CN1981152A - 由柔性塑料制成的具有抗菌保护层的卫生软管 - Google Patents

由柔性塑料制成的具有抗菌保护层的卫生软管 Download PDF

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CN1981152A
CN1981152A CNA2005800208808A CN200580020880A CN1981152A CN 1981152 A CN1981152 A CN 1981152A CN A2005800208808 A CNA2005800208808 A CN A2005800208808A CN 200580020880 A CN200580020880 A CN 200580020880A CN 1981152 A CN1981152 A CN 1981152A
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flexible pipe
antimicrobial agent
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surface layer
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A·法思
Z·阿卡尔坦
W·海恩泽尔曼
J·海斯特哈根
M·苏尔姆
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Hansgrohe SE
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    • EFIXED CONSTRUCTIONS
    • E03WATER SUPPLY; SEWERAGE
    • E03CDOMESTIC PLUMBING INSTALLATIONS FOR FRESH WATER OR WASTE WATER; SINKS
    • E03C1/00Domestic plumbing installations for fresh water or waste water; Sinks
    • E03C1/02Plumbing installations for fresh water
    • E03C1/025Water supply lines as such, e.g. shower hoses
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • EFIXED CONSTRUCTIONS
    • E03WATER SUPPLY; SEWERAGE
    • E03BINSTALLATIONS OR METHODS FOR OBTAINING, COLLECTING, OR DISTRIBUTING WATER
    • E03B7/00Water main or service pipe systems
    • E03B7/006Arrangements or methods for cleaning or refurbishing water conduits
    • EFIXED CONSTRUCTIONS
    • E03WATER SUPPLY; SEWERAGE
    • E03CDOMESTIC PLUMBING INSTALLATIONS FOR FRESH WATER OR WASTE WATER; SINKS
    • E03C1/00Domestic plumbing installations for fresh water or waste water; Sinks
    • E03C1/02Plumbing installations for fresh water
    • E03C1/021Devices for positioning or connecting of water supply lines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/15Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/151Coating hollow articles
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    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C53/00Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/56Winding and joining, e.g. winding spirally
    • B29C53/58Winding and joining, e.g. winding spirally helically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04Polymers of ethylene
    • B29K2023/06PE, i.e. polyethylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/06PVC, i.e. polyvinylchloride
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2075/00Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2083/00Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2101/00Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12Thermoplastic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0011Biocides
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0082Flexural strength; Flexion stiffness
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29L2023/00Tubular articles
    • B29L2023/005Hoses, i.e. flexible
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C02F1/505Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24HEATING; RANGES; VENTILATING
    • F24DDOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
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    • F24D17/0073Arrangements for preventing the occurrence or proliferation of microorganisms in the water

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Abstract

本发明涉及一种由柔性塑料制成的卫生软管,特别是一种淋浴软管,其具有一个内表面(17)和一个外表面(14),并且具有一种抗菌保护层。至于抗菌保护层,将至少一种抗菌剂嵌入至少内表面(17)的材料中。

Description

由柔性塑料制成的具有抗菌保护层的卫生软管
本发明涉及一种由柔性塑料制成的卫生软管,尤其是一种淋浴软管,具有一个内表面和一个外表面以及一种抗菌保护层。
在饮用水和工业用水中的微生物杂质不仅仅在发展中国家中造成了严重的健康危险。在发达国家,这种威胁生命的微生物杂质在盛放饮用水或工业用水的器皿、管道或热水器中出现的频率越来越高。特别是在原本污染物很少的水在其中停留、加热或者输送一段时间的管道、器皿或者榨取设备中,这种污染物产生很大的影响。
这些微生物是由于水在非常适合于微生物繁殖的周围温度下停留在器皿或者管道区段中而生成的。最大的危险来自于热水器或热水管道,热水最初在其中流过,但在水被抽出后,残余的水慢慢地冷却,并且在此过程中在一个较长的时间范围内都一直存在对于微生物繁殖最佳的温度范围。这导致这些致病的微生物急剧繁殖,并且很快就超过为饮用水、为水中所含的病原体所规定的极限值,并且达到对人类有毒的浓度。最危险的病原体之一是军团菌(嗜肺军团菌),它的最佳繁殖温度范围是30℃到50℃。
目前已知,水箱或罐中的水通过添加含银或含氯的添加剂形式的化学药剂来有效防止污染,其中水在这些水箱或者罐中要保存一段较长的时间。但这种方法只对水容器有效,对于水管或软管则不适用,因为水会反复在管道中流动,这就需要不断地加入这种类型的抗菌添加剂。
除了将水温保持在30℃到50℃的范围内很长时间的热水容器外,空调系统、空气加湿器、淋浴器喷头和淋浴软也特别危险,在这些设备中水被暴露在周围温度中,尤其在夏天和浴室中,温度在25℃到30℃之间。在这些设备和装置中,病原体即使在很短的时间内也会急剧繁殖,也就是例如在不规则取水时就会导致病原体急剧繁殖,当这些装置和设备启动时,这些病原体就作为悬浮微粒进入被呼吸的空气中,并因此直接进入肺中。在这种感染路线中,有时会发生非常严重的致命的感染,在军团菌的情况下尤其如此。
从DE 42 26 810 C1中可知一些塑料部件,其不会被细菌潜入,因而主要被用于医学领域。杀毒作用可以通过在塑料本身的表面上和/或表面中的银化合物实现。为此,将塑料用溶胀剂处理,并将溶胀塑料与一种银化合物(例如硝酸银)的溶液进行处理。这种银化合物存在一个问题,即由于这种银化合物的水溶性而很快会被从要保护的材料上洗掉。这是一个严重的缺陷,尤其当管道是用来承载强液流时。此外,用这种方法涂层的管子或淋浴喷头经过长期的使用后,被冲洗掉的硝酸银和皮肤接触时会局部产生讨厌的黑斑。
从DE 44 36 927 C2中可知一种口腔冲洗器,其中液体容器或泵腔的部分都涂有银合金,以防止残留在液体容器或泵中的水被污染。
从DE 101 34 468 A1中可知一种杆状的由银和特种钢制成的嵌入件,其被插入现有的淋浴软管中,并且随着银离子的释放可以防止软管中微生物的生长。除了要大量的银,这个杆状嵌入件的缺点主要是,该嵌入件消弱了软管的柔性,并且尤其是减小了软管的横截面积。其结果是导致了水流量的减小。此外,在卷绕的杆状嵌入件上的沉积物具有阻塞软管的危险。
众所周知,银是对微生物有剧毒的金属,并拥有极广泛抗菌范围。对于致病微生物来说,其有效性来源于银离子能够侵入横跨膜能量代谢,并且另外还不仅对抗革兰氏阴性病菌,还对抗革兰氏阳性细菌,同时也能对抗各种其他对人体有毒的微生物,尤其是军团菌。
另外还已知由不同材料借助于等离子辅助涂层方法在真空设备中用一层精细的金属银制成的气相喷镀产品。然而,这种喷镀过程需要很复杂的设备,因此很昂贵,并且主要用于与医学工程相关的产品。
本发明的任务是提供一种卫生软管,其中即使在各次取水之间数天的间隔之后,在取水之后残留在该卫生软管中的水也不会被致病的微生物污染。
该任务通过一种由柔性塑料制成的卫生软管、尤其是一种淋浴软管来解决,该淋浴软管具有一个内表面、一个外表面和一种抗菌保护层,其中将至少一种抗菌剂嵌入至少是内表面的材料。
根据本发明,所述至少一种抗菌剂被嵌入软管材料。这种嵌入不会阻碍水流流过卫生软管,并且在制造这种软管时也可以廉价地实现。抗菌剂能够从软管表面的材料渗出或扩散以发挥它的功效。
在本发明的一种优选的实施方式中,抗菌剂不仅被嵌入形成软管内侧面的材料中,而且被嵌入成形软管外侧面、也就是外表面的材料中。这样,就可以防止软管外侧面被污染,否则,很容易由附着在软管外侧面上的污物或肥皂残留物引起污染。对于软管的结构,它可以是一种常规的淋浴软管。该软管最好是一种至少双层壁的软管,一般是一种双层壁软管。
软管材料的塑料可以完全配有抗菌剂,也就是说,抗菌剂可以与材料完全一体化。然而,这是不必要的,并且在许多情况下也不希望。在一种优选的实施方式中,将所述至少一种抗菌剂仅仅在至少一个表面的区域中嵌入软管的材料中。这就确保了软管材料保留了期望的材料特性,更确切地说与之前完全一样。此外,微量的抗菌剂就足够了,不会削弱其功效。
抗菌剂可以以不同的方式引入软管的表面材料中,也可以将多种方式进行组合。例如,在本发明的一种实施方式中,抗菌剂能够被射入塑料表面。对此,特别是对于外表面,适合使用所谓的冷气喷射。这样,抗菌剂的颗粒尤其以金属颗粒的形式在高压(例如35bar)下与氮一起被射入塑料表面。这种方式获得的颗粒渗入深度足够使抗菌剂发挥很多年的作用。
在本发明的一种实施方式中,内和/或外表面由含有抗菌剂的表面层形成。这样的表面层最好和软管的底层由相同的塑料制成。这种软管的柔性塑料优选是一种柔性的热塑性塑料和/或热塑性弹性。这样的塑料是公知的,并且例如包括软聚氯乙烯、软聚乙烯、柔性聚氨酯和硅树脂。
表面层可以是一种独立的层。有利的是它与底层软管材料的区别仅仅在于它另外含有抗菌剂。在本发明的一种实施方式中,所述至少一个表面层由热塑性塑料形成,其优选被挤压到软管底层上。表面层最好与底层相连。尤其当表面层与底层通过共挤压连接到一起时特别有利。由熔液联合挤压的结果是使材料紧密结合,而没有明显分离的边界。
抗菌剂能够以从表面向内降低的浓度存在于表面材料中。例如,当抗菌剂的颗粒被射入表面时,就是这种情况。另一方面,抗菌剂也可以均匀地分布在表面层中。优选当表面层通过挤压涂层形成时就是这种情况。为此,可以由在其熔液中混入抗菌剂的材料形成表面层。
表面层的层厚与软管材料其余部分的层厚相比较薄。它通常低于软管材料厚度的20%,特别是低于10%。表面层的层厚最好为0.05-1mm,特另为0.2-0.5mm。
正如前面提到的,所述至少一种抗菌剂优选以颗粒形式存在。颗粒尺寸处于5μm-200μm的范围内,特别是20μm-100μm的范围内。颗粒尺寸最好能与抗菌剂的溶解度和扩散度相匹配。
最好考虑将没有特殊作用的物质作为抗菌剂。这种抗菌剂要具有非常广泛的活性范围,但没有形成抵抗的危险。同样也可以采用这种抗菌剂,它的副产品显示出实际效果。抗菌剂在表面塑料的外面慢慢扩散,或者从上述的塑料中被慢慢冲洗,然后开始产生效果,当水在软管内停留较长时间时,这种效果尤其值得期待。
在本发明的一种实施方式中,抗菌剂是一种金属和/或金属盐。作为金属,优选考虑重金属如铜、特别是银。铜和银的氧化物也有实际的抗菌效果。氧化物由金属形式形成。直接采用盐或其他化合物或者例如在硅酸盐基材中的重金属复合物也是可以的,如果必要,与颗粒形式的金属形式相结合。作为抗菌剂,也可以采用非特定的有机抗菌剂。这种抗菌剂是公知的。例如,三氯生和PHMB展示了良好的抗菌性。也可以采用各种抗菌剂的混合物,或者在软管的内表面和外表面上采用不同的抗菌剂。
抗菌剂在表面中的浓度、特别是在软管表面层中的浓度可以与抗菌剂的活性和保持时间相匹配。一般地,抗菌剂在表面材料中的质量浓度在0.01至10%的范围内,特别在0.1至2%的范围内。
卫生软管在其端部通常具有连接头以便安装。例如,淋浴软管在其端部通常设有软管螺纹接头,通过该螺纹接头该淋浴软管可以在一端连接到手拉喷头上,在另一端与供水管连接。按本发明的软管优选是不透明或不透光的,因此软管内不会产生不受欢迎的藻类,于是抗菌剂的效果可以全部用来消灭有害细菌。
本发明其它的优点和特征由下面对优选实施方式的描述结合从属权利要求和附图获得。在这里,单个的特征可以分别单独实现,或者将多个特征相互组合在相关的实施方式中实现。
在图中所示的本发明的实施方式中,示意性地示出了一种用于生产根据本发明的软管的例子。这里涉及淋浴软管的连续生产。从连续的软管上切出所需长度的淋浴软管,并且软管端部以常用的方式设有螺纹接管以便使用。按本发明的软管是一种双层壁淋浴软管1,其具有一个由黑色软聚氯乙烯制成的内管2、一个由透明的软聚氯乙烯制成的外管3和一个位于它们之间的由硬聚氯乙烯制成的增强线圈4。增强线圈4的外表面可以用铝进行气相喷镀或者配有铝箔,以便获得金属外观。
淋浴软管以根据传统方法的原理通过挤压机制造,在现有的情况下可以进行特殊的装备。挤压机螺杆或螺杆对(没有示出)驱动用于形成内管2的熔融物质5穿过环形喷嘴6,在该环形喷嘴6内部有一个芯轴7,通过该芯轴7形成软管空腔8。在软管空腔8内维持升高的内压以防止软管塌陷。加强带9缠绕在仍旧暖和的内管2上,同时构成加强线圈4,随后,通过一个由共挤压喷嘴构成的第二环形挤压喷嘴10使外管3在加强线圈4上形成,并且外管6容易与加强线圈4粘附在一起。
共挤压喷嘴10由独立的挤压机供给两种不同的软聚氯乙烯熔液,准确地说,一种在环形道通11中的普通聚氯乙烯熔液和一种在环形通道12中的掺入抗菌剂的熔液。相应地,在本实施方式中,根据本发明的淋浴软管的外管3是双层结构。通过环形通道11进入的熔液形成外管3的底层13,该底层13与加强线圈4接触。形成软管外表面的顶层14远比底层13薄,但是由于采用相同的基材进行共挤压导致固定连接到底层。
顶层或表面层14的熔液由聚氯乙烯颗粒形成,其中嵌入质量百分比为1%的银颗粒。银颗粒平均尺寸范围为50至100μm。该熔液形成的顶层或表面层的层厚在0.3mm的范围内。
对于内管2的结构,可以采用已经含有抗菌剂的颗粒。在这种情况下,非特别起作用的有机化合物如三氯生(2,4,4’三氯-2’-羟基二苯醚)或PHMB(聚六亚甲基双胍盐酸盐)形式的抗菌剂是合适的。
相反,在图示的实施方式中,只要其预先形成但仍以熔液5的形式存在,内管的内表面中就会嵌有抗菌剂。从挤压机外部引出的计量管15引入芯轴7,并且通过多个径向的单个喷嘴到达芯轴7的外表面。通过施加压力,粉末状或糊状的抗菌剂可以挤出径向喷嘴16,并且在那里被通过的熔液清扫和吸收,特别是熔入其中以形成内表面17。抗菌剂同样可以通过预先例如与聚氯乙烯粉末混合并融合在其中以熔液的形式存在。因此,在这里颗粒形式的银同样适合作为抗菌剂。银可以以金属形式和盐的形式存在,或以具有足够溶解力的复合物的形式存在,用以在开始就达到良好抗菌作用,如果这样要求的话。如果需要,径向喷嘴16可以组合成径向环形喷嘴。当内管的整个内表面打算装配抗菌剂时这点就有好处。

Claims (19)

1.由柔性塑料制成的卫生软管,特别是淋浴软管,具有一个内表面(17)和一个外表面(14),并且具有一种抗菌保护层,其特征在于,将至少一种抗菌剂嵌入至少内表面(17)的材料中。
2.如权利要求1中所述的卫生软管,其特征在于,所述抗菌剂也嵌入外表面(14)的材料中。
3.如权利要求1或2所述的卫生软管,其特征在于,所述软管是一种至少双层壁的软管(1),尤其是一种双层壁的软管(1)。
4.如前述权利要求中任一项所述的卫生软管,其特征在于,所述抗菌剂仅仅在至少一个表面(14、17)的区域内嵌入软管的材料中。
5.如前述权利要求中任一项所述的卫生软管,其特征在于,所述抗菌剂是射入表面中的。
6.如前述权利要求中任一项所述的、尤其是权利要求1到4中任一项所述的卫生软管,其特征在于,所述内和/或外表面由含有抗菌剂的表面层(14)形成。
7.如权利要求6所述的卫生软管,其特征在于,所述表面层(14)由与软管的底层(13)相同的塑料制成。
8.如前述权利要求中任一项所述的卫生软管,其特征在于,所述柔性塑料是一种柔性热塑性塑料和/或热塑性弹性体。
9.如权利要求6至8中任一项所述的卫生软管,其特征在于,所述表面层(14)由热塑性塑料制成,特别是挤压到底层(13)上。
10.如权利要求6至9中任一项所述的卫生软管,其特征在于,所述表面层(14)与底层(13)相连接。
11.如权利要求6至10中任一项所述的卫生软管,其特征在于,所述表面层(14)与底层(13)通过共挤压连接。
12.如前述权利要求中任一项所述的卫生软管,其特征在于,所述至少一种抗菌剂以从表面向内降低的浓度存在。
13.如权利要求6至12中任一项所述的卫生软管,其特征在于,所述抗菌剂熔入形成表面层(14、17)的塑料组分中。
14.如权利要求6至13中任一项所述的卫生软管,其特征在于,所述表面层(14)的层厚为0.05至1mm。
15.如前述权利要求中任一项所述的卫生软管,其特征在于,所述抗菌剂以颗粒形式存在,其颗粒尺寸尤其在5μm至200μm的范围内。
16.如前述权利要求中任一项所述的卫生软管,其特征在于,所述至少一种抗菌剂是一种金属和/或一种金属盐,特别是银。
17.如前述权利要求中任一项所述的卫生软管,其特征在于,所述至少一种抗菌剂是一种非特定的有机抗菌剂。
18.如前述权利要求中任一项所述的卫生软管,其特征在于,所述至少一种抗菌剂以至少两种抗菌剂的混合物的形式存在。
19.如前述权利要求中任一项所述的卫生软管,其特征在于,所述抗菌剂存在于表面(14)中,特别是在表面层中,质量浓度范围为0.01至10%,特别为0.1至2%。
CNA2005800208808A 2004-06-23 2005-06-23 由柔性塑料制成的具有抗菌保护层的卫生软管 Pending CN1981152A (zh)

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