CN1149327A - 三维、无缝、防水、透气、柔性的复合制品 - Google Patents
三维、无缝、防水、透气、柔性的复合制品 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/22—Making multilayered or multicoloured articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
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- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
- D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
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- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
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- B29C41/14—Dipping a core
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING 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
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING 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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, 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
- B29K2105/0809—Fabrics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
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- 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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Abstract
披露了透气、防水、柔性、无缝的成型制品,如手套或短袜,该制品包括一层柔性的复合层,该复合层包括:(a)一层水蒸气渗透性的微孔、弹性、热塑性聚酯型聚氨酯或聚醚型聚氨酯层;(b)一层防水但不能透过水蒸气的亲水性无孔共聚物层,该层对微孔聚合物具有改进防水性作用。
Description
发明的领域
本发明涉及用于衣物织物(如手套和长袜)的三维、无缝、防水、透气、柔性的复合制品。
发明的背景
薄、透气、形状吻合(form-fitting)的制品(如手套或短袜)可用于许多场合,例如用于医学上、牙科上或净化室。
制造这种制品的一个方便的方法是简单地将适当形状的模型浸渍在液态的高弹体组合物中,以便在模型的表面形成连续的膜。然后将该膜干燥成具有模型形状的固态膜。通过选择防水、但可透气的高弹体,可很容易地通过一步步骤制得舒适的形状吻合的手套。这种手套最好较薄(如0.1-0.5mm),并要求能容易地进行拉伸。
一类这种可浸渍模型的高弹体组合物是形成防水、透气、微孔聚酯型或聚醚型聚氨酯涂层(参见美国专利4,888,829)的高弹体组合物。但是,当向这种微孔聚氨酯施加水压时,它会部分地丧失其防水性。另外,这种微孔聚氨酯的空穴易受到汗液等的阻塞和污染。
另一类可浸泡模型的高弹体组合物是亲水性聚合物溶液,这种溶液干燥后在成形的模型上形成无孔的、不渗透液态水但渗透水蒸气的膜。通常,这种无孔膜比微孔膜具有更高的硬度,这可从其在拉伸变形时具有较高的模量得到证明。由于这种无支承体的无孔膜需要达到某种最小的厚度才能用作如手套和短袜制品,所以这种制品使用时不是很舒服。具体地说,它们会产生噪声并且较硬,使得它们具有较差的形状适合性和灵活性。因此,需要开发一种能用于形状吻合的手套、或用于织物结构上但无上述缺陷的膜。
发明的综述
本发明提供由柔性的层状复合材料制得的无缝成形制品(如手套、短袜或膜)以克服上述缺陷。复合层之一(层I)是微孔、弹性、可渗透水蒸气的热塑性聚酯型聚氨酯或聚醚型聚氨酯。第二层无孔层(层II)是亲水性无孔连续聚合物,该聚合物能防水、但可渗透水蒸气,它改善了复合材料的防水性,使其防水性超过了单独使用微孔聚氨酯层(I)的防水性。
该制品的一种形状是手套形状。另一种形状是短袜形状。
层II的厚度最好为0.5-2mils,层I的厚度最好为5-50mils。
术语“亲水性”是指该材料对水具有强烈的亲合力并能允许水分子穿透其本身。一种方便的水亲合力的衡量方法是在一定条件下聚合物的吸水量。ASTMD570是这种测定塑料吸水率的标准试验方法。在本说明书中,亲水性指吸水率大于5重量%(按照ASTM D570,24小时吸水率)的任何聚合物。
术语“微孔的”指塑料层具有从一面至另一面连续的、相当小的孔。
术语“可透气的”指制品能够透过水蒸气(如蒸发的汗液)。
术语“形状吻合的”指手套、短袜等紧贴地围绕在手或足的周围。该手套应该薄并具有弹性,以使穿戴者保持良好的感觉。
术语“无孔的”指不存在穿透塑料层的孔或通道。其产生的结果是该塑料层不渗透空气,
术语“成形制品”指具有三维特殊形状的模型。用于服装上,它是指手套、帽子或短袜而不是平面的膜。
附图简述
图1是实施例1中所述的样品横截面的放大400倍的显微照相图。
图2是实施例4中所述的样品横截面的放大200倍的显微照相图。
图3是比较例C-1中所述的样品横截面的放大200倍的显微照相图。
图4是比较例C-5中所述的样品横截面的放大60倍的显微照相图。
图5是比较例C-4中所述的样品横截面的放大100倍的显微照相图。
图6是实施例11中所述的样品横截面的放大100倍的显微照相图。
图7是实施例12中所述的样品横截面的放大75倍的显微照相图。
图8是实施例13中所述的样品横截面的放大55倍的显微照相图。
本发明的详细描述层I-聚氨酯
在室温下,用于层I的微孔高弹体热塑性聚酯型聚氨酯或聚醚型聚氨酯最好具有介于纯橡胶和纯热塑性材料之间的形变回复性能。
层I的聚氨酯可基于各种前体,所述前体可与各种多元醇、多元胺和多元异氰酸酯进行反应。正如已知的那样,可通过适当地选择反应试剂、反应顺序和反应条件在很大程度上选择产物聚氨酯的性质。
用于层I的较好的聚氨酯是基于线型、羟基封端的聚酯(尽管可使用聚醚多元醇或聚醚/聚酯混合物)和二异氰酸酯、以及少量的二官能低分子量反应试剂的高弹体聚氨酯。最后提到的组分可与其它反应试剂一起在一步聚合反应开始时加入,或者主要作为增链剂在随后的步骤中加入,或者部分在开始时加入、另一部分随后加入。
优选的用于层I的聚氨酯是聚酯和二元醇以及二异氰酸酯反应得到的产物。由美国专利2,871,218可知,可使用各种不同的聚酯、二元醇和二异氰酸酯,但是特别合适的聚酯体系是:由乙二醇和己二酸制得的聚酯与1,4-丁二醇以及二苯基甲烷-4,4’-二异氰酸酯反应形成的产物。
聚酯和二元醇的摩尔比可在相当大的区域内变化,但是聚酯和二元醇的总摩尔数应与二异氰酸酯的摩尔数基本相等,以便在产物聚合物中基本不存在未反应的羟基或异氰酸基团。
用于层I的较好的聚氨酯聚合物是由二异氰酸酯、单体二元醇和分子量为1,000-3,000的聚酯多元醇或聚醚多元醇制得的线型聚氨酯。该聚氨酯在二甲基甲酰胺中的特性粘度至少为0.5dl/g。
用于层I特别好的聚氨酯的含氮量约为3.0-4.0%(如3.5%左右)。可通过提高聚酯对二元醇的比例来制备这种材料,制备时需要较少的二异氰酸酯(相对于较高含氮量(如4.5%或更高)的聚氨酯)。
可通过本体聚合方法制备本聚合物并随后溶解在合适的溶剂中。或者也可以用溶液聚合方法直接在溶液中制备。
在本聚合物中可以包括常规的稳定剂、填料、加工助剂、颜料、染料以及添加剂如表明活性剂或上胶剂,当在权利要求中引用本聚合物的含量时,该含量包括占高达10重量%的聚合物重量的任何这种添加剂。
另一种适合于作为层I的聚氨酯体系使用由己内酯制得的聚酯。这种聚酯披露在英国专利859640中。层II-无孔聚合物
现在让我们来看层II的亲水性聚合物组分,当按照ASTM D570进行试验时,该聚合物组分必须具有大于5%的24小时吸水率。
层II可由美国专利4,194,041中披露的材料制得,该专利所披露的内容列于此引为参考;也可由亲水性高弹体,包括(但不限于)聚酯、聚酰胺、纤维素衍生物、聚丙烯酸及其同系物、带亲水性杂质的天然或合成橡胶、共聚草酰胺、聚脲、聚合电解质、聚磷酸酯、聚乙烯胺、聚乙烯醇、聚醚及其共聚物、聚硫醚、聚硫醚-聚醚、共聚表氯醇醚、聚硫磷酸酯、共聚醚-酯及其混合物或衍生物制得。较好的亲水性聚合物是共聚醚-酯、聚氨酯或共聚醚-酯-酰胺。所有这些聚合物都具有水蒸气渗透性,但对液态水具有较高的防渗性。
较好的聚合物是亲水性共聚醚-酯-酰胺类聚合物。这种聚合物是聚醚嵌段酰胺聚合物化学家族的一部分(参见N.R.Legge,G.Holden和H.E.Schroeder编著的“Thermoplastic Elastomers-A Comprehensive Review”)。这种共聚物的通式为:
其中PA是聚酰胺聚合物段;PE是聚醚聚合物段。这种树脂的制备可参见美国专利4,230,838,该专利还讨论了在聚酯聚合物段中使用聚环氧烷二元醇以配制亲水性级别的可能性。这种树脂的具体例子是PEBAXMX1074(购自ElfAtochem North America,Inc.)。根据ASTM D570测得的该具体聚合物的24小时吸水率约为48%。
较好的亲水性共聚醚-酯聚合物是含有重复的长链二羧酸酯单元和长链二元醇,同时还含有重复的短链二羧酸酯单元和短链二元醇的嵌段共聚酯。该二元醇可含有醚单元,在这种情况下该共聚酯有时也称为共聚醚-酯。亲水性共聚醚-酯组合物可参见Ostapchenko的美国专利4,493,870和4,725,481。亲水性共聚醚-酯的具体例子有HytrelHTR 8171(购自E.I.Dupont Nemoursand Co.)。根据ASTMD570试验的该具体聚合物的24小时吸水率约为61%。
较好的亲水性聚氨酯聚合物是具有高浓度氧化乙烯单元(赋予亲水性)的嵌段共聚物。这种亲水性聚氨酯的合适的组合物可参见Gore的美国专利4,194,041和Henn的美国专利4,532,316中的实施例,还可参见出版物如N.S.Schneider、J.L.Illinger和F.E.Kanasz发表在Journal of Applied Polymer Science,vol 47,pp1419中的文章。各种形式的亲水性聚氨酯(如固态树脂,活性预聚物、在有机溶剂或溶剂混合物中的溶液)可市售购得。制备-成形制品
本发明还涉及复合层的形成方法。一种制备无缝、防水、透气并且形状吻合的本发明制品的方法是:将一种无孔成形模型浸渍在一个含有亲水性聚合物(层H)溶液的槽中,然后以一定的速率将该模型从所述溶液中取出,以便在该模型的表面形成要求的溶液分布,然后从涂覆的模型上除去溶液(如通过干燥)以便在模型上形成一层亲水性聚合物的固体薄膜。如果该聚合物是活性的(如聚氨酯预聚物),则可固化该膜以便形成无孔膜。这种固化方法的例子有:通过与环境中的水分相反应、通过加热激活(unblock)混合在预聚物中的固化剂、或通过各种类型的辐照以引发并加速固化反应。
然后将带有无孔亲水性涂层(层II)的模型浸渍在热塑性聚氨酯(层I)组合物的极性溶剂(如二甲基甲酰胺(DMF)、二甲基乙酰胺、二甲亚砜、N-甲基吡咯烷酮等能与所使用的非溶剂相混溶的溶剂)溶液中,以一定的速度将该模型从所述溶液中取出。然后转动经涂覆的模型以便在模型的表面形成要求的溶液分布。接着将涂覆的模型浸没在含有非溶剂或溶剂/非溶剂混合物的槽中,以便将聚氨酯涂层转化成微孔、可透水蒸气的涂层。一些非溶剂的具体的例子是水和醇(如甲醇、乙醇、异丙醇)。但是从环境因素看,水是较好的,并且它易于操作。然后在环境条件下或在烘箱中,在脱离成形模型之前或之后,干燥如此形成的成形复合制品。
这种复合结构的附加的有利之处在于:由于亲水性聚合物层II的膨胀,所以成形制品在湿润时相对较容易从模型中剥离(与干燥的成形制品相比)。
或者,为了形成微孔层,可先将模型浸渍在形成层I的热塑性聚氨酯溶液中。当该步骤完成后,可形成亲水性聚合物层。所述模型的形状最好是手或足的形状。
在另一种情况中,亲水性聚合物层II可夹在两层微孔聚氨酯层中间。同样,微孔聚氨酯层I也可夹在两层亲水性聚合物中间。
还可以通过在可以或不可以拉伸的织物,如纺织物或非纺织物成形的织物内衬上形成复合涂层,制得增强型的上述组合制品。通过控制涂布溶液渗入织物内衬的渗透深度,可控制产物制品的手感或覆盖度(drape)。这可以通过改变织物内衬的表面特性(用防水剂对其进行处理)使得涂覆溶液不能立即湿润该内衬。因此,可使用涂覆液沉积和开始凝固之间的时间间隔来控制涂覆溶液渗透的程度。当对织物内衬进行了适当的处理后,可以使用许多方法形成组合涂层。例如:
(i)在经处理的织物内衬上形成无孔聚合物层,接着在该聚合物层上形成微孔聚氨酯层。
(ii)在经处理的织物上形成微孔聚氨酯层,接着在该微孔膜上形成无孔聚合物层。
(iii)将无孔聚合物层夹在两层微孔聚氨酯层的中间。
制备无缝成形制品的实施例
溶液A:
亲水性无孔共聚醚-酯高弹体溶液制备如下:
将10加仑Versamix(购自纽约州Charles Ross & Son Co.)在40℃下加热,加入19000g1,1,2-三氯乙烷和2200g亲水性共聚醚-酯高弹体(HytrelHTR8171)。将该物料搅拌3小时以得到清澈的溶液。然后将该溶液取出并储存在室温下。
溶液B:
热塑性聚酯型聚氨酯溶液制备如下:
将10加仑Versamix在40℃下加热,加入12200g N,N-二甲基甲酰胺(DMF)和3100g热塑性聚酯型聚氨酯TPU1(重均分子量约25000,比重为1.18,24小时吸水率为1-2%,通过MDI(二苯基甲烷二异氰酸酯)与聚己内酯二醇反应,并使用丁二醇作为扩链剂制得)。将该物料在搅拌器中在氮气氛下搅拌4小时以得到清澈的溶液。然后将该溶液从混合器中倒至塑料容器中并在环境条件下冷却。
将13527g上述溶液与458ml蒸馏水和67.5g非离子表面活性剂(购自3M的FLUORAD-430)的混合物一起装入上述混合器中。在环境温度下将该物料搅拌1小时以得到清澈的溶液。然后将该溶液从混合器中倒出并储存在环境条件下。实施例1
将无孔的陶瓷手模型(新泽西州General Porcelain Co.,釉面涂层)浸入(手指先浸入)Hytrel溶液A。然后将该模型以一定的速度取出,并使手指向下将该模型沥干3分钟。然后翻转该模型,使手指向上将该模型沥干60秒。接着再翻转模型,使手指向下在空气中干燥。
将如此涂覆的模型浸在聚氨酯溶液B中。然后以一定的速度将该模型取出,手指向下沥干1分钟,接着翻转模型,使手指向上沥干30秒。最后将该模型手指向下浸没至50/50DMF(二甲基甲酰胺)/水的混合物中。在DMF/水混合物中浸泡15分钟后,取出该模型并在水中浸泡45分钟,然后取出该模型并在空气中干燥之。通过在手套和模型之间注入水可很方便地将手套成形制品从模型中剥离。破坏性地试验手套的手心和手背区域的各种性能。结果列于表1。实施例2
使用相似于实施例1的方法,但经溶液B浸渍后,浸泡在50/50DMF/水以及水中的时间分别为15分钟和75分钟。实施例3
使用相似于实施例1的方法,但使用的陶瓷手模型是素瓷涂层的(购自GeneralPorcelain Co.)。经溶液B浸渍后,浸泡在50/50DMF/水以及水中的时间分别为5分钟和45分钟。实施例4
使用相似于实施例3的方法,但在步骤2,经溶液B浸渍后,经涂覆的手模型仅在水中浸泡60分钟。比较例C-1
使用相似于实施例1的方法,但模型不浸渍在溶液A中。仅浸入聚氨酯溶液B中。此外,使用素瓷涂层的手模型。结果形成的手套没有亲水性无孔聚合物膜层。从手模型上剥离时,手套在手指的根部区域(crotcharea)撕裂。比较例C-2
将带釉面涂层的陶瓷手模型浸入(手指先浸入)溶液B,以一定的速度将其取出,并手指向下沥干1分钟。然后翻转该模型,使手指向上沥干20秒。接着再翻转模型并将其在水中浸泡90分钟,再将其取出并在空气中干燥。因此该手套没有亲水性无孔聚合物层。然后将干燥的手套层模型上剥离。该手套相当脆弱并在剥离过程中在手指根部区域撕裂。
表1
实施例 | 1 | 2 | 3 | 4 | C-1 | C-2 |
手背区域的样品 | ||||||
厚度1 | 7.80 | 7.20 | 8.35 | 12.3 | 9.3 | 3.4 |
MVTR2 | 1502 | 1418 | 1109 | 1081 | 1902 | 7327 |
Suter试验4 | P3 | P3 | P3 | P3 | F1 | F1 |
进水压力3 | 119 | 123 | 114 | 108 | 很低 | |
100%应变时的应力5 | 289 | 288 | 258 | 180 | 114 | 176 |
断裂应力5 | 797 | 823 | 713 | 351 | 311 | 578 |
断裂伸长5 | 539 | 545 | 551 | 418 | 472 | 483 |
撕裂蔓延6 | 48.5 | 51.9 | 49.8 | 58.3 | 33.0 | 35.0 |
手心区域的样品 | ||||||
MVTR2 | 1996 | 1707 | 1222 | 1222 | 1215 | 4123 |
Suter试验4 | P3 | P3 | P3 | P3 | F1 | F2 |
进水压力3 | 120 | 124 | 110 | 120 | 很低 |
1详细描述可参见美国专利5,036,551中的“厚度”一节。其单位为mils。
2详细描述可参见美国专利5,036,551中的“水蒸气透过率”一节。其单位为
g/sq.m/天。
3按照联邦试验方法标准191A,方法5512进行。其单位是psi。使用一种符合MIL-C-21852的III型、I类限制器的塔府绸织物限制器。
4按照联邦试验方法标准191A,方法5516进行。第一个字符f或p分别表示样品是或否泄漏水。第二个数字表示当发生水泄漏时的水压(psi)。
5按照ASTM D882-83,应力的单位为psi。
6按照ASTM D1938,单位是每英寸样品厚度的最大负荷。
*在1-5psi之间,不能准确地进行测定。实施例5
使用相似于实施例1的方法,但是使用带素瓷涂层的陶瓷手模型。试验手套的MVTR,在手心区域的测得的结构是1186。然后根据美国专利5,036,551提供的“液态水渗漏”试验方法测定手套的防水性。该手套的水渗透率的测定结果为合格。
图1、图2和图3分别是实施例1、4和比较例C-1样品的剖面SEM显微照相图。实施例6
溶液C
将10加仑Versamix在45℃下加热,加入17759g溶液A和3541g1,1,2-三氯乙烷。将整个物料搅拌1小时。然后将清澈的溶液倒出并储存在室温下备用。
溶液D
在10加仑Versamix中,在40℃将3550g热塑性聚酯型聚氨酯TPU2(Texin480A,购自Miles Inc.,重均分子量为133000,比重为1.20,24小时的水吸收为1.5%)和19310gDMF混合搅拌5小时,制得一种溶液。然后倒出该溶液并储存在环境条件下备用。在50℃时将20517g上述溶液加入Versamix中,然后加入100g表面活性剂(FluoradFC-430)、721g蒸馏水和110g消泡剂(BYK-066,购自BYK Chemie)形成的预混合物。将整个物料混合150分钟,得到清澈的均相液体。然后倒出该液体并将其储存在环境条件下。
将无孔手模型(带素瓷涂层)浸渍在溶液C中(手指先浸入)。10秒钟后,以一定的速度取出该模型,使用60秒钟沥去多余的液体。然后,缓慢地旋转以及翻转该模型使之手指向上以沥去液体,使用的时间为150秒,接着翻转该模型,手指向下再沥干180秒。最后手指向上使该模型在空气中完全干燥。一旦涂层干燥后,重复整个上述过程。
将如此涂覆的手模型浸渍在聚氨酯溶液D中。然后以一定的速度取出该模型,并手指向下沥干1分钟,然后缓慢地翻转并旋转该模型,使手指向上沥干60秒,最后手指向下将该模型浸泡在水中。60分钟后,取出该模型,除去过量的水,然后将涂覆的模型在80℃的烘箱中放置30分钟。接着将干燥的模型浸入水中,从模型上剥离手套并在空气中干燥之。
从手套的手心或手背区域取样破坏性地试验其各种性能。试验结果列于表2。比较例C-3
使用相似与实施例6的方法,但模型不浸入溶液C。而仅浸渍在聚氨酯溶液D中。在从手模型上剥离过程中,该手套在手指根部区域被撕裂。
表2
实施例7
实施例6 | 比较例C-3 | |
厚度1 | 9.63 | 12.58 |
MVTR2 | 713 | 1996 |
Suter试验4 | P3 | F1 |
进水压力3 | 173 | 6 |
100%应变时的应力5 | 686 | 82 |
断裂应力5 | 1677 | 403 |
断裂伸长5 | 313 | 383 |
撕裂蔓延6 | 62.7 | 23.5 |
使用与实施例6相同的方法,但手模型仅在溶液C中浸渍一次,形成薄的亲水性涂层。然后使用实施例5中的方法测得该手套的防水性,测定结果该手套的水渗透率为合格。在手心区域。MVTR为1223,Suter试验表明在3psi水压下不发生水渗透。实施例8
在本实施例中使用根据美国专利4,532,316和美国专利5,036,551制得的亲水性聚氧乙烯-聚酯-聚氨酯。按照ASTM D570对这种亲水性聚氨酯的湿致固化膜进行试验,其24小时吸水率为132%。
溶液E:
将100克上述亲水性、活性聚氨酯溶入225克四氢呋喃(THF)和75克DMF的混合液中制得溶液,在室温下搅拌使之成为清澈的溶液。
将一清洁的300ml玻璃烧杯手工地浸入溶液E中,然后缓慢地将其取出,使之干燥并通过与环境中的水分相反应而固化。
将涂覆的玻璃烧杯手工地浸渍在溶液D中,沥去多余的液体,在环境条件下将其干燥前,将其在水中浸泡60分钟。接着将成形的制品从玻璃烧杯上剥离,向该制品中充入水以试验水的渗透。没有观察到水的渗漏。
然后使该制品在空气中干燥,割去烧杯的底使之成为圆筒,接着撕开圆筒形成光滑的膜。在膜厚约为30mils处,MVTR为879,进水压力为172psi,在Suter试验中甚至在2.25psi的压力下也没有观察到水的渗透。与比较例C-3相比,该结果证明了本发明对防水性的改进。实施例9
溶液F:
从Soluol Chemical Co.购得透气的聚氨酯溶液SOLUCOTE TOP 932(固体约占42%)。使用20mil的刮板(drawdown bar)(BYK Gardner)在剥离纸上将该溶液浇铸成膜,并在环境条件下干燥之。在将该膜从剥离纸上剥离前,将其在155℃的烘箱内加热5分钟。这种膜的24小时吸水率为66%。
在室温下,使用132克甲苯和243克DMF稀释125克SOLUCOTE TOP 932溶液。将一清洁的300ml玻璃烧杯手工地浸渍在溶液F中,然后将其缓慢地取出并在环境条件下干燥之,形成半透明的膜。将该涂覆的玻璃烧杯在155℃的烘箱中加热90分钟。
将该涂覆的玻璃烧杯手工地浸渍在溶液D中,沥去多余的液体,在环境条件下将其干燥前,将其在水中浸泡60分钟。接着将成形的制品从玻璃烧杯上剥离并在空气中干燥之。割去烧杯的底使之成为圆筒,接着撕开圆筒形成光滑的膜。在膜厚约为30-35mils,MVTR为1483,进水压力为26psi。该结果表明,组合制品的防水性比仅仅由微孔聚氨酯(如比较例C-3所述)制得的制品有所改进。实施例10
将一清洁的大试管形模型(直径约3英寸)手工地浸渍至溶液F中(浸入约5英寸深),接着缓慢地将其取出并在环境条件下干燥之,形成半透明的膜。以后,将涂覆的玻璃模型在155℃的烘箱中加热2分钟。随后将涂覆的玻璃模型手工地浸渍在溶液D中(浸入约5英寸深),沥去多余的液体,并在环境条件下将其干燥前,将其在水中浸泡60分钟。接着将成形的制品从玻璃模型上剥离,向该制品中充入水。没有观察到水的渗漏。然后干燥该制品,并将其撕开以进行进一步的试验。在膜厚约为25mils,MVTR为1497,进水压力为14psi,在Suter试验中仅在1.5psi的压力下才观察到水的渗透。与比较例C-3的结果相比,本制品具有经改进的防水性。具有织物支承体的无缝成形制品的制备实施例
这些实施例描述通过形成织物支承体增强的上述组合膜制备无缝短袜(sockinsert)。所使用的针织物为流行色及膝中统袜(Fashion Color Knee High)(100%尼龙,犹太州84130,Saltlake,American Stores Buying Company制),该长统袜经过氟化物基防水剂处理,使之按照AATAA方法No.118-1983测得的含油等级(oilrating)为6。处理前,含油等级小于1并容易被水所湿润。实施例11
步骤1-将经处理的及膝中统袜穿入一鞋楦上(纽约Sterling Last Co.制,10号男用鞋楦),并拉伸使之正好符合鞋楦的形状。然后将整个组合件浸渍在溶液A中(足尖先浸入),接着使足尖向下沥干3分钟。再翻转鞋楦使足尖向上沥干60秒,之后使足尖向下在空气中干燥。
步骤2-将上述带有亲水性聚合物涂层织物的鞋楦浸渍在溶液B(足尖先浸入)中,取出并沥干1分钟,接着在水中浸泡48小时。取出鞋楦并在空气中干燥之。干燥后,将组合涂层从鞋楦上剥离,得到无缝、柔软、具有弹性的鞋状制品。它可用作短袜。随后试验该制品的水蒸气透过率和防水性。结果列于表3。
当上述短袜穿在脚上时,由于袜子的透气性和弯成足形时具有较低的应力,使得其能紧贴地吻合并且相当舒服。向该袜子中灌入500ml水试验其水的渗透性,观察任何水渗透的迹象。结果没有观察到水渗透的迹象。实施例12
使用相同与实施例11的方法,但是在步骤2中先进行16小时的水浸泡。然后对经干燥的微孔层(在经处理的织物支承体上)如实施例11的步骤1那样涂覆亲水性聚合物薄层。当灌入水后,进行如实施例11的试验,没有观察到水渗透现象。比较例C-4
使用相似于实施例12的方法,但是在微孔层上不涂覆亲水性涂层。得到的样品比实施例11和12中的样品更柔软并更有弹性。尽管它具有完全吻合的形状并且穿着舒服,但是当灌入500ml水以后,水从单个涂布缺陷(如针孔)中渗出并在很小的水压下,出现水通过微孔层渗漏的迹象。比较例C-5
使用相似与比较例C-4的方法,但是织物支承体没经防水剂处理。得到的样品同样具有吻合的形状,但当灌入水以后,出现水渗漏现象。
表3
实施例 | 11 | 12 | C-4 | C-5 | 基层织物 |
足尖区域的样品 | |||||
MVTR2 | 644 | 1215 | 1852 | 2155 | 5573 |
Suter试验4 | F2 | P3 | F1 | F1 | - |
后根区域的样品 | |||||
MVTR2 | 846 | 9111 | 2948 | 2539 | 5573 |
Suter试验4 | F2 | P3 | F1 | F1 | - |
图4、5、6和7分别是比较例C-5、C-4和实施例11、12的横截面SEM图。实施例13
用氟化物处理由93/7棉/lycraSpandex(女式9031 Charter Club,R.H.Macyand Co.,Inc制)制成的纺织短袜,得到#6的含油等级。处理前,该短袜的含油等级为#1。然后依次用相似于实施例11的步骤1和2的方法涂布经处理的短袜,但是使用更小的足模型(女式6号尺寸)。接着将足模型从水中取出并在空气中干燥之。将涂覆短袜从足模型上剥离,得到无缝的成形制品。尽管该制品比原始的短袜硬,但是这种经涂覆的短袜具有足够的弹性和柔软性以便与足紧密和舒服地吻合。当灌入500ml水后,没观察到该涂覆短袜有水渗透的迹象。在近踝部上面区域的MVTR为422。
图8是实施例13中描述的样品横截面的SEM显微照相图。
Claims (11)
1.一种透气、防水、柔性、无缝的成形制品,包括一层柔性的复合层,该复合层包括:
(a)一层水蒸气渗透性的微孔、弹性、热塑性聚酯型聚氨酯或聚醚型聚氨酯层I;
(b)一层防水但不能透过水蒸气的亲水性、连续的无孔聚合物层II。
2.一种透气、防水、柔性、无缝的成形制品,包括一柔性的复合层,该复合层包括:
(a)一层水蒸气渗透性的微孔、弹性、热塑性聚酯型聚氨酯或聚醚型聚氨酯层I;
(b)一层防水但不能透过水蒸气的亲水性、连续的无孔层II;
(c)至少一层织物层。
3.如权利要求1或2中所述的成形制品,其特征在于层I的聚氨酯是线型羟基封端的聚酯或聚醚多元醇和二异氰酸酯以及低分子量二元醇的反应产物。
4.如权利要求1或2中所述的成形制品,其特征在于当按照ASTM D570进行试验时,所述亲水性聚合物至少能吸收占其本身重量5%的液态水。
5如权利要求1或2中所述的成形制品,其特征在于亲水性聚合物选自弹性共聚醚-酯、弹性聚氨酯或弹性共聚醚-酯-酰胺。
6.如权利要求1或2中所述的成形制品,其形状是手套、连指手套、短袜和长袜。
7.如权利要求3中所述的成形制品,其形状是手套、连指手套、短袜和长袜。
8.如权利要求4中所述的成形制品,其形状是手套、连指手套、短袜和长袜。
9.如权利要求5中所述的成形制品,其形状是手套、连指手套、短袜和长袜。
10.一种制备如权利要求1中所述成形制品的方法,包括将无孔成形模型浸渍在亲水性聚合物溶液中,干燥后在模型上形成亲水性聚合物的干膜,随后将涂覆的模型浸渍在热塑性聚醚型或聚酯型聚氨酯溶液中,然后将所述模型浸泡在含有对热塑性聚醚型或聚酯型聚氨酯是非溶剂的液体或液体混合物的槽内,接着干燥该涂覆的模型,最后从模型上剥离成形制品。
11.一种制备如权利要求2中所述的成形制品的方法,包括对成形的织物预型件进行处理使之具有防水性,随后将经处理的预型件装在相同形状的无孔模型上,将得到的模型浸渍在亲水性聚合物溶液中,干燥后形成亲水性聚合物的干膜,然后将涂覆的模型浸渍在热塑性聚醚型或聚酯性聚氨酯溶液中,接着将该模型浸泡在含有对热塑性聚醚型或聚酯型聚氨酯是非溶剂的液体或液体混合物的槽内,接着干燥该涂覆的模型,最后从模型上剥离成形制品。
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Families Citing this family (53)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19506255A1 (de) * | 1995-02-23 | 1996-08-29 | Bayer Ag | Sandwich-Strukturelement aus Polyurethan und Verfahren zu dessen Herstellung |
US6114024A (en) * | 1995-08-01 | 2000-09-05 | Kimberly-Clark Worldwide, Inc. | Multilayer breathable film |
GB9612324D0 (en) * | 1996-06-13 | 1996-08-14 | Lrc Products | Polyurethane articles |
DE19625389A1 (de) * | 1996-06-25 | 1998-01-02 | Gore W L & Ass Gmbh | Flexibler Verbundstoff |
US6929853B2 (en) | 1996-07-31 | 2005-08-16 | Kimberly-Clark Worldwide, Inc. | Multilayer breathable film |
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US5829061A (en) * | 1997-04-08 | 1998-11-03 | Visgil; Jane T. | Work gloves |
DE19754251C2 (de) * | 1997-12-06 | 2003-04-17 | Coronor Composites Gmbh | Kunststoffolie, welche wasserdicht und wasserdampfdurchlässig ist |
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ES2187194T3 (es) | 1998-09-08 | 2003-05-16 | Brookwood Companies Inc | Laminado transpirable impermeable y procedimiento de fabricacion de dicho laminado. |
US5962179A (en) * | 1998-11-13 | 1999-10-05 | Xerox Corporation | Toner processes |
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JP2003526557A (ja) * | 1999-06-17 | 2003-09-09 | ミリケン・アンド・カンパニー | エアバッグファブリックのための2層コーティングシステム |
US6794024B1 (en) | 1999-11-01 | 2004-09-21 | Kimberly-Clark Worldwide, Inc. | Styrenic block copolymer breathable elastomeric films |
US6479154B1 (en) | 1999-11-01 | 2002-11-12 | Kimberly-Clark Worldwide, Inc. | Coextruded, elastomeric breathable films, process for making same and articles made therefrom |
US6415447B1 (en) | 1999-11-24 | 2002-07-09 | The Burton Corporation | Leakproof and breathable hand covering and method of making the same |
NL1016779C2 (nl) | 2000-12-02 | 2002-06-04 | Cornelis Johannes Maria V Rijn | Matrijs, werkwijze voor het vervaardigen van precisieproducten met behulp van een matrijs, alsmede precisieproducten, in het bijzonder microzeven en membraanfilters, vervaardigd met een dergelijke matrijs. |
US20020066212A1 (en) | 2000-12-06 | 2002-06-06 | Sympatex Technologies Gmbh | Waterproof shoe |
US6796865B2 (en) | 2001-12-06 | 2004-09-28 | Ingo Raithel | Inflatable insulation incorporating pressure relief means |
ATE384615T1 (de) * | 2001-12-07 | 2008-02-15 | Regenesis Llc | Hydrophile polymere enthaltender reinigungsartikel |
US7178171B2 (en) * | 2002-08-19 | 2007-02-20 | Kimberly-Clark Worldwide, Inc. | Elastomeric gloves having enhanced breathability |
US7270723B2 (en) * | 2003-11-07 | 2007-09-18 | Kimberly-Clark Worldwide, Inc. | Microporous breathable elastic film laminates, methods of making same, and limited use or disposable product applications |
US7932196B2 (en) * | 2003-08-22 | 2011-04-26 | Kimberly-Clark Worldwide, Inc. | Microporous stretch thinned film/nonwoven laminates and limited use or disposable product applications |
ITPD20030314A1 (it) * | 2003-12-30 | 2005-06-30 | Geox Spa | Articolo stratiforme impermeabile all'acqua e permeabile al vapore |
ITMI20050385A1 (it) | 2005-03-10 | 2006-09-11 | Nextec Srl | Procedimento e sistema per impermeabilizzare semilavorati di calzature guanti capi ed accessori di abbigliamento nonche' prodotti ottenuti con questo procedimento o sistema |
US8216660B2 (en) | 2005-05-04 | 2012-07-10 | Shawmut Corporation | Halogen and plasticizer free permeable laminate |
US20070049149A1 (en) * | 2005-08-24 | 2007-03-01 | Brookwood Companies, Inc. | Chemical-resistant breathable textile laminate |
US7662531B2 (en) * | 2005-09-19 | 2010-02-16 | Xerox Corporation | Toner having bumpy surface morphology |
US8353883B2 (en) * | 2005-12-15 | 2013-01-15 | Kimberly-Clark Worldwide, Inc. | Elastomeric glove containing a foam donning layer |
US20090011671A1 (en) * | 2007-06-11 | 2009-01-08 | Doesburg Van I | Polyurethane coated non-flooring products and methods for making same |
US20090029097A1 (en) * | 2007-06-11 | 2009-01-29 | Riddle Dennis L | Flooring products and methods |
US20090062432A1 (en) * | 2007-06-11 | 2009-03-05 | Doesburg Van I | Novel polyurethane compositions including castor oil |
US7665150B2 (en) * | 2007-09-24 | 2010-02-23 | Tyco Healthcare Group Lp | Double-cuffed chemotherapy gloves |
CN101270196B (zh) * | 2007-12-29 | 2011-06-01 | 武汉科技学院 | 一种吸湿透汽聚氨酯膜的生产方法 |
CN101959681A (zh) | 2008-02-27 | 2011-01-26 | 巴斯夫欧洲公司 | 包含塑料或金属箔的多层复合材料,相应生产方法及其用途 |
WO2010053797A2 (en) * | 2008-10-28 | 2010-05-14 | Janice Jaraicie | Undergarments with transparent paneling |
KR100903046B1 (ko) * | 2008-12-22 | 2009-06-18 | 이명철 | 방수용 장갑 및 그 제조방법 |
WO2010082648A1 (ja) * | 2009-01-19 | 2010-07-22 | ユニチカトレーディング株式会社 | 透湿防水性布帛及びその製造方法 |
US9643840B2 (en) * | 2012-06-27 | 2017-05-09 | Covestro Deutschland Ag | Dielectric polyurethane film |
CN102757637A (zh) * | 2012-07-06 | 2012-10-31 | 昆山华阳复合材料科技有限公司 | 具有防水透湿功能的可降解薄膜 |
US8663894B1 (en) | 2012-08-29 | 2014-03-04 | Xerox Corporation | Method to adjust the melt flow index of a toner |
FR2998142B1 (fr) * | 2012-11-21 | 2015-07-03 | Decathlon Sa | Procede de fabrication d’un article vestimentaire impermeable et respirant |
CN103485192B (zh) * | 2013-09-24 | 2015-08-19 | 安徽安利材料科技股份有限公司 | 一种无缝粘接聚氨酯合成革的制备方法 |
US20150230542A1 (en) * | 2014-02-14 | 2015-08-20 | W. L. Gore & Associates, Gmbh | Conformable Booties, Shoe Inserts, and Footwear Assemblies Made Therewith, and Waterproof Breathable Socks |
CN108135310B (zh) | 2015-08-13 | 2021-10-29 | W.L.戈尔及同仁股份有限公司 | 含有无缝可延伸膜的内靴和鞋类组件及其方法 |
US10314353B2 (en) | 2015-08-19 | 2019-06-11 | W. L. Gore & Associates, Inc. | Conformable seamless three dimensional articles and methods therefor |
JP6908607B2 (ja) | 2015-11-19 | 2021-07-28 | オーアンドエム ハリヤード インターナショナル アンリミテッド カンパニー | 手袋の着用側及び把持側間に高いコントラストを有する損傷検出手袋 |
CN107091704B (zh) * | 2016-02-17 | 2020-10-09 | 北京小米移动软件有限公司 | 压力检测方法和装置 |
TWM531145U (zh) * | 2016-04-19 | 2016-11-01 | Shuang Bang Ind Corp | 透濕防水襪 |
CN111065290A (zh) * | 2017-09-01 | 2020-04-24 | 巴斯夫欧洲公司 | 焊接多孔膜的方法 |
US11666106B2 (en) | 2018-11-30 | 2023-06-06 | O&M Halyard, Inc. | Low friction glove for easy double gloving |
CN111171554A (zh) * | 2020-03-02 | 2020-05-19 | 美瑞新材料股份有限公司 | 一种超高透湿型雾面热塑性聚氨酯组合物及其制备方法 |
US20240138501A1 (en) * | 2022-10-31 | 2024-05-02 | Jeffrey D. Heyd | Hand protection device and method of use |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3501326A (en) * | 1965-09-24 | 1970-03-17 | Du Pont | Glossy microporous sheet material |
US3660218A (en) * | 1968-10-15 | 1972-05-02 | Nat Patent Dev Corp | Hydrophilic polymer containing synthetic leather |
US3650880A (en) * | 1968-11-20 | 1972-03-21 | Hooker Chemical Corp | Porous polyurethanes and method of manufacture |
US3694301A (en) * | 1971-01-04 | 1972-09-26 | Minnesota Mining & Mfg | Hydrophilic nonwoven web and method of making it |
US3836423A (en) * | 1971-09-09 | 1974-09-17 | Hooker Chemical Corp | Method of introducing air permeability into a non-porous continuous film and resultant film |
US4216251A (en) * | 1977-09-05 | 1980-08-05 | Kuraray Co., Ltd. | Method of producing a leather-like sheet material having a high-quality feeling |
US4194041A (en) * | 1978-06-29 | 1980-03-18 | W. L. Gore & Associates, Inc. | Waterproof laminate |
JPS58197381A (ja) * | 1982-05-10 | 1983-11-17 | 株式会社クラレ | 低滑り特性を有する皮革様シ−ト物 |
DE3374656D1 (en) * | 1982-08-12 | 1988-01-07 | Smith & Nephew Ass | Wound dressing and its manufacture |
US4443511A (en) * | 1982-11-19 | 1984-04-17 | W. L. Gore & Associates, Inc. | Elastomeric waterproof laminate |
US4632860A (en) * | 1984-03-02 | 1986-12-30 | D'antonio | Waterproof breathable fabric |
GB2181691B (en) * | 1985-10-21 | 1990-05-23 | Porvair Ltd | Gloves |
DE3882319T2 (de) * | 1987-09-28 | 1994-02-17 | Kuraray Co | Lederartiges Schichtprodukt und Verfahren zu dessen Herstellung. |
GB8802933D0 (en) * | 1988-02-09 | 1988-03-09 | Porvair Ltd | Porelle/stretchable fabric composite & socks therefrom |
US4961985A (en) * | 1988-07-06 | 1990-10-09 | W. L. Gore & Associates, Inc. | Fabrics for protective clothing |
US5351698A (en) * | 1988-11-15 | 1994-10-04 | Family Health International | Bidirectionally donnable generally tubular sheath articles, and apparatus and method for making and using same |
GB8911409D0 (en) * | 1989-05-18 | 1989-07-05 | Woodcock Ashley | Infection barrier |
US5204156A (en) * | 1989-10-17 | 1993-04-20 | Malden Mills Industries, Inc. | Windproof and water resistant composite fabric with barrier layer |
JP3209367B2 (ja) * | 1992-08-25 | 2001-09-17 | セイコー化成株式会社 | 透湿性防水布帛の製造方法 |
-
1994
- 1994-06-24 EP EP94923246A patent/EP0758416A1/en not_active Withdrawn
- 1994-06-24 JP JP7528914A patent/JPH09512760A/ja active Pending
- 1994-06-24 CN CN94195104A patent/CN1149327A/zh active Pending
- 1994-06-24 AU AU73171/94A patent/AU7317194A/en not_active Abandoned
- 1994-06-24 CA CA002187634A patent/CA2187634A1/en not_active Abandoned
- 1994-06-24 WO PCT/US1994/007168 patent/WO1995030793A1/en not_active Application Discontinuation
-
1996
- 1996-08-08 US US08/694,223 patent/US5650225A/en not_active Expired - Fee Related
Cited By (13)
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CN101809224A (zh) * | 2007-10-05 | 2010-08-18 | 东丽株式会社 | 包含来自植物的成分的防水加工布帛 |
CN101481579B (zh) * | 2008-12-23 | 2011-06-08 | 中国人民解放军总后勤部军需装备研究所 | 一种防水透湿改性聚氨酯涂层胶及其制备方法 |
CN102753324A (zh) * | 2009-11-02 | 2012-10-24 | Atg锡兰(私人)有限公司 | 防护服装及其材料 |
CN101929081A (zh) * | 2010-08-05 | 2010-12-29 | 中国纺织科学研究院 | 一种高耐水压高透湿性涂层面料及其制备工艺 |
CN102631114A (zh) * | 2012-04-28 | 2012-08-15 | 德清舒华泡沫座椅有限公司 | 一种枕头 |
CN102631114B (zh) * | 2012-04-28 | 2014-06-04 | 德清舒华泡沫座椅有限公司 | 一种枕头 |
CN103921524A (zh) * | 2013-01-15 | 2014-07-16 | 海洲工业股份有限公司 | 一体成形防水透气袜的制法及防水透气袜 |
CN106413457A (zh) * | 2014-02-14 | 2017-02-15 | W.L.戈尔及同仁股份有限公司 | 顺应性防水透气短袜及其方法 |
CN106413457B (zh) * | 2014-02-14 | 2019-10-11 | W.L.戈尔及同仁股份有限公司 | 顺应性防水透气短袜及其方法 |
CN108936838A (zh) * | 2017-05-20 | 2018-12-07 | 宜兴市艺蝶针织有限公司 | 一种复合型防水袜生产工艺 |
CN108978252A (zh) * | 2018-08-23 | 2018-12-11 | 江苏恒辉安防股份有限公司 | 一种双层pu手套的加工方法 |
CN112726222A (zh) * | 2020-12-11 | 2021-04-30 | 苏州维明化学工业有限公司 | 一种热熔型反应性聚氨酯涂层胶及防水透湿面料 |
CN112726222B (zh) * | 2020-12-11 | 2023-05-05 | 苏州维明化学工业有限公司 | 一种热熔型反应性聚氨酯涂层胶及防水透湿面料 |
Also Published As
Publication number | Publication date |
---|---|
AU7317194A (en) | 1995-11-29 |
CA2187634A1 (en) | 1995-11-16 |
EP0758416A1 (en) | 1997-02-19 |
JPH09512760A (ja) | 1997-12-22 |
US5650225A (en) | 1997-07-22 |
WO1995030793A1 (en) | 1995-11-16 |
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