CN1981010B - 护理组合物 - Google Patents

护理组合物 Download PDF

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CN1981010B
CN1981010B CN2005800225589A CN200580022558A CN1981010B CN 1981010 B CN1981010 B CN 1981010B CN 2005800225589 A CN2005800225589 A CN 2005800225589A CN 200580022558 A CN200580022558 A CN 200580022558A CN 1981010 B CN1981010 B CN 1981010B
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antioxidant
polar
aqueous medium
antioxidants
polymer matrix
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CN1981010A (zh
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S·N·巴彻洛尔
J·利恩克
M·佩里
J·B·瓦纳尔
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Unilever Nederland BV
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Abstract

本发明公开了一种保持弹性聚合物纤维完整性的方法。

Description

护理组合物
发明领域
本发明涉及用于织物的固化聚合物的处理。
发明背景
在服装领域普遍使用聚合物纤维。在服装工业中广泛采用聚丁二烯粘结剂以在衣物上印刷图案。许多衣物的腰带也使用了天然橡胶(天然聚合物)。
弹性纤维是一种广泛使用的人造纤维。在服装生产中，弹性纤维既可以单独使用，也可以与各种天然纤维混合使用。应用得较广的商品弹性纤维有著名品牌Lycra和Dorlastan弹性纤维。1937年德国首先发明了弹性纤维，它具有天然纤维所不具有的特性，最重要的是其超强的弹力性能。泳衣的主轮廓部分(contour)都含有弹性纤维。
弹性纤维可被伸长至其原长的四到七倍，松开张力后，又能回复至原长。弹性纤维在所有纺织物原料中具有最高的弹性张力。如只要使用2％的弹性纤维就足以使裤子保持形状。由于既要体现身体形状又需要高弹性，在泳衣、紧身衣或运动服中使用15％-40％的弹性纤维。弹性纤维给予良好的舒适度以及很大的运动自由度。在机织纤维和针织纤维中，弹性纤维可提高保持形状的能力并且可以使折痕快速复原。
但前述聚合物且容易降解。含有这些类型聚合物的服装发生降解的一个明显表现是在服装使用过程中，在相当短的时间内出现破裂。破裂的另一个例子是，在印刷粘结剂降解的地方，由于粘结剂的降解而出现印花剥落和裂开。
诸如次氯酸盐、臭氧、日光(紫外线)、单线态氧及三线态氧等都是促使这些聚合物失去完整性的恶化因素。
由于许多游泳池中都含有次氯酸盐，因此缩短了许多泳衣的寿命。由于泳衣中的弹性纤维失去完整性而造成泳衣出现不期望的摆动以及下滑。
发明概述
本发明涉及一种处理聚合物的方法。本发明特别应用于处理弹性聚合物。在这里，弹性体指可被拉长至原长的至少两倍而仍能维持在其弹性限度内(即没有发生塑性形变)的聚合物。
本发明提供了一种组合物在提高非极性固化弹性聚合物基体的完整性寿命中的用途，所述用途通过向所述非极性固化弹性聚合物基体施加在水溶液介质中的抗氧化剂来实现，其中所述非极性基体构成了纺织服饰(服装制品)的一部分或全部。
通过提供由弹性聚合物组成或含有弹性聚合物的服装的处理方法，使用者在服装的使用期内可以选择性地对其进行重复处理，由此使得服装得到护理。这提供了可在制成服装后处理聚合物的优点。而且，本发明方法可抑制聚合物基体黄变。
本发明也延伸包括商品包装及与所述包装一起使用的说明书。
发明详述
抗氧化剂
抗氧化剂在含水介质中的浓度为0.01-1000ppm，优选0.1-100ppm，最优选0.1-50ppm。为得到所需浓度的抗氧化剂溶液，将含有抗氧化剂的组合物加入到含水介质中，直至在含水介质中抗氧化剂达到所需含量。
在下述文献中公开了抗氧化剂物质，Kirk-Othmers(第3卷，424页)、Uhlmans Encyclopedia(第3卷，91页)、Jan Pospisil和Peter P.Klemchuk编辑的CRC Press Oxidation Inhibition in Organic Materials，第I和II卷，ISBN 0-8493-4767-X and 0-8493-4768-8。
log P是指辛醇/水的分配系数，可用于衡量分子的疏水性。采用Daylight Chemical Information Systems，Inc.Sheraton House-CastlePark-Cambridge，UK CB3OAX的daylight软件(PC模式4.8版)计算C Log P值。
适用于本发明的一类抗氧化剂是具有以下通式的烷基化酚类：
Figure S05822558920070108D000031
其中R是C1-C22的直链或有支链烷基，优选甲基或支链C3-C6烷基；C3-C6烷氧基，优选甲氧基；R1是C3-C6支链烷基，优选叔丁基；x为1或2。抗氧化剂优选为受阻酚类化合物。
适用于本发明的另一类抗氧化剂是具有以下通式的苯并呋喃或苯并吡喃衍生物：
其中R1和R2各自独立为烷基，或R1和R2可结合在一起形成C5-C6环烃基；B不存在或为CH2；R4是C1-C6烷基；R5是氢或-C(O)R3，其中R3是氢或C1-C19烷基；R6是C1-C6烷基；R7是氢或C1-C6烷基；X是-CH2OH基或-CH2A基，其中A是含氮单元、苯基或取代苯基。优选的含氮A单元包括氨基、吡咯烷-1-基、哌啶子基、吗啉代基、哌嗪-1-基以及它们的混合物。
以下为其它适合的抗氧化剂：α-生育酚、β-生育酚、γ-生育酚或δ-生育酚的衍生物，没食子酸的烷基酯，优选没食子酸辛酯和没食子酸月桂酯。
合适的抗氧化剂的另一实例为受阻胺光稳定剂(HALS)类，特别是2，2，6，6-四甲基哌啶类。
适用于本发明的抗氧化剂的非限制性实例包括酚类，特别是2，6-二-叔丁基-苯酚、2，6-二-叔丁基-4-甲基苯酚、2-叔丁基-4-甲基苯酚与3-叔丁基-4-甲基苯酚的混合物。
抗氧化剂分子上的烷基链取代基用来控制C log P值，使之在所需的范围内。
也可以采用各种抗氧剂的混合物，尤其是可以采用如WO02/072746公开的具有抗氧化协同效应的混合物。
氢过氧化物分解抗氧化剂
氢过氧化物分解抗氧化剂(HAD)是一类可引发氢过氧化物降解的化合物。HAD的实例有含硫(s)有机化合物和三价磷有机化合物，在工业上这类化合物用以稳定组合物，并广泛与酚类抗氧化剂联合使用。二烷基二硫代磷酸锌(ZDDP)是在汽车燃油工业广泛使用的HAD实例。通常，与硫化物相比，亚磷酸盐在低得多的温度下分解氢过氧化物。三苯基膦(一种氢过氧化物分解抗氧化剂)已被普遍用作氢过氧化物的还原剂，其能在室温条件下起作用。受阻胺光稳定剂(HALS)也具有如同HAD的效能，其为用于本发明的一类优选的HAD的实例。J.
Figure S05822558920070108D000041
，P.P.Klemchuk(编辑)的Oxidation inhibition in organicmaterials，第I卷.CRC Press 1990，38-47页文献中有关于各种HAD的评述。本发明的漂白组合物优选包含一种或多种HAD，特别是三苯基膦，最优选与非HAD抗氧化剂联合使用。
防晒剂
防晒剂用于减少来自太阳光和白炽灯光的辐射。防晒剂用于进一步保护聚合物。本发明所用的防晒剂具有光稳定性。
采用高吸光系数的可吸收UVA和UVB的材料以防止太阳光辐射。通常称这些化合物为防晒剂。但是这些化合物在400nm以上的全部或部分的谱线有颜色，因此优选仅使用这类材料抗400nm以下波长的UV辐射。
优选防晒剂的C log P值范围为1.5-8.5。
防晒剂或各种防晒剂混合物在含水溶液中的优选浓度范围是0.01-1000ppm，优选0.1-100ppm，最优选0.1-50ppm。为得到所述浓度的防晒剂溶液，将含有防晒剂的组合物加入到含水介质中，直至防晒剂在含水介质中达到所需含量。
在本说明书中，防晒剂指任何吸收UVA或UVB的材料。优选所述防晒剂在300nm处的摩尔吸光系数(ε)大于2000mol-1cm-1，最优选在300nm处的摩尔吸光系数大于5000mol-1cm-1。还优选所述防晒剂在400～750nm的任意单波长处的吸光系数小于100mol-1cm-1。
国际照明协会(CIE)于1970年就UV波长分出如下子类：
UVA    315-400nm
UVB    280-315nm
UVC    100-280nm
优选防晒剂的吸收波长为280-400nm的光线。
在下述文献中公开了适合的防晒剂：Jan Pospisil和Peter P.Klemchuk编辑的CRC Press Oxidation Inhibition in Organic Materials第I和II卷，ISBN 0-8493-4767-X和0-8493-4768；由Nicholas J.Lowe，Nadim A.Shaath和Madhu A.Pathak编著的Sunscreens：Development，Evaluation，and Regulatory Aspects，第二版，ISBN：0824793064。
可以在本发明中使用的防晒剂的典型实例有：肉桂酸盐、羟基二苯甲酮、α-氰基丙烯酸酯、N，N’-草酰二苯胺、水杨酸苯酯以及2-羟苯基苯并三唑。
以下是防晒剂的典型实例，但不限于这些：
UVA吸收剂：
羟甲氧苯酮
舒利苯酮(Suisobenzone)
二羟苯宗
tinuvin329
tinuvin327
tinuvin328。
UVB吸收剂：
氨基苯甲酸
对二甲基氨基苯甲酸戊酯
对甲氧基肉桂酸2-乙氧基乙酯
对二甲基氨基苯甲酸戊酯(padimate A)
水杨酸2-乙基己酯(Sunarome WMO)
4-二(羟丙基)氨基苯甲酸乙酯
2-氰基-3，3-二苯基丙烯酸2-乙基己酯
对甲氧基肉桂酸乙基己酯
水杨酸2-乙基己酯(Sunarome WMO)
氨基苯甲酸甘油酯(甘油基PABA)
水杨酸高盖酯
2-羟基-1，4-萘醌和二羟基乙酸酯
对二甲基氨基苯甲酸辛酯(padimate O)
2-苯基苯并咪唑-5-磺酸
水杨酸三乙醇胺、
Cyasorb UV 2908
Cyasorb UV 24
Chimassorb 81。
平衡载体及附加成分
这些物质可以是表面活性剂、助洗剂、发泡剂、消泡剂、溶剂和酶。这些物质的使用或用量取决于所述漂白组合物的经济成本、环境等因素和所述漂白组合物的用途。
所述漂白组合物可包含表面活性剂和任选的其它常用洗涤剂成分。所述漂白组合物还包括含酶洗涤剂组合物，所述洗涤剂组合物含有占其总重量的0.1-50％的一种或多种表面活性剂。这种表面活性剂体系可依次含有0-95％重量的一种或多种阴离子表面活性剂和5-100％重量的一种或多种非离子表面活性剂。所述表面活性剂体系中还可含有两性或两性离子洗涤剂化合物，但因为其成本较高通常并不采用。依据本发明，所述含酶洗涤剂组合物通常以约0.05-2％的水稀释液形式使用。
所述漂白组合物优选含有2-60％重量的表面活性剂。通常而言，表面活性剂体系中的非离子表面活性剂和阴离子表面活性剂可从下述文献中公开的表面活性剂中选择，Schwartz和Perry的″SurfaceActive Agents″，第1卷；Schwartz、Perry和Berch的Interscience 1949，第2卷；Interscience 1958；Manufacturing Confectioners Company出版的″McCutcheon’s Emulsifiers and Detergents″；或H.Stache的″Tenside-Taschenbuch″，第2版，Carl Hauser Verlag，1981。
可采用的合适的非离子洗涤剂化合物特别包括具有疏水基和活性氢原子的化合物与氧化烯的反应产物，其中所述具有疏水基和活性氢原子的化合物如脂族醇、酸、酰胺或烷基苯酚，氧化烯特别指单独的环氧乙烷或环氧乙烷与环氧丙烷的混合物。特别的非离子洗涤化合物是C6-C22烷基苯酚-环氧乙烷缩合物，通常含5-25个EO单元，即每分子中含5-25个环氧乙烷单元；或是C8-C18脂族直链或支链伯或仲醇与环氧乙烷的缩合产物，通常含5-40个EO单元。
可采用的合适的阴离子洗涤剂化合物通常是烃基部分含8-22个碳原子的有机硫酸或磺酸的水溶性碱金属盐，其中烷基包括高级酰基的烷基部分。适合的合成阴离子洗涤剂化合物的实例有烷基硫酸钠盐和钾盐，特别是将高级C8-C18醇硫酸化而制得的盐，其中所述醇可从例如牛油或椰子油制得；C9-C20烷基苯磺酸钠和钾，尤指直链C10-C15仲烷基苯磺酸钠；烷基甘油基醚硫酸钠，特别是衍生自牛油或椰子油的高级醇的醚，以及衍生自石油的合成醇的醚。阴离子洗涤剂化合物优选C11-C15烷基苯磺酸钠或C12-C18烷基硫酸钠。也可采用如EP-A-328177(Unilever)中公开的可防止盐析的表面活性剂、EP-A-070074中公开的烷基聚苷表面活性剂以及烷基单苷。
优选的表面活性剂体系是阴离子和非离子洗涤剂活性物质的混合物，特别是EP-A-346995(Unilever)文献中公开的各种阴离子和非离子表面活性剂实例。特别优选的表面活性剂体系是C16-C18伯醇硫酸碱金属盐和C12-C15伯醇3-7EO乙氧基化物的混合物。
非离子洗涤剂用量优选大于10％，例如25-90％，基于表面活性剂体系重量计算。阴离子表面活性剂用量例如占所述表面活性剂体系重量的约5％-约40％。
阳离子化合物
当本发明用作织物调节剂时，需要含有阳离子化合物。
最优选季胺化合物。
可有利地采用至少具有一个C12-C22烷基链的季铵化合物。优选的季铵化合物具有以下通式结构：
式中R1是C12-C22烷基链或烯基链；R2、R3及R4独立选自C1-C4烷基链；X-是配伍阴离子。优选这种类型的季铵化合物是溴化十六烷基三甲基铵。
本发明采用的第二类季铵化合物具有以下通式结构：
Figure S05822558920070108D000091
式中R1和R2独立选自C12-C22烷基链或烯基链；R3和R4独立选自C1-C4烷基链；X-是配伍阴离子。
在一种权利要求1中所述的洗涤剂组合物中，(ii)阳离子物质与(iv)阴离子表面活性的比例最少是2∶1。
其它合适的季胺化合物在EP 0239910(Procer and Gamble)中公开。
阳离子化合物与非离子表面活性的比例优选为1∶100至50∶50，最优选1∶50至20∶50。
阳离子化合物可占组合物总重量的0.02％-20％。
优选阳离子化合物占组合物总重量的0.05％-15％，更优选0.2％-5％，最优选0.4％-2.5％。
如果产品是液体，则优选阳离子表面活性剂占组合物总重量的0.05％-10％，更优选0.2％-5％，最优选0.4％-2.5％。
如果产品是固体，则优选阳离子表面活性剂占组合物总重量的0.05％-15％，更优选0.2％-10％，最优选0.9％-3.0％。
实验
首先将各种抗氧化剂溶于乙醇溶液中，以有助于其在含水介质中的溶解。采用十二烷基硫酸钠、pH为10的缓冲液和软化水制得原料洗涤液。
记录洗涤溶液的紫外-可见光谱。将等份的乙醇溶液滴加到各洗涤溶液部分中，并搅拌溶液以维持抗氧化剂溶解。
记录经上述所得混合物的紫外可见光谱。将试验用布(100％弹性纤维)的碎片加入到含有所述抗氧化剂的洗涤溶液中，搅拌30分钟。记录最终混合物的紫外可见光谱，并测定抗氧化剂/防晒剂的量。组合物
乙醇/抗氧化剂溶液
将每种经选择的抗氧化剂(0.12g)溶于乙醇中，至总体积为50ml。
洗涤溶液
因为SDS(十二烷基硫酸钠)在紫外可见光区内不吸收，因此选用其作为表面活性剂。为制得2g/l的制剂，将0.8gSDS(制剂的20％是表面活性剂)加入到21的容量瓶中，再用软化水和pH为10的碳酸盐缓冲液(与SDS相似的浓度水平)定容至21。
含抗氧化剂的洗涤溶液
洗涤实验中采用的溶液与布的比例为25∶1，将12.5克的洗涤溶液加入到120ml玻璃瓶中，再加入200ul乙醇/抗氧化剂溶液，制得抗氧化剂浓度为20ppm的溶液。
Figure DEST_PATH_IMAGE002
完整性实验1
在温度为293K下，在180ml水中洗涤1.8g含25％弹性纤维和75％尼龙纤维的织物片，所述水中含0.4g/L SDS表面活性剂，并用碳酸盐缓冲剂调整至pH值为10。之后用软化水将所述织物片漂洗三次并干燥。此后，将所述织物浸入二甲基乙酰胺中溶解弹性纤维部分，并采用凝胶渗透色谱法测定聚合物的分子量。重复所述步骤，但洗涤次数不同。结果如下表所示，表中的数值为两次平行实验的平均值。
  洗涤次数   Mn   PD
  1   37500   1.97
  2   36200   1.93
  3   34500   1.85
  4   29800   1.97
  5   30800   2.07
Mn＝平均分子量
PD＝多分散性
随着洗涤次数增加，Mn值缓慢降低，表明聚合物在逐渐受到破坏。
完整性实验2
重复实验1，只是在每次清洗之后，将织物放置于可模拟室外太阳光的老化试验机上照射7.2小时，设置老化试验机强度为385W/m2。
实验结果如下表所示，表中的数值为两次平行实验的平均值。
  洗涤次数   Mn   PD
  1   32500   2.32
  2   30200   2.63
  3   20300   4.00
  4   14600   4.93
  5   7030   8.91
随着清洗/照射循环次数的增加，Mn值降低而PD值增加，表明由于日光曝晒而使纤维受到很大的破坏。
完整性实验3
重复完整性实验2，但在每份洗涤液中加入20ppm的保护剂并且只在进行了5次清洗/照射循环后才采用色谱检测。
结果如下表所示，表中数值是两次平行实验结果的平均值。
  保护剂   Mn   PD
  无   7030   8.91
  Tinuvin 329   13600   4.94
  Tinuvin 770   17800   5.41
  没食子酸月桂酯   23200   4.46
Tinuvin 770[癸二酸双(2，2，6，6-四甲基-4-哌啶基)酯]是产自CibaSpeciality chemicals的受阻胺光稳定剂类抗氧化剂。
防晒剂和抗氧化剂都能减小由于日光曝晒造成的聚合物损害程度。这可以从相对较高的Mn值和较低的PD值而表明。

Claims (12)

1.在含水介质中的抗氧化剂的组合物在提高非极性固化弹性聚合物基体完整性寿命中的用途，所述用途包括向所述非极性固化弹性聚合物基体施加所述在含水介质中的抗氧化剂的组合物，其中所述非极性基体构成纺织服饰的部分或全部；其中所述抗氧化剂在水溶液中的浓度为0.01-1000ppm。
2.权利要求1的用途，其中所述抗氧化剂选自：
(i)酚类抗氧化剂；和
(ii)受阻胺抗氧化剂。
3.权利要求2的用途，其中所述抗氧化剂是受阻酚。
4.权利要求2的用途，其中所述抗氧化剂选自2，6-二-叔丁基羟基甲苯、没食子酸辛酯和没食子酸月桂酯。
5.权利要求1的用途，其中所述含水介质含有光稳定的有机防晒剂，所述有机防晒剂的C log P值至少是1.9、在300nm处的吸光系数大于2000mol-1cm-1、在400-750nm的任意单波长处的吸光系数小于100mol-1cm-1。
6.权利要求1的用途，其中所述非极性固化弹性聚合物基体为合成的非极性固化弹性聚合物基体。
7.权利要求1的用途，其中所述抗氧化剂的C log P值范围为1.5-8.5。
8.权利要求1的用途，所述用途包括施加后干燥所述服饰的步骤。
9.权利要求1的用途，其中所述含水介质含有织物调理剂。
10.权利要求1的用途，其中所述含水介质不含表面活性剂。
11.权利要求1的用途，其中所述含水介质含有表面活性剂。
12.权利要求1的用途，其中所述非极性固化聚合物选自聚丁二烯粘结剂、弹性纤维和胶乳。
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