g或以上的传统型厕所清洁剂。在所有将所述制剂成功冲掉的试验中,所用的表面活性剂均为阴离子表面活性剂。这些制剂所能经受的冲洗次数表明这些制剂具有较高至高耐久性。
测定表5及表6所给出的泡数时,将100ml被调温至20℃的母液导入250ml容量瓶内,用PTFE塞子封闭该容量瓶。随后将容量瓶来回翻转二十次(颠倒20次)。分别于30sec/5min/30min后读取并记录所产生的泡沫容积(ml)。
用Krüss公司的BP 2气泡压力测量仪测定表面张力。
按如下方式检验空白试验值:用Ufaryl DL 90C制备0.1%溶液,在20℃下通过预先测定的毛细管直径记录三次测量曲线,求其平均值。与平均值之间的允许偏差至多为1mN/m。
将初次试验作为初始值,并将所有逐次试验与该初始值比较(50/100/500ms)。当偏差大于±2mN/m时,更换毛细管。
测量时,测定0.1%溶液(20℃)与其表面年龄相关的表面张力。分别于100ms、500ms、1000ms后观察表面张力。
依据预定时间表以每次冲洗8l的冲洗容量及每日19次冲洗的冲洗频度进行冲洗次数测量。在较短的冲洗间隔时间内(例如在第三次与第五次冲洗之间),冲洗用水温度为13℃至14℃,在较长的休止期期间(例如在第十九次与第一次冲洗之间),冲洗用水温度为15℃至16℃。于每个工作日对冲洗用水的温度进行检查与记录。
表1
表1(续)
表2
表3
表4
Claims (22)
1.一种应用于卫浴领域的制剂,该制剂可直接施加于卫浴用品上,粘附于此,只有经相对多次数的冲洗操作后才会被冲掉,其中该制剂含有选自表面活性剂的填充剂以及粘合促进剂,其特征在于,
该粘合促进剂选自氢化的聚苯乙烯衍生物、烯烃均聚物及两种或更多种烯烃的共聚物,其中,烯烃均聚物及烯烃共聚物也可被部分氢化,该制剂的粘度至少为30Pas,其使用Haake粘度计测量,板/板***,板直径为10mm,剪切率为2.62s-1,20℃,该制剂所具有的粘性可将块状制剂固定在坐便器上,其中在粘度促进剂选自聚亚烷基亚胺的情况下,所述表面活性剂的浓度为7wt%-60wt%。
2.如权利要求1的制剂,其特征在于,
所述选自聚苯乙烯衍生物的粘合促进剂为溶于矿物油的交联聚苯乙烯衍生物,优选为亚烷基苯乙烯共聚物,特别而言选自氢化的丁烯/乙烯/苯乙烯共聚物及氢化的乙烯/丙烯/苯乙烯共聚物。
3.如权利要求1的制剂,其特征在于,
所述选自非水溶性烯烃均聚物以及两种或更多种烯烃的共聚物的粘合促进剂选自聚丁二烯橡胶、苯乙烯-丁二烯嵌段聚合物和共聚物、聚异丙烯、通过在苯乙烯或α-甲基苯乙烯上1,3-加成丁二烯或异戊二烯而制成的无规(嵌段)聚合物、乙烯及丙烯的均聚物或共聚物,如乙烯-丙烯二烯-三元共聚物、乙烯-环氧乙烷-共聚物、天然橡胶以及如聚双环戊二烯的降冰片烯聚合物。
4.如权利要求1的制剂,其特征在于,
该粘合促进剂在该制剂内的浓度为2wt%-60wt%,优选为7wt%-50wt%,特别优选8wt%-40wt%。
5.如权利要求1-3中任一项的制剂,其特征在于,
该粘合促进剂在该制剂内的浓度为15wt%-80wt%,优选20wt%-70wt%,特别优选30wt%-50wt%。
6.如前述权利要求中任一项的制剂,其特征在于,
所述填充剂选自下列:增稠剂、芳香剂、染料、盐类、泡沫稳定剂、增泡剂、起泡剂及聚合的天然材料。
7.如权利要求6的制剂,其特征在于,
该制剂内的表面活性剂含量为0wt%-80wt%,优选为10wt%-60wt%,特别优选为25wt%-45wt%。
8.如权利要求6或7中的制剂,其特征在于,
所述表面活性剂呈粉末状或硬糊状。
9.如权利要求1至8中任一项的制剂,其特征在于,
所述表面活性剂为阴离子表面活性剂,选自羧酸盐、硫酸半酯、磺酸、相对长链的醇及脂肪醇的乙氧基化物。
10.如权利要求6至9中任一项的制剂,其特征在于,
所述表面活性剂为非离子性表面活性剂,选自醇乙氧基化物、烷基糖苷、烷氧基化脂肪酸烷基酯、氧化胺及链烷醇酰胺。
11.如权利要求6的制剂,其特征在于,
该制剂含有浓度为0.25wt%-20wt%,优选3wt%-15wt%,特别优选5wt%-10wt%的芳香剂或香料油。
12.如权利要求6的制剂,其特征在于,
该制剂含有至多90wt%,特别而言至多10wt%,优选至多5wt%的盐类,所述盐类优选地选自强酸或单羧酸、二羧酸及多元羧酸的碱金属及碱土金属盐。
13.如权利要求6的制剂,其特征在于,
该制剂含有选自下列的(助)增稠剂:膨润土、粉末表面活性剂、黄原胶、聚丁二烯橡胶、聚异丙烯、嵌段共聚物、芳基乙氧基化物或烷基芳基乙氧基化物或聚合的天然物质。
14.如前述权利要求中任一项的制剂,其特征在于,
该制剂为水溶性/水分散性的暂时粘附的粘附剂。
15.如前述权利要求中任一项的制剂的应用,其特征在于,
所述可粘附于的块状制剂为具有一个或多个相的传统清洁块、具有芳香相的清洁块、含有漂白剂的清洁块、压制片剂、含有有效成分的水溶性或非水溶性塑料、芳香片剂、固态芳香凝胶、漂白片剂、去垢片剂或强效清洁片剂。
16.如前述权利要求中任一项的制剂,其特征在于,
该制剂含有具清洁作用和/或芳香作用和/或漂白作用和/或染色作用的添加剂。
17.如上述权利要求中任一项的制剂,其特征在于,
该制剂呈膏状、糊状和/或乳状,且形状稳定。
18.如前述权利要求中任一项的制剂,其特征在于,
该制剂的表面张力为50mN/m-65mN/m,特别而言小于60mN/m。
19.一种厕所清洁套组,其包括至少一种如前述权利要求中任一项的制剂及一种或多种选自下列的块状制剂:具有一个或多个相的清洁块、具有芳香相的清洁块、含有漂白剂的清洁块、压制片剂、含有有效成分的水溶性或非水溶性塑料、芳香片剂、固态芳香凝胶、漂白片剂、去垢片剂或强效清洁片剂。
20.一种如前述权利要求中任一项的制剂的应用,该制剂在卫浴领域内用作冷粘附剂,特别地用于在小便池、盥洗水槽或瓷砖上、或在厨房、餐厅、屠宰间、清洗设备中固定物体,或施用于下水道或排水沟之上或之中,或用作容纳防治害虫的饵料的软膏,或用于固定到窗玻璃或房屋正面。
21.如权利要求20的应用,其特征在于,
施加于该物体上的该制剂的质量占该物体的质量的3wt%-15wt%。
22.一种制备如前述权利要求中任一项的制剂的方法,其特征在于,
在室温下一起搅拌所述成分。
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