CN1167844C - 具有除臭或抗菌性的纤维构造物 - Google Patents
具有除臭或抗菌性的纤维构造物 Download PDFInfo
- Publication number
- CN1167844C CN1167844C CNB008055807A CN00805580A CN1167844C CN 1167844 C CN1167844 C CN 1167844C CN B008055807 A CNB008055807 A CN B008055807A CN 00805580 A CN00805580 A CN 00805580A CN 1167844 C CN1167844 C CN 1167844C
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- Prior art keywords
- fibrous structure
- deodorizing
- structure thing
- antibiotic property
- weight
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Classifications
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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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
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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
- 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
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- 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
- 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
- D06M11/77—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 silicon or compounds thereof
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Abstract
本发明涉及一种在纤维表面上具有由钛和硅构成的复合氧化物和粘合剂的纤维构造物。特别优选地,涉及一种在纤维表面上具有由钛和硅构成的复合氧化物、以及从硅酸烷基酯类树脂、其他的有机硅类树脂和氟树脂中选出的至少1种粘合剂的纤维构造物,提供一种具有耐久性的除臭性、抗菌性、防霉性或防污性的纤维构造物。
Description
技术领域
本发明涉及一种过去所没有的具有耐久性的除臭性、抗气味吸附性、抗菌性、防霉性等性能皆优良的纤维构造物。这些纤维构造物可广泛地应用于衣料、窗帘、墙壁装饰材料、薄板材料或床上用品等室内装饰材料或汽车等的车内装饰材料等。
技术背景
近年来,随着人民生活水平的提高,有关健康和卫生的意识也提高了,在衣食住各领域中,施行了除臭、抗菌、防霉和防污加工的制品和技术正在实用化。特别地,衣料领域中正在开发各种各样的除臭、抗菌、防污加工技术。目前,这些加工技术正朝着包括室内装饰材料等衣料以外的用途发展。
例如,被固定在陶瓷或玻璃等无机物表面上来使用的光催化剂,其除臭性、抗菌性、防霉性和防污性等性能很有效,为了将光催化剂固着到纤维上,过去使用的是丙烯酸类和聚氨酯类粘合剂,但由于这些粘合剂是有机物,因此,光催化剂的强氧化分解能力会将它们分解,这就出现了使纤维着色、产生恶臭等的问题。
另外,其他的除臭剂主要是利用中和作用等的物质,很少能够发挥具有持续性的除臭功能。例如,酸性的氧化钛、硫酸铝等,即使对碱性的氨等能够发挥除臭效果,却对中性的恶臭无能为力。另外,除臭剂本身为碱性的氧化锌可将酸性恶臭甲硫醇、硫化氢等中和成无气味的物质,但对于中性恶臭则无能为力。另外,这些利用中和作用的除臭方法中,一旦除臭剂饱和,就不能继续发挥效果,为了恢复除臭功能,必须进行洗涤等处理。
另外,还已知一类利用活性炭或二氧化硅等的物理吸附作用的除臭剂。由于这些除臭剂吸附恶臭成分而不是将其分解,不能从本质上解决问题。理想的是,必须将恶臭成分完全分解成无气味的成分,能够进行这种作用的化学物质知之甚少。例如有铁/酞菁,已确认进行氧化分解作用的这种物质混入人造丝纤维中来使用,例如将其用于被褥棉絮中,可除去氨的气味。另外,还已知可将硫化氢氧化成硫磺、将硫醇氧化成二硫化物、将醛氧化成羧酸、将胺氧化成酮和氨等的手段。但是,这些分解物也有气味,而且,这些化学物质不能说对全部的恶臭都有效。即,对除去烟味和汗味就没有效果。
另外,复合的恶臭,例如烟草的燃烧烟雾中,可以说含有数千种成分,很难将它们完全除去。进一步地,人体汗水中的主要成分是异戊酸,目前还没有对此有效的除臭剂,另外,腋臭的气味成分中混合有数种低级脂肪酸,很难将它们完全变为无气味的物质。
另外,这些经过除臭加工的纤维构造物中,被其吸附的成分有时会产生恶臭,或是被分解成其他的成分,反而会产生臭的成分。本发明就是鉴于这种传统技术的问题,提供一种在使用时不发生变色和劣化、具有能够同时满足具有持续性的除臭、抗菌、防霉和防污性等的优良功能的纤维构造物。
发明的公开
本发明为了解决这种课题,采用如下的手段。
即,本发明的纤维构造物的特征是,在纤维表面上具有由钛和硅构成的复合氧化物和粘合剂。特别优选一种在纤维表面上具有由钛和硅构成的复合氧化物和选自硅酸烷基酯类树脂、其他的有机硅类树脂和氟树脂中的至少1种粘合剂的除臭、抗菌性等优良的纤维构造物。
对附图的简单说明
图1示出实施例9中使用的纤维截面的形状。
实施发明的最佳方案
本发明中,光催化剂具有一种利用由紫外线激发的强氧化力将有机物氧化分解的特性,具体地说,包括具有被称为锐钛矿型和金红石型的结晶型构造的光催化剂。
这种光催化剂具有除臭性、着色物分解除去性(防污性)、杀菌性(抗菌、防霉)。本发明着眼于这一事实,将其用于纤维构造物中。
例如,具有除臭功能的加工技术迄今为止已有许多介绍,但传统的除臭技术中,存在着只能消除某种特定的臭味而使臭味残留,或是缺乏持续性和耐久性等问题。
但是,本发明的光催化剂可均衡地将至今难以消除的烟味和汗味等体臭除去,而且,还具有将这种臭味氧化分解的功能,因此,可以达到所谓抗气味吸附的、迄今为止所没有的、非常优良的效果。另外,由于具有分解除去烟袋油子等着色物的功能,因此,也可以达到对着色物的防污效果。进一步地,本发明的光催化剂,由于其氧化能力,而对MRSA菌、大肠菌、黄色葡萄球菌等具有杀菌力,因此,还可以达到抗菌、防霉加工的效果。
如果这种光催化剂的粒径过大、而比表面积过小,则对有机物、特别是对细菌的分解速度有降低的倾向。另外,考虑到除臭反应要经过将恶臭成分吸附到催化剂上,然后受紫外线氧化分解的过程,还考虑到恶臭成分中的吸附良好的恶臭对除臭效率有很大影响,因此,优选使用一次粒径在20nm以下、比表面积为100~300m2/g的光催化剂。如果这种光催化剂对纤维构造物的附着量过少,则恶臭成分等有机物的分解速度低,得不到充分的性能,而如果附着量过多,则光催化剂会引起纤维布帛劣化,并使手感发硬,不实用,进一步地,由于光催化剂的氧化分解作用使纤维本身和粘合剂等分解,从而产生恶臭,因此,光催化剂对纤维构造物的附着量优选为0.03~10重量%,较优选为0.05~5重量%,更优选为0.08~3重量%。
作为本发明中的光催化剂,重要的是使用钛与硅的复合氧化物。这种复合氧化物可以使用以特公平5-55184号公报中记载的方法制造的催化剂。正如田部浩三(《触媒》,第13卷,No.3,72页1975年)所提出的那样,一般来说,由钛与硅构成的二元复合氧化物显示出作为固体酸已知的、各自单独构成的氧化物所见不到的显著酸性,另外,还具有高的表面积。即,钛与硅的复合氧化物,不是氧化钛与氧化硅的简单的混合物,可以断定,通过钛与硅形成所谓的二元氧化物,可使其出现特异的性能。进一步地,从X射线衍射的分析结果看出,上述复合氧化物具有非品质或几乎接近非晶质的微细结构。钛与硅的比例,换算成氧化物优选为,氧化钛20~95摩尔%,氧化硅5~80摩尔%,处于这一范围内,就可获得好的结果。如果氧化硅的比例增多,则氧化钛的光催化剂活性有变弱的倾向,可根据使用目的来决定最适宜的比例。作为钛与硅的复合氧化物的优选的制造方法是,将四氯化钛与二氧化硅溶胶共同混合,向其中滴入氨水,使其生成沉淀,过滤该沉淀物,洗涤并干燥后,在300~650℃下焙烧而制得。与一般公知的氧化钛光催化剂相比,这种光催化剂具有如下特征:对有机物的氧化分解特性不是过分的强,而且如上所述的抗菌、除臭、抗气味附着、防污性等性能优良,同时,还可以抑制随着粘合剂的分解而使效果降低、发生恶臭和着色等。
特别优选的是,将光催化剂与作为粘合剂的选自硅酸烷基酯类树脂、其他有机硅类树脂和氟树脂中的至少1种粘合剂一起附着到纤维表面上。钛与硅的复合氧化物在紫外线的照射下有时会引起有机物的分解,使纤维构造物或粘合剂等树脂分解而引起着色,例如,如果使聚氨酯树脂、丙烯酸类树脂等与光催化剂共存,并照射紫外线,则由于有机物的分解而发生着色和臭味。
本发明中,为了使钛与硅的复合氧化物构成的光催化剂附着到纤维构造物上,使用从硅酸烷基酯类树脂、其他的有机硅类树脂和氟树脂中选出的至少1种粘合剂,由此可以防止有机类树脂特有的、由于光催化剂的氧化作用而引起的分解、着色和臭味的产生。另外,为了保护纤维不受光催化剂的氧化作用而引起分解,也可以在纤维与含有光催化剂的粘合剂之间设置过氧化钛等无机物的中间层。
本发明中使用的硅酸烷基酯的特征是,主要由Si-O键部分和直链或支链的饱和烷基构成,其两端具有OH基团。即,含有下述式所示的结构。
OH-(Si-O)n-R-OH
式中,R为碳原子数1~10的直链或支链的饱和烷基,n为1以上的整数,为了提高无机性,优选为1000~10000。
这种烷基为甲基、乙基、丙基、异丙基等直链或支链的饱和烷基。这些硅酸烷基酯可以是1种,也可以是2种以上的混合物。这些化合物的特征是,在热的存在下容易发生脱水反应,形成聚硅氧烷被膜。硅酸烷基酯是水溶性的,如果使纤维构造物浸渍到它的水溶液中,然后用轧液机挤干,在200℃以下的温度下进行处理,就会在纤维表面上形成薄薄的一层被膜。
也可以使这种硅酸烷基酯直接附着到纤维构造物的表面上。
另外,也可以使光催化剂与有机硅类树脂或氟树脂等粘合剂混合使其附着。这些粘合剂的耐热性、耐光性、耐药品性优良,对于光催化剂的氧化能力也具有优良的耐久性。
作为此处所说的其他的有机硅树脂,可以使用属于有机硅树脂或有机硅清漆的缩合交联型树脂,这种树脂包括四乙氧基硅烷、甲基三甲氧基硅烷等的单独的缩合交联型树脂,也包括使它们几种的配合物缩合而获得的缩合物。它们形成三维构造的树脂,即使在有机硅树脂中,也是耐热性和耐药品性最好的树脂。另外,有机硅树脂具有这样一个特征,如果将四异丙氧基硅烷或四乙氧基硅烷在醇/水混合溶剂中用强酸水解,并将获得的氧化硅溶胶干燥,就会形成一层玻璃质的被膜。由于采用这种溶胶/凝胶法获得的构造物接近于无机质,因此是本发明中更优选的构造物。
另外,作为氟树脂,氟代烯烃聚合物、乙烯基醚和/或乙烯基酯与氟代烯烃的共聚物具有非常优良的特性,是优选使用的。例如,聚氟化乙烯和聚四氟乙烯、四氟乙烯-全氟烷基乙烯基酯共聚物和乙烯基酯-氟代烯烃共聚物等,由于分解、劣化少,是优选使用的。
这种有机硅类树脂和氟树脂与通常使用的丙烯酸类树脂、聚氨酯树脂、环氧树脂等有机树脂的不同之处在于,几乎不含有在热和药品的作用下容易分解的烃基,有机硅类树脂主要由Si-O键构成,氟树脂主要由F-C键构成,端基或侧链上含有少量的甲基或苯基作为烃
作为向这种粘合剂或者向被附着这种粘合剂而形成的含有光催化剂的纤维构造物全体赋予吸水性的方法,可以采用将具有选自羟基(-OH)、羧基(-COOH)、氨基(-NH2)和酰胺基(-CONH2)中的至少1种亲水性基团的吸水性有机硅类树脂、大量加成乙二醇的吸水性有机硅类树脂、含有聚氧化乙烯基的化合物、纤维素系化合物等的亲水化加工剂混合到粘合剂中或附着到整个布帛的手段。后者的亲水化加工剂中,优选以聚亚烷基二醇-聚酯嵌段共聚物为主要成分的亲水性聚酯树脂。另外,前者的吸水性有机硅类树脂可以单独作为粘合剂使用。
将这种亲水化加工剂作为吸水剂使用,可以获得可用于需要吸水性的运动用途等的含有光催化剂的纤维构造物。在使用有机系吸水剂树脂或亲水化加工剂时,优选在不会因为该光催化剂半导体的氧化作用而发生分解、着色和臭气的范围内使用。
还可以在上述的粘合剂中添加偶合剂,由此可以提高无机物与有机物的粘结力,这样就可以在纤维、粘合剂和光催化剂半导体的相互之间起着化学键合力的作用,其结果,可以提高洗涤耐久性。
另外,进一步向上述的粘合剂中添加沸石,可提高对臭气成分的吸附力并使构造物中的无机成分比增加,具有抑制光催化剂引起的分解的效果。另外,也可以使用担持0.01~5重量%的金、铂、银、钯等贵金属的沸石。由此可以进一步提高抗菌效果。
本发明的纤维构造物可以使用合成纤维、天然纤维,没有特别的限定,但优选含有50重量%以上聚酯类纤维。此处,作为聚酯类纤维,优选使用聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸己二醇酯等。另外,作为构成这种聚酯类纤维的聚酯,可以使用共聚有第三成分的共聚物,优选使用作为这种第三成分共聚有间苯二甲酸、5-磺基间苯二甲酸钠、聚氧乙烯二醇甲醚等的共聚物。在纤维构造物中含有50重量%以上、较优选70%以上、更优选100%聚酯类纤维的场合下,本发明的功能性显示出优良的效果。应予说明,本发明中,除了聚酯类纤维以外,还可以含有例如聚酰胺、聚丙烯酸酯等合成纤维、醋酸纤维、人造丝等半合成纤维、羊毛、蚕丝、棉花、麻等天然纤维。
本发明中所说的纤维构造物,除了布帛状物以外,还包括带状物、绳状物、丝状物等由纤维构成的构造物。可以任何一种构造和形状,优选以合成纤维为主的布帛状构造物,即织物、编物、非织造织物,也可以是复合材料。
本发明中,聚酯类纤维中也可以含有惰性氧化钛。该惰性氧化钛可以举出例如在通常的聚酯类合成纤维的制造中作为消光剂使用的氧化钛。通过添加这种惰性氧化钛,可以减少表层部分使用的光催化剂的氧化还原作用对聚酯类纤维的影响。这种惰性氧化钛通常在聚酯类纤维的聚合时添加,从纺纱性和丝的物性考虑,其平均粒径优选为0.1~0.7μm,更优选为0.2~0.4μm。
另外,作为这种惰性氧化钛的添加量,对于纤维重量来说,优选含有0~5重量%,可根据需要含有0.5~4重量%。如果超过5重量%,则对纺纱性和丝的物性有影响。
本发明中所说的聚酯类纤维的异形截面系数是具有与圆形截面丝相同的截面积,换句话说,相同旦数的异形截面丝的外周长与圆形截面丝的外周长之比,具体地以异形截面丝的外周长除以圆形截面丝的外周长的值来表示。本发明多采用圆形截面丝,但异形截面系数越大,单位重量的丝的表面积越大,随之而来的光催化剂层的面积也越大,因此,往往相应地使效果增加。作为这种异形截面系数,为1.2~2,优选为1.3~1.8。但是,超过2的纤维存在着难以纺纱的缺点。
以下,说明本发明的一例纤维构造物的制造方法。
优选向粘合剂中添加沸石微粒,特别是担持0.01~5重量%的金等贵金属的沸石,进一步优选还添加偶合剂,接着,与钛和硅的复合氧化物的水分散液混合,将其制成加工液。
然后,使纤维构造物浸渍到该加工液中,然后用轧液机挤干,经过干燥烘焙(dry cure)的工序,或者将该加工液调整至适当的粘度,用刮刀涂布机、凹槽辊涂布机、印花(机)等涂布后,在200℃以下的温度下干燥固定。
这样,就可以提供一种能够满足过去所没有的具有耐久性的除臭性、抗菌性、防霉性和防污性、同时抗气味吸附效果优良的功能性纤维构造物。
实施例
以下用实施例更详细地说明本发明。实施例中的品质评价采用如下的方法。
(洗涤)
使用自动反向旋转涡流式电动洗衣机VH-3410(东芝(株)制),在市售洗涤剂浓度0.2%、温度40±2℃、浴比1∶50的条件下,以强反向旋转洗涤5分钟,然后,排水、一边溢流一边进行漂洗2分钟,将这种操作重复2次作为1次洗涤。
(采用检测管法的除臭性评价)
向装有10g试样的500ml容器中装入初期浓度为200ppm的氨气,密闭,放置1小时后,用气体检测管测定残留的氨气浓度。然后,按照下述公式计算除臭率(%)。
除臭率(%)=[1-(气体检测管测定浓度)/(初期浓度)]×100
采用同样的方法,测定乙醛200ppm-1小时后以及甲硫醇60ppm-3小时后的残留气体浓度,分别计算出各气体的除臭率。
(对烟草气味除臭性的嗅觉评价)
将500ml的玻璃三角烧瓶的瓶口朝下,将点燃着的卷烟在瓶口的正下方放置5秒钟后,迅速地将三角烧瓶转过来,投入3g试样,用玻璃塞密闭。放置1小时后,打开玻璃塞,由10个人闻一闻残留的气味,进行感官评价。将此时的臭味按下述评价点数进行评价,列出平均值。
5:强烈的臭味
4:很强的臭味
3:可轻松地感觉到的臭味
2:感觉到有点臭味
1:勉强能感觉到的臭味
0:无臭味
(用异戊酸气味进行抗气味吸附性的嗅觉评价)
将0.01%的异戊酸水溶液用微量注射器量取25μl,在切割成10cm×10cm大小的布帛中央部位每5μl一滴地滴下5滴。滴下的方法是,在布帛中央部位滴下1滴,接着在中央部位那1滴的周围,刚好形成骰子的五个点那样地滴下4滴。将该布帛在荧光灯下放置3小时后,由10个人闻一闻此时布帛上的臭味,按与烟草臭味评价点数相同的基准评价此时的臭味,列出平均值。
(分解臭)
将10cm×10cm试样展开地放入500ml玻璃三角烧瓶的底部,用玻璃塞密闭,在室内西侧玻璃窗处放置48小时。然后取下玻璃塞,由10个人用鼻子闻一闻烧瓶内的臭气,进行感官评价。按与烟草臭味评价点数相同的基准评价此时的臭味,列出平均值。
(抗菌评价方法)
评价方法采用统一的试验方法,试验菌株使用黄色葡萄球菌临床分离株。试验方法是,在灭菌试验布上注入上述试验细菌,测定培养18小时后的活菌数,求出增加细菌的菌数,按照下述基准进行评价。
log(B/A)>1.5的条件下,将log(B/C)作为细菌数的增减数值差,在2.2以上为合格。
其中,A表示未加工制品接种之后分散回收的细菌数,B表示未加工制品培养18小时后分散回收的细菌数,C表示加工制品培养18小时后分散回收的细菌数。
(吸水性(滴下法))
采用JIS L-1018 A滴下法测定吸水时间。数值越小,表示吸水性越好。
(防污性评价方法)
顺序1:在聚乙烯袋(20升)中装入在100℃下干燥2小时的表1所示组成的污染物0.2g和长10cm、宽16cm的样品和ICI织物起球用橡胶管1根。用20℃×65%RH的空气充入聚乙烯袋使其膨胀(约为10升),用橡皮筋进行限制。
表1
药品名 | 重量% | 规格 |
粘土 | 55.00 | 用乳钵将信乐粘土研碎而成 |
硅酸盐水泥 | 17.00 | JIS R5210 |
二氧化硅 | 17.00 | JIS K8885 |
三氧化二铁 | 0.50 | CP级试剂 |
正癸烷 | 8.75 | EP级试剂 |
炭黑 | 1.75 | 玉川炭黑 |
顺序2:将顺序1的聚乙烯袋放入ICI试验器的箱中,使其旋转1小时。然后取出样品。
顺序3:将处理样品在标准洗涤条件下洗涤1次。将顺序1~3再重复2次。
顺序4:用测色计测定将上述的污染剂附着·洗涤操作重复3次后的样品和未经处理的样品的L值,计算出其差值ΔL值。
实施例1
纤维布帛中含有0.35重量%的平均粒径0.3μm的惰性氧化钛,单丝的平均纤度为3.3dtex,由圆截面的聚酯65重量%和棉35重量%构成,单位面积重量为180g/m2。采用通常的加工条件对这种纤维布帛进行精炼、干燥、中间定形和染色。
进一步地,作为光催化剂,使用平均一次粒径7nm、平均比表面积150m2/g的钛与硅的复合氧化物,将其制成浓度20%的水溶液分散体。此时的平均粒径为0.3μm。使用该光催化剂分散液,制成实施例1中使用的由下述成分构成的加工液(水溶液)。
钛与硅的复合氧化物(浓度20%) 1.0重量%
(大京化学(株)制TR-T2)
硅酸烷基酯类树脂(浓度20%) 1.0重量%
(共荣社化学(株)制CLG-520)
有机硅类树脂(浓度45%) 1.5重量%
(东丽·陶氏康宁·Silicon(株)制BY22-826)
硅烷偶合剂(浓度100%) 0.2重量%
(东芝Silicon(株)制TSL-8350)
贵金属担持型沸石(浓度20%) 0.3重量%
((株)Cynanenzeomic制Zeomic AW10N)
将上述染色后的纤维布帛浸渍到该加工液中,用轧液机以80重量%的轧液率挤干,在120℃下干燥2分钟后,在180℃下进行1分钟热处理,获得纤维表面上含有光催化剂的构造物。对该纤维布帛进行除臭性、抗菌性、防污性、吸水性等的评价。结果示于后面的表中。
实施例2
向实施例1的加工液中再加入0.5重量%的氟树脂(浓度20%)(大日本油墨化学工业(株)制Dickgard-F-90),将其作为加工液2。使用加工液2,与实施例1同样地进行加工,获得具有光催化剂的处理布帛。对该纤维布帛进行除臭性、抗菌性、防污性等的评价。结果示于后面的表中。
实施例3
实施例1的加工液中不添加硅烷偶合剂,将其作为加工液3。使用加工液3,与实施例1同样地进行加工,获得具有光催化剂的处理布帛。对该纤维布帛进行除臭性、抗菌性、防污性等的评价。
实施例4
实施例1的加工液中不添加硅烷偶合剂和贵金属担持型沸石,将其作为加工液4。使用加工液4,与实施例1同样地进行加工,获得具有光催化剂的处理布帛。对该纤维布帛进行除臭性、抗菌性、防污性等的评价。结果示于后面的表中。
实施例5
向实施例1的加工液中添加1.0重量%的以聚亚烷基二醇-聚酯嵌段共聚物(日华化学(株)制Nicepol PR-99)为主要成分的亲水性聚酯树脂,将其作为加工液5。使用加工液5,与实施例1同样地进行加工,获得具有光催化剂的处理布帛。对该纤维布帛进行除臭性、抗菌性、防污性、吸水性等的评价。结果示于后面的表中。
实施例6
向四氯化钛TiCl4的30重量%溶液中加入氢氧化钠NaOH的5重量%溶液,放置一会儿后,获得氢氧化钛Ti(OH)4。将其用25重量%的过氧化氢处理,获得由非结晶质过氧化钛溶胶构成的加工液6。使用加工液6,在其中浸渍实施例1中使用的染色后的纤维布帛,用轧液机以80重量%的轧液率挤干,在120℃下干燥2分钟,然后在180℃下进行1分钟热处理,获得纤维表面上具有非结晶质过氧化钛粒子层的纤维布帛。与实施例1同样地用实施例1中使用的加工液对该纤维布帛进行加工,获得具有光催化剂的处理布帛。对该纤维布帛进行除臭性、抗菌性、防污性等的评价。结果示于后面的表中。
实施例7
采用PVD法将沸石微粒气相淀积到实施例1的染色后的纤维布帛上,使其熔融附着。然后,与实施例1同样地用加工液1对该纤维布帛进行加工,获得具有光催化剂的处理布帛。对该纤维布帛进行除臭性、抗菌性、防污性等的评价。结果示于后面的表中。
实施例8
硅酸烷基酯类树脂(浓度20%) 20.5重量%
(三菱化学(株)制 MS51)
甲醇 8.5重量%
精制水 70.0重量%
硫酸(浓度20%) 1.0重量%
将这样构成的加工液作为加工液8。将加工液8用凹槽辊附着到由非织造织物制成的仿麂皮风格人工皮革的染色后的纤维布帛表面上,使干燥后的附着量为5g/m2。然后,在该纤维布帛表面上,用加工液1同样地进行凹槽辊加工,使干燥后的附着量为7g/m2,由此获得具有光催化剂的处理布帛。对该纤维布帛进行除臭性、抗菌性、防污性等的评价。结果示于后面的表中。
实施例9
纤维布帛中含有平均粒径0.3μm的惰性氧化钛0.35重量%,单丝的平均纤度为3.3dtex,由截面形状为图1所示扁平十字形的异形截面系数为1.5的聚酯65重量%和棉35重量%制成,单位重量面积为180g/m2。采用通常的加工条件对该纤维布帛进行精炼、干燥、中间定形和染色。
将上述染色后的纤维布帛浸渍到加工液1中,用轧液机80重量%的轧液率挤干,在120℃下干燥2分钟,然后在180℃下进行1分钟热处理,获得纤维表面上含有光催化剂的构造物。对该纤维布帛进行除臭性、抗菌性、防污性、吸水性等的评价。结果示于后面的表中。
实施例10~15
除了改变粘合剂、钛与硅的复合氧化物的量以外,与实施例1同样地进行试验。结果示于后面的表中。
比较例1
作为光催化剂使用由TiO2单一组成构成的浓度40%的水系分散体,制成下述成分构成的加工液,用该加工液与实施例1同样地对实施例1的染色后的布帛进行加工。但是,该光催化剂的平均一次粒径为20nm,平均比表面积为50m2/g。
氧化钛光催化剂(浓度40%) 0.5重量%
(石原产业(株)制STS-21)
硅酸烷基酯类树脂(浓度20%) 1.0重量%
(共荣社化学(株)制CLG-520)
有机硅类树脂(浓度45%) 1.5重量%
(东丽·陶氏康宁(株)制BY22-826)
硅烷偶合剂(浓度100%) 0.2重量%
(东芝Silicon(株)制TSL-8350)
贵金属担持型沸石(浓度20%) 0.3重量%
((株)Synamenzeomic制Zeomic AW10N)
结果示于后面的表中。
比较例2
除了不向该加工液中添加光催化剂以外,重复实施例1的操作。
结果示于后面的表中。
各实施例、比较例的条件和结果示于表2和表3中。由此可以看出,实施例1~9与比较例相比,除臭性的平衡良好,可发挥出优良水平的功能,而且实施例1、2和5的除臭性、抗菌性、防污性和耐久性优良。其中,实施例1和实施例9相比,异形截面系数大的实施例9的除臭性、抗菌性、防污性优良,表现出异形截面系数不同的效果。另外可看出,实施例5与实施例1和比较例1相比,吸水性优良。
表2
处理液组成(处理液中的有效成分的重量%) | 备注 | |||||||
硅酸烷基酯类树脂 | 其他的有机硅类树脂 | 氟树脂 | 沸石 | 硅烷偶合剂 | 钛与硅的复合氧化物 | 亲水性聚酯类树脂 | ||
实施例1 | 0.2 | 0.68 | - | 0.06 | 0.2 | 0.2 | - | |
实施例2 | 0.2 | 0.68 | 0.1 | 0.06 | 0.2 | 0.2 | - | |
实施例3 | 0.2 | 0.68 | - | 0.06 | - | 0.2 | - | |
实施例4 | 0.2 | 0.68 | - | - | - | 0.2 | - | |
实施例5 | 0.2 | 0.68 | - | 0.06 | 0.2 | 0.2 | 0.2 | |
实施例6 | 0.2 | 0.68 | - | 0.06 | 0.2 | 0.2 | - | 过氧化钛被覆纤维 |
实施例7 | 0.2 | 0.68 | - | 0.06 | 0.2 | 0.2 | - | 沸石被覆纤维 |
实施例8 | 0.2 | 0.68 | - | 0.06 | 0.2 | 0.2 | - | 硅酸烷基酯被覆纤维 |
实施例9 | 0.2 | 0.68 | - | 0.06 | 0.2 | 0.2 | - | 使用异形截面系数=1.5的聚酯纤维 |
实施例10 | 0.2 | 0.68 | - | 0.06 | 0.2 | 0.1 | - | |
实施例11 | 0.2 | 0.68 | - | 0.06 | 0.2 | 1.0 | - | |
实施例12 | 0.2 | 0.68 | - | 0.06 | - | 3.0 | - | |
实施例13 | 0.8 | - | - | - | - | 0.2 | - | |
实施例14 | - | 0.68 | - | - | - | 0.2 | - | |
实施例15 | - | - | 0.5 | - | - | 0.2 | - | |
比较例1 | 0.2 | 0.68 | - | 0.06 | - | - | - | 添加0.2重量%氧化钛系光催化剂 |
比较例2 | 0.2 | 0.68 | - | 0.06 | - | - | - | 无光催化剂 |
表3
除臭率(%) | 烟草除臭性(点) | 异戊酸臭味除臭性(点) | 抗菌性 | 吸水性(秒) | 防污性 | 分解(点) | ||||||
臭味A | 臭味B | 臭味C | 洗涤0次 | 洗涤10次 | 洗涤0次 | 洗涤10次 | 洗涤0次 | 洗涤10次 | 洗涤0次 | ΔL值 | 洗涤0次 | |
实施例1 | 100 | 98 | 93 | 2.2 | 2.7 | 0.5 | 1.0 | 5.9 | 5.8 | 180 | 7.7 | 1.9 |
实施例2 | 100 | 97 | 92 | 2.4 | 2.6 | 0.5 | 1.2 | 5.3 | 5.0 | - | 5.1 | 2.1 |
实施例3 | 100 | 96 | 91 | 2.4 | 3.8 | 0.6 | 3.4 | 5.2 | 4.3 | - | 17.1 | 2.1 |
实施例4 | 100 | 95 | 90 | 2.7 | 3.8 | 0.7 | 3.4 | 4.4 | 3.0 | - | 16.8 | 2.0 |
实施例5 | 98 | 98 | 90 | 2.4 | 2.6 | 0.5 | 1.0 | 5.6 | 5.3 | 0.5 | 8.3 | 2.3 |
实施例6 | 96 | 97 | 89 | 2.5 | 3.7 | 0.6 | 3.6 | 5.4 | 3.1 | - | 16.1 | 1.7 |
实施例7 | 98 | 95 | 90 | 2.8 | 3.5 | 0.6 | 3.5 | 5.3 | 3.1 | - | 16.4 | 1.6 |
实施例8 | 97 | 93 | 90 | 2 7 | 3.7 | 0.6 | 3.6 | 5.5 | 3.3 | - | 16.9 | 1.8 |
实施例9 | 100 | 99 | 93 | 2.1 | 2.5 | 0.5 | 1.0 | 6.1 | 5.9 | - | 7.5 | 2.2 |
实施例10 | 95 | 93 | 91 | 3.3 | 4.0 | 2.0 | 4.0 | 3.1 | 2.3 | - | 18.0 | 1.0 |
实施例11 | 98 | 98 | 98 | 2.0 | 2.2 | 0.1 | 1.0 | 6.5 | 6.2 | 6.3 | 3.5 | |
实施例12 | 100 | 100 | 100 | 2.0 | 2.3 | 0.1 | 0.8 | 7.5 | 7.3 | 6.8 | 4.0 | |
实施例13 | 98 | 97 | 91 | 2.2 | 3.9 | 0.5 | 1.9 | 4.3 | 3.0 | 8.9 | 2.0 | |
实施例14 | 99 | 98 | 92 | 2.1 | 3.2 | 0.5 | 1.2 | 4.4 | 3.9 | 8.5 | 2.0 | |
实施例15 | 100 | 99 | 93 | 2.4 | 3.8 | 0.6 | 2.8 | 4.5 | 3.1 | 4.8 | 2.5 | |
比较例1 | 78 | 75 | 78 | 4.3 | 4.5 | 3.5 | 4.0 | 2.4 | 2.9 | - | 19.8 | 5.0 |
比较例2 | 60 | 43 | 35 | 4.5 | 4.8 | 4.8 | 4.8 | 3.1 | 2.0 | - | 19.9 | 1.0 |
*臭味A:氨 臭味B:乙醛 臭味C:甲硫醇
产业上的利用领域
根据本发明,可以提供能够广泛应用于衣料、窗帘、墙壁装饰材料、薄板材料、床上用品等室内装饰材料、汽车等的车内装饰材料等的功能性纤维构造物。
Claims (14)
1.一种具有除臭或抗菌性的纤维构造物,其特征在于,在纤维表面上具有由钛与硅构成的复合氧化物和粘合剂。
2.权利要求1中所述的具有除臭或抗菌性的纤维构造物,其中,该粘合剂以选自硅酸烷基酯类树脂、其他的有机硅类树脂和氟树脂中的树脂为主体。
3.权利要求1中所述的具有除臭或抗菌性的纤维构造物,其中,在该纤维表面上还具有沸石。
4.权利要求1中所述的具有除臭或抗菌性的纤维构造物,其中,在该纤维表面上还具有偶合剂。
5.权利要求1中所述的具有除臭或抗菌性的纤维构造物,其中,在该纤维表面上还具有吸水剂。
6.一种具有除臭或抗菌性的纤维构造物,其中,在纤维表面上,具有作为中间层的从过氧化钛粒子层、沸石层和硅酸烷基酯层中选出的至少一层,进一步在其上层部还具有权利要求1中所述的结构。
7.权利要求1中所述的具有除臭或抗菌性的纤维构造物,其中,该复合氧化物为具有100~300m2/g比表面积的微粒。
8.权利要求1中所述的具有除臭或抗菌性的纤维构造物,其中,该复合氧化物为平均一次粒径处于1~20nm范围内的微粒。
9.权利要求1中所述的具有除臭或抗菌性的纤维构造物,其中,该复合氧化物的附着量,相对于该纤维构造物来说,为0.03~10重量%。
10.权利要求9中所述的具有除臭或抗菌性的纤维构造物,其中,该复合氧化物的附着量,相对于该纤维构造物来说,为0.05~5重量%。
11.权利要求10中所述的具有除臭或抗菌性的纤维构造物,其中,该复合氧化物的附着量,相对于该纤维构造物来说,为0.08~3重量%。
12.权利要求1中所述的具有除臭或抗菌性的纤维构造物,其中,含有50重量%以上的聚酯类纤维。
13.权利要求12中所述的具有除臭或抗菌性的纤维构造物,其中,该聚酯类纤维中含有0.3~5重量%的惰性氧化钛。
14.权利要求12中所述的具有除臭或抗菌性的纤维构造物,其中,该聚酯类纤维的异形截面系数为1.2~2。
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EP (1) | EP1188854B1 (zh) |
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AT (1) | ATE267907T1 (zh) |
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