CN107075760B - 液体浸渍的含有含氧化锌的纤维素纤维的非织造织物 - Google Patents
液体浸渍的含有含氧化锌的纤维素纤维的非织造织物 Download PDFInfo
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- CN107075760B CN107075760B CN201580057309.7A CN201580057309A CN107075760B CN 107075760 B CN107075760 B CN 107075760B CN 201580057309 A CN201580057309 A CN 201580057309A CN 107075760 B CN107075760 B CN 107075760B
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- Prior art keywords
- nonwoven fabric
- zinc oxide
- fibers
- liquid
- cellulose
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- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
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- GAMIYQSIKAOVTG-UHFFFAOYSA-L zinc;2-aminopentanedioate Chemical compound [Zn+2].[O-]C(=O)C(N)CCC([O-])=O GAMIYQSIKAOVTG-UHFFFAOYSA-L 0.000 description 1
- AGFGXVAAIXIOFZ-UHFFFAOYSA-L zinc;butanedioate Chemical compound [Zn+2].[O-]C(=O)CCC([O-])=O AGFGXVAAIXIOFZ-UHFFFAOYSA-L 0.000 description 1
- ZJVTYKZWDWVIFD-UHFFFAOYSA-N zinc;hydrochloride Chemical compound Cl.[Zn] ZJVTYKZWDWVIFD-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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Abstract
本发明涉及含有至少部分地结合式含有氧化锌‑颗粒的纤维素纤维并且另外浸渍有液体的非织造织物,以及其制备方法和其特别是用于制备不含防腐剂的湿擦巾的用途。
Description
本发明涉及含有至少部分地结合式含有氧化锌-颗粒的纤维素纤维并且另外浸渍有液体的非织造织物,以及其制备方法和其特别是用于制备不含防腐剂的湿擦巾的用途。
现有技术
在剧烈变化的生活环境和生活习惯,包括流动性的增加,提高的富裕,对卫生的更高的要求和越来越缺乏时间的背景下,近年来对清洁湿巾(所谓的湿巾)的需求急剧增加,其用于清洁硬和软的表面。在此是基材,优选无纺布,其用含有效物质或活性物质的浸渍溶液处理、分装成小包并在湿润状态下,例如,作为清爽型(Erfrischungs)-、家庭型-、厕用型-、卸妆型-或婴儿型巾销售。主要使用在化妆品(个人护理、婴儿护理)和物件清洁的领域。根据不同的应用领域在产品要求方面,高的清洁性能和/或护理皮肤的作用处于重要位置。
为避免微生物污染,按照标准化妆品-微生物学-化妆产品的抗微生物保护评价(ISO11930),所有化妆产品必须具有足够的防腐。为了这个目的,防腐剂通常被加入,由此一方面确保了未开封的产品的耐久性和储存能力,并且另一方面避免了在其打开之后的包装的病原菌污染(Verkeimung)。在使用阶段,最终消费者取出巾的过程是病原菌的主要引入源。对于本发明的目的,术语“防腐剂”应理解为,像这样在于2014年09月03日颁布的欧盟化妆品指令(76/768/EEC)的附录VI中定义的物质。
防腐剂是阻止或抑制微生物如细菌、真菌和酵母的生长,或将这些杀死的抗微生物的有效的杀生物剂。然而,这也可能对皮肤菌群产生不利的影响,并表现为皮肤刺激和皮肤发红、过敏反应和湿疹的频繁出现。因此,特别是在受损的或像婴儿的那种敏感的皮肤的情况下,向化妆产品和药用产品添加防腐的物质应被严格看待。与此有关不确定的是,这种有效物质是否并以何种量经皮肤吸收。关于毒理学的数据状况必须在很多情况下被归为不足够的。所以一些动物测试引起了揣测,对羟基苯甲酸酯类经较长的使用寿命会影响荷尔蒙系统。苯氧乙醇(一种经常使用的防腐剂)可能具有损害肝的作用。
因此需要找到耐受的并且同时有效的防腐剂的替代物。氧化锌在医学中由于其消毒和消炎的作用早就用作用于皮肤护理和伤口处理的产品中的有效物质。提供含氧化锌的软膏、橡皮膏或绷带,其适合于在皮肤发红、皮疹和皮炎(例如尿布皮炎)以及轻微的烧伤的情况下的表面使用。锌是人体必需的微量元素,其显著影响抵抗力和众多自身酶的作用。因此含锌的产品具有高的生物耐受性。
根据现有技术,在制备湿巾中不仅利用了氧化锌的护理皮肤和治疗的作用,还利用了其抗微生物性能,通过用含氧化锌的乳状液或其它浸渍溶液处理呈无纺布形式的不同的基材例如纤维素基材。这尤其在US20060171971 (A1)和WO9959540 (A1)中描述。在提及的专利中还指出以下选择:向液体配制物掺入防腐剂。在这些文件中描述的应用形式中的氧化锌明显仅具有护理和治疗的作用,而不具有防腐的作用。
这些产品的一个显著的缺点在于,必须间或向浸渍液体添加高量的化学助剂,如表面活性剂或用于设定粘度的增稠剂,以避免在产品的制备过程和储存期间氧化锌颗粒的非期望沉降,其由于ZnO颗粒的高的比密度会发生。
将氧化锌结合在聚烯烃物料中以根据熔融纺丝法或熔喷法来制备非织造布,和这类抗微生物产品在医学和卫生领域例如作为湿擦布的用途在JP2006249615 (A)中被要求保护。然而这类非织造布由于聚烯烃的疏水特性具有小的吸收力和低的含水液体的吸收能力,和因此在与含水配制物组合时仅非常受限地适合作为湿巾。此外,与由纤维素纤维制成的非织造布相比,这些无纺布不能生物降解。
还由于其亲水性(以纤维素的性质为依据),与水分子形成强的氢键,以及与其相联系的高的含水液体的吸收力,在制备湿擦巾中纤维素纤维比化学纤维如聚酯或聚丙烯更优选。除了纤维素外,还使用纤维素人造纤维,所谓的再生纤维素纤维,如粘胶纤维或Lyocell纤维。后者关于均匀性、纯度(例如杀虫剂残留物)、柔软度和吸收性能在广泛的领域中都超越天然纤维素纤维。特别是Lyocell纤维以与其它纤维素纤维相比高的干强度和尤其是高的湿强度著称,并且使得可能制备具有高的强度的软的最终产品。
日常需求的物品,其包含含氧化锌的Lyocell纤维并且此外具有抗微生物或不刺激皮肤的和治疗的性能,例如由DE202010010803 (U1)以敏感洗涤物的形式或由DE202012011814 (U1)以用于新生儿和婴儿的嘴护理或牙齿护理的指套的形式已知,其中后者同样优选地实施为纺织物的形式。
总的来说,在文献中还提到了众多可能性来制备具有治疗伤口、护理皮肤或抗微生物的作用的含氧化锌的纤维素湿巾。然而这些方法都局限于浸渍方法,其特征在于,使呈无纺布形式的基材负载有含氧化锌的液体配制物。通常向这些浸渍液体中掺入防腐剂用以确保耐久性,和其它助剂如表面活性剂用以避免在生产和储存中的氧化锌颗粒的沉降。然而使用化学添加剂和尤其是防腐剂鉴于消费者保护和消费者的健康不是期望的。
具有抗微生物性能的无纺布,由含氧化锌的Lyocell纺丝物料根据熔喷法制备,在WO2009006206 (A1)中描述。WO2012034679 (A1)要求保护纺粘无纺布,其根据已知的纺粘无纺布方法由掺有金属氧化物的纤维素溶液在使用N-甲基吗啉-N-氧化物作为直接溶剂的情况下制备。在该两个专利中研究了在卫生领域使用这类无纺布,而不是特别地作为湿擦巾。除此之外,所述的非织造织物还在其制备方法上受到限制。因此在WO2009006206 (A1)中描述的无纺布的半纤维素含量为4至18 %;在WO2012034679 (A1)中规定纤维中的添加剂含量为大于40重量%。因此在该两种情况下,纤维的纺织机械性能大大降低。这些纤维还显示小的抗拉强度。
在EP 2334853 B1中同样公开了含锌颜料的Lyocell纤维。那里描述了这种纤维的一种特定形式,在其中锌至少部分地作为锌酸盐存在。本领域技术人员已知,锌酸盐仅能够在碱性环境中存在。这些纤维还应具有抗菌的作用,其特别地由此实现,即在颜料中除氧化锌外还包含硫化锌。这些纤维的浅显意图在于在多次洗涤过程之后仍保留这些性能。因为在湿擦巾例如婴儿擦巾中含有的洗液总具有酸性的pH-值,在这类应用中没有出现锌酸盐。人皮肤的pH值通常为约pH 5.5,其中擦巾中的洗液通常稍酸性一点,以便不会对皮肤产生不利的影响。
WO 2004081267 A1在其中的实施例V中具体公开了具有特定的 UV-吸收能力的含ZnO的Lyocell-纤维的制备。这些纤维的具体用途在WO 2004081267 A1中没有提及;然而从该描述中可推断出,WO 2004081267 A1以制备吸收UV的纤维为目的。
目的
与所述的现有技术相比,目的在于,提供非织造织物,其在用于湿的再加工产品中时不需要另外的防腐剂或仅需要比至今通常的显著更小的含量的防腐剂,尤其用以在这些湿产品的制备、储存和从包装中取出时避免受病原菌污染,并且使消费者与这类防腐剂的接触最小化。然而这些非织造织物除了上述功能外还应具有关于湿强度、吸水等的理想的性能。
发明描述
上述目的的解决方案在于提供含有纤维素纤维的非织造织物,其中纤维素纤维至少部分地结合式含有氧化锌-颗粒,并且所述非织造织物另外浸渍有液体。含氧化锌的纤维素纤维根据本发明为纤维素人造纤维,例如根据粘胶法、Modal法或Lyocell法制备,其基本上为本领域技术人员所已知。将固体物质纺入这种纤维中基本上也是本领域技术人员所已知的,例如由针对粘胶纺丝溶液的WO 2011/026159或由针对Lyocell纺丝溶液的WO 2007/022552。除了其它优点外,本发明的非织造织物由于ZnO的酶失活性能以及过敏原物质的吸附还具有抗过敏原的性能。本发明的另一意料之外的优点为,这些性能在此通过比根据现有技术可行的这样显著更小的ZnO-含量来实现(还参见以下描述的实施例和表2)。
优选非织造织物,其中所述液体具有小于7的pH。特别优选非织造织物,其中所述液体具有介于3和6之间的pH,优选具有介于4.5和5.5之间的pH。这通过用具有相应pH-值的酸性液体浸渍非织造织物来实现。因此本发明的一个优选的实施方案为非织造织物,其中所述液体含有有机酸或无机酸,其形成可溶性锌盐。为了本发明的目的,应将可溶性锌盐理解为,在25°C和1013 hPa的气压下在18-MOhm-水中具有大于50 ppm的溶解度的锌盐。一般将“18-MOhm-水”理解为经离子交换器或其它已知的方法去离子化的水,其具有最大18MOhm的传导性。
这些酸应已在化妆品中广泛传播。这些酸优选选自甲酸、乙酸、乳酸、柠檬酸、葡糖酸、谷氨酸、琥珀酸、盐酸和硫酸,并且所述可溶性锌盐相应地优选选自甲酸锌、乙酸锌、乳酸锌、柠檬酸锌、葡糖酸锌、谷氨酸锌、琥珀酸锌、盐酸锌和硫酸锌。
在本发明的非织造织物中的氧化锌-结合的纤维素纤维含有介于0.1和10重量%之间的氧化锌,优选介于0.3和4.5重量%之间的氧化锌,特别优选介于0.3和3.5重量%之间的氧化锌,基于绝对干燥的纤维素。至最多17重量%氧化锌也是可行的,但由于经济的因素考虑不经常使用。
本发明的非织造织物除氧化锌-结合的纤维素纤维外还可含有不含氧化锌的纤维素纤维。为此除了纤维素人造纤维,例如根据粘胶法、Modal法或Lyocell法制备,还可以考虑天然纤维素纤维如棉、大麻等。
本发明的非织造织物除氧化锌-结合的纤维素纤维外还可含有合成纤维。为此基本上可以考虑所有已知的合成纤维。聚对苯二甲酸乙二醇酯和聚丙烯是特别合适的。
在本发明的非织造织物中,所述纤维素纤维是短纤维或连续长丝纤维。由连续长丝纤维制成的非织造织物在此还可包括根据熔喷法(参见例如EP 1093536 B1)制备的非织造织物。
本发明的非织造织物具有 8.5 N或更高的纤维粗糙度,用在实施例中描述的滑车测试(Sledgetest)测量。已发现,较高的纤维粗糙度导致更佳的清洁作用,此外还通过增加湿擦巾的清洁表面。
本发明还涉及借助常规的无纺布制备方法来制备非织造织物的方法,其中使用含有结合了的氧化锌的纤维素纤维来成网,并且用液体浸渍所述非织造织物。作为成网方法可以考虑机械成网、流动成网、气动成网以及熔喷;作为纤维网加固方法尤其可以考虑水刺加固(Wasserstrahlverfestigung)、针刺加固(Vernadelung)、热加固和化学加固。
此外,本发明涉及含有氧化锌-结合的纤维素纤维并且浸渍有液体的非织造织物的用途,其用于制备湿擦巾,特别地作为婴儿型湿巾、卸妆型巾、清洁型巾等。
特别优选的是本发明的用途,其中所述湿擦巾不另外含有防腐剂。„防腐剂“在此被理解为列在于2014年09月03日颁布的欧盟化妆品指令(76/768/EEC)的附录VI中的物质。
因此本发明还包含湿擦巾,其含有上述的本发明的非织造织物并且因此不需要这种另外的防腐剂。
改善的清洁力还通过使阴离子污物(例如排泄物、有机酸等)吸附在表面处的和纤维横截面内的 ZnO处产生。
此外,本发明还涉及含有氧化锌-结合的纤维素纤维并且浸渍有液体的非织造织物的用途,其用于制备湿面膜。这种湿面膜可浸渍有物质,其具有护理皮肤的作用。结合入纤维的ZnO(其以其护理皮肤的作用出名)本身同样有助于整个产品的护理皮肤的作用。
以下借助实施例描述本发明。然而本发明明确不限于这些实施例,而是还包含了所有其它的实施方案,其以相同的本发明设想为依据。
实施例
湿擦巾的制备:
首先根据现有技术已知的Lyocell法来制备Lyocell-纤维,在其中纺入0.0、1.2、3.0和16.7 wt% (基于绝对干燥的纤维) ZnO,以便根据Lyocell法产生纺丝物料,其含有13wt%纤维素和上述的ZnO-量(基于纤维素)。该纺丝物料随后根据Lyocell法进行纺制(单根纤维纤度2.5 dtex,切削长度38 mm),配备有上油处理,其不具有任何防腐或生物杀灭性能并且随后干燥。由这样制备的纤维各制备针刺无纺布 (克重60 g/m2, 300刺孔/cm2),其随后水刺加固并随后干燥(在具有以下设置的Fleissner-设备上:35 bar 水压;具有2排喷嘴列的1个喷嘴梁;去离子水:pH 7.6;无纺布的通过速度 2 m/min;100 µm 水射流喷嘴的孔直径;118°C 干燥温度)。如此制备的无纺布用290 wt%洗液(基于无纺布的干重)浸渍,以获得相应的婴儿-湿巾。洗液的确切组成在表1中给出。洗液的pH-值在与非织造织物接触48h后设定在pH 3.00。
表1:
INCI名称 | 商品名 | 制造商 | 功能 | wt% |
水 | VE-Wasser | 自己 | 溶剂 | 96.15 |
丙二醇 | Propylenglycol | Sigma Aldrich | 湿润剂 | 3.00 |
聚山梨酯20 | Tween 20 | Sigma Aldrich | 增溶剂 | 0.60 |
辛酰/癸酰氨丙基甜菜碱(35 %) | Tego Betain 810 | Evonik | 表面活性剂 | 0.25 |
乙酸 | Essigsäure pA | Sigma Aldrich | pH-设定 | 1.44 |
根据ISO 11930的对足够防腐的测试:
将100条尺寸为15 x 10 cm的由具有0.0、1.2或16.7wt%ZnO的纤维构成的擦巾用洗液浸渍(290 wt%洗液,基于无纺布的干重,组成根据表1) 并接着进行对足够防腐的测试。出于该目的,所述擦巾用培菌液接种,其含有定义的浓度的在化妆品中常见的病原菌(金黄色葡萄球菌(S. aureus): 7.40E+05 KBE; 绿脓杆菌(P. aeruginosa): 2.80E+05KBE; 大肠杆菌(E. Coli): 4.40E+05 KBE; 白色念珠菌(C. albican): 6.90E+05 KBE;巴西诺卡氏菌(A. brasiliensis): 1.70E+05 KBE)。在接种后搁置擦巾28天。在7、14和28天的观察时间后各测定湿擦巾上的微生物的病原菌数(参见表2),以能够确定病原菌减少。
根据ISO 11930的测试显示,针对在绝对干燥的纤维上具有1.2和16.7wt%ZnO的擦巾就化妆品中常见的病原菌而言防腐是成功的,因为实现了足够的病原菌减少。较高的ZnO-量(根据DIN EN 11930的标准A)显示比较小的ZnO-浓度(根据DIN EN 11930的标准B)显著更佳的作用。
根据EN 1202 PPS的滑车测试:
纤维的柔软度用滑车测试测定,其描述在EN 1202 PPS中。该测试的重要条件为:5g 纤维试样进行两次梳理,例如在Uster MTDA-3 Rotorring-仪器上。所述纤维根据EDANA-规定(ERT 60.2-99)预处理至少24 h并且随后借助模板切割。该材料随后放入测试装置中,并且安装担负2000 g重量的滑车和置于模型上。开始测试并在10秒后测量力,其为将滑车拉到模型上方所需。纤维表面越软,则需要越小的力用以将滑车拉向前。该测试在各材料上重复4次。结果示于表3中。
表2:
表3:
试样名称 | 纤维-纤维摩擦 (平均值) [N] | 标准偏差 [N] |
3.0 wt% ZnO | 9.23 | 0.25 |
1.2 wt% ZnO | 6.86 | 0.14 |
Claims (15)
1.非织造织物,其含有纤维素纤维,其中所述纤维素纤维至少部分地结合式含有氧化锌-颗粒,并且所述非织造织物另外浸渍有液体,特征在于,所述液体具有介于4.0和5.5之间的pH。
2.根据权利要求1的非织造织物,其中所述液体含有有机酸或无机酸,其形成锌盐,所述锌盐在25°C和1013 hPa的气压下在18-MOhm-水中具有大于50ppm的溶解度。
3.根据权利要求1的非织造织物,其中基于绝对干燥的纤维素,所述氧化锌-结合的纤维素纤维含有介于0.1和10重量%之间的氧化锌。
4.根据权利要求3的非织造织物,其中基于绝对干燥的纤维素,所述氧化锌-结合的纤维素纤维含有介于0.3和4.5重量%之间的氧化锌。
5.根据权利要求4的非织造织物,其中基于绝对干燥的纤维素,所述氧化锌-结合的纤维素纤维含有介于0.3和3.5重量%之间的氧化锌。
6.根据权利要求1的非织造织物,其中所述氧化锌-颗粒涂覆有合成制备的聚合物。
7.根据权利要求6的非织造织物,其中所述氧化锌-颗粒涂覆有聚丙烯酸酯。
8.根据权利要求1的非织造织物,其除了氧化锌-结合的纤维素纤维以外还含有不含氧化锌的纤维素纤维。
9.根据权利要求1的非织造织物,其除了氧化锌-结合的纤维素纤维以外还含有合成纤维。
10.根据权利要求1的非织造织物,其中所述纤维素纤维是短纤维或连续长丝纤维。
11.根据权利要求1的非织造织物,其具有8.5 N或更高的纤维-纤维摩擦,用滑车测试测量。
12.借助常规的无纺布制备方法来制备非织造织物的方法,其中使用含有结合了的氧化锌的纤维素纤维来成网,并且所述非织造织物用液体浸渍,其特征在于,所述液体具有介于4.0和5.5之间的pH。
13.含有氧化锌-结合的纤维素纤维并且浸渍有液体的非织造织物用于制备湿擦巾的用途,所述液体具有介于4.0和5.5之间的pH。
14.根据权利要求13的用途,其中所述湿擦巾不另外含有防腐剂。
15.含有氧化锌-结合的纤维素纤维并且浸渍有液体的非织造织物用于制备具有护理皮肤作用的湿面膜的用途,其中所述液体具有介于4.0和5.5之间的pH。
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