CN1102683C - 除臭纤维材料及其制造方法 - Google Patents
除臭纤维材料及其制造方法 Download PDFInfo
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- CN1102683C CN1102683C CN97114871A CN97114871A CN1102683C CN 1102683 C CN1102683 C CN 1102683C CN 97114871 A CN97114871 A CN 97114871A CN 97114871 A CN97114871 A CN 97114871A CN 1102683 C CN1102683 C CN 1102683C
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- Prior art keywords
- fibrous material
- deodorant
- compound
- poly
- owf
- 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.)
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Abstract
一种除臭纤维材料,含有(1)作为第一除臭材料,至少一种除臭组分选自无机型和聚有机酸、酯或盐型的组分,(2)作为第二除臭材料,酰肼化合物和给定的聚乙烯胺化合物中的至少一种和(3)合成树脂粘合剂。除臭纤维材料可以这样制得,即用浸轧法或涂覆法将含有上述组分(1)-(3)的液体组合物涂于纤维材料上,随后进行热处理。
Description
本发明涉及一种除臭纤维材料及该材料的制造方法。更具体地说,涉及一种对恶臭味如铵、胺、硫化氢、硫醇等以及烟味等中所含的醛、醋酸等具有持久的优良的除臭性能并且质地柔软的除臭纤维材料,以及制造该除臭纤维材料的方法。
近年来,对高水平除臭功能的纤维产品如衣物、家庭用品、室内产品、各种工业材料等的需求进一步增加。通常提出的为纤维材料提供除臭性能的方法包括一种方法,即在合成的纤维纱制品中将一种除臭物质揉和到聚合物内部;另一种方法是将除臭剂用一种粘合剂附着在纤维的表面。作为前一种方法的实例,引用一种含有其上带有酞菁聚羧酸酯的二氧化钛粒子等的聚酯纤维(日本专利公开JP-B-7-81206)。作为后一种方法的实例,引用一种涂有用于气味组分等的氧化分解的除臭催化剂的纤维(日本专利申请公开平JP-A-189120)。
然而,根据通常的方法,能够被除臭的气味组分的种类受到限制,而且,对于如复杂的气味如烟味,含有大量气味组分如醛、醋酸等的除臭效果不是十分理想。况且,传统方法还存在一些问题,因为除臭剂的选择,粒子的直径、耐热性、与纤维聚合物的亲和性等受到很大限制,材料纱线的物理性质因此而降低。另外,前述后一种方法还存在质地变粗糙,耐洗性下降等问题。
本发明的目的之一是提供一种对恶臭味如铵、胺、硫化氢、硫醇等以及烟味等中所含的醛、醋酸等具有持久的优良的除臭性能的除臭纤维材料,该纤维材料质地柔软,以及一种制造该除臭纤维材料的方法。
本发明一方面提供一种纤维材料,其中(1)一种无机型组分(部分或全部可被一种聚有机酸或它的酯或盐代),(2)一种由以下的通式[I]表示的聚乙烯胺化合物和/或一种酰肼化合物和(3)一种合成树脂,被附着在纤维材料的表面。(在该通式中,R表示一个CHO基团或一个CH3CO基团,n和m分别为相互独立的整数。)
本发明的另一方面是提供一种由上述除臭纤维材料制得的产品。
本发明的又一方面是提供一种制造除臭纤维材料的方法,包括将一种液体除臭剂组合物涂覆到一种纤维材料的表面,优选的通过一种浸轧或涂覆方法。该液体除臭剂组合物包括上述组分(1)-(3)的每一种,相互独立的各个组分中的每一种可分散或溶解在一种液体介质中,然后对该纤维材料进行热处理。
在如上所述的涂覆除臭组合物之前,可将纤维材料浸入到一种含有环烷基卤化物的液体处理浴中。
特别地,在用环烷基卤化物预处理之后,纤维材料可用一种除臭组合物处理,该组合物除含有除臭剂和粘合剂(1)-(3)外,还含有一种聚亚烷基二醇与芳族二羧酸和亚烷基二醇的共聚物。
本发明能够提供一种对恶臭味如铵、胺、硫化氢、硫醇等以及烟味等中所含的醛、醋酸等具有持久的优良的除臭性能的纤维材料,并且该纤维材料质地柔软。
作为本发明所用的纤维材料,可使用任何通常用作纤维产品的纤维,如衣服、家具、室内产品和各种工业材料。例如合成纤维或由合成树脂制得的半合成纤维,如一种聚对苯二甲酸亚烷基酯如聚对苯二甲酸乙二醇酯,聚对苯二甲酸丁二醇酯等;或者为一种上述聚对苯二甲酸亚烷基酯和一种第三组分的聚酯共聚物;一种聚酰胺如尼龙6,尼龙66等;一种上述聚酰胺和第三组分的聚酰胺共聚物;一种聚烯烃如聚乙烯、聚丙烯等;聚氯乙烯;一种丙烯酸树脂;一种乙酸树脂等;一种再生纤维如本伯格铜铵丝(Bemberg)、人造纤维等;一种纤维素纤维如棉、亚麻、大麻、苎麻、黄麻、蕉麻等,一种蛋白质型纤维如羊毛、丝等等均可被列举。
这些纤维可作为单一组份单独使用或者以复合的纤维材料的形式使用,复合的纤维材料是通过将两种或更多种的纤维进行揉和、长丝胶合、捻度、编织或针织获得的。纤维可以为各种形式,如长丝、短纤维、纺织品、无纺布、缝合产品等。
这些纤维材料可以是含有一种添加剂或用该添加剂处理过的材料,如一种染料、颜料、抗氧化剂、耐热剂、抗紫外光剂、增塑剂、抗菌剂、阻燃剂等,它们在纤维制造步骤或后处理步骤中被添加。
在上述纤维材料中,一种由聚酯形成的聚酯纤维,如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等,或含有上述聚酯纤维的纺织品、无纺布或缝合产品都可以是适于用作本发明的纤维材料。如果材料中使用环烷基卤化物提供阻燃性,聚酯是特别合适的。
作为本发明除臭纤维材料的除臭剂,可使用无机型组分,如组分中可提供至少一种无机元素(除含活性炭外),和用通式[I]表示的聚乙烯胺化合物和/或酰肼化合物。
优选的无机型组分是由二氧化硅、二氧化钛、氧化锌、氧化铝等形成的多孔物质,多孔物质如沸石、硅胶、活性炭等;或金属的有机酸盐如醋酸盐或柠檬酸盐,金属的无机酸盐如硫酸盐、硝酸盐、氯化物、氢氧化物或氧化物,其中金属如铜、锌、银、铅、铁、铝、钙、镁、锰、镍、钴等等。在合成树脂中特别优选的是与氮原子螯合的铜化合物,可因此而改善处理液的相容性并提高这些化合物的耐洗性。
如果所用无机型化合物多孔物质是一种难溶于水的化合物,则其平均粒径优选的是0.3-100μm,特别优选的为0.5-10μm,平均粒径如果大于100μm,纤维材料的表面粗糙感变得十分可观,质地也变得粗和硬。如果平均粒径太小,工业制造变得困难,使生产率降低。因此,优选的为至少0.3μm。
对于多孔物质,在前述的物质中由二氧化硅和氧化锌形成的无定形物质是尤其优选的。在这些多孔物质中,优选所用的多孔物质比表面积为10-150m2/g,优选的为50-100m2/g。
如果铜和锌中的至少一种的金属化合物被用作无机型化合物,可使对气味如硫化氢或硫醇的除臭效果增加。作为锌或铜的金属化合物的优选实例,铜或锌的有机酸盐如柠檬酸盐、醋酸盐等,铜或锌的无机酸盐如硝酸盐、硫酸盐、氯化物、氢氧化物、氧化物可被列举。
所附的无机型化合物的量对于纤维材料而言,优选的为0.05-10%owf,更优选的为0.1-5%owf。如果所附的量少于0.05%owf,便不容易获得充分的除臭效果。如果所附的量大于10%owf,纤维材料的质地有变得粗和硬及表面粗糙感增加的趋势。就染色产品而言,则其色泽或颜色发暗的趋势增加。
用通式[I]表示的聚乙烯胺化合物用作醛除臭的除臭剂是有效的,将N-乙烯甲酰胺,N-乙烯乙酰胺或其类似物在水溶液中聚合后再用酸或碱水解可制得聚乙烯胺化合物。在聚乙烯胺化合物聚合时还可能与其它的乙烯基单体共聚,如丙烯酸、丙烯酰胺、丙烯腈、乙烯、苯乙烯、醋酸乙烯或类似物。
聚乙烯胺化合物的分子量优选的在约1万到20万的范围内。如果分子量少于1万,水溶性增加,因此附着到纤维材料上后的耐洗性变得不够。如果分子量大于20万,粘度增加,因此难以与无机型化合物混合。在所述通式[I]中,n优选的范围为约150-4650,m优选的范围为约0-850。
作为本发明所用的酰肼化合物的实例,可列举一酰肼化合物如甲酰肼、乙酰肼、丙酰肼、月桂酰肼、硬脂酰肼、水扬酰肼、苯甲酰肼、对羟基苯甲酰肼、肼基甲酸甲酯、肼基甲酸乙酯、氨基脲化氢氯等,二酰肼化合物如碳酰肼、乙二酰肼、丙二酰肼、丁二酰肼、戊二酰肼、己二酰肼、庚二酰肼、辛二酰肼、壬二酰肼、癸二酰肼、对苯二甲酰肼、间苯二甲酰肼、2,3-二羟基丁二酰肼、苹果二酰肼、亚氨基二乙酰肼、亚甲基丁二酰肼、十二烷二酰肼、十六烷二酰肼、2,6-萘甲二酰肼、1,4-萘甲二酰肼、4,4-二苯并二酰肼、2,6-吡啶二酰肼、1,4-环己烷二酰肼、N,N’-环己基氨基脲等,三酰肼类化合物如柠檬三酰肼、1,2,4,5-苯四三酰肼、1,2,4-苯三酰肼、次氮基乙三酰肼、环己烷三羧三酰肼等,四酰肼类化合物如乙二胺四乙四酰肼、1,4,5,8-萘甲四酰肼等。带两个或更多肼基的酰肼化合物是尤其合适的。
所附的聚胺化合物或酰肼化合物的量对于纤维材料而言,优选的为0.01-20%owf,更优选的为0.05-5%owf。如果所附的量少于0.01%owf,将难以获得对醛的充分除臭效果。如果所附量大于20%owf,纤维材料的质地有变得粗和硬的趋势。
根据本发明,为使作为除臭剂的无机型化合物均匀地分散在水溶液中,以阻止无机型化合物的沉降,特别优选的是使用一种乳化分散剂。因为如果一种无机型化合物和一种聚乙烯胺化合物或一种酰肼化合物和一种合成树脂进行简单混合,就会发生聚结,使之不能均匀地附着在纤维材料的表面。一种优选的乳化分散剂是聚乙烯醇或具有渗透性能的溶剂,如能够渗透纤维材料的。
聚乙烯醇不仅可以有效地用作乳化分散剂,并且对于提高无机型化合物的耐洗性也是有效的。聚乙烯醇的分子量优选的为约2000-100,000,更优选的为5000-50,000。如果分子量少于2000,除臭剂的粘度小,无机型化合物有不容易均匀分散而易于沉降的趋势;或者如果有交联剂存在时,纤维材料的质地有易变得粗和硬的趋势。如果分子量大于100,000,有易使水溶性变小,并且不容易起到乳化分散剂作用的趋势。
作为溶剂的实例,它具有渗透性,用于均匀分散无机型化合物,从而阻止聚结,可列举醇、二元醇、溶纤剂等。具体地说,有异丙醇、甲醇、乙醇、乙二醇、丙二醇、甲基溶纤剂、乙基溶纤剂等是合适的。
本发明所用的合成树脂是作为一种粘合剂将用作除臭剂的无机型化合物和聚胺化合物或酰肼化合物保留(附着)在纤维材料的表面。优选的合成树脂可列举以氨基甲酸乙酯为基的树脂,以丙烯酸为基的树脂,氨基塑料树脂,以环氧为基的树脂,以乙二醛为基的树脂,以亚乙基脲为基的树脂等。从质地和耐久性考虑,其中优选的是以氨基甲酸乙酯为基的树脂或以丙烯酸为基的树脂。特别优选的是以氨基甲酸乙酯为基的树脂。
所用的氨基甲酸乙酯树脂优选的是以聚氨酯树脂为基的乳液或水溶液。以聚氨酯树脂为基的乳液或水溶液其具体实例可使用“Elastoron”(商品名)和“SuperFlex”(商品名),Dai-ichi Kogyo Seiyaku(Kabushiki Gaisha)生产,“Hydran”(商品名),Dainippon Ink Kagaku Kogyo(Kabushiki Gaisha)生产,等。
附着在纤维材料上的合成树脂的量优选的为0.01-10%owf,更优选的为0.03-2%owf。如果所附合成树脂的量少于0.01%owf,耐洗性变得不够。如果量大于10%owf,纤维材料的质地有易变得粗和硬的趋势。
根据本发明,可用聚有机酸、酯或盐替代上述的由铜、锌等形成的金属化合物,或与之共同使用。作为聚有机酸、酯或聚有机酸盐的实例,可列举聚丙烯酸、聚甲基丙烯酸和这些物质的烷基酯,与醋酸乙烯、氯乙烯、1,1-二氯乙烯、烯丙基磺酸、甲基丙烯酰磺酸、乙烯基磺酸、苯乙烯磺酸等适当结合的共聚物,以及这些物质的金属盐,可列举金属如铜、锌、银、铅、铁、铝、钙、镁、锰、镍、钴等。聚有机酸、酯或盐可存在于多孔无机型组分中。
附着在纤维材料上的聚有机酸、酸酯、或酸盐的量优选的为0.01-10%owf,特别优选的在0.03-2%owf的范围内。如果所附的聚有机酸、酯或盐的量少于0.01%owf,除臭性能变得不够。如果量大于10%owf,纤维材料的质地有易变得粗和硬的趋势。
当本发明的除臭纤维材料用在聚酯纤维,尤其适于用在带有前述的环烷基卤化物阻燃剂的聚酯纤维上时,可获得非常好的优点。
用作阻燃剂的环烷基卤化物是一种环状饱和碳水化合物或一种带至少一个环状饱和碳水化合物基团的饱和碳水化合物,其中至少一个氢原子被一个卤素原子如溴、氯等取代。作为环烷基卤化物的具体实例,可列举1,2,3,4,5,6-六溴环己烷,1,2,3,4-四溴环辛烷(TBCO),1,2,5,6,9,10-六溴环十二烷(HBCD),1,2-二(3,4-二溴环己基)-1,2-二溴乙烷,以及这些化合物中溴被氯取代的等。在上述化合物中,绝大部分或全部的卤素原子为溴的化合物是尤其优选的,因为它们能获得非常高的吸收率。
环烷基卤化物可在成纤前化合到聚酯中,或成纤后提供到聚酯纤维的表面。其含量相对于聚酯纤维而言优选地为1.0-20%owf。如果少于1.0%owf,阻燃性低,而且阻燃性很可能会在除臭过程中降得更低。如果其含量超过20%owf,吸收率降低,经济损失增加,而且耐光牢度下降。
在本发明具体的一种优选的除臭纤维材料中,附着在纤维材料表面的除臭组合物另外包括:作为一种阻燃剂的一种聚亚烷基二醇,芳族二羧酸和亚烷基二醇的共聚物。
聚亚烷基二醇可以是一种二醇,其主链为-(CnH2nO)-,(n=2-4),分子量为300-40,000,优选的为1,000-10,000。例如聚乙二醇,聚丙二醇或这些化合物的嵌段共聚物等,可以被使用。如果分子量为300或更少,则其耐久性不够。分子量为40,000或更多是不优选的,因为这样的分子量使分散性下降。
芳族二羧酸是,如对苯二甲酸或对苯二甲酸的低级烷基酯和/或间苯二甲酸或间苯二甲酸的低级烷基酯。
亚烷基二醇是,如用以下通式表示的化合物:HO-CnH2n-OH,(n=2-4)。例如乙二醇、丙二醇、丁二醇等可被列举。聚亚烷基二醇、芳族二羧酸和亚烷基二醇嵌段共聚物的嵌段共聚摩尔比优选的为1-31∶1∶2-3,用于改善防污性。建议将嵌段共聚物用非离子或阴离子表面活性剂分散在水中,以供使用。
附着在纤维材料上的嵌段共聚物,其固体含量相对于纤维材料的重量而言,优选的为0.01-3%(重量),更优选的为0.05-0.5%(重量),相对于纤维材料的重量而言,优选的是以聚酯为基的纤维材料。通过提供嵌段共聚物,可防止溶液中与Ca离子或Mg离子相结合的金属皂在水洗过程中沉积在以聚酯为基的纤维上。如果嵌段共聚物的量为0.01%(重量)或更少,不能获得充足的防污性,且水洗后残留的金属皂的量增加,因此阻燃性大大降低。如果用量为3%(重量)或更多,由纤维材料制得的织物的质地变硬,且染料的牢度下降。因此在实际使用中这样的量不是优选的。
作为将环烷基卤化物涂覆到以聚酯为基的纤维上的方法,可采用在液池中浸渍、浸轧法等。考虑到吸收率,特别优选的是用浸渍处理法。对于浸渍处理的条件,该处理优选的是在110-150℃,更优选的在120-140℃下,通常进行10-60分钟。浸渍处理优选的与通常的以聚酯为基的纤维的染色过程同时完成。因此在对以聚酯为基的纤维染色的过程中,在染浴中可能将环烷烃化合物和分散染料如杂料在一起使用。
如果含有环烷基卤化物的聚酯纤维被用作本发明的纤维材料,附着在合成树脂纤维材料上的合成树脂的量优选的为0.01-2%owf,更优选的在0.1-1%owf的范围内,以获得充分的阻燃性。
本发明的除臭纤维材料可以这样制得,用一种处理液,该处理液含有一种上述的无机型化合物,一种用通式[I]表示的聚乙烯胺化合物或一种酰肼化合物和一种合成树脂处理纤维材料,然后再对该材料热处理。
只要没有明显削弱理想的除臭性能,该处理液还可进一步含有一种织物质地处理剂、一种赋予柔软度的织物整理剂、一种抗静电剂、一种阻燃剂、一种抗菌和抗味处理剂、一种防水剂、一种防污剂等中的任何一种或多种。
作为在处理液中处理纤维材料的方法,可列举浸轧法、浸渍法、喷涂法、涂覆法、印染法等。具体地说,为了使无机型化合物,用通式[I]表示的聚乙烯胺化合物或酰肼化合物,和合成树脂均匀地附着在纤维材料上,并具有好的耐久性,采用浸轧法或涂覆法是最具优势的。
浸轧法是将纤维结构本体或树脂成形制品浸入到含有无机型化合物,用通式[I]表示的聚乙烯胺化合物或酰肼化合物,和合成树脂粘合剂的处理液中,处理适当的一段时间,然后用两个旋转的滚轴将其拉出或挤干。只要没有明显削弱除臭性能,添加到处理液中的还可有织物质地处理剂、赋予柔软度的织物整理剂、抗静电剂、抗菌和抗味处理剂、以及防水剂等。
根据本发明所附的合成树脂粘合剂的量取决于除臭成形制品所要求的耐久性、质地等。如果粘合剂是通过浸轧法附着在纤维结构本体上,通常的用量为0.01-10%owf,优选的为0.02-5%owf,以获得柔软的质地和耐洗性。如果用量少于0.01%owf,耐洗性有变得不够的趋势。如果用量大于10%owf,质地有易变得粗和硬的趋势。
如果用涂覆法涂覆除臭组合物,合成树脂粘合剂通常以乳液或溶液的形式存在于有机溶剂中。尽管无机型化合物,用通式[I]表示的聚乙烯胺化合物和/或酰肼化合物,和合成树脂粘合剂实质上可能以任何理想的比例进行混合,优选的添加的无机型化合物,用通式[I]表示的聚乙烯胺化合物和酰肼化合物的总量在0.05-50%(重量)范围内,以固体量计。含有无机型化合物,用通式[I]表示的聚乙烯胺化合物或酰肼化合物,和合成树脂的处理液,另外还可含一种或多种化合物,以使之具有理想的粘度,然后用作被涂液。优选的是制备这样一种涂覆液,使其粘度在500-50000CPS范围内,优选的为1000-30000CPS,以改善其成膜性。涂覆的厚度优选的为5-500g/m2(湿),特别优选的为20-300g/m2(湿)。
至于涂覆方法,通常的方法,例如可使用刮刀涂布机、辊涂机、窄缝涂布机等,还可以使用层压法或粘合法。涂覆之后,通过湿法或干法形成涂膜。在涂膜形成后,还可采用化学处理操作,如防水处理,或物理处理操作,如砑光处理等。本发明的热处理是指干热处理或湿热处理。湿热处理包括浸渍处理和蒸汽热处理。作为蒸汽热处理,可列举常压饱和蒸汽处理,过热蒸汽处理和高压蒸汽处理。干热处理或湿热处理的温度应在约80-210℃的范围内。如果热处理的温度低于80℃,耐洗性变得不够。如果温度超过210℃,纤维材料就有变黄或变脆的危险。在实际使用中,干热处理的温度在110-190℃是合适的。
由上述方法获得的本发明的除臭纤维材料对恶臭味如铵、胺、硫化氢、硫醇等,以及烟味等中所含的醛、醋酸等具有持久的优良的除臭性能,并且质地柔软。
本发明的除臭纤维材料适合用于建筑、床上用品,室内或室外材料,包括窗帘、地毯、垫席、毛毯、被单、futon和盖被的套子、枕套织物、futon和盖被的填料、汽车内用材料等。而且还可有更广泛的用途,如用于套服、制服、衬衣、罩衫、长裤、裙、毛线衫、短袜、短内裤、长统袜、衬里、中间衬料等的服饰材料,用于鞋底垫块、鞋衬、包壳、furoshki或包装纸(wrap-and-carry sheets)、垫子、填塞玩具动物等的材料,用于布尿布、尿布套等的卫生材料,用于家具、冰箱等的除臭材料、过滤材料等,以及无纺布等。
而且,聚酯纤维上带有环烷基卤化物的除臭纤维材料作为一种纤维材料,用于需要阻燃的建筑、床上用品、室内或室外材料,如窗帘、地毯、垫席、毛毯、被单、futon和盖被的套子、枕套织物、futon和盖被的填料、汽车内用材料等时特别有效。
下面将描述实施例。实施例中所用的洗涤方法以及阻燃性和除臭性的评估方法如下:
[洗涤方法]
所用的洗衣机是一种自动转向涡轮型电动洗衣机VH-3410(东芝(KakushikiGaisha)生产),洗涤剂为0.2%的“Zabu”(Kao(Kakushiki Gaisha)生产),洗涤是在强转向涡流模式下进行,温度为60±2℃,浴比为1∶40,洗涤75分钟,然后排水,再用溢流水漂洗25分钟,该排水和漂洗程序重复三次。规定该洗涤操作进行5次。
[阻燃性评估]
测试通过JISL 1091 D法(火焰接触测试)完成。
[通过检测管法评估除臭性能]
铵气导入到一含有3g样品的550ml的容器内,其初始浓度为200ppm,然后将容器密封。容器放置30分钟后,用测气管测定残余铵的浓度。
用硫化氢气、乙醛气和醋酸气,其初始浓度分别为20ppm,200ppm和20ppm,残余气体用相似方法测试。
[对烟味除臭性能的嗅觉评估]
将一支冒烟的香烟置于一进气口打开的500ml的玻璃锥形烧瓶下,并使进气口开口向下。5秒钟后,迅速将锥形烧瓶转为水平,然后放入3g样品,将烧瓶用玻璃塞子密封。烧瓶放置一小时后,拿走玻璃塞子,闻残留气作评估。
○:几乎无气味残留
△:轻微气味残留
×:大量气味残留
[目视观察无机型化合物的分散性]
无机型化合物在纤维表面的分散性是通过检查成品表面质量得到的。
○:几乎无聚结
△:轻微聚结
×:大量聚结
实施例1
一种聚酯织物(#F1305GN,Toray(kabushiki Gaisha)生产,经线和纬线均为150D-48fil)。对其进行退浆、后处理和干热处理后,被用作样品织物。在含有下面所示组合物的处理液中浸渍后,样品织物用砑光机牵拉或挤压(牵拉或挤压率为65%),在120℃干燥3分钟,然后通过针板拉幅机在170℃干热处理1分钟。
关于成品织物,对洗涤前原始织物的状态和洗涤10次后的形态其除臭性能和表面质量进行了评估。其结果列于表1和表2中。
用于处理的一种无机化合物是一种乳化分散溶液,其固体含量为45%。作为乳化分散剂,可使用下面的非离子分散材料:
非离子分散剂:异丙醇 3% owf
聚乙烯醇 1% owf
水 51% owf
(处理液的成分)
无机化合物:
多孔二氧化硅微粒 10g/L
硫酸锌 10g/L
聚乙烯胺化合物(固体含量45%) 10g/L
合成树脂:Elastoron W-11P(主成分为氨基甲酸乙酯,固体含量25%)
20g/L
催化剂:Elastoron催化剂64 0.5g/L
PH调节剂:碳酸氢钠 0.5g/L
实施例2
通过对与实施例1中相同的样品织物进行处理而制成样品,不同的是所用处理液的成分如下所示。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态其除臭性能和表面质量进行了评估。其结果列于表1和表2中。
(处理液的成分)
无机化合物:
多孔二氧化钛微粒 10g/L
硫酸铜 5g/L
聚乙烯胺化合物(固体含量45%) 10gL
合成树脂:Elastoron W-11P(主成分为氨基甲酸乙酯,
固体含量25%) 20g/L
催化剂:Elastoron 催化剂64 0.5g/L
PH调节剂:碳酸氢钠 0.05g/L
实施例3
通过对与实施例1中相同的样品织物进行处理而制成样品,不同的是所用处理液的成分如下所示。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行评估。其结果列于表1和表2中。
(处理液的成分)
无机化合物:
多孔二氧化碳微粒 10g/L
硫酸铜 5g/L
酰肼:己二酰肼 10g/L
合成树脂:Elastoron W-11P(主成分为氨基甲酸乙酯,
固体含量25%) 20g/L
催化剂:Elastoron催化剂64 0.5g/L
PH调节剂:碳酸氢钠 0.05g/L
实施例4
通过对与实施例1中相同的样品织物进行处理而制成样品,不同的是所用处理液的成分如下所示。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行了评估。其结果列于表1和表2中。
(处理液的成分)
无机化合物:
由二氧化硅和氧化锌形成的多孔微粒(二氧化硅∶
氧化锌=3∶1) 10g/L
聚乙烯胺化合物(固体含量45%) 10g/L
合成树脂:Elastoron W-11P(主成分为氨基甲酸乙酯,
固体含量25%) 20g/L
催化剂:Elastoron催化剂64 0.5g/L
PH调节剂:碳酸氢钠 0.05g/L
实施例5
通过对与实施例1中相同的样品织物进行处理而制成样品,不同的是所用处理液的成分如下所示。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行了评估。其结果列于表1和表2中。
(处理液的成分)
无机化合物
由二氧化硅和氧化锌形成的多孔微粒(二氧化硅∶氧化锌=3∶1)
10g/L
聚乙烯胺化合物(固体含量45%) 10g/L
聚丙烯酸锌 10g/L
合成树脂:Elastoron W-11P(主成分为氨基甲酸乙酯,
固体含量25%) 20g/L
催化剂:Elastoron 催化剂64 0.5g/L
PH调节剂:碳酸氢钠 0.05g/L
实施例6
通过在实施例1所用的相同的样品织物上用刮涂法涂覆一种含如下所示组合物的处理液,用量为50g/m2(湿),然后在120℃进行干热处理5分钟,制得一种样品。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行评估。其结果列于表1和表2中。
无机化合物:
多孔二氧化钛微粒 10份
硫酸铜 1份
酰肼化合物:苹果酰肼 1份
合成树脂:以丙烯酸为基的树脂(固体含量45%) 50份
非离子型粘度增稠剂 5份
水 33份
实施例7
将实施例1所用的相同的样品织物置于一种浴槽中处理,该浴槽中含有3.0%owf的分散染料Dianix Black BG-FS 200%(日本Deister(Kabushiki Gaisha)生产),0.5cc/L的醋酸(80%),0.5g/L的分散剂RAP-50(由Sanyo Kasei(KabushikiGaisha)生产),和15%owf的1,2,5,6,9,10-六溴环十二烷(HBCD),于130℃处理45分钟,然后用普通方法还原和洗涤,再用热水洗涤和干燥。
在含如下所示成分的处理液中浸渍后,样品织物用砑光机牵拉或挤压(牵拉或挤压率为65%),在120℃干燥3分钟,然后通过针板拉幅机于170℃干热处理1分钟,于是制得一种样品。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行评估。其结果列于表1和表2中。
(处理液的成分)
无机化合物:
由二氧化硅和氧化锌形成的多孔微粒(二氧化硅∶氧化锌=3∶1)
10g/L
硫酸铜 5gL
聚乙烯胺化合物(固体含量45%) 10g/L
合成树脂:Elastoron W-11P(主成分为氨基甲酸乙酯,
固体含量25%) 5g/L
催化剂:Elastoron催化剂64 0.1g/L
PH调节剂:碳酸氢钠 0.02g/L
实施例8
将实施例1所用的相同的样品织物置于一种浴槽中处理,该浴槽中含有3.0%owf的分散染料Dianix Black BG-FS 200%(日本Deister(Kakhiki Gaisha)生产),0.5CC/L的醋酸(80%),0.5g/L的分散剂RAP-50(Sanyo Kasei(KabushikiGaisha)生产),和15%owf的1,2,5,6,9,10-六溴环十二烷(HBCD),于130℃处理45分钟,然后用普通方法还原和洗涤,再用热水洗涤和干燥。
在含如下所示组合物的处理液中浸渍后,样品织物用砑光机牵拉或挤压(牵拉或挤压率为65%),在120℃干燥3分钟,然后通过针板拉幅机于170℃干热处理1分钟,于是制得一种样品。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行评估。其结果列于表1和表2中。
(处理液的成分)
嵌段共聚物:TO-SR-1(固体含量10%) 20g/L
无机化合物:
多孔二氧化硅微粒 10g/L
硫酸锌 10g/L
聚乙烯胺化合物(固体含量45%) 10g/L
合成树脂:Elastoron W-11P(主成分为氨基甲酸乙酯,
固体含量25%) 20g/L
催化剂:Elastoron 催化剂64 0.50g/L
PH调节剂:碳酸氢钠 0.05g/L
比较例1
通过对与实施例1中相同的样品织物进行处理而制成样品,不同的是所用处理液的成分如下所示。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行评估。其结果列于表1和表2中。
(处理液的成分)
无机化合物
多孔二氧化硅微粒 10g/L
硫酸锌 10g/L
合成树脂:Elastoron W-11P(主成分为氨基甲酸乙酯,
固体含量25%) 20g/L
催化剂:Elastoron 催化剂64 0.5g/L
PH调节剂:碳酸氢钠 0.05g/L
比较例2
通过对与实施例1中相同的样品织物进行处理而制成样品,不同的是所用处理液的成分如下所示。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行评估。其结果列于表1和表2中。
(处理液的成分)
聚乙烯胺化合物(固体含量45%) 10g/L
合成树脂:Elastoron W-11P(主成分为氨基甲酸乙酯,
固体含量25%) 20g/L
催化剂:Elastoron 催化剂64 0.5g/L
PH调节剂:碳酸氢钠 0.05g/L
比较例3
通过对与实施例1中相同的样品织物进行处理而制成样品,不同的是所用处理液的成分如下所示。
关于成品织物,对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行评估。其结果列于表1和表2中。
(处理液的成分)
无机化合物:
多孔二氧化硅微粒 10g/L
硫酸锌 10g/L
聚乙烯胺化合物(固体含量45%) 10g/L
比较例4
通过对与实施例1中相同的样品织物进行处理而制成样品,所不同的是没有使用用于无机化合物的乳化分散剂,而且所用处理液的成分如下所示。在成品织物中,多孔二氧化硅微粒分散很差,织物上带有斑渍。然而仍进行通常的评估。对洗涤前原始织物状态和洗涤10次后的状态的除臭性能和表面质量进行评估。其结果列于表1和表2中。
(处理液的成分)
无机化合物:
多孔二氧化硅微粒 10g/L
硫酸锌 10g/L
聚乙烯胺化合物(固体含量45%) 10g/L
从表1和表2可见,实施例1-7的织物被洗涤10次后,与洗涤前的织物状态一样具有优良的除臭性能。同时还可看出进行过阻燃处理的实施例6-7的织物,在被洗涤10次后仍保持优良的阻燃性。
本发明可应用到织物、家庭用品、室内产品、各种工业材料等上,具有高水平的除臭功能。
表1
洗涤后:洗涤10次后。ND:未发现。
残余气体浓度(ppm) | ||||||||
铵 | 硫化氢 | 乙醛 | 醋酸 | |||||
原始织物 | 洗涤后 | 原始织物 | 洗涤后 | 原始织物 | 洗涤后 | 原始织物 | 洗涤 | |
实施例1 | ND | 8 | ND | ND | ND | 30 | 1 | 2 |
实施例2 | ND | 5 | ND | ND | ND | 20 | ND | 1 |
实施例3 | ND | 6 | ND | ND | 5 | 40 | 1 | 3 |
实施例4 | ND | 3 | ND | ND | ND | 20 | ND | 2 |
实施例5 | ND | ND | ND | ND | 4 | 40 | ND | 1 |
实施例6 | ND | 3 | ND | ND | 4 | 40 | ND | 1 |
实施例7 | ND | 10 | ND | 1 | ND | 40 | ND | 4 |
实施例8 | ND | 12 | ND | ND | ND | 40 | 1 | 3 |
比较例1 | ND | 10 | ND | ND | 170 | 180 | 2 | 3 |
比较例2 | 150 | 180 | 17 | 18 | ND | 20 | 17 | 19 |
比较例3 | ND | 170 | ND | 18 | ND | 150 | 1 | 18 |
比较例4 | ND | 170 | ND | 20 | ND | 170 | 1 | 19 |
表2
洗涤后:洗涤10次后。
对烟味的嗅觉评估 | 阻燃性火焰接触数 | 表质量面 | |||
原始织物 | 洗涤后 | 原始织物 | 洗涤后 | 原始织物 | |
实施例1 | ○ | ○ | - | - | ○ |
实施例1 | ○ | ○ | - | - | ○ |
实施例1 | ○ | ○ | - | - | ○ |
实施例1 | ○ | ○ | - | - | ○ |
实施例1 | ○ | ○ | - | - | ○ |
实施例1 | ○ | ○ | - | - | ○ |
实施例1 | ○ | ○ | 5.0 | 5.5 | ○ |
实施例1 | ○ | ○ | 5.0 | 6.0 | ○ |
比较例4 | × | × | - | - | ○ |
比较例4 | × | × | - | - | ○ |
比较例4 | ○ | × | - | - | ○ |
比较例4 | ○ | × | - | - | × |
Claims (17)
1、一种除臭纤维材料,包括在纤维材料表面附着一种除臭组合物,该组合物包括:
(1)一种第一除臭材料,选自无机型、聚有机酸型、聚有机酸盐型和聚有机酸酯型组分中的至少一种,其含量对于该纤维材料而言为0.05-10%owf;
(2)一种第二除臭材料,选自酰肼化合物和通式[1]的聚乙烯胺化合物的中至少一种,其含量对于该纤维材料而言为0.01-20%owf;其中R为选自CHO和CH3CO的基团,n和m分别为互相独立的整数;和
(3)一种合成树脂粘合剂,其含量对于该纤维材料而言为0.01-10%owf。
2、权利要求1所述的除臭纤维材料,其中第一除臭材料是一种无机型组分,包括一种多孔物质和至少一种化合物,该化合物选自铜、锌、银、铅、铁、铝、钙、镁、锰、镍和钴的金属化合物。
3、权利要求2所述的除臭纤维材料,其中的无机型组分包括一种多孔物质和一种铜化合物。
4、权利要求2所述的除臭纤维材料,其中的无机型化合物包括一种多孔物质和一种锌化合物。
5、权利要求2所述的除臭纤维材料,其中的多孔物质至少是一种物质,选自二氧化硅、二氧化钛、氧化锌、氧化铝、沸石、硅胶和活性炭。
6、权利要求1所述的除臭纤维材料,其中所述第一除臭材料是均匀分散在纤维材料表面的。
7、权利要求1所述的除臭纤维材料,其中除臭组合物另外还包括:作为作用于所述第一除臭材料的乳化分散剂,分子量为约200-10万的聚乙烯醇和能渗透到纤维材料中的溶剂。
8、权利要求1所述的除臭纤维材料,其中的合成树脂粘合剂至少是一种树脂,选自以氨基甲酸乙酯为基的树脂、以丙烯酸为基的树脂、氨基塑料树脂、环氧树脂、以乙二醛为基的树脂和以亚乙基脲为基的树脂。
9、权利要求1所述的除臭纤维材料,其中所述第一除臭材料的至少一部分是选自聚有机酸、聚有机酸酯和聚有机酸盐中的至少一种。
10、权利要求9所述的除臭纤维材料,其中所述第一除臭剂还包括作为无机型组分的一种多孔物质。
11、权利要求1所述的除臭纤维材料,其中的纤维材料是一种聚酯纤维。
12、权利要求11所述的除臭纤维材料,其中的聚酯纤维含有一种作为阻燃剂的环烷基卤化物。
13、权利要求1所述的除臭纤维材料,其中的除臭剂组合物还包括:作为阻燃剂的聚亚烷基二醇与芳族二羧酸和亚烷基二醇的共聚物。
16、权利要求15所述的方法,其中的液体除臭组合物是用选自浸轧和涂覆的方法进行涂覆的。
17、权利要求15所述的方法,其中包括这样的步骤,在涂覆液体除臭组合物之前,将纤维材料浸入到含环烷基卤化物的液体处理浴中。
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JP03010697A JP3605985B2 (ja) | 1997-02-14 | 1997-02-14 | 消臭性成形品およびその製造方法 |
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EP (1) | EP0812948B1 (zh) |
KR (1) | KR100452034B1 (zh) |
CN (1) | CN1102683C (zh) |
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