CN116065401A - 聚合物织物 - Google Patents

聚合物织物 Download PDF

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Publication number
CN116065401A
CN116065401A CN202211375623.8A CN202211375623A CN116065401A CN 116065401 A CN116065401 A CN 116065401A CN 202211375623 A CN202211375623 A CN 202211375623A CN 116065401 A CN116065401 A CN 116065401A
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CN
China
Prior art keywords
functional layer
fabric
layer
polymer
polymer fabric
Prior art date
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Pending
Application number
CN202211375623.8A
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English (en)
Inventor
M·M·侯赛因
C·艾伦伯格
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Sefar AG
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Sefar AG
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Publication of CN116065401A publication Critical patent/CN116065401A/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
    • B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1692—Other shaped material, e.g. perforated or porous sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0004—Organic membrane manufacture by agglomeration of particles
    • B01D67/00042—Organic membrane manufacture by agglomeration of particles by deposition of fibres, nanofibres or nanofibrils
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    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/127—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction using electrical discharge or plasma-polymerisation
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    • B05D3/066—After-treatment involving also the use of a gas
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
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    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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    • D06M10/025—Corona discharge or low temperature plasma
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Abstract

本发明涉及一种聚合物织物，其包括由第一化合物制成的具有疏水和疏油特性的外功能层和由第二化合物制成的具有疏水特性的第二功能层，其中第一化合物和第二化合物彼此不同。此外，外功能层至少部分地涂覆第二层。另外，本发明涉及生产聚合物织物的方法和用于生产聚合物织物的设备。

Description

聚合物织物
技术领域
本发明涉及具有疏水和疏油特性的聚合物织物以及生产具有疏水和疏油特性的聚合物织物的方法。此外，本发明涉及用于生产聚合物织物的设备。
背景技术
在微滤应用中对通风场所、装置和配件的保护有着高的要求。这里的挑战之一在于防止有害液体、颗粒进入通风场所的内部。因此，液体排斥性涂料已因其能够排斥从高表面张力液体如水到低表面张力油的范围广泛的液体而在许多部门中频繁使用。
传统上，长分子链例如C8氟碳(FC)化合物被用于涂料，以保护人员不仅免受战剂的伤害，而且免受日常物质如水、油、燃料、润滑剂、清洁溶剂和其他污染物的伤害。然而，由于它们潜在的高毒性，立法已经落实到位来限制或禁止它们在世界范围内的使用。替代的涂料已被开发并投放市场。特别地，短链C6氟化学涂料在性能上已接近传统的C8基FC涂料，而没有高的环境风险。
C6基FC的使用仍然导致了全球环境污染，原因是它含有痕量的全氟辛酸(PFOA)及其盐类，并且由于这些物质的持续存在和潜在的生物累积性而已引起人们的关注。而且，自2020年12月3日起生效的新REACH法规(EU/784/2020)允许将PFOA阈值保持在25ppb (十亿分率)以下。因此，出于健康原因，总趋势是避免这些化学物质。而且，仍然需要对油脂具有高度排斥性的下一代超级疏水和疏油涂料。
六甲基二硅氧烷(HMDSO)是一种替代C6 FC的行业选择，因为它是无毒材料并且在加工过程中不会产生有害物质。由于其合适的蒸气压，它被广泛用作等离子体过程的前体单体。来自纯HMDSO的富碳、等离子体聚合的HMDSO (pp-HMDSO)显示出有前景的机械性质如低的内应力、良好的粘附和优异的疏水屏障性能。尽管pp-HMDSO涂料提供的耐水性是有前景的，但它不提供任何疏油性质。
随着薄膜技术中技术发展的进步，持续需要开发一种化学气相沉积方法，以使用超短链PFAS来制备具有永久性疏水和疏油官能团的薄膜，该薄膜对过滤应用表现出独特的功能性质。合适的挥发性前体的缺乏和涂料中组成控制的困难是阻碍实现这一目的的主要障碍。
发明内容
因此，本发明的目的在于提供一种坚固且可靠的织物、制造所述织物的方法和用于生产所述聚合物织物的设备，所述织物具有疏水和疏油特性，用于卫生和过滤应用如水分离、声学、医学、健康护理、食品。
根据本发明，在一个方面，此目的通过具有权利要求1的特征的聚合物织物和通过具有权利要求9的特征的生产聚合物织物的方法以及具有权利要求14的特征的用于生产聚合物织物的设备来实现。
本发明的优选实施方案在相应的从属权利要求中陈述。
根据本发明的聚合物织物包括由第一化合物制成的具有疏水和疏油特性的外功能层和由第二化合物制成的具有疏水特性的第二功能层，其中第一化合物和第二化合物彼此不同。此外，外功能层至少部分地涂覆第二层。
此外，根据本发明的生产聚合物织物的方法的特征在于，借助于低压等离子体涂覆技术在聚合物织物上沉积提供疏水和疏油特性的外功能层，和借助于低压等离子体涂覆技术在聚合物织物上沉积提供疏水特性的第二功能层，其中所述外功能层和所述第二功能层彼此不同。另外，在聚合物织物上沉积外功能层之前在聚合物织物上沉积第二功能层，并且其中所述外功能层至少部分地涂覆所述第二层。
本发明的基本思想在于背离在织物上提供具有所有所需特性或性质的一层的现有技术体系的事实。基于本发明，提供相互交叠的两个层，其中这些层彼此不同。从而可以选择具有不同特性的不同层。因此，不再需要寻找和使用提供所有所需特性的材料，而是可以组合用于不同的层的不同材料，以便该组合提供所需的特性。
优选地，第二功能层不具有疏油特性。因此，它明显不同于提供疏水和疏油特性的外功能层。然而，由于这两个层彼此叠加的事实，例如外层的疏水特性不必处于非常高的水平，因为在下面提供的第二功能层也提供疏水特性。
在一个实施方案中，外功能层为等离子体纳米涂层，其基于仅包含一个、两个或三个C原子的全氟和多氟烷基物质(PFAS)和/或基于全氟聚醚化合物(PFPE)。此外，在另一个或组合实施方案中，第二功能层为等离子体纳米涂层，其基于六甲基二硅氧烷(HMDSO)或类金刚石碳(DLC)层。
如上所述，短分子链C6氟碳(FC)化合物的使用是成问题的，甚至在一些地区不再被允许。用超短链C3至C1氟碳(FC)化合物比如全氟和多氟烷基物质(PFAS)代替后者的直接步骤乍一看似乎是一个有前景的解决方案。然而，尽管这些化合物原则上提供疏水和疏油特性，但人们认识到在使用等离子体纳米涂覆将它们沉积在织物上时会出现问题。在等离子体聚合物涂覆过程期间，PFAS基C3至C1氟碳化合物(FC)层的厚度与先前的C6至C8基氟碳化合物(FC)层相比非常薄。因此，尤其是提供在织物、例如织造织物上的该层仅提供不足的层和因此可改善的疏水特性。令人惊奇的是，人们认识到即使是该较薄的层也提供良好的疏油特性。
在分析由基于全氟聚醚化合物(PFPE)的等离子体聚合物涂覆过程产生的层时，也得出了这一观察结果。然而，与基于仅包含一个、两个或三个C原子的全氟和多氟烷基物质(PFAS)的等离子体纳米涂层相比，全氟聚醚化合物的好处在于，全氟聚醚化合物(PFPE)更加环境友好。
基于本发明，外功能层为等离子体纳米涂层，其基于仅包含一个、两个或三个C原子的全氟和多氟烷基物质(PFAS)和/或基于全氟聚醚化合物(PFPE)，提供在具有疏水特性的第二功能层上。因此，外功能层的可改善的疏水特性可由本发明的第二功能层来改善。换言之，首先在织物上沉积具有良好疏水特性的层，并在第二个进一步的步骤中在已经被第二功能层所覆盖的织物上沉积具有疏水和疏油特性的外功能层。由于这种构造，该织物具有优异的疏水和疏油特性。
第二功能层可基于六甲基二硅氧烷(HMDSO)或类金刚石碳(DLC)层。使用等离子体聚合物涂覆，第二功能层由此可形成为pp-HMDSO基础涂层，即类聚(二甲基硅氧烷)(类PDMS)涂层、氟掺杂pp-HMDSO涂层和/或氟掺杂DLC涂层。在通过等离子体聚合物技术沉积时，这些涂层具有足够好的沉积速率以产生比先前提到的外功能层厚的层。因此，由于这些两层技术的组合，可通过聚合物等离子体涂覆为聚合物织物提供优异的疏水和疏油特性。
优选地，外功能层和/或第二功能层借助于低压等离子体涂覆技术沉积。该技术也被称为等离子体增强化学气相沉积(PECVD)方法。它使用冷等离子体。因此，该技术适合于对温度敏感的聚合物材料如单丝网状物、复合膜。使用PECVD可沉积具有结合到网络中的官能团的高度交联的聚合物网络，从而可获得改性表面的高度长期稳定性。
通常，聚合物织物可以是任何种类的织物。在一个实施方案中，聚合物织物包括由第一和第二单丝纱线织造的织造载体层，其中所述第一和第二单丝纱线由相同或不同的聚合物材料产生。提供的单丝纱线特别适合于所提出的基于等离子体的沉积方法。
为了改善聚合物织物的过滤性质，聚合物织物可以包括复合膜，该复合膜至少包括织造载体层和电纺膜层。电纺膜层可以具有0.20μm至2.0μm之间的孔隙尺寸。膜层可以直接纺到织造载体层上，或纺到基底上并在后来在粘结过程期间转移到织造载体层上。
如所说明的，外功能层的厚度小于第二功能层。如果第二功能层的厚度与外功能层的厚度之比为约2:1、3:1或更大，则可实现优异的疏水和疏油特性。例如，第二功能层可以具有20至300nm的层厚度，而外功能层可以具有优选10至150nm的层厚度。
根据本发明的生产聚合物织物的方法，借助于低压等离子体涂覆技术在聚合物织物上沉积提供疏水和疏油特性的外功能层，和借助于低压等离子体涂覆技术在聚合物织物上沉积提供疏水特性的第二功能层，其中所述外功能层和所述第二功能层彼此不同。另外，在聚合物织物上沉积外功能层之前在聚合物织物上沉积第二功能层，并且其中所述外功能层至少部分地涂覆所述第二层。
本发明的一个中心思想在于提供两个不同的层，一个至少部分地叠加另一个。因此，外功能层的特性可由第二功能层的特性支持。因此，只需使用一种具有所有所需特性的化合物，就可获得优异的结果，即就提供具有疏水和疏油特性的聚合物织物而论优异的结果。如果外功能层基于仅包含一个、两个或三个C原子的全氟和多氟烷基物质(PFAS)和/或基于全氟聚醚化合物(PFPE)，它们比先前使用的化合物更环境友好但提供相比较而言不那么好的疏水和疏油特性，则这一点尤其重要。
为了改善与第二功能层的粘附，可在沉积第二功能层之前，借助于低压等离子体技术使用不可聚合气体比如氩气、氦气、氮气、氧气和四氟甲烷气体和/或其气态混合物进行聚合物织物的预处理。
另外地或替代地，在第二功能层的沉积之前，可对聚合物织物进行两步预处理，其中在第一步中使用凹版印刷和/或狭缝模头涂覆方法用UV可固化压印树脂涂覆聚合物织物并在第二步中使用UV压印和/或热压花方法进行表面图案化。
最后，作为在沉积第二功能层之前的先前说明的预处理的补充或替代，可对聚合物织物进行预处理，其中用包含氢氧化钠(NaOH)的水溶液处理聚合物织物。
由于这些预处理，织物的表面可在沉积功能层之前被化学改性和/或形态学改性，结果是等离子体-聚合物可在等离子体聚合过程中特别牢固地粘附到基底。此外，还可经由纳米压印和等离子体预处理实现表面结构化以改善滚离效应(roll-off effect)，即所谓的莲花效应。通过这些预处理之一或它们的组合，实现了聚合物织物的清洁、活化和/或纹理化(texturing)，从而可增加第二功能层的粘附。基于本发明，织物的预处理或清洁不视为在织物上产生层。
基于改进的实施方案，外功能层和/或第二功能层在一个工艺中以一个加工步骤沉积，以获得氟掺杂的HMDSO等离子体纳米涂层和/或氟掺杂的DLC等离子体纳米涂层。
基于本发明，可提供耐水性和油排斥性提高的聚合物织物，和/或提供为110°至150°的与水、二碘甲烷和戊二醇的接触角及根据AATCC 118为5至8的油等级。
用于生产本发明的聚合物织物的本发明设备包括低压等离子体涂覆装置，其适于借助于低压等离子体涂覆技术在聚合物织物上沉积提供疏水和疏油特性的外功能层，适于借助于低压等离子体涂覆技术在聚合物织物上沉积提供疏水特性的第二功能层，其中所述外功能层和所述第二功能层彼此不同，并且适于首先在聚合物织物上沉积第二功能层，然后在聚合物织物上沉积外功能层，其中所述外功能层至少部分地涂覆所述第二层。
附图说明
下面通过附图中示意性地示出的优选示例性实施方案进一步描述本发明，在附图中：
图1为聚合物织物的示意图；
图2为根据本发明的包括膜(“单层”)的聚合物织物的示意性横截面图；
图3为呈所谓的“夹心”布置的根据本发明的复合材料的示意性横截面图；
图4为具有多层结构(“多层”)的根据本发明的复合材料的示意性横截面图；
图5为具有两个不同的载体层、呈“混杂”布置的根据本发明的复合材料的示意性横截面图；和
图6为生产本发明的聚合物织物的方法的示意图。
具体实施方式
图1示出了聚合物织物100的强烈示意图。在该图的左侧，聚合物织物100仅提供有外功能层120，其中在右侧，除了外功能层120外还提供了第二功能层110。下面将基于该实例进一步说明本发明的构思。
在图1中，示出了聚合物织物100的高度放大示意图，其中呈现了两根纬线102和一根经线104。
如果如左侧所示，仅提供基于包含1至3个C原子的PFAS的第一聚合物沉积，则由于该化合物的不最理想的沉积速率，该层将不会完全覆盖纱线。这尤其可在左边纬线102和经线104的接触区域中看到。如果代替包含1至3个C原子的PFAS，提供基于PFPE的第一聚合物沉积，会出现相同的结果。
与此相反，除了外功能层120外，还提供第二功能层110(例如基于HMDSO)，以确保在提供外功能层120之前，织物100被第二功能层110完全覆盖。一方面可实现外功能层120的更好沉积，另一方面，即使有区域不被外功能层120覆盖，它们也至少被第二功能层110覆盖。作为HMDSO第二功能层110的替代，该层也可基于F掺杂的HMDSO、DLC、F掺杂的DLC或其组合。
图2示出了聚合物织物的横截面图，这里聚合物织物作为具有载体层11的复合材料10。在载体层11上布置了膜12，其根据电纺方法形成并施加到载体层11上。为了改善膜12与载体层11的粘附性，复合材料可设计为具有至少一个将两层彼此牢固接合的接合点13。这可以是呈点或线的形式的熔融粘结或粘合剂粘结位置。由于载体材料11和膜12的层厚度小，复合材料可在接合位置处被接合点13完全穿透。
复合材料10，更特别地电纺膜12，可形成为具有多孔性。复合材料10的表面和孔隙的纤维可被涂覆有根据本发明的两步等离子体涂覆方法施加的涂层，如参考图1所说明。由此pp-HMDSO或DLC的第一等离子体涂覆仅施加以提供疏水特性。在施加提供基于仅包含一个、两个或三个C原子的PFAS和/或基于PFPE的层的进一步等离子体涂覆后，提供疏水和疏油特性。外功能层和第二功能层也可在一个等离子体加工步骤中沉积，以获得氟掺杂的HMDSO或氟掺杂的DLC层，从而提供疏水和疏油性质。任选地，F掺杂的HMDSO或F掺杂的DLC也可用作第二功能层。
纤维的表面涂层作为一个整体在附图中由描绘的点和线14示意性地示出。涂层还可涂覆在膜12的孔隙中的区域中的纤维，该区域位于复合材料10内部或更深的地方。因此，不仅可涂覆复合材料的宏观外表面，而且可涂覆微观内表面，即例如纤维、凹处和不平坦部分，在这种情况下，单根纤维被单独地包封或围绕。
图3示出了呈所谓的“夹心”布置的又一复合材料10。在这种情况下，膜12布置在两个载体层11之间，由此膜12被保护在层之间，特别是免受机械应力。在夹心布置的一个实施方案中，可例如达到200Pa下15.6 l/m2s的透气性。基本上，采用夹心、多层或混杂布置也可达到高达200Pa下80 l/m2.s的透气性。
在复合材料10中层的每个可能的布置中，这些层可通过简单的层压而相互层叠布置。然而，这些层也可通过接合点13牢固地彼此接合，由此可获得复合材料10的特别可靠的机械强度。
在图4中，示出了复合材料10 (多层)的多层布置。在此布置中，提供载体层11和膜层12，使得它们以交替的方式相互层叠地支撑。根据图4，提供了两个载体层11和两个膜层12。多层布置也可具有随机数量的载体层11和/或膜层12。根据需要，两个膜层12也可以在两个或更多个载体层之间相互直接层叠提供。即使在多层布置的情况下，也可在相互层叠地支撑的所有膜层12和载体层11的微观表面上提供本发明的两步等离子体涂层。因此，在多层结构中，同样可在复合材料10的内表面上提供本发明的两步等离子体涂层。
图5示出了复合材料10的一种变体，其中膜12布置在第一载体层11与第二载体层15之间。基本上，第一载体层11可特别地设计为织物，而第二载体层15不同于第一载体层11，并可特别地作为起绒布(fleece)提供。通过这样的“混杂”布置，不同材料的性质可有利地结合在复合材料中，从而可在复合材料10中以有利的方式实现过滤、保护性质和声传输性质。在如图5中示出的混杂布置中，同样可在复合材料10上提供本发明的两步等离子体涂层，在这种情况下，第二功能层和外功能层的等离子体聚合也可在复合材料10内更深的层中(如孔隙孔内)发生。
图6的方案示出了本发明的聚合物织物比如包括载体层的复合材料的制造过程的实例。提供收集基底(上图)，在其上形成电纺膜(第一生产步骤)。电纺膜根据通常已知的构思形成并在下文中进一步描述。
在第二步中，将形成的膜转移并粘结(粘结1)到载体层上，并且其上形成有电纺膜的原始收集基底可任选地去除(收集基底去除)。根据提供给图的上文，载体层可为网状物或织物。
任选地，它们的第二粘结(粘结2)可在第二外层引入之后进行，之后是任选的轧光工艺。因此，膜可任选地布置在两个同样或不同的层之间，从而形成夹心结构。第二外层可例如作为网状物、衬里或非织造材料提供。最后，本发明的两步等离子体涂覆被施加给至少一个载体层和膜。由此，首先沉积仅提供疏水特性的层，然后沉积提供疏水和疏油特性的层。第一层可以是pp-HMDSO、氟掺杂的HMDSO、DLC或氟掺杂的DLC层。另外的外层可以是基于仅包含一个、两个或三个C原子的PFAS和/或基于PFPE的层。
电纺
制备纳米纤维幅材的工艺在WO 2006/131081、WO 2008/106903中示出。
简言之，在电纺过程中，使用高电压产生离开吸移管(pipette)的聚合物溶液或熔体的带电射流。在到达收集屏之前，溶液射流蒸发或凝固，并作为小纤维的互连幅材而收集。一个电极被放置到纺丝溶液/熔体中，另一个被附接到收集器。在大多数情况下，收集器只是简单地接地。电场施加到容纳该溶液流体的毛细管的末端，该溶液流体由其表面张力保持。这会在液体的表面上诱导电荷。相互的电荷排斥和表面电荷向反电极的收缩导致与表面张力直接相反的力。随着电场强度增加，在毛细管尖端处的流体的半球形表面伸长，形成称为泰勒锥的圆锥形状。进一步增大电场，达到临界值，此时排斥性静电力克服表面张力，流体的带电射流从泰勒锥的尖端喷出。排出的聚合物溶液射流经历不稳定和伸长过程，这允许射流变得非常长且细。同时，溶剂蒸发，留下带电的聚合物纤维。在熔体的情况下，排出的射流在当其在空气中行进时凝固。
粘结方法
有不同的粘结技术可用。热熔凹版层压技术、超声粘结技术、浸渍粘结技术、UFD纤维化喷雾技术(热熔)和纺丝-幅材粘结(spun-web bonding)技术。
热熔凹版层压技术在工业上针对在线过程建立。因此，对于“夹心”类型的膜，也可在一条生产线上完成两步粘结。它使用多用途热熔层压和涂覆系统，该系统由用于点涂的凹版辊、旋转计量头(正/正或负/负)和施加辊及层压辊以及反压辊组成。
凹版辊用于点涂粘合剂，从而可使用两种不同的反应性PU基粘合剂(一种用于PU电纺膜，另一种用于PA6膜)。通过损失约15-25%的透气性，可获得高粘结强度。必须仔细选择粘合剂以避免在膜的最终应用过程中出现问题(符合度、物理和化学适用性、医疗和食品级等)。由于粘合剂，观察到材料的变硬。
浸渍粘结技术(化学粘结)可用于在电纺工艺之前对载体进行预处理，这有时是优选的。而且，可消除用于粘结的另外的工艺步骤，这是主要优点。然后可将两层层压物用于第二粘结，例如热熔、纺丝-幅材、UFD等，以形成多层通气孔。
UFD是一种纤维化喷雾技术，也是用于热熔粘合剂涂布机的最先进技术。应用层压板技术(LPT)来产生粘合剂的长丝股线。使用加热空气来使这些股线伸长，并将它们以随机或有序的图案铺放。在许多情况下，通过使用UFD技术，由于粘合剂的高精度应用，可将粘合剂用量减少20-50%而不会不利地影响粘结强度或耐久性。可利用非接触模式，其会减少层压过程中电纺纤维损坏的机会。UFD技术是一种比热熔凹版层压更清洁的工艺。
纺丝-幅材粘结技术产生三维结构而不是具有封闭表面的膜。开放式结构使得所得层压物更具柔韧性且透气性高。幅材由不同的材料制成：共聚酰胺、共聚酯、共聚烯烃、聚氨酯等。纺丝-幅材技术是一种非常简单的方法。层压过程中要考虑的三个主要参数为温度、压力和时间。
轧光
轧光被用在材料如织物、网状物、层压通气孔上以获得更光滑且更薄的材料，由此使材料在升高的温度和压力下通行过辊之间或辊下方。取决于轧光条件，孔隙的尺寸和形状可受到影响。
等离子体PECVD
纺织品材料的等离子体处理可作为用于技术和医用纺织品以及用于复合材料的纺织品整理工艺而应用，以改善其表面性质比如水和油排斥性。与常规的湿法化学纺织品整理相比，等离子体技术在环境问题方面显示出优势。使用PECVD处理，可例如获得粘附特性的改善、增加亲水性、在表面上引入特殊官能团或改变表面形态。
在通常称为等离子体聚合或PECVD的等离子体沉积中，可在基底表面上沉积非常薄的聚合物层(纳米级)。该层通过有机前体气体的聚合形成，该前体气体直接在基底表面上聚合。与典型的聚合相比，等离子体聚合可使用每一种单体气体或蒸气而不受限于其反应性。等离子体聚合物表现出非常规的聚合行为，具有支化和随机封端的链及高度的交联。
等离子体聚合物的本体结构完全不规则，与常规聚合物相去甚远。等离子体聚合物涂层(纳米薄膜)与常规聚合物的不同在于每体积高密度的官能团、高度交联和支化的等离子体聚合物网络、纳米厚的涂层(<200nm)、涂层与基底的高粘附和基底本体性质的无变化，基底可为聚合物织物。
根据本发明，等离子体处理可在等离子体室中进行，该等离子体室具有卷对卷系统中的多个辊和/或扩张器，该卷对卷系统以优选约13MHz至14MHz、优选约13.5MHz的射频操作，或使用直流(DC)电源操作。
实施本发明的一种方式可以是：首先在优选约70毫托(mTorr)至约200毫托的基础压力下，在优选约20℃直至约60℃的温度下，以优选约500瓦至约1800瓦的功率输出，进行优选约2分钟至约5分钟的预处理。随后，在优选约15毫托至约150毫托的基础压力下，在优选约20℃直至约60℃的温度下，以优选约100瓦至约1000瓦的功率输出，进行优选约2分钟至约5分钟的时间的第一涂覆步骤。然后，在优选约15毫托至约150毫托的基础压力下，在优选约20℃直至约60℃的温度下，以优选约100瓦至约800瓦的功率输出，进行优选约2分钟至约5分钟的时间的第二涂覆步骤，以沉积外功能层。在此实施方案中，外功能层基于的是C1-C3基PFAS，而第二功能层基于的是HMDSO或DLC。
实施例
实施例1
基于根据本发明的织物的过滤介质的一个优选实施方案包括具有不同图案的织造结构以获得最大排斥性，并因此可获得接触角大于110°的超疏水和疏油表面，如表1中可见。等离子体诱导的疏水和疏油的程度也与纺织品结构和组织构造有关。等离子体物质向纺织品结构中的渗透可以实现更高的排斥性。因此，基底的疏水和疏油性还取决于织物中纬丝和经丝两者的排列、最终长丝的细度、织物密度和组织结构以及纤维含量。
表1：三种液体在经涂覆聚酯网状物(物品编号3A07-0025-158-XX)上的比较示例接触角
实施例2
也根据AATCC 118平行地评价了经处理的聚合物织物的油排斥性，这也是一种“通过或失败”类型的方法，其测试油性液体排斥性而不是水性液体。AATCC 118使用八种表面张力递减的液态烃来测定油排斥性。油的等级的范围从使用Kaydol (一种矿物油，在25℃下表面张力为31.5mN/m)的0 (失败)，到使用正庚烷(其在25℃下具有19.8mN/m的表面张力)的8 (最高油排斥性)。分配给不润湿样品的油的数字被视为排斥性油等级。
表2：对经涂覆聚酯网状物(物品编号3A07-0025-158-XX)的比较示例喷雾测试和油滴测试
如在表2中可见，与C6基标准涂层相比，使用本发明的涂层可以获得相似和/更好的结果。这一发现可解释如下；物理改性促进滚离效应。类PDMS涂层(即，pp-HMDSO)增强而获得良好的水排斥性，并且氟化的顶部涂层对抗油、脂肪和牛奶有效。
基于本发明，可以产生用于过滤介质的聚合物织物，其中嵌入到织物上的疏水和疏油基团对根据ASTM F1980-16的加速老化处理具有稳定性和抵抗性。此外，分别根据ISO4920和AATCC 118，过滤介质两步疏水和疏油纳米涂层对水和油具有优异的排斥性。
基于本发明，可以提供具有疏水和疏油特性的坚固且可靠的织物。

Claims (14)

1.聚合物织物，包括：
由第一化合物制成的具有疏水和疏油特性的外功能层，
由第二化合物制成的具有疏水特性的第二功能层，
其中所述第一化合物和所述第二化合物彼此不同，并且
其中所述外功能层至少部分地涂覆所述第二层。
2.根据权利要求1所述的聚合物织物，其中所述第二功能层不具有疏油特性。
3.根据权利要求1所述的聚合物织物，其中所述外功能层为等离子体纳米涂层，其基于仅包含一个、两个或三个C原子的全氟和多氟烷基物质(PFAS)和/或基于全氟聚醚化合物(PFPE)。
4.根据权利要求1所述的聚合物织物，其中所述第二功能层为等离子体纳米涂层，其基于六甲基二硅氧烷(HMDSO)或类金刚石碳(DLC)层。
5.根据权利要求1所述的聚合物织物，其中所述外功能层和/或所述第二功能层借助于低压等离子体涂覆技术沉积。
6.根据权利要求1所述的聚合物织物，其中所述聚合物织物包括由第一和第二单丝纱线织造的织造载体层，其中所述第一和第二单丝纱线由相同或不同的聚合物材料产生。
7.根据权利要求1所述的聚合物织物，其中所述聚合物织物包括复合膜，所述复合膜至少包括织造载体层和电纺膜层。
8.根据权利要求1所述的聚合物织物，其中所述第二功能层的厚度与所述外功能层的厚度之比为约2:1、3:1或更大。
9.生产根据权利要求1所述的聚合物织物的方法，
其中借助于低压等离子体涂覆技术在所述聚合物织物上沉积提供疏水和疏油特性的外功能层，
其中借助于低压等离子体涂覆技术在所述聚合物织物上沉积提供疏水特性的第二功能层，
其中所述外功能层和所述第二功能层彼此不同，
其中在所述聚合物织物上沉积所述外功能层之前，在所述聚合物织物上沉积所述第二功能层，并且
其中所述外功能层至少部分地涂覆所述第二层。
10.根据权利要求9所述的方法，其中在沉积所述第二功能层之前，借助于低压等离子体技术使用氩气、氦气、氮气、氧气和四氟甲烷气体和/或其气态混合物进行所述聚合物织物的预处理。
11.根据权利要求9所述的方法，其中在沉积所述第二功能层之前对聚合物织物进行两步预处理，其中
在第一步中使用凹版印刷和/或狭缝模头涂覆方法用UV可固化压印树脂涂覆所述聚合物织物，和
在第二步中使用UV压印和/或热压花方法进行表面图案化。
12.根据权利要求9所述的方法，其中在沉积所述第二功能层之前进行所述聚合物织物的预处理，其中用包含氢氧化钠(NaOH)的水溶液处理所述聚合物织物。
13.根据权利要求9所述的方法，其中所述外功能层和/或第二功能层在一个工艺中以一个加工步骤沉积，以获得氟掺杂的六甲基二硅氧烷(HMDSO)等离子体纳米涂层和/或氟掺杂的DLC等离子体纳米涂层。
14.用于生产根据权利要求1所述的聚合物织物的设备，所述设备包括低压等离子体涂覆装置，所述低压等离子体涂覆装置适于：
- 借助于低压等离子体涂覆技术在所述聚合物织物上沉积提供疏水和疏油特性的外功能层，
- 借助于低压等离子体涂覆技术在所述聚合物织物上沉积提供疏水特性的第二功能层，其中所述外功能层和所述第二功能层彼此不同，并且
- 首先在所述聚合物织物上沉积所述第二功能层，且然后在所述聚合物织物上沉积所述外功能层，其中所述外功能层至少部分地涂覆所述第二层。
CN202211375623.8A 2021-11-04 2022-11-04 聚合物织物 Pending CN116065401A (zh)

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