CN1243858C - 可湿聚烯烃纤维和织物 - Google Patents
可湿聚烯烃纤维和织物 Download PDFInfo
- Publication number
- CN1243858C CN1243858C CNB018193803A CN01819380A CN1243858C CN 1243858 C CN1243858 C CN 1243858C CN B018193803 A CNB018193803 A CN B018193803A CN 01819380 A CN01819380 A CN 01819380A CN 1243858 C CN1243858 C CN 1243858C
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- China
- Prior art keywords
- fiber
- silk
- butyl
- compound
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2008—Fabric composed of a fiber or strand which is of specific structural definition
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2311—Coating or impregnation is a lubricant or a surface friction reducing agent other than specified as improving the "hand" of the fabric or increasing the softness thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T442/2418—Coating or impregnation increases electrical conductivity or anti-static quality
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T442/2484—Coating or impregnation is water absorbency-increasing or hydrophilicity-increasing or hydrophilicity-imparting
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Abstract
聚烯烃织造或非织造纤维或丝以及由它们制成的织物,它包含熔融共混物,该共混物包含,(a)聚烯烃;以及(b)至少一种通式(I)的化合物,其中R1是22~40个碳原子的直链或支链烷基,亲水低聚物是由2~10个由选自环氧乙烷、环氧丙烷、乙二醇、丙二醇、表氯醇、丙烯酸、甲基丙烯酸、乙烯亚胺、己内酯、乙烯醇和醋酸乙烯的单体衍生的单体单元组成的均聚-或共聚-低聚物。该布料可用于一次性尿布、训练裤、女性卫生巾、棉塞、失禁护理用品、湿和干抹布、伤口敷料、手术帽、过滤介质和电池隔膜等。
Description
本发明涉及一种表现出耐久可润湿性的新型烯烃聚合物织造或非织造纤维。该纤维尤其可用于诸如尿布、女性卫生用品和失禁护理产品之类的卫生制品。
聚烯烃,尤其是聚丙烯,被大量用于制造织造或非织造织物(fabrics)。聚烯烃非织造织物,如梳理纤网、纺粘、熔喷或其复合材料被优选作为诸如一次性尿布、女性卫生用品和失禁护理产品之类的卫生用品中的成分。基于,尤其是聚丙烯的织物,公认的优点包括,原料成本比较低、容易制造、希望的强度/基重比和柔软性。
卫生制品一般包含能吸入数倍于自身重量流体的材料组成的吸收剂芯成分。通常,该制品包括至少一个在芯的一侧接触使用者皮肤的外包覆层或衬里,和在芯的另一侧接触环境的外层。用于内衬层的织物要求柔软并透液。透液性应采取这样的形式,即,允许液体透过织物并进入到内吸收剂芯,然而在此期间却不实际地吸收流体。对内衬层,即吸收剂芯的包覆片,另外要求的特征是即便经过,像婴儿尿布日常就地所发生的那样,长时间穿戴和反复排液(insults)之后,依然保持流体可透。对内衬织物迫切希望但难以实现的另一个特征是,当施加压力,例如,婴儿坐在湿尿布上时,它们能防止已收集在吸收剂芯内的液体倒流直达使用者皮肤。
纤维素材料制成的非织造织物和复合材料即便在反复排液之后仍能透过和吸收液体,但它们在压力下不能照常阻止被保持流体的倒流。基于经济、审美和强度等原因,热塑性纤维,如聚酯和聚烯烃一向被描述为这些最终用途所优选的材料。然而,聚丙烯从本质上是疏水的。当纺成用于制造织物的纤维或丝时,所获得的织物也是疏水或不可湿的。因此,该织物必须进行特殊处理或以某种方式加以改变,使织物变得可湿,就是说,能让流体透过或转移,倘若该布料打算用作卫生制品的内衬的话。
为澄清起见,要指出的是,吸收说明当加水时某材料溶胀。与此相对照,可润湿性,按本文的定义代表表面张力的改变,以致容许在诸如纤维之类固体表面形成一层水以便促进液体流过或透过可湿材料运动。
在本工业上已知,某些表面活性剂如Rohm and Haas生产的TRITON X-100可以以一种水溶液或悬浮体形式施加到疏水纤维、丝或非织造织物表面,从而导致纤维、丝或织物变得可湿—尽管并不吸收的效果。此种局部处理剂可采用本领域技术人员熟悉的任何方式施加,例如,发泡喷涂、浸渍-和压榨或辊筒凹印。几乎每种情况下,都要求某种加热步骤以驱除表面活性剂溶液或分散体制备中使用的残余水或溶剂。这一步骤显著增加制造成本或复杂性。再者,热塑性塑料因加热会发生变化,因此要求小心检测加热过程,才能保证织物性能不受到不利影响。还有,表面活性剂并非牢固地化学键合在纤维或丝表面,故而此种局部处理效果不持久。它们往往在反复排液和使用期间的揉搓之下被冲掉。
为克服此种缺陷,已采用电晕放电处理来改变纤维或丝表面的电化学电位。其作用是要使表面变得更具反应性从而使疏水表面变成较为可湿。然而,这些电位的改变也不持久,尤其易受环境效应的影响,如在潮湿环境中储存。
另一项进步是表面化学处理的采用,其中表面活性剂共价键合到聚合物上。
另一种手法是将化学剂加入到热塑性聚合物中,然后再挤出为纤维、丝或非织造织物。诸如硅氧烷之类的活性剂曾被建议用于此目的。这里,目的是要赋予纤维或丝以耐久的可润湿性改变。性能模型理论指出,熔体添加剂在纤维或丝骤冷期间当聚合物冷却时变得分散在熔融聚合物中并结合在基质内。随着时间的推移,由于进一步加工的作用,添加剂到达纤维或丝表面,即一种被称之为喷霜(blooming)的现象,从而赋予持久的可润湿性。
Bergbreiter和Srinivas在《(Macromolecules(大分子)》25(1992),636~643中公开一种旨在给高密度聚乙烯表面进行改性的“包封(entrapment)官能化”方法。制备聚乙烯与聚乙二醇的嵌段共低聚物并与新鲜聚乙烯进行紧密混合。由此种混合物制备的聚合物经分析表明,聚乙二醇单元最终基本上都处于薄膜的最外层。
美国专利5,464,691公开旨在改变聚烯烃薄膜表面能的三-嵌段两亲树脂的应用。两亲树脂由两种烃段与极性段组成。烃段由例如长链脂族羧酸、脂族醇之类衍生而来,而极性段由例如聚乙二醇之类的链端官能二醇衍生而来。
美国专利5,240,985、5,272,196、5,281,438、5,328,951公开两亲物用于提高聚烯烃表面能的应用。该两亲物由中心亲水组分和两种亲脂组分组成。亲水组分由例如,聚二醇衍生而来,而亲脂组分由,例如脂肪酸或脂族醇衍生而来。
美国专利5,262,233公开一种农用薄膜,其中结合进可以是长链醇的聚环氧乙烷的消雾剂。
美国专利3,048,266公开一种具有消雾性能的聚烯烃薄膜,其中结合进环氧乙烷的酯或醚加成物。
美国专利5,001,015公开一种具有抗静电性能的聚烯烃薄膜,作为可能的抗静电剂它包含聚烷氧基化物与脂肪醇的反应产物。
美国专利4,304,234公开一种通过以诸如环氧丙烷和/或环氧乙烷加成物之类的极性化合物的处理来提高聚烯烃丝可润湿性的方法。
美国专利5,804,625公开一种亲水热塑性纤维的制备方法,其中该纤维中加入了一种或多种含氟代脂族基团的非离子表面活性剂和一种或多种非离子、非氟化的含聚氧乙烯基团的表面活性剂。
美国专利6,239,047公开一种加入了聚乙二醇油基醚添加剂的可湿聚烯烃纤维。
WO-A-00/28143公开一种聚烯烃或聚酯纤维的亲水整理的方法,其中采用烷基乙氧基化物类化合物。
EP-A-0 888 786、E P-A-0 800 833和WO-A-00/22061各自讨论了芯吸性能改善的非织造制品中的粘合剂组合物,该组合物包含诸如乙氧基化一元醇之类的表面活性剂。
WO-A-01/14621公开一种包含脂族聚酯、聚烯烃、微纤维和相容剂的可生物解体非织造材料。
目前,卫生制品、婴儿尿布之类仍需要可润湿性改善的织物。具体地说,由织造和非织造纤维制备的疏水聚烯烃织物仍需要改进可润湿性。本发明的特定聚烯烃组合物具有极优异的可润湿性。
本发明涉及一种可湿聚烯烃纤维或丝,它包含熔融共混物,该共混物包含,
(a)聚烯烃;和
(b)至少一种通式(I)的化合物
R1-(亲水低聚物) (I)
其中R1是22~40个碳原子的直链或支链烷基,亲水低聚物是由2~10个由选自环氧乙烷、环氧丙烷、乙二醇、丙二醇、表氯醇、丙烯酸、甲基丙烯酸、乙烯亚胺、己内酯、乙烯醇和醋酸乙烯酯的单体衍生的单体单元组成的均聚-或共聚-低聚物。
该亲水低聚物例如由2、3、4、5、6、7、8、9或10个单体单元组成。
在本发明通式(I)化合物中,R1例如是22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39或40个碳原子的直链或支链烷基。
通式(I)化合物例如可以是式中亲水低聚物由环氧乙烷衍生的那种,由通式(Ia)表示,
R1(OCH2CH2)xOH (Ia)
其中x是2~10,R1是22~40个碳原子的直链或支链烷基。下标“x”例如是2、3、4、5、6、7、8、9或10。
通式(I)化合物可看作AB二嵌段两亲共低聚物。R1烷基的链长和亲水低聚物的单体单元数目可以是分立的(discrete)数值。或者,就本发明通式(I)化合物而言,R1烷基的链长和亲水低聚物的单体单元数目皆可为平均值。
通式(Ia)化合物的具体例子是,它是一种通式(Ib)的乙氧基化脂族醇,其中R1是30个碳原子平均值的直链烷基,且x是等于2.5的平均值:
CH3CH2(CH2CH2)13CH2CH2(OCH2CH2)2.5OH (Ib)
本发明组合物还可包含二或更多种通式(I)化合物的添加剂混合物。本发明组合物还可包含其他已知的两亲添加剂。具体地说,附加的添加剂可以是乙氧基化脂族醇,例如Atmer_502,一种2摩尔乙氧基化的十八烷醇,C18H37(OCH2CH2)2OH,化学文摘(C.A.)登记号9005-00-9。Atmer_是Uniqema的商标。Atmer_502是一种不属于本发明通式(I)的乙氧基化脂族醇的例子。
化合物(Ib)可从Baker Petrolite按商品名Unithox_420,CAS #97953-22-5购得。
本发明组合物可通过熔融挤出方法形成纤维或丝来制备。按照已知技术,例如纱线或常产纤维的连续丝束纺丝,和诸如纺粘生产和熔喷生产之类的非织造方法,纤维或丝通过熔融聚合物经由小孔挤出来形成。一般而言,如此形成的纤维或丝随后进行拉伸或伸长以诱导分子取向并影响结晶性,从而使直径变小,物理性能改善。在诸如纺粘和熔喷之类的非织造方法中,纤维或丝直接沉积在多孔表面上,例如,移动的扁平输送带,并采用各种各样包括但不限于,热、机械或化学粘合方法之类的手段中的任何手段至少部分地进行加固。本领域技术人员知道,综合各种方法或来自不同方法的织物可生产出具备某种希望特性的复合织物。这方面的例子是综合纺粘与熔喷方法生产很著名的SMS层合织物,意指两个纺粘织物外层和熔喷内层。另外,这些方法之一或二者可以任何安排方式与常产纤维梳理方法,或来自非织造常产纤维梳理方法的粘合织物进行组合。在此种所述层合布料中,层一般通过上面列举的手段之一进行了至少部分加固。
本发明也适用于熔融挤出的双组分纤维,其中组分之一是本发明聚烯烃。
聚烯烃的非织造织物可具有梳理的纤维结构或包含一种垫,其中纤维或丝以无规阵列方式分布。该织物可通过多种已知方法当中任何一种来形成,包括:水力缠结(水刺)或射流喷网技术,或气流铺网或熔喷长丝、纤维层拉伸、缝编等,具体视用该织物制成的制品的最终用途而定。
对于预计类型可湿织物最有用的纺粘丝纤度为约1.0~约3.2旦。预计用途的典型熔喷纤维的直径小于15μm,最典型的纤维直径小于5μm,向下一直延伸至亚微米级。复合构造中的纤网可以以各种各样的基重加工。
如上所述,热塑性聚丙烯纤维(典型地在约210℃~240℃的温度下挤出)是本质疏水的,因为它们基本上无孔并且由不能吸引或结合水分子的连续分子链组成。结果,未处理的聚丙烯织物,即便当具有开孔结构时,仍具有阻止诸如水或尿透过布料或从一个表面到另一表面流动的倾向。
按照本发明,一种特定通式(I)乙氧基化两亲物以熔体形式结合到热塑性聚烯烃,如聚丙烯中,并与聚烯烃一起挤出为纤维和丝的形式,随后,在后续的或者同时进行的加工步骤中,骤冷,变细并成形为织物。
通式(I)化合物可与待熔融挤出聚合物粒料一起混炼。为改善加工情况,该配混料可预先配制或者混炼成为还可包含少量无机粉末,如滑石和其他传统稳定剂的低MFR聚丙烯。
通式(I)化合物向聚烯烃中的混合可通过按照诸如辊筒混炼、密炼机混炼或挤出机混炼之类的常用技术将它混入到熔融聚合物中。热历史(在升温下停留的时间)可这样缩短:将通式(I)化合物与未加热的聚合物粒料混合以达到在聚合物物质中的基本均匀分布,从而减少在熔融温度下剧烈混合所需要的时间。
方便的是,通式(I)化合物也可与任何其他在特定情况中要求的添加剂基本上同时或顺序地加入。通式(I)化合物也可与其他添加剂预掺混,然后再将共混物加入到聚合物中。本发明范围包括:在某些情况下,通式(I)化合物可具有帮助其他添加剂变得更容易或均匀地分散或溶解在聚烯烃中的附加功效。为更便于实施批与批之间的质量控制,优选使用聚合物/添加剂共混物的浓缩母料,随后将它作为一部分共混入到附加数量的聚合物中以达到最终希望配方。母料,或者纯净添加剂,可趁聚合物尚处于熔融并且在它离开聚合容器或系列(train)之后注入到新制备的聚合物中,并在熔融聚合物冷却为固体或送入下面加工之前与之共混。
组分(b)的化合物在本发明组合物中的总量为0.1%~15%,以组合物(a)的聚烯烃重量为基准。就许多用途而言,通式(I)化合物的典型用量为1%~7%,以组分(a)的重量为基准。
通式(I)化合物在本发明聚烯烃纤维或丝中的加入将导致这些天然疏水材料的可润湿性的可观察的改善。此种改进效果也是持久的,以致用它制成的纤维或丝和织物历经陈化或操作之后仍不丧失其可润湿性。可润湿性的改善虽经反复排液(insults)其依然不损失性能,即便在一段延长的时间里。
本发明的目的是织造或非织造织物,例如,聚丙烯织物。其目的还在于在传统纺织加工中的机织(weaving)或针织(knitting)用的线或纱。
本发明添加剂不论其他影响非织造织物性能的因素如何都有效,这些因素例如包括基重、纤维直径、纤维粘合程度和类型和复合物结构如上面所描述的SMS结构的协同效应和影响。
本发明不限于单组分纤维。聚烯烃双组分纤维,特别是聚丙烯和聚乙烯的并列或壳芯纤维,预计也将展示与这两种类型中任何一种的单组分纤维一样的实际功效。特别有效的是将熔融添加剂仅加入到聚乙烯组分中,因为较软的聚合物预计将更有效地促使本发明通式(I)添加剂“喷霜(blooming)”到组分纤维或丝的表面。
由本发明纤维或丝生产的可湿织物作为,例如,卫生制品,特别是一次性尿布、训练裤、女性卫生用品或失禁护理产品接触皮肤的内衬布料特别有用。该织物还可用于湿和干抹布、伤口敷料、手术帽、过滤介质、电池隔膜等。
尿布的结构例如描述在美国专利5,961,504、6,031,147和6,110,849中,这里全部收作参考。
另外,通常希望的是,赋予熔融挤出聚烯烃薄膜以可润湿性。此种薄膜当以多孔形式时被广泛用作卫生制品的包覆片材。
就作为卫生制品包覆面料而言,倒浸湿(wetback)性能的改进可通过将二或更多层织物粘合在一起使用来改善。例子包括两个纺粘层或SMS织物,其中熔喷层不含通式(I)的添加剂。
本发明织物可通过以约0.5~约10兆拉德伽马射线照射来消毒。伽马射线的消毒被用于医院服装等上面。
按本发明制备的聚烯烃织造和非织造纤维和织物还表现出格外好的适印性。由于其固有疏水本性,聚烯烃纤维和布料可能对标准印花技术存在适印性方面的问题。本发明组合物也克服了这些问题。
组分(a)聚烯烃的例子是:
1、单烯烃和二烯烃聚合物,例如,聚丙烯、聚异丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚异戊二烯或聚丁二烯,和环烯烃的聚合物,例如,环戊烯或降冰片烯的聚合物、聚乙烯(任选地可进行交联),例如,高密度聚乙烯(HDPE)、高密度和高分子量聚乙烯(HDPE-HMW)、高密度和超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(IDPE)、线型低密度聚乙烯(LLDPE)、(VLDPE)和(ULDPE)。
聚烯烃,即,在前面段中举例说明的单烯烃的聚合物,例如,聚乙烯和聚丙烯,可按不同,特别是以下方法来制备:
i)自由基聚合(通常在高压和升温下)。
ii)催化聚合,采用的催化剂通常包含元素周期表族IVa、Vb、VIb或VIII中的一种或多于一种的金属。这些金属一般具有一个或多个配位体,典型配位体为氧化物、卤化物、醇盐、酯、醚、胺、烷基、链烯基和/或芳基,可以是p-或s-配位的。这些金属络合物可处于游离形式或固定在基材上,一般在活化的氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可以是可溶于或不溶于聚合物介质的。该催化剂可以其本身用于聚合,或者另外还可使用活化剂,典型活化剂是烷基金属、金属氢化物、金属烷基卤化物、金属烷基氧化物或金属烷基环氧乙烷(alkyloxanes),所述金属是周期表的族Ia、IIa和/或IIIa的元素。该活化剂可用进一步的酯、醚、胺或甲硅烷基醚基团方便地改性。这些催化剂体系通常被称为菲利普、印第安纳标准油品、齐格勒(-纳塔)、TNZ(杜邦)、金属茂或单位点催化剂(SSC)。
2、在项1.)下面提到的聚合物的混合物,例如,聚丙烯与聚异丁烯的、聚丙烯与聚乙烯的混合物(例如,PP/HDPE、PP/LDPE)和不同类型聚乙烯的混合物(例如,LDPE/HDPE)。
3、单烯烃和二烯烃彼此或与其他乙烯基单体的共聚物,例如,乙烯/丙烯共聚物、线型低密度聚乙烯(LLDPE)和其与低密度聚乙烯(LDPE)的混合物、丙烯/丁-1-烯共聚物、丙烯/异丁烯共聚物、乙烯/丁-1-烯共聚物、乙烯/己烯共聚物、乙烯/甲基戊烯共聚物、乙烯/庚烯共聚物、乙烯/辛烯共聚物、丙烯/丁二烯共聚物、异丁烯/异戊二烯共聚物、乙烯/丙烯酸烷基酯共聚物、乙烯/甲基丙烯酸烷基酯共聚物、乙烯/醋酸乙烯酯共聚物和其与一氧化碳的共聚物或乙烯/丙烯酸共聚物和其盐(离子交联聚合物),和乙烯与丙烯和二烯,如己二烯、二环戊二烯或亚乙基降冰片烯的三元共聚物;此种共聚物彼此和与上面1)项中提到的聚合物的混合物,例如,丙烯/乙烯-丙烯共聚物、LDPE/乙烯-醋酸乙烯酯共聚物(EVA)、LDPE/乙烯-丙烯酸共聚物(EAA)、LLDPE/EVA、LLDPE/EAA和交替或无规聚链烯/一氧化碳共聚物和它们与其他聚合物,如聚酰胺的混合物。
本发明的聚烯烃例如是聚丙烯均聚-和共聚物和聚乙烯均聚-和共聚物。例如,聚丙烯、高密度聚乙烯(HDPE)、线型低密度聚乙烯(LLDPE)和聚丙烯无规和耐冲击共聚物。
烯烃聚合物的共混物或合金(alloys)的应用也属本发明范围内。
本发明聚烯烃纤维、丝和织物还可包含或在其表面施涂适当添加剂,如紫外光吸收剂、受阻胺光稳定剂、抗氧化剂、加工助剂和其他添加剂。
例如,本发明组合物可任选地还含有约0.01~约10%,优选约0.025~约5%,尤其约0.1~约3wt%各种各样传统稳定剂共添加剂,例如,下面列举的材料,或其混合物。
1、抗氧化剂
1.1.烷基化一元酚,例如,2,6-二叔丁基-4-甲基苯酚、2-叔丁基-4,6-二甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,6-二叔丁基-4-正丁基苯酚、2,6-二叔丁基-4-异丁基苯酚、2,6-二环戊基-4-甲基苯酚、2-(α-甲基环己基)-4,6-二甲基苯酚、2,6-二-十八烷基-4-甲基苯酚、2,4,6-三环己基苯酚、2,6-二叔丁基-4-甲氧基甲基苯酚,壬基苯酚,其侧链可以是直链或支链,例如,2,6-二壬基-4-甲基苯酚、2,4-二甲基-6-(1’-甲基-十一烷-1’-基)苯酚、2,4-二甲基-6-(1’-甲基十七烷-1’-基)苯酚、2,4-二甲基-6-(1’-甲基十三烷-1’-基)苯酚和它们的混合物。
1.2.烷硫甲基苯酚,例如,2,4-二辛硫甲基-6-叔丁基苯酚、2,4-二辛硫甲基-6-甲基苯酚、2,4-二辛硫甲基-6-乙基苯酚、2,6-二-十二烷硫甲基-4-壬基苯酚。
1.3.氢醌和烷基化氢醌,例如,2,6-二叔丁基-4-甲氧基苯酚、2,5-二叔丁基氢醌、2,5-二叔戊基氢醌、2,6-二苯基-4-十八烷氧基苯酚、2,6-二叔丁基氢醌、2,5-二叔丁基-4-羟基茴香醚、3,5-二叔丁基-4-羟基茴香醚、硬脂酸3,5-二叔丁基-4-羟苯基酯、己二酸双(3,5-二叔丁基-4-羟苯基)酯。
1.4.生育酚,例如,α-生育酚、β-生育酚、γ-生育酚、δ-生育酚和其混合物(维生素E)。
1.5.羟基化硫二苯基醚,例如,2,2’-硫双(6-叔丁基-4-甲基苯酚)、2,2’-硫双(4-辛基苯酚)、4,4’-硫双(6-叔丁基-3-甲基苯酚)、4,4’-硫双(6-叔丁基-2-甲基苯酚)、4,4’-硫双(3,6-二仲戊基苯酚)、4,4’-双(2,6-二甲基-4-羟苯基)-二硫醚。
1.6.烷叉双酚,例如,2,2’-亚甲基双(6-叔丁基-4-甲基苯酚)、2,2’-亚甲基双(6-叔丁基-4-乙基苯酚)、2,2’-亚甲基双[4-甲基-6-(α-甲基环己基)-苯酚]、2,2’-亚甲基双(4-甲基-6-环己基苯酚)、2,2’-亚甲基双(6-壬基-4-甲基苯酚)、2,2’-亚甲基双(4,6-二叔丁基苯酚)、2,2’-乙叉(ethylidene)双(4,6-二叔丁基苯酚)、2,2’-乙叉双(6-叔丁基-4-异丁基苯酚)、2,2’-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚]、2,2’-亚甲基双[6-(α,α-二甲基苄基)-4-壬基苯酚]、4,4’-亚甲基双(2,6-二叔丁基苯酚)、4,4’-亚甲基双(6-叔丁基-2-甲基苯酚)、1,1-双(5-叔丁基-4-羟基-2-甲基苯酚)丁烷、2,6-双(3-叔丁基-5-甲基-2-羟基-苄基)-4-甲基苯酚、1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷、乙二醇的双[3,3-双(3’-叔丁基-4’-羟苯基)丁酸酯]、双(3-叔丁基-4-羟基-5-甲基-苯基)-二环戊二烯、双[2-(3’-叔丁基-2’-羟基-5’-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯、1,1-双(3,5-二甲基-2-羟苯基)丁烷、2,2-双(3,5-二叔丁基-4-羟苯基)丙烷、2,2-双(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷、1,1,5,5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7.O-,N-和S-苄基化合物,例如,3,5,3’,5’-四-叔丁基-4,4’-二羟基二苄基醚、十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯、十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯、三(3,5-二叔丁基-4-羟苄基)胺、双(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫代对苯二甲酸酯、双(3,5-二叔丁基-4-羟苄基)硫醚、异辛基-3,5-二叔丁基-4-羟苄基巯基乙酸酯。
1.8.羟苄基化的丙二酸酯,例如,二-十八烷基-2,2-双(3,5-二叔丁基-2-羟苄基)丙二酸酯、二-十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯、二-十二烷基巯基乙基-2,2-双(3,5-二丁基-4-羟苄基)丙二酸酯、双[4-(1,1,3,3-四(甲基丁基)苯基]-2,2-双(3,5-二叔丁基-4-羟苄基)丙二酸酯。
1.9.芳族羟苄基化合物,例如,1,3,5-三(3,5-二叔丁基-4-羟苄基)-2,4,6-三甲基苯、1,4-双(3,5-二叔丁基-4-羟苄基)-2,3,5,6-四甲基苯、2,4,6-三(3,5-二叔丁基-4-羟苄基)苯酚。
1.10.三嗪化合物,例如,2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯氨基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氨基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪、2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、2,4,6-三(3,5-二叔丁基-4-羟苯基乙基)-1,3,5-三嗪、1,3,5-三(3,5-二叔丁基-4-羟苯基丙酰基)-六氢-1,3,5-三嗪、1,3,5-三(3,5-二环己基-4-羟苄基)异氰脲酸酯。
1.11.苄基膦酸酯,例如,二甲基-2,5-二叔丁基-4-羟苄基膦酸酯、二乙基-3,5-二叔丁基-4-羟苄基膦酸酯、二-十八烷基-3,5-二叔丁基-4-羟苄基膦酸酯、二-十八烷基-5-叔丁基-4-羟基-3-甲基苄基膦酸酯、3,5-二叔丁基-4-羟苄基膦酸的单乙酯的钙盐。
1.12.酰基氨基酚,例如,4-羟基月桂酰苯胺、4-羟基硬脂酰苯胺、N-(3,5-二叔丁基-4-羟苯基)氨基甲酸辛酯。
1.13.β-(3,5-二叔丁基-4-羟苯基)丙酸与单-或多羟基醇的酯,例如与:甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与单-或多羟基醇
的酯,例如与:甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷;3,9-双[2-(3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]-十一烷。
1.15.β-(3,5-二环己基-4-羟苯基)丙酸与单-或多羟基醇
的 酯,例如与:甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.16.3,5-二叔丁基-4-羟苯基乙酸与单-或多羟基醇
的酯,例如与:甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰尿酸酯、N,N’-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.17.β-(3,5-二叔丁基-4-羟苯基)丙酸的酰胺,例如N,N’-双(3,5-二叔丁基-4-羟苯基丙酰)六亚甲基二酰胺、N,N’-双(3,5-二叔丁基-4-羟苯基丙酰)三亚甲基二酰胺、N,N’-双(3,5-二叔丁基-4-羟苯基丙酰)酰肼、N,N’-双[2-(3-[3,5-二叔丁基-4-羟苯基]丙酰氧基)乙基]草酰胺(Naugard_XL-1,Uniroyal供应)。
1.18.抗坏血酸(维生素C)
1.19.氨的(Aminic)抗氧化剂,例如,N,N’-二异丙基-对苯二胺、N,N’-二仲丁基-对苯二胺、N,N’-双(1,4-二甲基戊基)-对苯二胺、N,N’-双(1-乙基-3-甲基戊基)-对苯二胺、N,N’-双(1-甲基庚基)-对苯二胺、N,N’-二环己基-对苯二胺、N,N’-二苯基-对苯二胺、N,N’-双(2-萘基)-对苯二胺、N-异丙基-N’-苯基-对苯二胺、N-(1,3-二甲基丁基)-N’-苯基-对苯二胺、N-(1-甲基庚基)-N’-苯基-对苯二胺、N-环己基-N’-苯基-对苯二胺、4-(对甲苯氨磺酰)二苯胺、N,N’-二甲基-N,N’-二仲丁基-对苯二胺、二苯胺、N-烯丙基二苯胺、4-异丙氧基二苯胺、N-苯基-1-萘胺、N-(4-叔辛基苯基)-1-萘胺、N-苯基-2-萘胺,辛基化二苯胺,如对,对’-二叔辛基二苯胺,4-正丁氨基苯酚、4-丁酰氨基苯酚、4-壬酰氨基苯酚、4-十二烷酰氨基苯酚、4-十八烷酰氨基苯酚、双(4-甲氧基苯基)胺、2,6-二叔丁基-4-二甲氨基甲基苯酚、2,4’-二氨基二苯甲烷、4,4’-二氨基二苯甲烷、N,N,N’,N’-四甲基-4,4’-二氨基二苯甲烷、1,2-双[(2-甲基苯基)氨基]乙烷、1,2-双(苯氨基)丙烷、(邻甲苯基)双胍、双[4-(1’,3’-二甲基丁基)苯基]胺、叔辛基化的N-苯基-1-萘胺,单-与二烷基化的叔丁基/叔辛基二苯胺的混合物、单-与二烷基化的壬基二苯胺的混合物、单-与二烷基化的十二烷基二苯胺的混合物、单-与二烷基化的异丙基/异己基二苯胺的混合物、单-与二烷基化的叔丁基二苯胺的混合物、2,3-二氢-3,3-二甲基-4H-苯并噻嗪、吩噻嗪,单-与二烷基化的叔丁基/叔辛基吩噻嗪的混合物、单-与二烷基化的叔辛基吩噻嗪的混合物、N-烯丙基吩噻嗪、N,N,N’,N’-四苯基-1,4-二氨基丁-2-烯。
2.紫外吸收剂和光稳定剂
2.1. 2-(2’-羟苯基)苯并三唑,例如,2-(2’-羟基-5’-甲基苯基)苯并三唑、2-(3’,5’-二叔丁基-2’-羟苯基)苯并三唑、2-(5’-叔丁基-2’-羟苯基)苯并三唑、2-(2’-羟基-5’-(1,1,3,3-四甲基丁基)苯并三唑、2-(3’,5’-二叔丁基-2’-羟苯基)-5-氯苯并三唑、2-(3’-叔丁基-2’-羟基-5’-甲基苯基)-5-氯苯并三唑、2-(3’-仲丁基-5’-叔丁基-2’-羟苯基)苯并三唑、2-(2’-羟基-4’-辛氧基苯基)苯并三唑、2-(3’,5’-二叔戊基-2’-羟苯基)苯并三唑、2-(3’,5’-双(α,α-二甲基苄基)-2’-羟苯基)苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-辛氧基羰乙基)苯基)-5-氯苯并三唑、2-(3’-叔丁基-5’-[2-(2-乙基己氧基)羰乙基]-2’-羟苯基)-5-氯苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧基羰乙基)苯基)-5-氯苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧基羰乙基)苯基)苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-辛氧基羰乙基)苯基)苯并三唑、2-(3’-叔丁基-5’-[2-(2-乙基己基氧基)羰乙基]-2’-羟苯基)苯并三唑、2-(3’-十二烷基-2’-羟基-5-甲基苯基)苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-异辛氧基羰乙基)苯基苯并三唑、2,2’-亚甲基双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];2-[3’-叔丁基-5’-(2-甲氧基羰乙基)-2’-羟苯基]-2H-苯并三唑与聚乙二醇300的酯交换产物;
其中R=3’-叔丁基-4’-羟基-5’-2H-苯并三唑-2-基苯基,2-[2’-羟基-3’-(α,α-二甲基苄基)-5’-(1,1,3,3-四甲基丁基)苯基]苯并三唑;2-[2’-羟基-3’-(1,1,3,3-四甲基丁基)-5’-(α,α-二甲基苄基)苯基]苯并三唑。
2.2. 2-羟基二苯酮,例如,4-羟基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苄氧基、4,2’,4’-三羟基和2’-羟基-4,4’-二甲氧基衍生物。
2.3.取代或未取代的苯甲酸的酯,例如,4-叔丁基苯基的水杨酸酯、水杨酸苯酯、水杨酸辛基苯酯、二-苯甲酰间苯二酚、双(4-叔丁基苯甲酰)间苯二酚、苯甲酰间苯二酚、2,4-二叔丁基苯基的3,5-二叔丁基-4-羟基苯甲酸酯、3,5-二叔丁基-4-羟基苯甲酸十六烷基酯、3,5-二叔丁基-4-羟基苯甲酸十八烷基酯、3,5-二叔丁基-4-羟基苯甲酸2-甲基-4,6-二叔丁基苯酯。
2.4.丙烯酸酯,例如,α-氰基-β,β-二苯基丙烯酸乙酯、α-氰基-β,β-二苯基丙烯酸异辛酯、α-甲氧甲酰肉桂酸甲酯、α-氰基-β-甲基-对甲氧基肉桂酸甲酯、α-氰基-β-甲基-对甲氧基肉桂酸丁酯、α-甲氧甲酰-对甲氧基肉桂酸甲酯和N-(β-甲氧甲酰-β-氰基乙烯基)-2-甲基二氢吲哚。
2.5.镍化合物,例如,2,2’-硫代双[4-(1,1,3,3-四甲基丁基)苯酚]的镍络合物,例如,1∶1或1∶2的络合物,带有或不带有附加配体,如正丁胺、三乙醇胺或N-环己基二乙醇胺,二丁基二硫代氨基甲酸镍、单烷基酯的镍盐,如4-羟基-3,5-二叔丁基苄基膦酸的甲酯或乙酯的镍盐,酮肟的镍络合物,例如,2-羟基-4-甲基苯基十一烷基酮肟的镍络合物,1-苯基-4-月桂酰-5-羟基吡唑的镍络合物,带或不带附加配体。
2.6.空间位阻胺,例如,双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)的正丁基-3,5-二叔丁基-4-羟苄基丙二酸酯、1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶与琥珀酸的缩合物、N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛基-2,6-二氯-1,3,5-三嗪的线型或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、1,1’-(1,2-亚乙基(ethanediyl))-双(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰-2,2,6,6-四甲基哌啶、4-硬脂酰氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯,N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-吗啉基-2,6-二氯-1,3,5-三嗪的线型或环状缩合物、2-氯-4,6-双(4-正丁氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙基氨基)乙烷的缩合物、2-氯-4,6-二-(4-正丁氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙基氨基)乙烷的缩合物、8-乙酰-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮,4-十六烷氧基-与4-十八烷氧基-2,2,6,6-四甲基哌啶的混合物,N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-环己氨基-2,6-二氯-1,3,5-三嗪的缩合物、1,2-双(3-氨基丙基氨基)乙烷与2,4,6-三氯-1,3,5-三嗪的缩合物,和4-丁氨基-2,2,6,6-四甲基哌啶(CA S登记号[136504-96-6]);1,6-己烷二胺与2,4,6-三氯-1,3,5-三嗪的缩合物和N,N-二丁胺和4-丁氨基-2,2,6,6-四甲基哌啶(CAS登记号[192268-64-7]);N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基琥珀酰亚胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基琥珀酰亚胺、2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺[4,5]癸烷,7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺-[4,5]癸烷与表氯醇的反应产物,1,1-双(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N’-双-甲酰-N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺、4-甲氧基亚甲基丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯,聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基]硅氧烷、马来酐-α-烯烃共聚物与2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物。
空间位阻胺也可以是GB-A-2 301 106中被描述为作为组分I-a)、I-b)、I-c)、I-d)、I-f)、I-g)、I-h)、I-i)、I-j)、I-k)或I-l)的化合物之一,特别是所述GB-A-2 301 106的68~73页中列举的光稳定剂1-a-1、1-a-2、1-b-1、1-c-1、1-c-2、1-d-1、1-d-2、1-d-3、1-e-1、1-f-1、1-g-1、1-g-2或1-k-1。
空间位阻胺也可以是EP-A-0 782 994中描述的化合物之一,例如,文中权利要求10或38或实例1~12或D-1或D-5中所描述的化合物。
2.7.N-原子上取代上了羟基
取代的烷氧基基团的空间受阻 胺,例如,以下化合物:1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2,2,6,6-四甲基哌啶、1-(2-羟基-2-甲基丙氧基)-4-十六烷酰氧基-2,2,6,6-四甲基哌啶,1-氧基-4-羟基-2,2,6,6-四甲基哌啶与来自叔戊基醇的碳基团(carbonradical)的反应产物、1-(2-羟基-2-甲基丙氧基)-4-羟基-2,2,6,6-四甲基哌啶、1-(2-羟基-2-甲基丙氧基)-4-氧代-2,2,6,6-四甲基哌啶、双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)癸二酸酯、双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)己二酸酯、双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)琥珀酸酯、双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)戊二酸酯和2,4-双{N-[1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基]-N-丁氨基}-6-(2-羟基乙氨基)-s-三嗪。
2.8草酰胺,例如,4,4’二辛氧基-N,N’-草酰二苯胺、2,2’-二乙氧基-N,N’-草酰二苯胺、2,2’-二辛氧基-5,5’-二叔丁基-N,N’-草酰二苯胺、2,2’-二-十二烷氧基-5,5’-二叔丁基-N,N’-草酰二苯胺、2-乙氧基-2’-二乙基-N,N’-草酰二苯胺、N,N’-双(3-二甲氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2’-乙基-N,N’-草酰二苯胺和其与2-乙氧基-2’-乙基-5,4’-二叔丁基-N,N’-草酰二苯胺的混合物,邻-与对-甲氧基二取代的N,N’-草酰二苯胺的混合物和邻-与对-乙氧基二取代的N,N’-草酰二苯胺的混合物。
2.9.2-(2-羟苯基)-1,3,5-三嗪,例如,2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2,4-二羟苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十三烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-丁氧基丙基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪、2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-十二烷氧基丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪、2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪、2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-1,3,5-三嗪、2-(2-羟苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪、2-{2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪。
3.金属去活化剂,例如,N,N’-二苯基草酰胺、N-水杨醛-N’-水杨酰肼、N,N’-双(水杨酰)肼、N,N’-双(3,5-二叔丁基-4-羟苯基丙酰)肼、3-水杨酰氨基-1,2,4-三唑、双(苄叉)草酰二酰肼、N,N’-草酰二苯胺、间苯二甲酰二酰肼、癸二酰双苯基酰肼、N,N’-二乙酰己二酰二酰肼、N,N’-双(水杨酰)草酰二酰肼、N,N’-双(水杨酰)硫代丙酰二酰肼。
4.亚磷酸酯和亚膦酸酯,例如,亚磷酸三苯酯、亚磷酸二苯基烷基酯、亚磷酸苯基二烷基酯、亚磷酸三(壬基苯基酯)、亚磷酸三月桂酯、亚磷酸三-十八烷基酯、二亚磷酸二-十八烷基季戊四醇酯、亚磷酸三(2,4-二叔丁基苯基酯)、亚磷酸二异癸基季戊四醇酯、二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯、二亚磷酸双(2,4-二-枯基苯基)季戊四醇酯、二亚磷酸双(2,6-二-叔丁基-4-甲基苯基)季戊四醇酯、二亚磷酸二异癸基氧基季戊四醇酯、二亚磷酸双(2,4-二-叔丁基-6-甲基苯基)季戊四醇酯、二亚磷酸双(2,4,6-三(叔丁基苯基)季戊四醇酯、三亚磷酸三-十八烷基山梨醇酯、二亚膦酸四(2,4-二叔丁基苯基)4,4’-亚联苯酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-dioxaphosphocin、亚磷酸双(2,4-二叔丁基-6-甲基苯基)甲基酯、亚磷酸双(2,4-二叔丁基-6-甲基苯基)乙基酯、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-dioxaphosphocin、2,2’,2”-次氮基-[三乙基三(3,3’,5,5’-四-叔丁基-1,1’-联苯-2,2’-二基)亚磷酸酯]、亚磷酸2-乙基己基(3,3’,5,5’-四-叔丁基-1,1’-联苯-2,2’-二基)酯、5-丁基-5-乙基-2-(2,4,6-三-叔丁基苯氧基)-1,3,2-dioxaphosphirane。
尤其优选下列亚磷酸酯:
亚磷酸三(2,4-二叔丁基苯基)酯(Irgafos_168,CibaSpecialty Chemicals Inc.)、亚磷酸三(壬基苯基)酯,
5.羟胺,例如,N,N-二苄基羟胺、N,N-二乙基羟胺、N,N-二辛基羟胺、N,N-二月桂基羟胺、N,N-二-十四烷基羟胺、N,N-二-十六烷基羟胺、N,N-二-十八烷基羟胺、N-十六烷基-N-十八烷基羟胺、N-十七烷基-N-十八烷基羟胺,由氢化的牛脂胺衍生的N,N-二烷基羟胺。
6.硝酮,例如,N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、由氢化的牛脂胺衍生的N,N-二烷基羟胺衍生的硝酮。
7.氧化胺,例如,如美国专利5,844,029和5,880,191公开的氧化胺衍生物、氧化二癸基甲基胺、氧化三癸基胺、氧化三-十二烷基胺和氧化三-十六烷基胺。
8.苯并呋喃酮和二氢吲哚酮,例如,美国专利4,325,863、美国专利4,338,244、美国专利5,175,312、美国专利5,216,052、美国专利5,252,643,DE-A-4316611、DE-A-4316622、DE-A-4316876、E P-A-0589839或EP-A-0591102公开的那些或3-[4-(2-乙酰氧基乙氧基)-苯基]-5,7-二叔丁基苯并呋喃-2-酮、5,7-二叔丁基-3-[4-(2-硬脂酰氧基乙氧基)苯基]-苯并呋喃-2-酮、3,3’-双[5,7-二叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮]、5,7-二叔丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮、3-(4-乙酰氧基-3,5-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(3,4-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(2,3-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮。
9.硫协合剂,例如,硫代二丙酸二月桂酯或硫代二丙酸二-十八烷基酯。
10.过氧化物清除剂,例如,β-硫代二丙酸酯,例如,月桂酯、十八烷基酯、肉豆蔻酯或十三烷基酯、巯基苯并咪唑,或者2-巯基苯并咪唑的锌盐、二丁基二硫代氨基甲酸锌、二-十八烷基二硫醚、四(β-十二烷基巯基)丙酸季戊四醇酯。
11.聚酰胺稳定剂,例如,铜盐与碘化物和/或磷化合物和二价锰盐的组合。
12.碱性助稳定剂,例如,三聚氰胺、聚乙烯基吡咯烷酮、双氰胺、氰尿酸三烯丙酯、尿素衍生物、肼衍生物、胺、聚酰胺、聚氨酯、高级脂肪酸的碱金属盐和碱土金属盐,例如,硬脂酸钙、硬脂酸锌、二十二烷酸镁、硬脂酸镁、蓖麻油酸钠和棕榈酸钾、焦儿茶酚锑或焦儿茶酚锌。
13.成核剂,例如,无机物,如滑石、金属氧化物,如二氧化钛或氧化镁、优选碱土金属的磷酸盐、碳酸盐或硫酸盐;有机化合物,如单-或多羧酸和其盐,例如,4-叔丁基苯甲酸、己二酸、二苯基乙酸、琥珀酸钠或苯甲酸钠;聚合化合物,如离子共聚物(离子交联聚合物)。尤其优选的是1,3:2,4-双(3’,4’-二甲基苄叉(benzylidene))山梨醇、1,3:2,4-二(对甲基苄叉)山梨醇和1,3:2,4-二(苄叉)山梨醇。
14.填料和增强剂,例如,碳酸钙、硅酸盐、玻璃纤维、玻璃泡、石棉、滑石、高岭土、云母、硫酸钡、金属氧化物或氢氧化物、碳黑、石墨、锯末和其他天然产物的粉末或纤维,合成纤维。
15.分散剂,如聚环氧乙烷蜡或矿物油。
16.其他添加剂,例如,增塑剂、润滑剂、乳化剂、颜料、染料、流变学添加剂、催化剂、流动控制剂、荧光增白剂、滑爽剂、交联剂、交联促进剂、卤素清除剂、消烟剂、防燃剂、抗静电剂、透明剂,如取代和未取代的双苄叉山梨醇、苯并噁嗪酮紫外吸收剂,如2,2’-对亚苯基双(3,1-苯并噁嗪-4-酮),Cyasorb_3638(CAS# 18600-59-4),和发泡剂。
还想到,本发明熔融共混物可形成为有效的微孔膜、多孔薄膜或网。也就是除纤维、丝或织物以外的其他可湿聚烯烃制品。
本发明还涉及一种赋予聚烯烃纤维、丝或用其制造的织造或非织织物的方法,包括:将包含热塑性聚烯烃和至少一种通式(I)化合物的混合物熔融挤出为多根纤维,并将纤维冷却。优选地,所述纤维被牵伸为多根连续丝,由所述丝形成为网并且将该丝至少部分地粘合从而形成织物。优选地,该纤维或丝是包含聚烯烃的双组分纤维或丝。
因此,本发明的优选实施方案是通式(I)化合物用于赋予聚烯烃纤维、丝或织造或非织造织物以永久可润湿性的应用。
下面的实施例仅用于说明的目的,从任何意义均不应构成对本发明的限制。添加剂用量以重量百分数给出。
实施例1:聚丙烯非织造布纤维
采用TURBULA Mixer型号T10B制备8.5kg聚丙烯粒料ExxonPolybond 3155 PP与1.5kg通式(Ib)的化合物的干混合物,
CH3CH2(CH2CH2)13CH2CH2(OCH2CH2)2.5OH (Ib)
该15%浓缩混合物利用Leistritz MIC 27/GL-32D双螺杆挤出机进行熔融混炼。挤出机加热区为190~220℃,螺杆速度400RPM,且加料器速度25RPM。熔融聚合物和添加剂通过两孔圆形口型(dye)放出。熔融物料立即在冷水槽内冷却并固化。固化的线料供入到CONAIR/JETRO 304切粒机中。
该浓缩物粒料以40kg附加的Exxon Polybond 3155 PP粒料稀释(let down)并用Marion SPS 1224混合机进行混合,结果获得一种3wt%的添加剂浓缩物。
由上面制备的3%添加剂粒料采用REICOFIL II Spunbonder制备非织造聚丙烯纤维,制备条件如下:
挤出机温度200~215℃,
换网温度205℃,
纺丝泵温度215℃,速度18.6rpm,
4,000孔纺丝板,温度梯度223~240℃,
粘合辊压力291 PSI,下辊138℃,上辊140℃,
冷却空气速度3020rpm,抽吸空气速度2510rpm,和
收集卷取速度调整到使生产的非织造物重量为20g/m2。
获得的非织造物通过测定液体透过时间,即,已知体积模拟尿(9.0g NaCl/L)透过非织造物的时间来评估渗透性和耐久性。INDA(国际非织造物与一次性制品协会)标准试验方法是#IST70.3(98),采用Lenzing Lister,型号1997。结果如下。
还评估了样品的连续透过和延时多次透过,仍采用LenzingLister仪器。较短时间代表一种要求的较快透液。结果如下。
最后,采用INDA标准试验方法#IST 10.1(95)部分8来评估样品的吸收模拟尿的容量。该方法还被用来测定延时的吸收容量。吸收容量是样品所保持的液体重量与干样品重量之比。结果如下。
INDA液体透过时间
试验方法#IST 70.3(98),结果,以s计
空白(无添加剂)
3%通式(Ib)的添加剂
>1,000s 3.63s
>1,000 3.64
4.21
该试验结果显示,本发明组合物提供一种具有优异可润湿性的非织造聚丙烯。
连续透过
两个透过之间最长30s,结果以秒表示,试验是针对3块具有3%通式(Ib)添加剂的相同非织造样品进行的。
透过1 透过2 透过3 透过4 透过5 透过6 透过7 透过8 透过9
4.40 | 4.53 | 4.26 | 4.63 | 4.25 | 4.72 | 4.99 | 5.00 | 5.50 |
2.55 | 3.42 | 3.98 | 4.14 | 4.43 | 4.46 | 4.53 | 4.82 | 5.08 |
3.41 | 3.71 | 3.79 | 3.99 | 3.98 | 4.72 | 4.63 | 4.35 | 4.97 |
连续透过试验的结果显示,本发明组合物能有效地让两个之间短时间的反复排液透过。这展示通式(Ib)添加剂的耐久或持久性。
延时的多次透过
两个透过之间晾干1h,结果以秒表示,试验是针对5个相同非织造样品进行的,每个具有3%通式(Ib)添加剂。
0h 1h 2h 3h 4h 5h 6h 7h
6.99 | 5.00 | 3.95 | 5.28 | 0.56 | 3.40 | 2.59 | 2.99 |
7.24 | 5.67 | 5.81 | 4.54 | 4.82 | 3.68 | 3.96 | 3.13 |
6.00 | 4.73 | 4.53 | 2.53 | 3.81 | 3.42 | 3.98 | 3.04 |
9.93 | 6.50 | 4.81 | 4.92 | 3.96 | 3.99 | 4.24 | 4.71 |
4.68 | 4.17 | 5.02 | 3.20 | 3.17 | 3.57 | 2.98 | 2.54 |
延时多次透过试验的结果显示,本发明组合物能有效地让两个之间长时间的反复排液透过。这展示通式(Ib)添加剂的耐久或持久性。
吸收容量
INDA标准试样#10.1(95)部分8,结果是样品所保持的模拟尿重量与干样品重量之比。
空白一无添加剂:0.4 3%通式(Ib)添加剂:8.8
这些结果展示本发明组合物惊人的亲水性。
延时吸收容量
INDA标准试样#10.1(95)部分8,样品以模拟尿饱和,风干24h,并再次吸饱。结果是对于样品所保持的模拟尿重量与干样品重量的原来比保持的百分率。试验是针对具有3%通式(Ib)添加剂的非织造样品进行的。
24h 48h 72h 96h
75% | 61% | 61% | 58% |
这些结果展示,本发明组合物在经过多次暴露于模拟尿之后仍有效地保持其亲水性。
实施例2:聚丙烯适印性
聚丙烯与5wt%通式(Ib)添加剂熔融掺混并纺成丝,进而簇绒(tufted)加工为地毯。在该地毯上印刷以染料索引(C.I.)酸性黄216:1,C.I.酸性红266和C.I.酸性蓝40的混合物,从而带上深褐三原色。印花色浆还包含增稠剂如瓜尔胶。印制后,施加上去的染料在蒸化机(steamer)中进行固色。固色后,地毯以冷水漂洗。用本发明纤维制备的地毯表现出优异的适印性。
实施例3:聚丙烯非织造纤维
重复实施例1但替代通式(Ib)的化合物,采用通式(Ib)和Atmer_502,2摩尔乙氧基化的十八烷醇的1∶1混合物。在液体透过时间、连续透过、延时多次透过和延时吸收容量试验中都取得优异结果。
实施例4:碱性电池隔膜—氢氧化钾吸收百分率
按实施例1制备聚丙烯非织造物。添加剂相对于配方所占重量载于下表中。非织造物被裁切为4平方英寸的段。非织造物在室温下浸泡在167mL 40%KOH溶液中。5min后取出样品,将其晾干1min。样品称重,从而获得初始%氢氧化钾吸收(湿重-干重/干重x100)。湿样品再次浸泡在加盖烧杯内的新鲜40%氢氧化钾溶液中。烧杯放在70℃烘箱内。7日后,样品取出并以去离子水漂洗。样品悬挂晾干1日后称重,从而获得70℃下7日后的%氢氧化钾吸收。结果如下。
Unithox_420(wt%) | Atmer_502(wt%) | 初始百分KOH吸收 | 百分KOH吸收70℃,7日后吸收 |
---1.53.01.50.75 | ---------1.50.75 | 618881777824889 | NA*9008221011987 |
不带添加剂的非织造聚丙烯具有过量水珠,不吸收。可以看出,本发明亲水非织造物即便在70℃退火(annealing)7日之后,其氢氧化钾溶液吸收能力仍表现良好。这些结果表明本发明组合物在碱性电池隔膜方面的应用潜力。Unithox_420等价于通式(Ib)的本发明化合物。
Claims (15)
1.一种可湿聚烯烃纤维或丝,它包含熔融共混物,该共混物包含,
(a)聚烯烃;和
(b)至少一种通式(Ia)的化合物
R1(OCH2CH2)xOH (Ia)
其中R1是22~40个碳原子的直链或支链烷基,并且x是2~10。
2.权利要求1的纤维或丝,其中聚烯烃是聚丙烯或聚乙烯。
3.权利要求1的纤维或丝,其中在通式(Ia)的化合物中,R1是碳原子数平均值为30的直链烷基,且x的平均值为2.5,该化合物由通式(Ib)代表:
CH3CH2(CH2CH2)13CH2CH2(OCH2CH2)2.5OH (Ib).
4.权利要求1的纤维或丝,其中熔融共混物包含两种不同的通式(Ia)化合物,其区别在于R1的平均值不同和/或单体单元数的平均值不同。
5.权利要求1的纤维或丝,其中熔融共混物另外还包含不属于通式(Ia)的乙氧基化脂族醇。
6.权利要求1的纤维或丝,其中熔融共混物另外还包含通式(Ic)的化合物
C18H37(OCH2CH2)2OH (Ic).
7.权利要求1的纤维或长丝,其中组分(b)的化合物总共占0.1%~15%,以组分(a)的重量为基准计。
8.一种包含聚烯烃组分的双组分纤维,其中聚烯烃组分包含熔融共混物,该共混物包含权利要求1的组分(a)和(b)。
9.一种织造或非织造织物,包含针织或粘合的权利要求1的聚烯烃纤维或丝。
10.一种织造或非织造织物,包含针织或粘合的权利要求8的双组分纤维。
11.一种赋予聚烯烃纤维、丝或者由它们制成的织造或非织造织物以永久可润湿性的方法,包括将包含热塑性聚烯烃与至少一种权利要求1的通式(Ia)化合物的混合物熔融挤出为多根纤维并将纤维冷却。
12.权利要求11的方法,其中所述纤维被牵伸为多根连续丝,由所述丝成形为网,并将该丝至少部分地粘合从而形成织物。
13.权利要求11的方法,其中纤维或丝是包含聚烯烃的双组分纤维或丝。
14.一种包含权利要求9的织造或非织造织物的制品,选自一次性尿布、训练裤、女性卫生巾、棉塞、失禁护理用品、湿和干抹布、伤口敷料、手术帽、过滤介质和电池隔膜。
15.权利要求1的通式(Ia)化合物用于赋予聚烯烃纤维、丝或者织造或非织造织物以永久可润湿性。
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