CN100509377C - 经处理的纺织品和纺织品处理组合物 - Google Patents

经处理的纺织品和纺织品处理组合物 Download PDF

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CN100509377C
CN100509377C CNB2004800273573A CN200480027357A CN100509377C CN 100509377 C CN100509377 C CN 100509377C CN B2004800273573 A CNB2004800273573 A CN B2004800273573A CN 200480027357 A CN200480027357 A CN 200480027357A CN 100509377 C CN100509377 C CN 100509377C
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textile
composition
component
fluorine
antimicrobial
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CN1856396A (zh
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X·方
S·S·小洛克
P·A·麦克卢尔
J·G·查伊
M·珀迪
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Sage Vehicle Interior Ltd By Share Ltd
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Milliken and Co
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/33—Esters containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • D—TEXTILES; PAPER
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D06M11/42—Oxides or hydroxides of copper, silver or gold
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/236—Esters of carboxylic acids; Esters of carbonic acid containing halogen atoms
    • D—TEXTILES; PAPER
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • 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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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
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    • Y10T428/2481—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including layer of mechanically interengaged strands, strand-portions or strand-like strips
    • 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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    • Y10T442/00—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
    • Y10T442/2041—Two or more non-extruded coatings or impregnations
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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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
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    • Y10T442/2041—Two or more non-extruded coatings or impregnations
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Abstract

某些化学品组合物当涂在纺织品或织物上时提供优良的拒斥性、耐久性和去污(去沾污)性。这些组合物可以含含有含氟化学品的去污组分或交联组分，或者二者均含有，还可以含抗微生物剂。在一些应用中，交联组分可以是疏水的，从而通常与含水环境不相容。在一些应用中，可以使用含有含氟化学品的去污组分占处理组合物重量不到约6wt%的组合物。

Description

经处理的纺织品和纺织品处理组合物
相关申请的交叉参考
本申请要求2003年9月22日提交的美国专利申请第60/504756号的优先权。
背景技术
例如Teflon
Figure C200480027357D0006105629QIETU
的碳氟化合物防污渍纺织品处理剂被用来使纺织品表面具有防护性能。这些处理剂一般为纺织品表面提供有限的抗污渍保护。一旦油渍被压入经防护碳氟化合物处理过的纺织品表面的纤维结构内，则通常不能可靠地将这样的污渍从纺织品表面除去。
抗微生物纺织品处理剂通过限制纺织品中的微生物生长，为纺织品提供减少或消除气味和霉变的额外优点。许多美国专利致力于抗微生物处理剂在纺织品或织物基质上的应用，这些专利包括：例如美国专利第5,968,207号、第6,479,144号、第6,024,823号、第6,492,001 B1号、第6,207,250号、第5,565,265号和公布的题为“Treated Textile Fabric(经处理的织物)”的美国专利申请第2003/0008585A1号，和题为“Treated Textile Fabric(处理过的织物)”的美国专利申请第2001/0021616A1号。但是这些引用文献中公开的许多纺织织物并不具有实质上的去污性能，使得它们难于清洁。
去污性一般是指纺织品或织物从织物表面释放污渍，例如油渍的能力。如果纺织品能够表现出对液体溅渍的斥污性(stain repellency)，而且其去污作用良好，则是很有益的。许多现有技术中经处理的纺织品提供斥污性方面的保护，但是却未能提供去污性方面的保护。能提供斥液性(repellency to liquid)、相当的去污性，而且还控制微生物、霉菌、霉变等生长的织物是许多纺织品表面非常需要的。
最近公开的Rubin等人题为“Treated Textile Fabric(经处理的纺织品)”的美国专利申请2003/0008585A1(“Rubin”)公开了制备经处理的纺织织物的组合物和工艺。通常，这种织物包含约6wt％至约12wt％的含氟化学品纺织品处理剂，其在织物上形成相对较重的膜。但是，含这种相对较大百分含量纺织品处理剂的纺织品可能不合需要地硬，或者手感相对较差。另外，这类化学品如此大量使用时费用很高。在纤维表面上使用相对大量的这类处理剂可以降低柔软度，这是不符合要求的。而且，这类织物的去污垢性不良。
发明内容
令人心惊奇的是，已经发现，某些组合物能够给予纺织品表面良好的斥液性，而且还使织物具有相当的去污性。而且，使用抗微生物组分或抗微生物剂可以同时控制细菌生长。还可以在这种组合物中采用交联组分作为任选组分。这种处理剂提供长期的耐久效果，即，经如此处理的纺织品通常对于例如自然磨损的正常使用是耐久的。所述的有利性能即使在多次洗涤和长期使用后仍然保持。而且，有可能提供这样的有利效果而又不在纺织品上形成厚重膜。本发明的许多应用(但非全部)中使用少于约6wt％的碳氟化合物，这是相对于总的或最初的处理用组合物的百分数。
定义和术语
“斥水性”和“斥油性”通常分别定义为基质阻挡水和油渗透到基质内的能力。例如，基质可以是能够阻挡水和油渗透到纺织品基质纤维内的纺织品基质。
＂去污和去沾污＂通常是指经沾污的基质由于护理工序而达到其最初未经沾污的外观的程度。
如本文所使用，术语“防污或防沾污组合物或者防污或防沾污处理剂”是指任何使纤维，特别是聚酯或混纺物具有防污性的处理剂或组合物。
“耐久性”通常定义为基质经过合理次数的洗涤或穿用循环后保持可接收水平的所需功能的能力。更具体地，如本文所述，耐久性描述基质在整个产品寿命中保持足够的防污性、斥水性、斥油性和去污性的能力。该基质可以是纺织品基质，例如，举例来说，聚酯纺织织物，或者另外，可以是地毯或再另一种纺织品材料。
本文的术语“碳氟化合物”、“含氟聚合物”和“含氟化学品”可互换使用，每一个均代表含有至少一个氟化链段的聚合材料。
“亲水”定义为具有较强的与水的亲和力或者具有较强的吸水能力。
“疏水”定义为缺少与水的亲和力或者缺少吸水能力。
去污(沾污)组分
举例来说，去污(或沾污)剂可以包括乙氧基化聚酯、氟化酯类、尿烷、丙烯酸酯、磺化聚酯、乙氧基化尼龙、羧化丙烯酸类、纤维素醚或酯、水解的聚马来酸酐聚合物、聚乙烯醇聚合物、聚丙烯酰胺聚合物、氟化去污聚合物、乙氧基化硅酮聚合物、聚氧乙烯聚合物、聚氧乙烯-聚氧丙烯共聚物及类似物，或者它们的组合。去污组分具体市售的例子包括但不限于Repearl SR-1100
Figure C200480027357D0008105735QIETU
(获自Mitsubishi InternationalCorporation)、Bayard SOCTM(Bayer)、Zonyl 7910
Figure C200480027357D0008105735QIETU
、9200
Figure C200480027357D0008105735QIETU
(CibaSpecialty Chemical)、Unidyne TG-992
Figure C200480027357D0008105735QIETU
或TG-993
Figure C200480027357D0008105735QIETU
(Daikin Corporation)和PM 490
Figure C200480027357D0008105735QIETU
(3M Company)。
可以使用去污和去沾污的含氟化学品，举例来说，如氟化的酯类、尿烷和(甲基)丙烯酸酯。这样的化合物充当去污组分。其例子包括Repearl SR-1100TM(获自Mitsubishi International Corporation)、BayardSOCTM(获自Bayer)、Zonyl 7910TM、9200TM(获自Ciba Corporation)、TG993TM(获自Daikin Corporation)、FC248TM和PM490TM(3MCompany)。
抗微生物组分
术语“抗微生物组分”或者“抗微生物剂”用来包括任何表现出抗微生物活性的化合物。在本发明的一个实施方式中，抗微生物剂包括以下的一种或多种：含银树脂、含银沸石、含银玻璃、银基离子交换化合物、无机抗微生物材料、金属基沸石、金属盐、金属氧化物、金属氢氧化物、过渡金属离子、三氯生、羟基吡啶氧化物和衍生物、氧化三丁基锡衍生物、3-碘-2-丙基氨基甲酸丁酯、正丁基-1，2-苯并异噻唑啉、10，10′-氧代双酚噁砒、邻苯基苯酚钠和其它，所提到的可用化合物的可能选择中的一些。
在许多应用中，要求使用银基离子交换化合物、银基沸石或银基玻璃，以及它们的任意组合。一种银基离子交换材料是Milliken &Company提供的商品名为ALPHASAN的抗微生物磷酸银锆
Figure C200480027357D00091
通常，这种金属化合物可以以占具体胶乳组合物总重约0.00001至10％的量添加；或者另外可选地，约0.001至约5％；或者不同地，约0.01至约1％；并且还是约0.1至约1.0％。
还可以使用抗微生物剂，例如Ultrafresh NMTM和UltrafreshDM-50TM、DM-25TM(获自Thompson Associates)、RC-5000TM(获自Milliken Chemical)、ChitosanteTM(VAG Bioscience，Inc.R.O.C.，Taiwan)、Kathon LMTM(获自Rohm and Haas Company)、锌万亩定(ZincOmadine)(获自Arch Chemical)、Reputex 20TM(获自Avecia)、AM5700TM(Dow Corning)、Amical 48TM(Dow Chemical Co.)。
在许多应用中，锌万亩定或钠万亩定是非常有效的抗微生物剂。
任选的交联组分
本发明中可以使用交联组分，其包括基本上不溶于水的交联组分，也称为疏水交联组分。在其它配制物中，可以使用亲水性交联剂。
在本发明的一个实施方式中，使用的交联组分包括以下一种或多种：蜜胺甲醛和衍生物、环氧化物及其酐和衍生物。
在其它实施方式中，疏水交联组分可以包括异氰酸酯和类似物的保护衍生物，或者它们的组合。保护的二异氰酸酯可以是合适的交联组分。含两个或多个封端异氰酸酯化合物的单体或聚合物可以是最优选的交联组分。一种可以使用的交联组分是同样由Mitsubishi Corp.提供的
Figure C200480027357D00092
METM。其它交联组分包括Clariant提供的 DAN和DuPont提供的
Figure C200480027357D00094
 XANTM。
任选的拒斥组分
多种组合物可以适合用作本发明的拒斥组分。特别有用的一种是含氟化学品组合物。已知许多种含氟化学品组合物能够在纤维基质上实现拒斥性。可以使用3M公司生产的含氟化学品组合物产品系列，其包括ScotchgardTM和类似物。而且，DuPont的ZonylTM产品系列也是本发明拒斥组分的候选产品。可以使用均为日本公司的Daikin America，Inc.和Mitsubishi International Corporation经销的其它产品，以及其它产品。也可以使用Mitsubishi International Corporation制造的
Figure C200480027357D00101
F-8025。可以使用含氟丙烯酸酯和尿烷衍生物。还可以使用酯类、(甲基)丙烯酰胺低聚物和聚合物。
防静电织物或纺织品的任选生成
本发明的一个具体实施方式可以使用制造具有导电表面的防静电纺织品所必需的材料。通过首先应用含氟化学品、抗微生物剂(分别或一起，顺序不限)以及任选的交联剂或拒斥剂，随后应用防静电材料，可以实现这一点。用导电涂料对织物进行筛网印刷可以实现导电表面，其中导电涂料包括导电剂和粘合剂，以及任选的分散剂和/或增稠剂。可以使用任何实现织物最终用途所需防静电性能的方式对织物进行涂层。织物可以单面涂层或双面涂层，这一点通常考虑到涂层织物的期望外观或者涂层织物的导电性能，由织物的最终用途决定。产生的导电织物可以适于多种应用的最终用途，如汽车装饰品和其它车内织物(如门板、扶手、头枕)、商业和/或家用室内装潢；无尘室服装、拭布(wipe)和/或其它无尘室附属品(如拖把、台布和覆盖物)。
在本发明的一个实施方式中，可能获得复合材料，其中防静电纺织品可以进一步包括至少一层放置成与导电涂层相邻的第二织物。第二织物可以是机织、针织或非织造织物。另外可选地，防静电纺织品可进一步包括至少一层放置成与导电涂层相邻的泡沫材料。复合材料可进一步包括一层或多层机织、针织或非织造织物；一层或多层薄膜；一层或多层粘合剂；和它们的组合。
举例来说，这种复合材料可以用于汽车内部，如汽车装饰品，其中通过使用粘合剂或热层压或者类似方式将装饰织物粘合到泡沫衬背上。这种复合材料可以应用于其它领域，例如举例来说，用于家用或商业装饰或用于地毯料。
本申请的另一目的是实现具有导电表面的防静电纺织品的制造方法。这种方法通常包括以下步骤：提供针织、机织或非织造织物、用导电涂料以含线条图案对织物的一面或双面进行涂层，和干燥该织物。然后可以将织物暴露在本领域技术人员熟知的一种或多种机械和/或化学纺织品整理工序中。
提供具有相对持久的抗静电性能的防静电纺织品，这些性能基本上在不显著损害纺织品的纺织品手感(或感觉)或者纺织品表面外观的情况下在所有相对湿度下均可以实现。防静电纺织品通常包括至少在一面涂有导电涂料图案的织物。
纺织品基质
实施本发明所使用的待处理的纺织品基质可以是合成、天然和/或混纺基质。它们可以是机织、针织、地毯或非织造的。可以通过公知的方法如浸渍、泡沫、喷洒、吸尽和涂层法将组合物(或多种组合物)涂在纺织品基质上。这类组合物可涂在纺织品基质的任一面或双面上。这类组合物还可以具有涂到基质上的一种或多种组分，接着是其它或全部组分。此外，这类组合物可以具有一种或多种涂在基质一面上的组分，以及其它或全部涂到基质任一面上的组分。
本发明的织物可以由纤维形成，例如合成纤维、天然纤维或者它们的组合。合成纤维包括，例如，聚酯、聚丙烯腈、聚酰胺、聚烯烃、聚芳酰胺、聚氨酯、再生纤维素及其混纺纤维。更具体地，聚酯包括，例如，聚对苯二甲酸乙二酯、聚对苯二甲酸亚丙基酯、聚对苯二甲酸亚丁基酯、聚乳酸及其组合。聚酰胺包括，例如，尼龙6、尼龙6，6及其组合。聚烯烃包括，例如，聚丙烯、聚乙烯及其组合。聚芳酰胺包括，例如，聚对苯二甲酰对苯二胺(即
Figure C200480027357D00111
聚间苯二甲酰间苯二胺(即，
Figure C200480027357D00112
及其组合。天然纤维包括，例如，羊毛、棉、亚麻及其混纺物。
织物可以由任意尺寸的纤维或纱线形成，其包括微细旦(microdenier)纤维和纱线(每根单纤维低于1旦尼尔的纤维或纱线)。而且，织物可以部分或全部含有可沿着长度方向以化学或机械作用分裂的多组分或双组分纤维或纱线。织物可以含有例如切段纤维、长丝纤维、短纤维或其组合的纤维。
可以在纺织品基底的任一面上一起或单独涂上其它纺织品处理剂。其例子包括耐久压烫树脂和催化剂、缝纫润滑剂、柔软剂、抗静电处理剂、阻燃剂和光稳定剂。
试验方法
防液或防污性能可以使用斥水和斥油试验测量。
a)斥水性可以根据3M斥水试验II(1992年5月)测试。评级量表为1-10，“1”表示斥水程度最差(基质的表面能较高)，“10”表示斥水程度最好(基质的表面能较低)。3M斥水等级为：
·1为10％IPA，90％水
·2为20％IPA，80％水
·3为30％IPA，70％水
·4为40％IPA，60％水
·5为50％IPA，50％水
·6为60％IPA，40％水
·7为70％IPA，30％水
·8为80％IPA，20％水
·9为90％IPA，10％水
·10为100％IPA
b)斥油性可以根据AATCC试验方法118-1983测试。评级量表为1-8，“1”表示斥油程度最差(基质的表面能较高)，“8”表示斥油程度最好(基质的表面能较低)。斥油等级为：
·1为NujolTM矿物油
·2为65/35Nujol/正十六烷(以体积计)
·3为正十六烷
·4为正十四烷
·5为正十二烷
·6为正癸烷
·7为正辛烷
·8为正庚烷
c)去污性能可以使用污斑清洁法测量。使用AATCC试验方法130-1981中描述的沾污法将诸如玉米油和鞣革油(tanning oil)的油污压入纺织品基质中；其在本文中得以改良。经沾污的纺织品在室温下经过24小时。使用一片纸巾拭去纺织品表面上的过量污渍。然后将4滴织物清洁剂(如Zout)轻轻地加入到沾污区域中。纺织品在室温下经过5分钟。最后，用约4＂×4＂的polycotton布擦洗沾污区域约40秒，然后用大量温水漂洗。用纸巾吸去多余的水。清洁过的纺织品在室温下风干后，对照AATCC130-1981评级复制品评价去污性能，评级量表分1至5级，5级为最好。通常认为3.5及更高的评级具有良好的去污/去沾污性能。
抗微生物试验
抗微生物性能(细菌和真菌)可以使用改良的AATCC方法147测试，该方法也称为平行条痕法(Parallel Streak Method)，其进一步描述如下。
在平行条痕法中，接种琼脂表面，从而使其更加容易区分试验有机体和未灭菌样品上可能存在的污染有机体。已经证实平行条痕法能够有效提供针对革兰氏阳性和革兰氏阴性细菌的抗菌活性的证据。
使用织物下的抑制区(毫米)和生长区测量纺织品基质的抗微生物性能。通常，基质下不生长和/或基质周围清晰的抑制区(ZOI)表明抗微生物性能良好。
抑制区
抗微生物剂的迁移由抑制区化验评价。对含胰蛋白酶大豆琼脂的培养皿进行接种，该接种使用0.5ml经稀释的试验微生物过夜培养物约5E5细胞/ml的Na/K磷酸盐缓冲液。将样品针对肺炎克雷氏杆菌(Klebsiella pneumoniae)ATCC第4362号和金黄色葡萄球菌(Staphylococcus aureus)ATCC第6538号以及A.niger(一种真菌)进行试验。将约1×1英寸的样品置于板中心。将琼脂板在35℃下保温24小时。最终数据是在样品的四个边上测量的抑制区平均值，并说明了样品下的生长程度。
效能由针对黑曲霉(Aspergillus niger)ATCC#6275的抑制区化验评价。对含Sabouraud葡萄糖琼脂的培养皿进行接种，接种使用0.5ml升的1E5菌孢/毫升。将约1×1英寸的样品置于板中心。将琼脂板在25℃下保温1-7天。最终数据是在样品的四个边上测量的抑制区平均值，并说明了样品下的生长程度。
化学品浓度
在本发明的实施中，全部处理组合物中含有含氟化学品组分的百分含量典型地低于处理组合物的约6wt％，通常介于处理组合物的约0.5wt％和约3wt％之间。在一个具体的实施方式中，该百分含量为约1-2wt％。
关于本发明应用中的吸液率(pickup)百分数，该吸液率通常介于碳氟化合物组分吸液率的约50％和约70％之间，但是本发明确实可以使用此范围之外的吸液率百分数。
实施例1(本发明)
将一块机织聚酯织物浸渍在水浴中，该水浴含：
2.0wt％Unidyne TG-993，
0.25wt％Arkophob DAN，和
1.0wt％RC5000。
使织物通过40psi压力的钳口，除去多余水分。然后将织物在典型的传输式烘箱中在360℉下经约4分钟完全干燥。将织物冷却，并进行上述的防水防油和去污试验。
所使用的吸液率百分数在约50-70％之间，使得含有含碳氟化合物组分的实际重量为处理组合物的约1-1.14wt％。
实施例2(本发明)
如实施例1那样制备本实施例，不同的是，用1.0％的锌万亩定fps分散液(获自自Arch Chemical)代替RC5000。
实施例3(本发明)
如实施例1那样制备本实施例，不同的是，化学品浴中含：
1.25％Unidyne TG-993，
1.0％Repearl F8025
1.0％锌万亩定fps分散液，和
0.25％Arkophob DAN。
实施例4(本发明)
如实施例3那样制备本实施例，不同的是，不使用
Figure C200480027357D00151
DAN。
实施例5(本发明)
如实施例4那样制备本实施例，不同的是，化学品浴中含：
1.25％Unidyne TG-992，
1.0％Repearl F7105，和
1.0％锌万亩定fps分散液。
实施例6(对比)
与实施例1相同，除了不使用疏水交联剂
Figure C200480027357D00152
 DAN，也不使用抗微生物剂RC5000。
实施例7(对比)
使用与实施例1相同的方法和材料，除了不使用RC5000。
实施例8(对比)
与实施例1相同，除了使用Repearl F8025代替Unidyne TG-993。
实施例9(现有技术)
织物是获自Rochester Hills，Michigan的C.F.Stinson and Company(Hi-Tex Crypton牌纺织品的经销商)的CryptonTM404。这是基于Rubin等人的美国专利第6,024,823号、第6,492,001 B1号和第5,565,265号所授内容的商品。
实施例10(现有技术)
与实施例10相同，除了使用获自C.F.Stinson的CryptonTM 61238代替CryptonTM 404。
实施例11(空白对照)
本实施例使用仅仅用水处理过的纺织品，以测定抗微生物活性的基线。
表1：结果
实施例         1    2    3    4    5    6    7    8    9    10    11
斥油性         6    6    6    6    6    6    6    7    6    2     X
斥水性         3    3    8    5    4    0*   3    10   9    6     X
玉米油去污     4.5  5.0  4.5  4.5  4.5  5.0  5.0  4.5  2.0  2.0   X
鞣革油去污     4.5  4.5  4.5  3.5  3.5  5.0  4.5  1.0  1.0  1.0   1.0
抑制(mm)//样品下生长(是/否)
金黄色葡
萄球菌     0//否4.3//否0.5//否6.5//否2.6//否0//是0/是0//是0//是3//否0//是
肺炎克雷
氏杆菌     1.8//否8.3//否3.8//否7.8//否5.8//否0//是0//是0//是0//是1//否0//是
A.niger    0//是0//否0//否5.8//否2//否0//是0//是0//是0//是X0//是
注：*未能斥水
以下公开更多的发明实施例，结果列于表2。这些实施例证明，多种其它的组合物及组合物化学品比例均能够为经处理的纺织品提供同样好的斥污和去污性质。
实施例12(本发明)
如实施例1那样制备本实施例，不同的是，化学品浴中含：
2.0％Unidyne TG-993，
1.0％Arkophob DAN，和
0.23％RC5000。
吸液率调节至65％。
实施例13(本发明)
如实施例12那样制备本实施例，不同的是，用0.48％的锌万亩定代替RC5000作为抗微生物组分/抗微生物剂。
实施例14(对比)
如实施例12那样制备本实施例，不同的是，用2.0％的RepearlF7105代替Unidyne TG-993。
实施例15(对比)
如实施例12那样制备本实施例，不同的是，化学品浴中含以下物质：
10.0％Zonyl 7040，
0.25％Aerotex M3，和
0.60％Ultrafresh DM-25。
表2：结果
  实施例           12        13         14         15
斥油性             7         6          6          7
斥水性             5         3          10         10
玉米油去污         4.0       4.0        2.0        1.5
焦化机油去污       4.0       4.0        2.0        1.0
抑制(mm)//样品下生长(是/否)
金黄色葡萄球菌       0//否      8.8//否        0//是       0//是
肺炎克雷氏杆菌       0//否      10.3//否       0//是       0//是
耐磨试验
如下文所示，使用Martindale耐磨试验仪根据ASTM D 4966-98在12kpa的条件下，将实施例12-17的织物磨损5000个周期。以与未磨损样品相同的方式再次测定斥污和去污性质。结果列于下表2A。
表2A：磨损后的结果
实施例     12        13       14       15
斥油性          4        3        2          4
斥水性          2        2        4          7
玉米油去污      5.0      4.5      3.5        1.5
焦化机油去污    4.5     4.0       2.0        1.5
已经发现，当本发明的组合物应用于纺织品时，织物上的浓度更低却导致拒斥性更好。在本发明的实施中，可以使用低于本领域公知量的处理剂量。而且，通过使用本发明的组合物可以获得优良的去污性。与现有技术的组合物相比，本发明的实施中需要更少的含碳氟化合物的材料。
本领域的普通技术人员均知晓，当前的论述仅仅是对示范性实施方式的描述，并无意限定本发明更广泛的方面，这些更广泛的方面在示范性解释中得以体现。本发明由所附权利要求书中的实施例表示。

Claims (24)

1.一种其上涂有处理组合物的经处理的纺织品，其包括：
(a)纺织品基质；
(b)处理组合物，所述的处理组合物包括：
(i)含有含氟化学品的去污组分；
(ii)抗微生物剂，和
(iii)其它组分，其是：
疏水交联组分，或
含有含氟化学品的拒斥组分；
其中所述的处理组合物以含有含氟化学品的组分占组合物重量0.5-3wt％的浓度涂在所述的纺织品基质上。
2.根据权利要求1的经处理的纺织品，其中所述含有含氟化学品的去污组分包括选自含有至少一个氟化链段的含丙烯酸酯的聚合物、含有至少一个氟化链段的含甲基丙烯酸酯的聚合物、含有至少一个氟化链段的含尿烷的聚合物和氟化酯类的聚合材料。
3.根据权利要求1的经处理的纺织品，其中所述的其它组分(iii)是疏水交联组分，而且其中所述的疏水交联组分包括异氰酸酯衍生物。
4.根据权利要求3的经处理的纺织品，其中所述的异氰酸酯衍生物包括封端异氰酸酯。
5.根据权利要求1的经处理的纺织品，其中所述的抗微生物剂包括选自有机抗微生物剂和无机抗微生物材料的试剂。
6.根据权利要求5的经处理的纺织品，其中所述有机抗微生物剂包括含银树脂、三氯生、巯基吡啶氧化物和衍生物、氧化三丁基衍生物、3-碘-2-丙基氨基甲酸丁酯、正丁基-1，2-苯并异噻唑啉、10，10′-氧代双酚噁砒和邻苯基苯酚钠。
7.根据权利要求5的经处理的纺织品，其中所述无机抗微生物材料包括含银玻璃、金属基沸石、金属盐、金属氧化物、金属氢氧化物和过渡金属离子。
8.根据权利要求7的经处理的纺织品，其中所述无机抗微生物材料包括含银沸石、银基离子交换化合物和氧化锌。
9.根据权利要求5的经处理的纺织品，其中所述的抗微生物剂包括锌巯基吡啶氧化物。
10.根据权利要求1的经处理的纺织品，其中所述处理组合物的所述其它组分(iii)包括含有含氟化学品的拒斥组分。
11.根据权利要求10的经处理的纺织品，其中所述的组合物另外包括疏水交联组分。
12.根据权利要求11的经处理的纺织品，其中所述含有含氟化学品的拒斥组分包括选自氟化酯类、氟化尿烷和氟化(甲基)丙烯酸酯的组合物。
13.根据权利要求1的经处理的纺织品，其中所述经处理的纺织品具有相对的两面，而且其中所述经处理的纺织品仅在所述经处理的纺织品的一面上包含所述的处理组合物。
14.一种纺织品处理组合物，所述的组合物基本上由以下组分组成：
(a)含有含氟化学品的去污组分；
(b)疏水交联组分，和
(c)抗微生物剂；
其中所述含有含氟化学品的组分的浓度为所述组合物总重的0.5-3wt％。
15.一种其上涂有根据权利要求14的组合物的纺织品。
16.一种纺织品处理组合物，其基本上由以下组分组成：
(a)含有含氟化学品的去污组分；
(b)疏水交联组分；
(c)抗微生物剂；和
(d)含有含氟化学品的拒斥组分，
其中所述含有含氟化学品的组分的浓度为所述组合物总重的0.5-3wt％。
17.一种组合物，其包括：
(a)含有含氟化学品的去污组分；
(b)疏水交联组分；
(c)抗微生物剂；和
(d)抗静电组分，
其中所述含有含氟化学品的组分的浓度为所述组合物总重的0.5-3wt％。
18.根据权利要求17的组合物，其中所述的抗静电组分包括含石墨的材料。
19.一种其上涂有根据权利要求17的组合物的纺织品。
20.根据权利要求17的组合物，其中所述的抗微生物剂包括含银材料。
21.根据权利要求17的组合物，其中所述的抗微生物剂包括含巯基吡啶氧化物的材料。
22.根据权利要求21的组合物，其中所述的抗微生物剂包括锌巯基吡啶氧化物。
23.一种纺织品或织物处理组合物，其包括：
(a)含有含氟化学品的去污组分；
(b)抗微生物剂；和
(c)碳氟化合物拒斥组分，
其中所述含有含氟化学品的去污组分和所述碳氟化合物拒斥组分当组合在一起时构成所述组合物的0.5-3wt％。
24.根据权利要求23的组合物，其进一步包括：
(d)交联组分。
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CN109310556B (zh) * 2015-12-30 2022-02-08 生活保卫股份公司 具有抗微生物性能的耐洗涤的流体吸收基材和卫生产品

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BRPI0414625B1 (pt) 2014-04-15
CN1856396A (zh) 2006-11-01
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US7399519B2 (en) 2008-07-15
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US20080139063A1 (en) 2008-06-12
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US20050062010A1 (en) 2005-03-24
US7524551B2 (en) 2009-04-28
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