CN100486803C - 叠层布帛 - Google Patents
叠层布帛 Download PDFInfo
- Publication number
- CN100486803C CN100486803C CNB038082500A CN03808250A CN100486803C CN 100486803 C CN100486803 C CN 100486803C CN B038082500 A CNB038082500 A CN B038082500A CN 03808250 A CN03808250 A CN 03808250A CN 100486803 C CN100486803 C CN 100486803C
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- China
- Prior art keywords
- layer cloth
- clothing
- film
- cloth
- top layer
- 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
本发明提供了叠层布帛,该布帛的特征是,具有在耐久薄膜的一面通过用于暂时粘接的粘合剂层层叠了表层布料,并且在该耐久薄膜的另一面通过耐久粘合剂层层叠了内层布料的结构。
Description
技术领域
本发明涉及具有优良的质感,同时又兼具防污性、防风性、柔软性、生产性、耐久性等的叠层布帛、衣物及该衣物的制造方法。
背景技术
通过用粘合剂在布帛上层叠防水性薄膜或涂布防水性的涂层,以提供防水性·防风性的布帛的技术是较常用的技术。经过这些加工,易于使布料具有防水性·防风性,但同时会破坏原布料的质感及悬垂性,如使布料硬梆梆的、厚墩墩的等。
在日本专利特公平6—61909号公报(文献1)中提出了一种解决该问题的方法,即在粗斜纹布基布的内面通过非水溶性粘合剂层贴合塑料薄膜,在该塑料薄膜的另一表面用水溶性粘合剂贴合内层布料,裁剪获得的叠层物,缝制后进行水洗,使水溶性粘合剂溶解,由此只剥离内层布料,就能够获得柔软质感的牛仔布料。
但是,文献1的方法中,表层布料采用粗纤度纤维的布料或目付(日本织物单位面积重量)大的布料,或看起来象斜纹绫绸、网眼织物等组织、提花织物的更具时尚性、装饰性的布料时,由于布料粘合面的凹凸增大,因此要以足够的粘合强度将塑料薄膜和表层布料粘合在一起,就必须增加非水粘合剂的涂布量,这样会使叠层布帛的质感变硬,从而难以获得使质感柔软的效果。而且,增加层叠时粘合剂的涂布量还会导致材料费的成本上升。
据文献1所述,缝制后经水洗除去水溶性粘合剂,层叠的内层布料从塑料薄膜剥离成为单独的结构,这种情况下,为了防止在该内层布料因穿着及洗涤产生滑移,必须预先对其进行树脂加工,如涂布丙烯酸树脂及利用防滑剂进行处理等,提高该内层布料的密度。上述处理不仅会缩小内层布料的选择余地,还会使布料本身的价格增高,以及产生多种缺陷,如布料的质量增加、透湿性降低、质感和手感差等。
随着经常穿着,衣服的表层布料侧会受到油及泥等污染物的污染,对文献1的叠层布帛而言,表层布料和塑料薄膜经采用非水溶性粘合剂进行层叠加工,总是处于贴合状态,一旦表层布料受到污染,则在洗涤时含洗涤剂的洗涤液受到塑料薄膜的阻碍无法通过表层布料,因此在纯布料很容易除去的污垢也难以洗去,有时成为污渍残留在表层布料和塑料薄膜间。而且,为洗去污垢进行长时间的洗涤时,会促进衣服的摩擦,使衣服本身的使用寿命降低。
衣服在长期地使用过程中,随着磨损、破损等造成的损伤或流行的变化,最终将不再被使用。对不再使用的衣服从环保的角度而言最好将其材料进行再循环。再循环有材料再循环和热再循环,要进行前一再循环必须对该材料进行分类回收。即,要以不再使用的衣服的原料作为原材料进行再循环,就必须将层叠在一起的布料和塑料薄膜分离。在文献1的叠层布帛中,内层布料原本就和塑料薄膜分离,容易回收,但是质量比率高于内层布料的表层布料和塑料薄膜由非水溶性粘合剂牢固地粘合在一起,因此不易于分离,这样就难以高效率地回收材料。
而且,在将衣服用作驾车用及户外用的衣服时,不仅防风性,防水性也成为重要的功能。一般,防水性布料的衣服的缝制部(衣服的内面)用填缝带进行防水加工,但文献1的叠层布帛的衣服的缝制部由于要采用水洗从塑料薄膜剥离内层布料,因此不能进行填缝加工。
本发明的目的就是提供质感柔和,且制造成本低的高功能性叠层布帛及衣物,同时提供该衣物的制造方法。
发明的揭示
本发明者为了解决前述课题,研究了各种使布料和塑料薄膜等耐久薄膜的叠层布帛的质感、耐久性、防污性、防风性、防水性、耐久性、再循环率等提高的方法,结果发现,用水溶性粘合剂等进行暂时粘接的粘合剂粘合作为表层布料的布帛和耐久薄膜,在耐久薄膜的另一面用非水溶性粘合剂等耐久粘合剂贴合作为内层布料的布帛,由此加工而成的叠层布帛能产生出以往无法想象的效果。
即,粗纤度纤维的布料或目付(日本织物单位面积重量)大的布料,或看起来象斜纹绫绸、格纹织物等组织、提花织物的更具匠心性的布料等的表面的凹凸大,但采用水溶性粘合剂等进行暂时粘接的粘合剂进行这种布料和耐久薄膜的粘合加工,并且用非水溶性粘合剂等耐久粘合剂对内层布料和耐久薄膜进行粘合加工所形成的叠层布帛经裁剪、缝制,成为衣物后,再进行水洗等后加工,使薄膜和表层布料剥离,则不会破坏其表层布料的质感,从而能够制得具有更柔软的质感、悬垂感的衣物。
而且由于内层布料用耐久性粘合剂和耐久薄膜粘合在一起,因此即使是薄的织物或针织物,也不会发生滑移、洗涤等过程中的尺寸变化等问题,这是因为它们中的每根线都通过耐久性粘合剂和薄膜固定在一起。因此,无需用于防止高织密度化及滑移的后加工,而这在以往技术中是必须的,并且布料的选择范围广,这样就能够实现低成本化。
本发明就是基于如上所述的发现完成的。
即本发明提供以下所示的叠层布帛、衣物及衣物的制造方法。
(1)叠层布帛,该布帛的特征是,具有在耐久薄膜的一面通过用于暂时粘接的粘合剂层层叠了表层布料,并且在该耐久薄膜的另一面通过耐久粘合剂层层叠了内层布料的结构。
(2)如上述(1)所述的叠层布帛,该耐久薄膜是防水透湿性薄膜。
(3)如上述(2)所述的叠层布帛,该防水透湿性薄膜是多孔质聚四氟乙烯薄膜。
(4)如上述(3)所述的叠层布帛,该多孔质聚四氟乙烯薄膜的骨架表面用防水·防油剂包覆。
(5)如上述(3)或(4)所述的叠层布帛,在该多孔质聚四氟乙烯薄膜的一面或两面设置了亲水性树脂的连续被膜。
(6)如上述(1)~(5)中任一项所述的叠层布帛,该表层布料的目付(日本织物单位面积重量)比该内层布料的目付大。
(7)如上述(1)~(6)中任一项所述的叠层布帛,该表层布料为织物,且该内层布料为针织物。
(8)如上述(1)~(7)中任一项所述的叠层布帛,该用于暂时粘接的粘合剂为水溶性粘合剂。
(9)衣物,该衣物的特征是,由上述(1)~(8)中任一项所述的叠层布帛制得。
(10)如上述(9)所述的衣物,该衣物的接缝部分的一部分或全部用填缝带进行填缝处理。
(11)如上述(9)或(10)所述的衣物,该衣物经用于剥离该表层布料和该耐久薄膜的后处理,剥离了该表层布料和该耐久薄膜。
(12)如上述(11)所述的衣物,该用于暂时粘接的粘合剂为水溶性粘合剂,该后处理为水洗处理。
(13)如上述(9)~(12)中任一项所述的衣物,该衣物为雨衣或防寒衣。
(14)衣物的制造方法,该方法的特征是,裁剪上述(1)~(8)中任一项所述的叠层布帛,经缝制,制成衣物后,通过后处理剥离该表层布料和该耐久薄膜。
(15)衣物的制造方法,该方法的特征是,裁剪上述(1)~(8)中任一项所述的叠层布帛,缝制后,用填缝带进行接缝的填缝处理,制成衣物,然后通过后处理剥离该表层布料和该耐久薄膜。
附图的简单说明
图1为本发明的叠层布帛的结构示意图,图2为本发明的叠层布帛的缝合部填缝后的状态示意图。
发明的最佳实施方式
本发明的叠层布帛由耐久薄膜、表层布料、内层布料构成,该布帛的特征是,该表层布料通过用于暂时粘接的粘合剂层层叠在该耐久薄膜的一面,该内层布料则通过耐久粘合剂层层叠在该耐久薄膜的另一面。
在作为衣物实际使用时,本发明的叠层布帛的表层布料和耐久薄膜是处于剥离的状态,因此即使在表层布料上附着有污垢,也能够在洗涤时使洗涤液通过表层布料而洗净表层布料,因此能够和普通的衣物一样通过洗涤除去污垢。
由于用本发明的叠层布帛制成的衣物穿旧后最终进行材料再循环时,能够较容易地回收表层布料,因此能够以高回收率进行材料回收。
本发明的叠层布帛由于能够极大地降低作为内层布料的布料的密度,并且内层布料和薄膜由耐久性粘合剂总是粘合在一起,因此通过用填缝带对缝制部进行填缝,能够填盖缝制时所产生的针孔,使其具备防风性、防水性。
接着,利用附图详细说明本发明。
图1为本发明的叠层布帛1a的结构模式示意图。该叠层布帛的表层布料1和耐久薄膜3通过用于暂时粘接的粘合剂2粘合在一起,耐久薄膜3的背面和内层布料5通过耐久粘合剂4粘合在一起。
在经裁剪、缝制,加工成衣物的形态为止,上述叠层布帛1a一直保持表层布料、薄膜及内层布料分别由用于暂时粘接的粘合剂、耐久粘合剂连接成为一体的状态。但由于该叠层布帛的表层布料1和薄膜3由用于暂时粘接的粘合剂2暂时粘结,因此能够根据需要使表层布料1和薄膜3剥离。剥离后的表层布料1独立于薄膜3存在,因此其质感、悬垂性不会受薄膜3影响,可保持表层布料自身的质感、悬垂性。
上述叠层布帛在到裁剪·缝制为止的工序中能够作为叠层布帛这一整体进行加工,因此相比于分别裁剪表层布料、内层布料,再将这些部分彼此间合在一起进行缝制的方法能够更简便地制成衣物。
而且,上述叠层布帛由于其薄膜3由耐久粘合剂4与内层布料粘固在一起,因此对拉伸、撕扯等来自外部的物理应力具有较高的耐久性。
图2为对本发明的叠层布帛的缝制部进行填缝加工后的剖面结构模式图。在该图中,叠层布帛1a端部的折回部分和表层布料彼此重合,由缝制部7缝合,叠层布帛1a的折回部分的内侧(内层布料侧)采用填缝带6进行填缝处理以覆盖缝制部及叠层布帛的端部。这样能够防止水滴及空气从在缝制部分所开的针孔流入,可使其具备防风性、防水性。
用作本发明的叠层布帛的构成材料的耐久薄膜为在通常的使用条件下不容易发生变质及破损的薄膜。一般采用高分子薄膜,有时也可采用金属薄膜,以及金属和高分子薄膜的复合薄膜等,可按照叠层布帛的用途选择适宜的。
在上述高分子薄膜中,其厚度可根据叠层薄膜的用途进行适当选择,但通常为5~500μm,将叠层布帛用作衣物材料时,一般为5~300μm,最好为10~100μm。
高分子薄膜的材料可采用以往公知的各种材料。这些材料例如有聚氨酯系树脂、丙烯酸系树脂、聚氯乙烯系树脂、聚酯系树脂、聚乙烯系树脂、聚丙烯系树脂、含氟树脂、聚酰胺树脂、聚酰亚胺树脂等。
在前述高分子薄膜的内部可以含有填充剂、阻燃剂、着色剂、除臭剂、抗菌剂、导电剂、防氧化剂等。此外,该薄膜可以是通气性及透湿性的薄膜。
将本发明的叠层布帛用于防水透湿性的衣物时,较好的是使用由聚氨酯系树脂、聚酯系树脂、含氟树脂等形成的防水透湿性薄膜,其中特别好的是使用多孔质聚四氟乙烯薄膜,其防水性和透湿性及其耐久性优良。
多孔质聚四氟乙烯薄膜的最大细孔径为0.01~10μm,较好为0.1~1μm。前述最大细孔径如果小于0.01μm,则制膜上有难度,反之如果超过10μm则薄膜的耐水度降低,薄膜强度变弱,由此使层叠等后工序中的操作变得困难,因此不理想。多孔质聚四氟乙烯薄膜的空孔率为50~98%,较好为60~95%。最大细孔径的测定方法按照ASTM F-316的规定,空孔率的测定方法为由依据JIS K 6885的表观密度测定测得的表观密度(ρ)用下式计算求得。
空孔率(%)=(2.2—ρ)/2.2×100(1)
多孔质聚四氟乙烯薄膜的空孔率如果小于50%,则透湿性降低,反之如果超过98%则膜的强度降低。
多孔质聚四氟乙烯薄膜的厚度为5~300μm,较好为10~100μm。多孔质聚四氟乙烯薄膜的厚度如果小于5μm,则制造时的可操作性发生问题,如果超过300μm则会破坏薄膜的柔软性,并且透湿性降低。
薄膜厚度的测定采用由度盘式指示表测得的平均厚度(采用テクロツク公司制1/1000mm表盘式厚度规,在没有加本体弹性荷重以外的荷重的状态下测得的)。
使用时最好使防水性及防油性聚合物被覆在上述多孔质聚四氟乙烯薄膜的细孔内表面。这种情况下,该聚合物可以采用具有含氟支链的聚合物。这种聚合物及将其与多孔质薄膜复合化的方法的详细说明公布于WO94/22928公报等,下述为其一例。
被覆用聚合物较好的是采用由下述通式(1)
(式中,n为3~13的整数,R为H或甲基)表示的氟烷基丙烯酸酯及/或氟烷基甲基丙烯酸酯聚合得到的含氟树脂聚合物(氟烷基部分最好具有6~16个碳原子)。要采用该聚合物被覆多孔质薄膜的细孔内部,使用含氟表面活性剂(例如,全氟辛酸铵)形成该聚合物的水性微细乳浊液(平均粒径0.01~0.5μm),使其含浸于多孔质薄膜的细孔内,然后加热。由此,除去水和含氟表面活性剂,同时含氟聚合物溶融,被覆多孔质薄膜的细孔内表面,获得保持连续孔的防水性·防油性优良的多孔质薄膜。也可以使用其它的聚合物,如[AF聚合物](杜邦公司的商品名)及[サイトツプ](旭硝子公司的商品名)等。要将这些聚合物被覆在高分子多孔质膜的细孔内表面,可以使这些聚合物溶解于例如[フロリナ—ト](3M公司的商品名)等非活性溶剂,使其含浸于高分子多孔质薄膜后,再蒸发除去溶剂。
通过用上述有机聚合物被覆多孔质聚四氟乙烯薄膜的细孔内表面,能够在该多孔质薄膜受到各种污染物污染时,使污染物难以浸透到多孔质薄膜的内部,防止多孔质薄膜的疏水性的劣化。
前述多孔质聚四氟乙烯薄膜可以是在其一面形成有亲水性树脂被膜的复合膜。
前述亲水性树脂是具有羟基、羧基、磺酸基、氨基酸基等亲水性基的高分子材料,最好采用水膨润性、且水不溶性的树脂。具体来说例如有至少一部分经过交联的聚乙烯醇、乙酸纤维素、硝酸纤维素等亲水性聚合物,以及亲水性聚氨酯树脂,如果考虑耐热性、耐药性、加工性、透湿性等,则亲水性聚氨酯树脂特别理想。
亲水性聚氨酯树脂可采用含羟基、氨基酸基、羧基、磺酸基、氧乙烯基等亲水基的聚酯系或聚醚系的聚氨酯或预聚物,为了调整树脂的熔点(软化点),可以单独或混合使用具有2个以上异氰酸酯基的二异氰酸酯类、三异氰酸酯类、它们的加成化合物体作为交联剂。对末端为异氰酸酯的预聚物可以使用2官能团以上的二醇类、三醇类及二胺类、三胺类作为固化剂。为了保持较高的透湿性,2官能团的比3官能团的好。
使亲水性聚氨酯树脂等亲水性树脂含浸添加在多孔质聚四氟乙烯薄膜的多孔结构中的方法是,利用溶剂将聚氨酯树脂等形成溶液,通过加热进行熔液化,制成涂布液,采用辊涂等将其涂布于多孔质聚四氟乙烯薄膜。在涂布温度下,适于含浸添加的涂布液的粘度较好为20000cps以下,更好为10000cps以下。用溶剂进行溶液化时还依赖于溶剂组成,但如果粘度过低,则涂布后溶液扩散到整个多孔质聚四氟乙烯薄膜,使整体具有亲水性,很有可能影响防水性,因此最好保持500cps以上的粘度。粘度的测定采用东机产业株式会社制的B型粘度计。
这样制得的复合膜,能够利用在多孔质聚四氟乙烯的至少一面形成的亲水性树脂层,防止多孔质聚四氟乙烯薄膜被体脂及机械油、饮料等各种污染物亲水化,而且由于薄膜的机械强度也得到提高,因此耐久性优良。
本发明的叠层布帛所用的表层布料可酌情使用以往公知的各种布状物。对该表层布料的材料也没有特别的限制,可酌情使用天然纤维及合成纤维、金属纤维、陶瓷纤维等。
前述表层布料除了可以是织布及针织布、网眼织物等外,也可以是无纺布、毛毡等。可按照叠层布帛的用途选择合适的。
前述合成纤维较好采用聚酰胺系、聚酯系、聚氨酯系、聚烯烃系、聚氯乙烯系、聚偏氯乙烯系、聚氟化碳系、聚丙烯酸系等纤维。天然纤维较好采用棉、麻、兽毛、绢等纤维。从美观和强度、耐久性、成本上出发,由棉、尼龙(聚酰胺)、聚酯等原材料形成的织布更好。
表层布料用进行暂时粘接的粘合剂和薄膜层叠在一起后,从薄膜剥离,作为独立于薄膜的单独的布料被实际使用,因此要求表层布料为难以因洗涤等负荷发生滑移等的布料。本发明者发现了洗涤引起的滑移的易发程度和布料的目付(坪量)有关系。本发明所用的表层布料较好为具有40~400g/m2的目付的布料,更好为60g/m2以上的布料。布料的目付如果未满40g/m2,则密度过低,产生滑移,磨损耐久性不够,制成衣物时会产生质量问题。目付如果超过400g/m2,就会失去叠层布帛的轻量性,而且质感也变硬,因此不理想。
根据需要,可以对表层布料进行以往公知的防水处理、防静电处理等。
本发明的叠层布帛所用的内层布料可酌情采用和前述表层布料同样的原材料,但用于衣物时,特别好的是使用针织布。由于衣物中的内层布料是与肌肤接触的面,因此无需象表层布料那样太注重外观。此外,如果将衣物用作雨衣等,在粘合或熔接填缝带时,作为粘合面的内层布料面使用网纹粗的原材料能提高填缝带的密封性,因此可以采用网纹比织布等粗的针织布。此外,使用针织布时比织布等更能使叠层布帛轻量化,还有成本低的优点。
在本发明的叠层布帛中,用于将耐久薄膜和表层布料暂时粘合的用于暂时粘接的粘合剂只要是在粘合后能使两者剥离的用于暂时粘接的粘合剂既可,能够使用以往公知的各种粘合剂。这种粘合剂例如有,粘合强度因水而降低的粘合剂、粘合强度因加热而降低的粘合剂、粘合强度因紫外线而降低的粘合剂等。叠层布帛用于衣物的情况下,较好采用粘合强度因水而降低的水溶性粘合剂。
前述水溶性粘合剂可以采用以往公知的各种水溶性粘合剂。这种粘合剂例如有聚乙烯醇、聚丙烯酰胺、聚环氧乙烷、聚乙烯吡咯烷酮、水性乙烯尿烷系、淀粉系、羧甲基纤维等,它们可以单独使用,也可以2种以上混合使用。将粘合剂涂布于薄膜时的粘合剂的粘度只要是在可涂布于薄膜的范围内的粘度既可,通常在室温下的粘度为500cps~5000cps,较好为2000cps左右。在室温即使是5000cps以上的粘度,通过提高涂布温度(加热)也能够进行涂布。此外,粘合剂的固形成分较好为5wt%以上,更好为10wt%以上。如果干燥后的固形成分未满5wt%,则表层布料和薄膜的粘合性不够,可能会妨碍叠层物的处理。例如,在进行裁剪等加工时,如果表层布料从薄膜剥离,则在其后的缝制工序中难以进行缝制加工。此外,也可以在前述水溶性高分子粘合剂中添加作为添加剂的表面活性剂、粘合剂、增稠剂。特别是在粘合疏水性高的高分子薄膜及表层布料时,最好在前述水溶性高分子粘合剂中添加表面活性剂及粘着剂。由此,能够使高分子粘合剂的表面张力降低,提高对基材的附着力。在将粘合剂粘度控制在前述适合粘度时,可以使用增粘剂。
本发明的叠层布帛中,用于粘合耐久薄膜和内层布料的耐久粘合剂只要是在通常的使用条件下粘合强度不易降低的耐久粘合剂既可,可以使用以往公知的各种粘合剂。一般采用非水溶性的粘合剂。在这种水溶性粘合剂中除了热塑性树脂之外,还包含利用热及光等固化的固化性树脂。
非水溶性粘合剂的具体例,例如可酌情采用聚酯系、聚酰胺系、聚氨酯系、硅系、聚丙烯酸系、聚氯乙烯系、聚丁二烯系、橡胶系、聚烯烃系等各种树脂。
聚氨酯系粘合剂特别好的是采用固化反应型热熔粘合剂。这种固化反应型热熔粘合剂是在常温下为固体状,加热溶融后成为低粘度的液体,通过保持这种状态或进一步升温发生固化反应,成为高粘度的液体或固化物的粘合剂。这种情况下,加热溶融时,即向内层布料涂布之前的溶融液的粘度为500~30000cps,较好为500~3000cps,另一方面该溶融液高粘度化时,即使用该溶融液层叠薄膜和内层布料时的溶融液的粘度为500~20000cps,较好为10000cps以上。
前述溶融液的固化反应在固化催化剂及固化剂、水分的存在下进行。
前述的固化反应型粘合剂是目前已知的粘合剂。其较好的例子是利用湿气(水分)发生固化反应的聚氨酯预聚物。该聚氨酯预聚物能够通过(I)聚酯多元醇及聚醚多元醇等多元醇成分,和(II)甲苯二异氰酸酯(TDI)、亚甲基双苯基二异氰酸酯(MDI)、二甲苯二异氰酸酯、异氟尔酮二异氰酸酯等脂肪族或芳香族系的二异氰酸酯及三异氰酸酯等聚异氰酸酯成分进行加成反应而获得。这种情况下,该聚氨酯预聚物的末端具有异氰酸酯基,在湿气的存在下发生固化反应。该聚氨酯预聚物的溶融温度应略高于室温,在50℃以上,较好为80℃~150℃。这种聚氨酯预聚物可以使用由日本ェヌェスシ—株式会社制的[ボントマスタ—]。通过将该聚合物加热至70~150℃,形成可向基材涂布的粘度的溶融液,用该溶融液贴合表层布料和高分子薄膜后,冷却至室温,形成半固体状,能够防止粘合剂向布料过度的浸透扩散,而且通过进行湿固化处理能够以较柔和的状态获得牢固的粘接。
耐久薄膜和内层布料的粘合只要是如前所述的具有粘合耐久性的方法既可,可以利用热量熔化内层布料及/或耐久薄膜进行热熔接。
使薄膜和表层布料暂时粘合的粘合剂的涂布方法,可采用以往公知的各种方法,例如辊涂法、喷涂法、刷涂法等。
为了较好地进行薄膜和表层布料的暂时粘合,可酌情采用例如在薄膜上用形成有凹印图案的涂辊涂布水溶性粘合剂,在其上贴合表层布料,用压辊压接,然后加热干燥的方法;或在薄膜上喷涂水溶性粘合剂,在其上贴合表层布料,用压辊压接,然后加热干燥的方法。
用于暂时粘接的粘合剂的印刷量(涂布量)还必须考虑表层布料的凹凸、相关粘合性的亲水性·疏水性等特性、粘合剂的表面张力、粘度等,但通常为5~100g/m2,更好为10~30g/m2。用于暂时粘接的粘合剂的印刷量如果未满5g/m2,则粘合力不足,如果超过100g/m2,则粘合剂从表层布料渗出,发生粘合剂附着于加工装置的压辊上等问题。此外,涂布量多会导致材料费用上升。
使薄膜和内层布料持久粘合的粘合剂的涂布方法可采用以往公知的各种方法,例如辊涂法、喷涂法、刷涂法等。
为了较好地进行薄膜和内层布料的持久粘合,可酌情采用例如在薄膜上用形成有凹印图案的涂辊涂布聚氨酯系粘合剂,在其上贴合内层布料,用压辊压接的方法;或在薄膜上喷涂聚氨酯系粘合剂,在其上贴合内层布料,用压辊压接的方法等。
将薄膜和内层布料热熔接时,可酌情采用以往公知的方法,如在将薄膜和内层布料合在一起的状态下用热辊进行热熔接的热辊涂法及火焰熔接法等。
从质感、粘合力、有效利用率等观点出发,本发明的叠层布帛中的内层布料和薄膜的粘合加工,较好采用如下的方法,即用形成有凹印图案的涂辊涂布聚氨酯系粘合剂,在其上贴合内层布料,再用压辊压接的方法。
用粘合剂使内层布料和薄膜层叠粘合时,内层布料和薄膜的粘合是点状粘合及线状粘合等部分粘合,其粘合面积为10~95%,较好为15~50%。此外,粘合剂的印刷量必须考虑内层布料的凹凸、纤维的密度、粘合性、耐久性等以求最优化,一般为2~50g/m2,较好为5~20g/m2。印刷量如果超过50g/m2,则叠层布帛的质感变得过硬,不理想。而如果未满2g/m2,则粘合性不足,不能获得经得起洗涤的耐久性。
前述内层布料和薄膜间的粘合耐久性的评价,可以通过用普通的洗衣机反复进行洗涤来确认布帛有无发生剥离等的方法进行。本发明的薄膜和内层布料的叠层布帛的粘合耐久性使用ISO6330记载的B类家庭用洗衣机、KenmoreModel 110.20912(SEARS ROEBUCK AND CO制),在浴比1/60、浴温45℃以下,以Heavy-Duty(强力)模式,用不添加洗涤剂的自来水进行连续搅拌洗涤时,目视观察到发生剥离前的时间在50小时以上,较好为100小时以上。
在本发明中,作为制作叠层布帛的工序,可以是用用于暂时粘接的粘合剂层叠表层布料和薄膜,然后在所得到的薄膜和表层布料的叠层布帛上,用耐久粘合剂层叠内层布料的方法;以及用耐久粘合剂层叠内层布料和薄膜,然后用用于暂时粘接的粘合剂将所得到的薄膜和内层布料的叠层布帛与表层布料层叠在一起的方法中的任一种。用于暂时粘接的粘合剂使用水溶性粘合剂时,在其干燥工序中要加热除去水分,因此当耐久粘合剂是聚氨酯系的湿固化热熔型粘合剂,在其处于未固化的状态下必须预先考虑热的影响。
本发明的叠层布帛可以用作各种衣物用原材料。使用本发明的叠层布帛制作衣物的方法可以采用包括裁剪、缝制工序等的以往公知的方法,该衣物为要求具有防水性及防风性的雨衣及防寒衣时,最好对衣物的接缝部分的一部分或全部用填缝带进行填缝处理。
使本发明的叠层布帛互相缝合时,该缝合采用缝纫机等进行缝制加工。缝制线可以采用棉、绢、麻、尼龙、聚酯、维尼纶、粘液丝、聚氨酯等单独或者混合而成的材质,从强度、耐热性出发,较好的是使用尼龙系、聚酯系等。线的粗细必须根据所要缝合的布料的厚度和所要求的产品强度进行调整,作为一个示例,在缝合具有以下结构的布料时,最好使用233分特的缝制线,上述结构为在表层布料(78分特的尼龙塔夫绸)的一面用用于暂时粘接的粘合剂层叠拉伸的多孔质聚四氟乙烯,再用耐久粘合剂层叠内层布料(25分特尼龙特里科经编织物)。
缝合方法为使用1根或多根线进行缝合。针脚形式可以酌情采用平缝、单线链缝、双线链缝等,缝制加工成直线状、曲线状、锯齿形状等。
前述填缝带可酌情采用由高熔点树脂的表皮和低熔点树脂层叠而成的填缝带等。可以在前述高熔点树脂的表面层叠针织物及网眼织物等。例如高熔点树脂使用聚氨酯树脂薄膜、低熔点树脂使用聚氨酯热熔物的SAN CHEMICAL公司制商品名为T-2000、FU-700的产品,以及日清纺织公司制商品名为MF-12T、MF-12T2、MF-102F的产品;高熔点树脂采用多孔质聚四氟乙烯薄膜、低熔点的粘合树脂采用聚氨酯热熔物的ジヤパンゴアテツクス公司制GORE-SEAMTAPE等。
前述填缝带的热熔部分的树脂厚度较好为25μm~40μm,更好为50μm~200μm。热熔物层如果未满25μm,则树脂的绝对量过少,不能以足够的粘合强度将内层布料彼此间及缝合部的线的凹凸部粘合在一起。而如果热熔物层的厚度超过40μm,则在热压接填缝带时需要较长的时间才能充分溶解,加工性降低。如果缩短热压接时间,则片材不能充分溶解,无法获得足够的粘合强度。此外,粘合加工后的填缝部的质感变硬,如果用于制作衣物,则在填缝部会硬梆梆的。
这些填缝带可以采用现有的热空气密封器进行熔接加工,其加工过程是用热风吹填缝带的热熔物侧,在使树脂溶融的状态下,用压辊压接层叠于非粘合体。例如可以使用クインライト电子精工公司制的クインライトModelQHP-805及W.L.GORE&ASSOCIATES公司制MODEL 5000E等。
要更简便地对短的缝合部进行熔接加工,可以用市场上出售的熨斗进行填缝加工。这时将填缝带重叠在缝合部,从其上加热。
前述填缝带的热压接条件可以根据填缝带所用的热熔物的熔点、防水布料的厚度、材质、熔接速度等进行适当设定。下面例举一个填缝带热压接的例子,在表层布料(78分特的尼龙塔夫绸)的一面用水溶性粘合剂层叠多孔质聚四氟乙烯膜、再用非水溶性粘合剂层叠内层布料(25分特的尼龙特里科经编织物)而形成的叠层布帛中,用前述填缝带将其尼龙特里科经编织物彼此间热压接时,将填缝带(较好为聚酯聚氨酯系热熔物、180℃时的流动值为40~200×10-3cm3/s,更好为100×10-3cm3/s,厚度为25~200μm,更好为50~150μm)装入热空气密封器,将热熔树脂的表面温度设定在150℃~180℃,更好为160℃进行热压接。然后,加热部分直接放置冷却到室温,完成热压接。热熔物的流动值如果过低则粘合力不足,如果过高则树脂从缝制孔渗出附着于压辊等。此外,热熔树脂的表面温度如果过低,则溶解不充分,使粘合力不足,如果过高则流动性过高,会发生树脂从缝合部分渗出的问题,并且还会引起热熔树脂自身热分解,粘合强度降低。
本发明的叠层布帛制成的衣物在该衣物制作后进行后处理以使其耐久薄膜和表层布料间剥离。这种情况下,该后处理可以根据将薄膜和表层布料暂时粘合在一起的用于暂时粘接的粘合剂的种类采用合适的方法进行。例如,如果该用于暂时粘接的粘合剂会因水的作用而使其粘合强度降低,就可以进行水洗,如果因热的作用而使其粘合强度降低,就可以进行热处理,如果因紫外线的作用而使其粘合强度降低,就可以进行紫外线照射。
对由采用作为用于暂时粘接的粘合剂的水溶性粘合剂形成的叠层布帛制成的衣物而言,其后处理可以通过一般的水洗进行。例如,采用本发明的叠层布帛制造清洗工序包含在制造阶段的牛仔衣物时,可以将清洗工序直接用作薄膜和表层布料的剥离工序。这时,为了完全除去该水溶性粘合剂,可以在水中添加脱浆剂等洗涤添加剂。此外,还可以和酶漂白、stone wash(石磨洗)等工序一起并用。
本发明的衣物包含各种样子。例如有手套、上衣、裤子、帽子、袜子、鞋罩、围巾、尿布等。
本发明的叠层布帛除了适用为衣物原材料之外,还能够用作窗帘布料、被褥、床单、睡袋、帐篷、各种套子用原材料等。
实施例
以下例举实施例进一步详细说明本发明。
实施例1
在室温下,用表面覆盖率45%的凹印辊在作为防水透湿性的耐久薄膜的聚氨酯复合膜的聚氨酯膜面,以18g/m2的印刷量涂布聚乙烯醇水溶液(三和油脂公司制、ポパ—ル洗涤糊)与0.1wt%的表面活性剂(明成化学株式会社制、AG稳定剂S)混合而成的溶液(水溶性粘合剂),前述聚氨酯复合膜由单位面积质量为33g/m2的拉伸多孔质聚四氟乙烯膜(空孔率80%、最大细孔径0.2μm、平均厚度30μm)和二苯基甲烷二异氰酸酯及多元醇构成。然后,用压辊在其表面压接表层布料,该表层布料是单位面积质量为170g/m2、密度纵向和横向分别为174根/英寸和94根/英寸,纤度纵向和横向分别为56分特和71分特的聚酯平织布料,用加热到110℃的热风炉使水分从聚乙烯醇水溶液中蒸发,进行了粘合加工。然后,在该层叠了表层布料的复合膜的另一面使用作为非水溶性粘合剂的聚氨酯系固化反应型热熔粘合剂(日本ェヌェスシ—株式会社制、ボンドマスタ—、170-7254),将粘合剂温度控制在120℃,并且使粘合剂印刷量为5g/m2,在薄膜上点状涂布该溶融液,然后在其上重叠单位面积质量为33g/m2、25分特的尼龙特里科经编织物,用热辊压接,进行了层叠加工。得到的叠层物在60℃、80%RH的恒温高湿容器中放置24小时,使反应型热熔粘合剂固化。这样就获得了叠层布帛(1)。该叠层布帛在用剪刀及切断刀进行裁剪时也不会发生剥离,能够很容易地进行裁剪。还确认了能够用缝纫机将裁剪片互相缝制在一起。
实施例2
除了将前述实施例1中的水溶性粘合剂对耐久薄膜的涂布量改为12g/m2,表层布料采用单位面积质量为67g/m2、密度纵向和横向分别为20根/英寸和88根/英寸、纤度纵向和横向都为78分特的尼龙平织布料之外,其它的材料、加工方法和实施例1相同,制成叠层布帛(2)。所得的叠层布帛(2)在用剪刀及切断刀进行裁剪时也不会发生剥离,能够很容易地进行裁剪。还确认了能够用缝纫机将裁剪片互相缝制在一起。
实施例3
除了将前述实施例1中的水溶性粘合剂对耐久薄膜的涂布量改为12g/m2,表层布料采用单位面积质量为52g/m2、密度纵向和横向分别为53根/英寸和122根/英寸、纤度纵向和横向都为44分特的尼龙平织布料之外,其它的材料、加工方法和实施例1相同,制成叠层布帛(3)。所得的叠层布帛(3)在用剪刀及切断刀进行裁剪时也不会发生剥离,能够很容易地进行裁剪。还确认了能够用缝纫机将裁剪片互相缝制在一起。
实施例4
除了将前述实施例2中的聚氨酯系固化反应型热熔粘合剂的涂布量改为10g/m2,内层布料采用单位面积质量为67g/m2、密度纵向和横向分别为120根/英寸和88根/英寸、纤度纵向和横向都为78分特的尼龙平织布料之外,其它的材料、加工方法和实施例1相同,制成叠层布帛(4)。所得的叠层布帛(4)在用剪刀及切断刀进行裁剪时也不会发生剥离,能够很容易地进行裁剪。还确认了能够用缝纫机将裁剪片互相缝制在一起。
比较例1
采用和前述实施例1所用相同的表层布料、耐久薄膜、内层布料,表层布料和耐久薄膜的粘合使用实施例1所用的作为非水溶性粘合剂的聚氨酯系固化反应型热熔粘合剂(印刷量18g/m2、覆盖率45%),作为内层布料的针织物和耐久薄膜的粘合使用实施例1所用的水溶性粘合剂(10g/m2),得到了叠层布帛(11)。
比较例2
采用和前述实施例2所用相同的表层布料、耐久薄膜、内层布料,表层布料和耐久薄膜的粘合使用实施例1所用的作为非水溶性粘合剂的聚氨酯系固化反应型热熔粘合剂(印刷量10g/m2、覆盖率45%),作为内层布料的针织物和耐久薄膜的粘合使用实施例1所用的水溶性粘合剂(10g/m2),得到了叠层布帛(12)。
比较例3
采用和前述实施例3所用相同的表层布料、耐久薄膜、内层布料,表层布料和耐久薄膜的粘合使用实施例1所用的作为非水溶性粘合剂的聚氨酯系固化反应型热熔粘合剂(印刷量8g/m2、覆盖率40%),作为内层布料的针织物和耐久薄膜的粘合使用实施例1所用的水溶性粘合剂(10g/m2),得到了叠层布帛(13)。
比较例4
除了将前述实施例1中的水溶性粘合剂对耐久薄膜的涂布量改为10g/m2,表层布料采用单位面积质量为39g/m2、密度纵向和横向分别为140根/英寸和133根/英寸、纤度纵向和横向都为33分特的尼龙平织布料之外,其它的材料、加工方法和实施例1相同,制成叠层布帛(14)。
比较例5
采用和前述实施例4所用相同的表层布料、耐久薄膜、内层布料,表层布料和耐久薄膜的粘合使用实施例1所用的作为非水溶性粘合剂的聚氨酯系固化反应型热熔粘合剂(印刷量10g/m2、覆盖率45%),作为内层布料的布料和耐久薄膜的粘合使用实施例1所用的水溶性粘合剂(10g/m2),得到了叠层布帛(15)。
比较例6
采用和前述实施例4所用相同的表层布料、耐久薄膜、内层布料,在内层布料的粘合中,使非水溶性粘合剂的印刷量为5g/m2,其它的材料、加工方法和实施例4相同,制成叠层布帛(16)。
[性状评价]
对前述实施例1~4及比较例1~6所获得的各叠层布帛的性状进行如下评价。
(1)裁剪性及缝制性
用剪刀及切断刀裁剪各叠层布帛时,表层布料、耐久薄膜、内层布料都没有各自剥离,能够以一个整体进行裁剪。还确认了能够用缝纫机将裁剪片互相缝制在一起。
(2)布帛目付
以从各叠层布帛的质量中减去水溶性粘合剂的质量所得到的值作为布帛目付,计算出布帛目付。
(3)质感试验
(前处理)
将各叠层布帛裁剪成20cm见方的正方形,用缝纫机缝制外周边,使用家庭用全自动洗衣机(松下公司制、NA-F70PX1),用自来水(不含洗涤剂)进行自动洗涤,在室温下吊晒干燥,制得试样。
(质感值)
对于经上述前处理的各试样的质感的物理特性,用纯弯曲试验机(KATOTECH公司制、KES-FB2、PURE BENDING TESTER(纯弯曲试验机))进行了弯曲特性的评价。其结果示于表1。
(手感)
用手分别触摸各叠层布帛,进行了质感的排序。排序大致按照下述的基准进行。其结果示于表1。
◎:非常柔软,○:略微柔软,△:略微刚性,×:非常刚性。
(4)洗涤后的滑移状态
将各叠层布帛裁剪成35cm×70cm的长方形,用缝纫机缝制外周边以防止绽线,使用家庭用全自动洗衣机(松下公司制、NA-F70PX1),用自来水(不含洗涤剂)进行自动洗涤,在室温下吊晒干燥。观察干燥后的试样的表层布料、内层布料,目视检查有无滑移等外观异常。外观检查在前述洗涤进行10次然后吊晒干燥后进行。其结果示于表1。表中的数字表示通过目视发现的损伤处数量。此外,在整个面都有损伤的情况标记为多数。
(5)去污性试验
将各叠层布帛裁剪成38cm四方的正方形,用缝纫机缝制外周边,使用家庭用全自动洗衣机(松下公司制、NA-F70PX1),用自来水(不含洗涤剂)进行自动洗涤,在室温下吊晒干燥,制得去污试验用试样。在该布料表面的中央滴下0.2ml矿物油(关东化学株式会社制),在其上覆载玻璃纸(日本制纸株式会社制、薄的白色玻璃纸),再在其上放置直径6.4cm、2268g的铁锤,过60秒后,移去铁锤制得污染试样。
对该污染试样用前述家庭用全自动洗衣机以全自动模式洗涤1次,并调整污染试样和负载布(JIS L0803中规定的3号(棉)使其达到1.8kg,投入了20g家庭用洗衣剂(花王株式会社制、アタック),在室温下吊晒干燥一昼夜。将所得试样的去污状况和AATCC TEST METHOD(美国纺织品染化师协会试验方法)130-1981 SOIL REREASE(污物清除):OILY STAIN REREASE METHOD的STAINREREASE REPLICA(油污清除方法的去污样品)进行目视比较,分成5个等级。其结果示于表1。数值中的5表示去污性最优秀,反之1表示最差。
(6)再循环率
计算可剥离的布料与在各叠层布帛的质量中减去水溶性粘合剂的质量所得到的值(布帛目付)的质量比率,作为再循环率。得到的计算结果示于表1。
(7)洗涤耐久性
将各叠层布帛裁剪成35cm×70cm的长方形,用缝纫机缝制外周边以防止绽线,使用ISO6330记载的B类家庭用洗衣机Kenmore Model 110.20912(SEARSROEBUCK AND CO株式会社制),在浴比1/60、浴温45℃以下,以Heavy-Duty(强力)模式,用不添加洗涤剂的自来水进行50小时的连续搅拌洗涤,这时通过目视确认由非水溶性粘合剂层叠加工的薄膜和表层布料或内层布料是否发生剥离。没有剥离的为合格(PASS)。得到的结果示于表1。
(8)填缝部的防水性试验
如图2所示,缝合各叠层布帛,再用市场上销售的填缝带(サンケミカル株式会社制、T-2000)对缝合部进行填缝加工。使用前述全自动洗衣机,将经过填缝加工的部分用自来水(不含洗衣剂)进行1次自动洗涤,在室温下吊晒干燥,供填缝部的防水性试验用。防水性试验按照JIS L 1092 A法(低水压法)进行。其试验结果示于表2。
表2
(评价结果)
(布帛目付)
从表1可知,实施例2和比较例2的目付分别为138g/m2、143g/m2,可以说实质上基本相同。但是,在比较例2中,轻量的内层布料针织物因洗涤产生滑移,因此实际上无法使用。另一方面,在比较例5中,虽然没有发生类似比较例2的内层布料滑移的问题,但目付达到177g/m2,与实施例2相比,布料要重近30%。
(质感)
从表1可知,由实施例的叠层布帛所获得的物理特性是,如果表层布料、内层布料都由相同的组合构成,则弯矩在以比较例为100时,降低20%~50%,采用本发明能够得到质感柔软的叠层布帛。此外由表1可知,从利用手感进行的质感评价也能够得到和上述弯矩同样的结果。
(洗涤后的滑移状态)
从表1可知,洗涤后的滑移,越是轻量的布料越容易发生,洗涤没有用非水溶性粘合剂层叠的33分特的布料(比较例4)时,经过10次家庭洗涤在布料产生4处损伤。此外,洗涤同样没有用非水溶性粘合剂层叠的25分特的尼龙特里科经编织物(比较例1~3)时,针织物经过洗涤产生较多的损伤。由此可知,在本发明中针对洗涤后的滑移,对表层布料而言,如果是至少大于33分特、例如44分特的布料就能够防止布料的损伤。而对内层布料而言,只要用非水溶性粘合剂进行层叠,就可改善内层布料的损伤,因此对内层布料的使用没有特别的限定。
(去污性)
从表1可知,由表层布料仅和耐久薄膜重叠的叠层结构的布帛和相同种类的表层布料由非水溶性粘合剂层叠于耐久薄膜而形成的布帛相比,去污性好。具体来说,实施例2的去污性的等级为4,与此相对的比较例2的等级为3。实施例3的等级为3,而比较例3的等级为2。这是由于本发明以表层布料从耐久薄膜分离的状态进行洗涤,因此洗衣液容易通过表层布料,使去污性得到提高。
(再循环率)
实施例1~4及比较例1~6的可进行材料再循环的布料的比率示于表1。由此可知,如果由相同的表层布料和内层布料构成的叠层布帛相互间进行比较,则本发明的叠层布帛的再循环率都较高。具体来说,实施例1的再循环率约为70%,与此相反,比较例1的再循环率约为13%,可再循环的质量比率大大降低。虽然随着表层布料目付的降低,其差距越小,但即使是77分特的表层布料,其再循环率也要达到约2倍,因此可以说和以往技术相比,再循环率得到大幅度提高。
(洗涤后剥离状态)
50小时洗涤后布帛的剥离状态的结果示于表1。在实施例2中,由于内层布料的粘合以10g/m2的用量使用非水溶性粘合剂,因此剥离状态是合格(PASS)的,而在比较例6中,由于非水溶性粘合剂的用量为5g/m2,因此缺乏粘合耐久性,是不合格(NG)的。
(填缝部的防水性)
由实施例1~3及比较例5的叠层布帛形成的填缝部的防水性试验结果示于表2。任一实施例的叠层布帛都具有20kPa以上的耐水度,防水性良好,而比较例5在5kPa发现漏水,防水性不佳。这是由于内层布料的密度高,填缝带的粘合剂不能充分浸透到内层布料中,水在内层布料和耐久薄膜的间隙通过的缘故。
产业上利用的可能性
本发明的叠层布帛具有叠层结构,前述叠层结构的特征是表层布料和耐久薄膜由用于暂时粘接的粘合剂粘合在一起,且在耐久薄膜的另一面由耐久粘合剂粘合内层布料,因此具有以下所示的各种优良效果。
(1)由于耐久粘合剂的用量少,因此很轻,不会使表层布料的质感发生变化,柔软性优良。
(2)内层布料由耐久薄膜固定,因此即使采用轻量的内层布料,也能够防止布料因洗涤等受到损伤,拓宽了内层布料的选择范围。
(3)由于是在表层布料从耐久薄膜分离的状态下进行洗涤,因此去污性优良。
(4)由于表层布料是可分离的,因此材料再循环性优良。
使用本发明的叠层布帛,能够提供具有上述优良效果的衣物。
Claims (14)
1、由叠层布帛制得的衣物,其特征在于,所述的叠层布帛具有在耐久薄膜的一面通过用于暂时粘接的粘合剂层层叠了表层布料,并且在该耐久薄膜的另一面通过耐久粘合剂层层叠了内层布料的结构,且所述衣物的接缝部分的内层布料的一部分或全部用填缝带进行填缝处理。
2、由叠层布帛制得的衣物,其特征在于,所述的叠层布帛具有在耐久薄膜的一面通过用于暂时粘接的粘合剂层层叠了表层布料,并且在该耐久薄膜的另一面通过耐久粘合剂层层叠了内层布料的结构,且表层布料为织物,内层布料为针织物。
3、如权利要求1或2所述的衣物,其特征还在于,该耐久薄膜为防水透湿性薄膜。
4、如权利要求3所述的衣物,其特征还在于,该防水透湿性薄膜是多孔质聚四氟乙烯薄膜。
5、如权利要求4所述的衣物,其特征还在于,该多孔质聚四氟乙烯薄膜的骨架表面用防水·防油剂包覆。
6、如权利要求4或5所述的衣物,其特征还在于,在该多孔质聚四氟乙烯薄膜的一面或两面设置了亲水性树脂的连续被膜。
7、如权利要求1所述的衣物,其特征还在于,该表层布料的目付比该内层布料的目付大。
8、如权利要求1所述的衣物,其特征还在于,该用于暂时粘接的粘合剂为水溶性粘合剂。
9.如权利要求2所述的衣物,其特征还在于,该衣服的接缝部分的内层布料的一部分或全部用填缝带进行填缝处理。
10、如权利要求1所述的衣物,其特征还在于,该衣物经用于剥离该表层布料和该耐久薄膜的后处理,剥离了该表层布料和该耐久薄膜。
11、如权利要求10所述的衣物,其特征还在于,该用于暂时粘接的粘合剂为水溶性粘合剂,该后处理为水洗处理。
12、如权利要求1或2所述的衣物,其特征还在于,该衣物为雨衣或防寒衣。
13、权利要求2所述的衣物的制造方法,其特征在于,裁剪所述的叠层布帛,经缝制制成衣物后,进行使该表层布料和该耐久薄膜剥离的后处理。
14、权利要求1所述的衣物的制造方法,其特征在于,裁剪所述的叠层布帛,缝制后,用填缝带进行接缝的填缝处理,制成衣物,然后进行使该表层布料和该耐久薄膜剥离的后处理。
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EP1486323A1 (en) | 2004-12-15 |
EP1486323A4 (en) | 2010-06-23 |
KR100725077B1 (ko) | 2007-06-08 |
JP2003236963A (ja) | 2003-08-26 |
AU2003211994A1 (en) | 2003-09-04 |
US20100311297A1 (en) | 2010-12-09 |
WO2003068495A1 (fr) | 2003-08-21 |
EP1486323B1 (en) | 2012-10-17 |
KR20040085195A (ko) | 2004-10-07 |
JP4015434B2 (ja) | 2007-11-28 |
US20080050555A1 (en) | 2008-02-28 |
US20080047654A1 (en) | 2008-02-28 |
CA2476487A1 (en) | 2003-08-21 |
CN1646307A (zh) | 2005-07-27 |
US20050208854A1 (en) | 2005-09-22 |
CA2476487C (en) | 2011-07-26 |
US20100306900A1 (en) | 2010-12-09 |
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