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    • 专利摘要:
    The present invention relates to a method of depositing a halogen-free water-repellent nano-coating on textile products via a low-pressure plasma polymerization deposition process, wherein the halogen-free water-repellent nano-coating is resistant to washing and dry cleaning.
    公开号:BE1024821B1
    申请号:E2015/5507
    申请日:2015-08-12
    公开日:2018-07-13
    发明作者:Filip Legein；Eva Rogge
    申请人:Europlasma Nv；
    IPC主号:
    专利说明:

    (73) Holder (s):
    EUROPLASMA NV 9700, OUDENAARDE Belgium (72) Inventor (s):
    EMPTY Filip
    3140 REVERSE
    Belgium
    RYE Eva
    9770 CROSS HOUSE
    Belgium (54) Surface coatings (57) The present invention relates to a method of depositing a halogen-free water-repellent nano-coating on textile products via a low-pressure plasma polymerization deposition process, wherein the halogen-free water-repellent nano-coating is resistant to washing and dry cleaning
    Figure 1
    BELGIAN INVENTION PATENT
    FPS Economy, K.M.O., Self-employed & Energy
    Publication number: 1024821 Filing number: BE2015 / 5507
    Intellectual Property Office
    International classification: D06M 10/10 D06M 15/643 D06M 11/79 Date of issue: 13/07/2018
    The Minister of Economy,
    Having regard to the Paris Convention of 20 March 1883 for the Protection of Industrial Property;
    Having regard to the Law of March 28, 1984 on inventive patents, Article 22, for patent applications filed before September 22, 2014;
    Having regard to Title 1 Invention Patents of Book XI of the Economic Law Code, Article XI.24, for patent applications filed from September 22, 2014;
    Having regard to the Royal Decree of 2 December 1986 on the filing, granting and maintenance of inventive patents, Article 28;
    Having regard to the application for an invention patent received by the Intellectual Property Office on 12/08/2015.
    Whereas for patent applications that fall within the scope of Title 1, Book XI, of the Code of Economic Law (hereinafter WER), in accordance with Article XI.19, § 4, second paragraph, of the WER, the granted patent will be limited. to the patent claims for which the novelty search report was prepared, when the patent application is the subject of a novelty search report indicating a lack of unity of invention as referred to in paragraph 1, and when the applicant does not limit his filing and does not file a divisional application in accordance with the search report.
    Decision:
    Article 1
    EUROPLASMA NV, De Bruwaan 15, 9700 OUDENAARDE Belgium;
    represented by
    BRANTS Johan Philippe Emile, Pauline Van Pottelsberghelaan 24, 9051, GHENT;
    a Belgian invention patent with a term of 20 years, subject to payment of the annual fees as referred to in Article XI.48, § 1 of the Code of Economic Law, for: Surface coatings.
    INVENTOR (S):
    LEGEIN Filip, Acaciadreef 12C, 3140, KEERBERGEN;
    ROGGE Eva, Waregemsesteenweg 57 box 0, 9770, KRUISHOUTEM;
    PRIORITY:
    BREAKDOWN:
    Split from basic application: Filing date of the basic application:
    Article 2. - This patent is granted without prior investigation into the patentability of the invention, without warranty of the Merit of the invention, nor of the accuracy of its description and at the risk of the applicant (s).
    Brussels, 13/07/2018,
    With special authorization:
    BE2015 / 5507
    SURFACE COATINGS
    Technical field
    The present invention is related to a low pressure plasma polymerization process applied to textile products, in particular with methods, systems and methods of depositing a durable water-repellent polymeric nano coating on a textile product as well as with products that can be achieved through such methods and systems turn into. The textile products can be cloths, or partially finished or completely finished textile products.
    Background of the invention
    Durable water-repellent (DWR) coatings on textile products are used worldwide today. The DWR market for Outdoor textiles is a volume market with sales of EUR 10 trillion in 2011 in Europe only, and outdoor clothing and accessories account for 52% of this market. The DWR section is about 22%, or 2.2 trillion EURO.
    Textile products have a certain degree of breathability. DWR coatings applied to textiles for clothing should generally maintain the breathability of the textile product. Therefore, the thickness of the DWR coating is typically taken in the micrometer range. Applicants have discovered that optimum breathability is guaranteed when the thickness is maintained in the nanometer range. Typically, coatings are deposited less than 1000 nm, and preferably even less than 500 nm.
    Textile products are also subjected to repeated washing. In addition, a coating, deposited on a textile product, is also subjected to washing. The coating is hereby exposed to a combination of abrasion and extensive rinsing with water and detergent. As a consequence, a textile coating with good washability properties is a coating that is resistant to abrasion and rinsing with water and detergent, the DWR properties being maintained after (repeated) washing.
    Coatings with good washability properties on textile products typically need a minimum thickness and must adhere well to the textile product. Typically, a thickness of at least 20 nm is desired, and preferably at least 50 nm. Furthermore, in order to have good adhesion, it is desirable that the coating penetrates the yarns and fibers of the textile products as deeply as possible.
    BE2015 / 5507
    Polymeric coatings deposited on a textile product via a low pressure plasma polymerization process typically have a thickness between 20 nm and 1000 nm, preferably between 50 nm and 500 nm. In a low pressure plasma polymerization process, a monomer is introduced into a vacuum chamber at low pressure, and a plasma is ignited, bringing the monomers into the plasma state allowing polymerization of the monomers directly on the textile surfaces, and in particular on the surfaces of individual fibers and yarns of the textile. The inventors have further discovered that the degree of penetration of the coating into the textile product is much more difficult or even impossible to achieve with other types of deposition processes such as wet (chemical) deposition processes or vapor deposition processes, including graft processes. Such processes are clearly even less suitable for applying a DWR coating to 3D products, finished textile products after final confection, such as jackets, trousers and gloves.
    DWR coatings make all types of textile water-repellent, and often also provide oil-repellent properties for stain-resistant properties. Today, the best repellency performance is achieved with fluorine-based or halogen-based chemicals deposited on textile products. The coating can be deposited with a low pressure plasma polymerization process.
    Historically, DWR technology based on long-chain perfluoroalkyl tails has been the first choice due to the highest levels of water, oil and stain repellency. Typical monomers used in the polymerization processes are monomers that lead to a high content of fluorine per surface, such as perfluoroalkyl acids (PFAs) or other high fluorine alkyl acids, which have long perfluor chains of 8 or contain more carbon atoms.
    For example, document EP0988412A1 describes a method of depositing a coating on a surface by exposing the surface, optionally a textile surface, to a plasma of 1H, 1H, 2H-perfluoro-1-dodecene or 1H, 1H, 2H, 2H- heptadecafluorodecyl acrylate.
    Document WO2014056968A1 describes a method and an apparatus for depositing a surface coating on, for example, a cloth textile, and further provides a plasma chamber for depositing a polymeric layer on a textile cloth,
    BE2015 / 5507 e.g. a textile material, wherein the plasma chamber contains a plurality of specifically suitable electrode layers. Preferred monomers are acrylates and methacrylates with perfluorocarbon chains consisting of two to six carbon atoms, such as 1H, 1H, 2H, 2H-perfluorooctyl methacrylate or 1H, 1H, 2H, 2H-perfluorooctyl acrylate.
    However, during the production of these preferential monomers harmful by-products are formed, such as perfluorooctanoic acids (Eng. Perfluoro octanoic acids, PFOAs) and perfluorooctane sulfonates (Eng. Perfluorooctane sulfonates, PFOSs). Research showed that they are persistent in the environment, in animals and in humans. Consequently, when the monomers thus produced are used in a plasma polymerization process, these by-products are also deposited on the textile, thereby posing a health and environmental hazard.
    Since 2012, it has been banned in many countries to produce products containing PFOS and high amounts of PFOA. This has initiated a switch from low-chain perfluoroalkyl-based DWRs to short-chain based DWRs, which have 6 or fewer carbon atoms in the perfluoroalkyl chain.
    However, these short chain monomers and polymers still contain a relative amount of fluorine, a halogen, so that a highest performance DWR coating would be obtained after the performance of the long chain perfluoroalkyl based DWRs. Since the effects of long-term exposure of humans and flora and fauna to halogen-containing chemicals are not yet fully known, even for the short-chain perfluoroalkyl-based DWR coatings there is a potential health hazard.
    The present invention provides a solution to the problem of DWR coatings on textile products with good washability and guaranteed absence of halogens, such as fluorine, by-products, and in particular the absence of PFOSs and PFOAs in the full process to produce a textile product of provide a DWR coating.
    To this end, the present invention is related to a method of depositing a DWR polymeric nano-coating on a textile product via a low-pressure plasma polymerization process, wherein the coating is completely halogen-free. The method
    BE2015 / 5507 advantageously combines a halogen-free health aspect with a low environmental impact of the technology used.
    The halogen-free water-repellent nano-coatings of the present invention are deposited by a low-pressure plasma polymerization, a technology known for its dry and clean aspect, since no water is consumed, a reduced amount of chemicals are used, and no drying process or curing process is required, leading to a significant reduction in energy consumption and CCL emissions.
    The halogen-free low pressure plasma polymerization coatings of the present invention provide a solution to deposit a coating on both textile and fabric on roi (2D) and on finished textile products (3D), since the technology does not use a continuous line mill to to dip, dry and harden.
    The method of the present invention provides a number of advantages over the known method in terms of the obtained coating:
    Halogen-free water-repellent coatings, therefore no health risks compared to the use of halogens such as fluorine Nanometers thick coatings - nano coatings - which retain the breathability of the textile and make the coatings suitable for use on textile
    Method with the lowest environmental impact Excellent resistance to washing and dry cleaning
    - Applicable on textile on rolls (2D) and on finished textile products (3D)
    No toxic by-products are formed during the deposition process. No change in feel and color of the textile materials
    Summary of the invention
    The present invention solves the aforementioned Problems by providing a method for depositing a halogen-free durable water-repellent nano-coating on a textile product by means of a low pressure plasma polymerization process with an organosilane monomer. The coating obtained in this way provides the textile product with water-repellent properties that are retained after washing and dry cleaning. In addition, the breathability of the fabric is retained after the coating has been applied.
    BE2015 / 5507
    The present inventors have discovered that the properties of the coatings on textile products deposited using halogen-free organosilane monomers of the present invention are DWR and wax have properties similar to prior art halogen-containing coatings. In addition, the resulting coatings do not contain halogens and no halogen-containing products, by-products or residues are formed.
    In a second aspect, the present invention is concerned with a method of improving the quality of the halogen-free coatings by post-treatment on a substrate having a coating obtained by a low pressure plasma polymerization process with an organosilane monomer. Preferably, the substrate is or comprises a textile material. The post-treatment comprises the step of exposing the treated substrate, which is obtained by treating a substrate with a low pressure plasma polymerization process with an organosilane monomer, to a low pressure after-treatment gas. In one embodiment, no plasma is re-ignited, i.e. the post-treatment gas consists essentially of neutral gas molecules. However, in a preferred embodiment, the post-treatment gas is provided with a post-treatment capability comparable to a plasma polymerization power, i.e., the power applied during plasma polymerization processes to ignite the monomers, and thus a plasma is ignited during the post-treatment. The after-treatment capacity is preferably at least 10% of the plasma polymerization capacity and / or at most 190% of the plasma polymerization capacity. The inventors have discovered that a post-treatment can improve the strength and durability of the coating. Without wishing to be bound by any theory, it is believed that the post-treatment with a substantially neutral gas, and preferably when applied, will promote cross-linking in the deposited polymer topcoat.
    Alternatively or additionally, the inventors have discovered that the aforementioned post-treatment step for a substrate provided with a nano-coating via a low-pressure plasma polymerization process with an organosilane monomer can also improve the coating properties for other substrates, in particular for substrates with flat and smooth surfaces, such as electronic components.
    BE2015 / 5507
    Brief description of the figures
    Figure 1 shows the spray test results and Figure 2 shows the water contact angle measurements for the different pre-treatments, before and after washing.
    Figure 3 shows the spray test results for varying additional gas mixtures, depending on the number of washing cycles.
    Figure 4 shows the water contact angles for varying additional gas mixtures, depending on the number of washing cycles.
    Detailed description of the invention
    As used herein, the following terms have the following meanings:
    One, the and the as used herein refer to both singular and plural unless the context clearly indicates otherwise. For example, a compartment refers to one or more compartments.
    Approximately as used herein refers to a measurable value such as a parameter, an amount, a length of time, and so on, and is used to include variations of +/- 20%, Never +/- 10% or less, Never + / -5% or less, Never +/- 1% or less, and Never +/- 0.1% or less relative to the specified value, insofar as such variations are applicable to be performed in the present invention. However, it should be understood that the approximate value is specifically mentioned.
    Include, includes and includes as used herein, its synonyms for contain, contain, contain, and consist of, consist of, consist of and are inclusive terms that specify the presence of what follows, e.g. a component, and do not exclude the presence of additional, non-listed components, aspects, elements, members, parts or steps known in the art or mentioned herein.
    BE2015 / 5507
    The numerical intervals, summed by final values, contain all values and fractions within that range, as well as the stated final values.
    The term weight percent, throughout and throughout the description, unless otherwise defined, refers to the relative weight of the respective component based on the overall weight of the formulation.
    The terms outgassing on degassing as used herein are used interchangeably and refer to a process for removing gases and liquids, more particularly within the context of this document, for removing contamination, gases and liquids from footwear or parts of footwear, to ensure good adhesion between the cover layer and at least a portion, and preferably the entire internal surface of the footwear.
    The terms fabric, cloth, textile or textile product as used herein are used interchangeably for any material made by interlocking fibers, fabrics, non-fabrics, which may be fabricated by knitting, crocheting, knotting, felting or other types of binding.
    The present invention solves the aforementioned technical problems by providing a method for depositing a halogen-free DWR nano-coating on textiles, by means of low-pressure plasma polymerization, which retains the water repellency after washing, and wherein the breathability of the textile does not change after the coating has been deposited.
    It is a first aspect of the present invention to provide a method of depositing a halogen-free water-repellent nano-coating on textiles, the coating being deposited by low pressure plasma polymerization, the coating being resistant to repeated washing and dry cleaning cycles, and wherein the coating does not change the breathability of the textile, measured in terms of air permeability and water vapor permeability.
    The textile is preferably a cloth, e.g. wrapped on a roi (2D).
    On the other hand, the textile is a finished textile product, made up to the final design, with zippers, buttons, pockets, etc. (3D). In another alternative, the textile is a semi-finished textile product,
    BE2015 / 5507 made to a semi-final design, such as a shirt with seams but without the buttons.
    The fabric is preferably a fabric, non-fabric, knit, film, foil, membrane, or multi-layer laminate of the foregoing.
    Fabrics, non-fabrics and knits can have smooth or textured surfaces, for example in the case of a woven pile (pile weave) or knitted pile (pile knit).
    The fabric preferably contains a synthetic material, a natural material or a mixture. Examples of materials include, but are not limited to:
    Synthetic: polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polyphenylene sulfide (PPS), polyacrylonitrile (PAN), polyurethane (PUR), polyurea, polytetrafluoroethylene (PTFE) and expanded polytetrafluoroethylene (ePTFE) , polyester (PES) such as polyethylene terephthalate (PET), recycled PET and polybutylene terephthalate (PBT), polyamide (PA) - such as PA6, PA66, and PA12, polyaramide, elastane (polyurethane-polyurea copolymer).
    Natural and man-made: cotton, cellulose, cellulose acetate, silk, wool, etc.
    Mixtures: cotton / PES 50:50, PES / carbon 99: 1, recycled PES / elastane
    92: 8, etc.
    Fabrics and knits can have a thickness of 50 µm to 10 mm. Non-woven fabrics can have a thickness from 5 µm to 10 mm. Films and foil can have a thickness of 20 µm to 1 mm. Membranes and laminates can have a thickness of 20 µm to 20 mm.
    In one embodiment, the low pressure plasma polymerization is a low pressure plasma polymerization of an organosilane precursor monomer introduced into a plasma chamber, wherein the organosilane is of formula (I), (II), (III), (IV), or (V) is:
    Yi-XY 2
    - [Si (CH 3 ) q (H) 2 - q -X-] n (I) or (Π) or
    BE2015 / 5507
    CH 2 = C (Ri) -Si (R 2 ) (R 3 ) -R4 R 5 -Si (R 6 ) (R 7 ) -R8 (III) or (IV) or
    CH2 = C (R9) C (0) -0- (CH 2 ) p -Si (Rio) (Rii) -Ri 2 (V) where for Formula (I) X, O or NH is Yi -Si (Y 3 ) (Y4) Ys and Y 2 is Si (Y3 ') (Y 4 ) Y5' where Y 3 , Y 4 , Ys, Y37 Y47 and Υ 5 - are independently H or an alkyl group up to 10 carbon atoms in length; wherein at most one of Y 3 , Y 4 and Y 5 is H, and at most one of Y 3 ', Y 4 - and Υ 5 - is H; and the total number of carbon atoms is not more than 20;
    wherein Formula (II) is cyclic, wherein n is 2 to 10, where q is 0 to 2, and the total number of carbon atoms is not more than 20;
    wherein for Formula (III) R 1 is H or an alkyl group, e.g. -CH 3 , and wherein R 1, R 2 and R 3 are independently H, or an alkyl group up to 10 carbon atoms or an alkoxy group -OZ, wherein Z is preferably -C t H 2t + 1, where t 1 to 10 is;
    wherein for Formula (IV) R 5 is H or an alkyl group, e.g. -CH 3, and where R o, R 7 and R are each, independently of one another are H or an alkyl group of up to 10 carbon atoms, or an alkoxy group -OZ, wherein Z is preferably -C t H 2t + i, where t is 1 to 10; or wherein according to Formula (V) R 9 is H or an alkyl group, e.g. -CH 3 , where p is from 0 to 10, and wherein R 1, R 1 and R 12 are each independently H or an alkyl group up to 10 carbon atoms or an alkoxy group-O 2 wherein Z is preferably -C t H 2t + i, where t is 1 to 10.
    The alkyl groups can be linear or branched, but linear groups are preferred. Preferably such alkyl groups are methyl or ethyl groups of which methyl is preferred. Preferably Y 3 , Y 4 , Ys, Y37 Y4 'or Y 5 ' are alien alkyl groups.
    The alkoxy groups can be linear, branched or cyclic, but linear groups are preferred. Such alkoxy groups are preferably methoxy or ethoxy groups.
    The monomer of Formula I can contain six methyl groups. Preferably, the monomer is hexamethyldisiloxane. Preferably, the monomer of Formula I is hexamethyldisilazane.
    10 BE2015 / 5507
    The monomer of Formula II may be one wherein n is 3, or 4 or 5 or 6. Preferably, the monomer of Formula II is oxtamethylcyclotetrasiloxane. Preferably, the monomer of Formula II is hexamethylcyclotrisilazane.
    The monomer of Formula V can be one where p is 2 and where Rio, Rn,
    R 12 alien are an alkoxy group, e.g. methoxy. Preferably, the monomer of Formula V is 3- (trimethoxysilyl) propyl methacrylate. Preferably the monomer is of Formula V.
    3- (trimethoxysilyl) propyl acrylate.
    The liquid monomer is preferably transported to the plasma chamber without the use of a carrier gas. However, in certain embodiments, an additional gas can be used as a carrier gas to introduce the organosilane precursor monomer into the plasma chamber.
    The organosilane monomer precursor is preferably supplied when a liquid monomer which is subsequently evaporated is transported to the plasma chamber in its evaporated form. The evaporated monomer is preferably transported to the chamber without using a carrier gas. Instead, if necessary, a carrier gas can be used in the liquid monomer feed system to transport the vaporized organosilane monomer precursor to the plasma chamber.
    Preferably, the carrier gas when used is H 2 , N 2 , O 2 , N 2 O, CH 4 ,
    He, or Ar, and / or a mixture of these gases. In a preferred process, a single gas is used, which is preferably O 2 , He or Ar.
    When a carrier gas is used, the amount of carrier gas is preferably about 5% to about 1500% carrier gas, based on the monomer flow rate.
    Preferably, about 10% to about 1000% carrier gas is used, still 50% to 750%, e.g. 25% to 500%, such as 500, 450, 400, 350, 300, 250,
    200, 150, 125, 100, 90, 80, 75, 70, 60, 50, 40, 35, 30, or 25% carrier gas.
    In other embodiments, the additional gas can be used as a functional gas. A functional gas is defined as a gas that contributes to the low pressure plasma polymerization reaction in terms of ignition of the plasma, or in terms of influencing the low pressure plasma polymerization reaction to deposit better performance coatings.
    BE2015 / 5507
    The additional, functional gas is preferably brought into the room via a separate supply line, which comes from eg. the gas cylinder, and is not used as a carrier gas to introduce monomer vapor into the plasma chamber.
    In one embodiment, the additional functional gas may be introduced into the plasma chamber along with the monomer precursor vapor through the same plasma chamber inlets or inlets, the additional functional gas supply line and the liquid monomer supply line converging just before the chamber inlets or inlets, and they are thus brought together into the plasma chamber. This embodiment makes it possible to control the relative amounts of monomer and additional, functional gas very precisely.
    In another embodiment, the monomer supply line and the additional functional gas supply line remain separate and one or more separate gas inlets and one or more separate monomer precursor inlets are provided in the chamber.
    In another embodiment, the additional gas is both a carrier gas and a functional gas.
    In one embodiment, the organosilane precursor monomer can be used to ignite the plasma without an additional gas being present in the chamber.
    BE2015 / 5507
    In some embodiments, the organosilane precursor monomer has a carbon-carbon double bond. Carbon-carbon double bond monomers do not always need an additional gas to ignite a plasma and start polymerization. In such embodiments, the organosilane precursor monomer can be used to ignite the plasma without the presence of an additional gas in the chamber.
    In other embodiments, one or more additional gases in the plasma chamber, which additionally also contains the organosilane precursor monomer, can be passed to generate and ignite a stable plasma, and therefore these gases are considered functional gases.
    In prior art methods in which the monomer typically contains long chain perfluoroalkyl chains, fragmentation of the perfluoroalkyl chain is an undesirable phenomenon because it leads to a decrease in water-repellent character. Surprisingly, specific for the organosilane monomers of the present invention, controlled fragmentation can lead to improved water repellency, and certainly also the resistance of the resulting coating to washing.
    In a preferred embodiment, applicants have surprisingly discovered that an additional gas or a mixture of additional gases can be used to create more fragmentation in a controlled manner, resulting in a better cross-linked, denser polymer, which has better water-repellent properties and better resistance to washing and dry cleaning. The additional gas or gas mixture can be a carrier gas, a functional gas, and / or a functional carrier gas.
    Preferably the carrier gas, when used, is H 2 , N 2 , O 2 , N 2 O, CH 4 , He, or Ar, and / or a mixture of these gases. In a preferred process, a single gas is used, which is preferably O 2 , He or Ar.
    Preferably, the amount of additional gas, when used as a functional gas with the organosilane monomer precursor, is about 5% to about 50% additional gas, calculated versus the monomer flow rate, preferably about 5% to about 40% additional gas, such as 40, 35, 30, 25, 20, 15, 10 or 5% extra gas.
    When two or more additional gases are used, the total amount of additional gas used together with the organosilane monomer precursor is preferably
    BE2015 / 5507 about 5% to about 50% extra gases, calculated against the monomer flow rate, preferably about 5% to about 40% extra gases, such as 40, 35, 30, 25, 20, 15, 10 or 5% extra gases.
    When two additional gases are used, the flow rate of the first additional gas is approximately 5% to 95% of the total flow of additional gases, Never 10% to 90%, e.g. 15% to 85%, such as 20% to 80%, e.g. 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25 or 20%.
    When two additional gases are used, the flow of the second additional gas is approximately 5% to 95% of the total flow of additional gases, Never 10% to 90%, for example 15% to 85%, such as 20% to 80%, eg. 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25 or 20%.
    In order to carry out the low pressure plasma polymerization step, the plasma chamber is evacuated, preferably to a predetermined base pressure, after the substrates to be treated have been placed in the plasma chamber and the door has been closed. After this, one or more monomer inlets are opened to obtain a constant monomer flow rate inside the plasma chamber, optionally together with a constant flow rate of additional gas.
    After stabilizing the monomer in the plasma chamber to a predetermined operating pressure, optionally in combination with an additional gas, a power is applied to the radio frequency electrode or electrodes to create an electromagnetic field. A plasma is thus ignited and the monomer molecules are reactivated. The substrates or products in the plasma chamber act as an initiation promoter or facilitator for the initiation of the plasma polymerization reaction, which starts upon contact of the reactive monomer molecules, and will continue as long as reactive monomer molecules are present in the plasma chamber to allow polymerization to proceed. to keep.
    When a predetermined plasma polymerization time is reached, the power applied to the radio frequency electrode or electrodes is turned off, and the chamber is brought back to atmospheric pressure to allow the treated products to be removed from the chamber. A post-treatment as described in this document can optionally be performed after the predetermined plasma polymerization time has been reached and before the chamber is brought back to atmospheric pressure.
    BE2015 / 5507
    A halogen-free water-repellent nano-coating is deposited by a method according to the present invention. This coating is also resistant to washing and dry cleaning and has no negative impact on the breathability of the textile.
    The plasma polymerization time (3D) or speed (2D roll-to-roll) required to deposit this coating of the present invention using the method and monomers of the present invention is determined in function of the substrate and chamber design, the type of substrate being treated (thickness, openness, polymer type) and depending on the performance required in terms of resistance to washing - a ski jacket is washed less often than a running shirt.
    When 3D items are coated (e.g. finished garments), the plasma polymerization is expensive, expressed in the time that power is applied to the electrodes, preferably from about 1 minute to about 30 minutes, Never from about 2 minutes to about 25 minutes, such as from about 5 minutes to about 20 minutes, such as 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, or 5 minutes.
    The plasma polymerization can be a continuous plasma polymerization. The plasma polymerization can be a pulsed plasma polymerization. Whether a continuous plasma or a pulsed plasma is used for the polymerization depends on the chemistry used and the volume and design of the plasma chamber.
    In an 1836 liter plasma chamber, designed with 4 vertical spaces to accommodate, for example, 8 to 12 coats, the power applied is deposited, when applied in continuous mode, preferably about 5 to 5000 W, Never about 10 to 2500 W, Never about 15 to 2000 W, for example 20 to 1500 W, such as 25 to 1000 W, 30 to 750 W, 35 to 500 W, or 500, 475, 450, 425, 400, 375, 350, 325, 300, 275 , 250, 225, 200, 175, 150, 125, 120, 110, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40 or 35 W. The applied power density ( this is the power per unit of chamber volume) for the deposition process, when applied in continuous mode, is equal to the above-mentioned interval, ie the power density is about 5 to 5000 W, Never about 10 to 2500 W, Never about 15 to 2000 W, for example, 20 to 1500 W, such as 25 to 1000 W, 30 to 750 W, 35 to
    BE2015 / 5507
    500 W, or 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 120, 110, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40 or 35 W, divided by 1836 liters.
    In an 1836 liter plasma chamber, designed with 4 vertical spaces to accommodate, for example, 8 to 12 coats, the applied power is for the deposition process, when applied in pulsed mode, preferably about 5 to 5000 W, more preferably about 10 to 2500 W, more preferably about 15 to 2000 W, for example 20 to 1500 W, such as 30 to 1000 W, 50 to 900 W, 75 to 800 W, 100 to 750 W, or 750, 725, 700, 675, 650, 625, 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 120, 110 or 100 W. The applied power density (this is the power per unit of chamber volume) for the deposition process, when applied in continuous mode, is equal to the above-mentioned interval, ie the power density is about 5 to 5000 W, more preferably about 10 to 2500 W, more preferably about 15 to 2000 W , for example, 20 to 1500 W, such as 30 to 1000 W, 50 to 900 W, 75 to 800 W, 100 to 750 W, or 750, 725, 700, 675, 650, 625, 600, 5 75, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 120, 110 or 100 W divided by 1836 liters.
    When applied in pulsed power, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching time of about 0.05 to 50%, with the optimal parameters depending on the monomer used.
    The plasma chamber preferably has one or more electrode layers, which may be radio frequency electrode layers or grounded electrode layers, to generate an electromagnetic field.
    The or each radio frequency electrode preferably generates a high frequency electric field at frequencies between 20 kHz and 2.46 GHz, such as between 40 kHz and
    13.56 MHz, where 13.56 MHz is the preferred frequency.
    The operating pressure for the deposition step is preferably 10 to 500 mTorr, more preferably about 15 to 200 mTorr, more preferably about 20 to 150 mTorr, such as 30 to 100 mTorr, for example less than 100, 90, 80, 70, 60, 50, 40 or 30 mTorr. Such values are preferred in, for example, a CD1836 liter plasma chamber, used to deposit a coating on 8 to 12 coats in a single process run.
    BE2015 / 5507
    When treating textile and cloth on a roll (2D), the speed during the deposition step is preferably 0.1 m / min to 20 m / min, such as 0.5 m / min to 15 m / min, for example 1 m / min to 10 m / min , such as less than 9, 8, 7, 6, m / min, preferably between 1 and 5 m / min.
    In a 12000 liter plasma chamber designed to handle rolls up to 1.8m wide, the deposition power applied is when applied in continuous mode, preferably about 10 to 5000 W, more preferably about 20 to 4000 W, more preferably about 25 to 3000 W, for example 30 to 2000 W, such as 40 to 1500 W, 50 to 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200 , 175, 150, 125, 120, 110, 100, 90, 80, 75, 70, 60 or 50 W. The applied power density (this is the power per unit of chamber volume) for the deposition process, when applied in continuous mode, is equal to the above-mentioned interval, in other words the power density is about 10 to 5000 W, more preferably about 20 to 4000 W, more preferably about 25 to 3000 W, for example 30 to 2000 W, such as 40 to 1500 W, 50 to 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 175, 150, 125, 120, 110, 100, 90, 80, 75, 70, 60 or 50 W, gede eld by 12000 liters.
    In a 12000 liter plasma chamber designed to handle rolls up to 1.8m wide, the applied power is deposited, when applied in pulsed mode, preferably about 10 to 5000 W, more preferably about 25 to 4000 W, more preferably about 50 to 3500 W, for example 75 to 3000 W, such as 100 to 2500 W, such as 150 to 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200 or 175 W. The applied power density (this is the power per unit of chamber volume) for the deposition process, when applied in continuous mode, is equal at the above-mentioned interval, in other words the power density is about 5 to 5000 W, more preferably about 10 to 5000 W, more preferably about 25 to 4000 W, even more preferably about 50 to 3500 W, for example 75 to 3000 W, such as 100 to 2500 W, such as 150 to 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200 or 175 W divided by 12000 liters.
    BE2015 / 5507
    When applied in pulsed power, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching time of about 0.05 to 50%, with the optimal parameters depending on the monomer used.
    The plasma chamber preferably has one or more electrode layers, which may be radio frequency electrode layers or grounded electrode layers, to generate an electromagnetic field.
    The or each radio frequency electrode preferably generates a high frequency electric field at frequencies between 20 kHz and 2.46 GHz, such as between 40 kHz and
    13.56 MHz, where 13.56 MHz is the preferred frequency.
    The operating pressure for the deposition step is in a 12000 liter plasma chamber designed to handle rolls up to 1.8m wide, preferably 10 to 500mTorr, more preferably about 15 to 200mTorr, more preferably about 20 to 150mTorr, such as 25 to 100mTorr, for example less than 100, 90, 80, 70, 60, 50, 40, 30 or 25 mTorr.
    In another embodiment, an outgassing step and / or a pretreatment step can be performed for the low pressure plasma polymerization processes. The outgassing is preferably carried out in the low pressure plasma chamber. The pretreatment is preferably a low pressure plasma process.
    A gassing can be performed before the first process step is started. Applicants have surprisingly discovered that an outgassing allows to deposit a more uniform coating, which has better performance in terms of water repellency and resistance to washing. This is because the fumigation removes not only contamination and moisture from the surface and from the plasma chamber, but also from the inner surfaces and deeper areas of the fabric, which is not the case when no fumigation is performed.
    In an embodiment for treating clothing (3D), this textile product (s) is gassed out to an outgassing level of maximum 50 mTorr. Additionally, or alternatively, the garment is outgassed in a vacuum chamber until this vacuum chamber has an outgassing level of up to 100 mTorr, more preferably up to 50 mTorr, such as 40 mTorr or less. Note it
    BE2015 / 5507 outgassing level of the vacuum chamber depends on the loading, in particular on the number of pieces and the design of the textile product to be placed in the chamber.
    In an embodiment for treating textile and cloths on rolls (2D), the textile roll is outgassed to an outgassing level of maximum 50 mTorr, Never maximum 40 mTorr, Never maximum 25 mTorr. Additionally, or alternatively, the roll of textile material is outgassed in a vacuum chamber until this vacuum chamber has an outgassing level of up to 100 mTorr, Never up to 50 mTorr, such as 40 mTorr or less. Note that the outgassing level of the vacuum chamber depends on the load, in particular on the structure of the textile, the polymer, the thickness and openness, and on the dimensions of the roll of textile that is placed in the chamber.
    To determine the outgassing level of a finished textile (3D) or a roll of textile (2D), the pressure rise in a vacuum chamber due to gases released from the textile must be determined. To do this, the item is placed in a vacuum chamber, e.g. a plasma chamber, which is evacuated to an outgassing pressure P degassing, which is less than 200 mTorr, preferably less than 100 mTorr, such as less than 50 mTorr, after which the inlets and outlets of the vacuum chamber are closed. After a pre-determined time of 60 seconds, the pressure rise in the chamber, ΔΡ, is measured. The level of outgassing of an item is then given by the pressure rise, ΔΡ, minus the leakage pressure of the vacuum chamber at the outgassing pressure Pdegassing. When more than one finished textile product (3D) is placed in the chamber, the outgassing level of one textile product is given by the pressure rise ΔΡ minus the leakage pressure of the vacuum chamber at the outgassing pressure Pdegassing, divided by the number of Substrates in the vacuum chamber. Here, the leakage pressure of the vacuum chamber at the outgassing pressure Pdegassing is determined by repeating the same procedure, pumping an empty chamber with all textile products removed from the vacuum chamber to the same outgassing pressure Pdegassing, closing off all inlets and outlets of the vacuum chamber, and measuring the pressure rise after the same pre-determined time as for the loaded chamber, e.g. 60 seconds.
    To determine the outgassing level of a chamber loaded with multiple textile products, the pressure rise in a vacuum chamber due to gases released from the textile products must be determined. For this purpose, the textile products are placed in a vacuum chamber, e.g. a plasma chamber, which
    BE2015 / 5507 is evacuated to an outgassing pressure Pdegassing, which is less than 200 mTorr, preferably less than 100 mTorr, such as less than 50 mTorr, after which the inlets and outlets of the vacuum chamber are closed. After a pre-determined time of 60 seconds, the pressure rise in the chamber, ΔΡ, is measured. The level of outgassing of an item is then given by the pressure rise, ΔΡ, minus the leakage pressure of the vacuum chamber at the outgassing pressure Pdegassing. Here the leakage pressure of the vacuum chamber at the outgassing pressure Pdegassing is determined by repeating the same procedure for an empty chamber with all textile products removed from the vacuum chamber - pumping down to the same outgassing pressure Pdegassing, closing all inlets and outlets of the vacuum chamber, and measuring the pressure rise after the same pre-determined time as for the loaded chamber, e.g. 60 seconds.
    In certain embodiments, the low pressure plasma polymerization is preceded by a low pressure plasma pretreatment step, preferably combining the pretreatment and outgassing in a single process step.
    A pretreatment step can be performed before the deposition polymerization step and after the outgassing step, if an outgassing is performed. The pretreatment is preferably a low pressure plasma process. Whether or not a low pressure plasma pretreatment is carried out depends on the purity of the Substrates to be treated, and also on the monomer used in the low pressure plasma polymerization process.
    Applicants have surprisingly discovered that for certain monomers the performance and quality of the coating is better when no pretreatment step is performed. For other monomers, pre-treatment in the form of low-pressure plasma cleaning and / or activation and / or etching is recommended.
    The best performance of the coatings is measured by a water contact angle measurement according to ASTM D5946-04, a spray test according to AATCC 22-2010, or ISO 9073 - section 17, and ISO 4920, and wash resistance. Resistance to washing and dry cleaning is typically tested by washing or dry cleaning the cloths or products, followed by a spray test assessment or a water contact angle measurement as a function of the number of washing cycles or dry cleaning cycles.
    BE2015 / 5507
    To achieve the aforementioned best performance, it is necessary that the adhesion between the coating and the substrate is sufficient, that there is uniform coverage of the surfaces of the substrate - such as the surfaces of the yarns, and that the coating is free from pinhead holes and water is repellent.
    In one embodiment, a pretreatment step in the form of an activation and / or cleaning and / or etching is performed for the plasma polymerization processes. A pre-treatment step in the form of an activation and / or cleaning and / or etching step can be advantageous to improve the adhesion and cross-linking of the polymeric coating.
    When a pretreatment is carried out, it is preferably carried out with reactive gases, such as H 2 or O 2 , or with etching gases such as CF 4 , but inert gases, such as Ar, N 2 or He, can also be used. Mixture requirement of previous gases can also be used.
    In certain embodiments of the invention, the polymer deposition step is performed in the presence of an additional gas, which may be the same gas (or gas mixture) used in the pretreatment step, if such pretreatment step is performed.
    The pretreatment is preferably carried out with O 2 , Ar or a mixture of O 2 and Ar, with O 2 being preferred.
    The pretreatment, when performed in a batch process to treat finished textile products such as clothing (3D), preferably takes from 15 seconds to 15 minutes, for example from 30 seconds to 10 minutes, more preferably from 45 seconds to 5 minutes, e.g. 5, 4, 3, 2, or 1 minutes. The duration of the pre-treatment depends on the precursor monomer used, on the design and materials of the substrates to be treated, on the degree of contamination on the substrate to be treated, and on the low-pressure plasma device.
    The power of the pretreatment can be applied continuously or in a pulsed manner.
    Preferably, when applied continuously in an 1836 liter plasma chamber, the pretreatment takes place at a power of 10 to 5000 W, more preferably 25 to 4000 W, more preferably 50 to 3000 W, such as 75 to 2500 W, such as 100 to 2000 W,
    BE2015 / 5507 e.g. 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 175, 150, 125, or 100 W. In plasma chambers of a different volume, preferably a power density equivalent to the above Intervals for an 1836 liter plasma chamber is used.
    Preferably, when applied in a pulsed manner in an 1836 liter plasma chamber, the pretreatment takes place at a power of 10 to 5000 W, Never 25 to 4000 W, Never 50 to 3000 W, such as 75 to 2500 W, such as 100 to 2000 W, e.g. 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 175, 150, 125, or 100 W. In plasma chambers of a different volume, preferably a power density equivalent to the above Intervals for an 1836 liter plasma chamber is used.
    When applied in pulsed power, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching time of about 0.05 to 50%, with the optimal parameters depending on the gas or gas mixture used.
    The pretreatment operating pressure, in an 1836 liter plasma chamber or in a 12000 liter plasma chamber, is preferably 10 to 500 mTorr, Never 15 to 250 mTorr, Never 20 to 200 mTorr, such as 25 to 175 mTorr, such as 30 to 150 mTorr , e.g. 150, 140, 130, 125, 120, 110, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, or 30 mTorr.
    When performed in a roll-to-roll process to treat textiles and cloths on rolls, the activation and / or cleaning and / or etching is performed at a speed of 1 to 30 m / min, e.g. 2 to 20 m / min, such as 3 m / min to 15 m / min, preferably about 5 to 10 m / min.
    Preferably, when applied in a continuous manner in a 12000 liter plasma chamber, the pretreatment takes place at a power of 25 to 10000 W, Never 50 to 7500 W, Never 100 to 5000 W, such as 200 to 4000 W, such as 300 to 3000 W, e.g. 3000, 2900, 2800, 2750, 2700, 2600, 2500, 2400, 2300, 2250, 2200, 2100, 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350 or 300 W. In plasma chambers of a different volume, preferably
    BE2015 / 5507 uses a power density equivalent to the above Intervals for a 12000 liter plasma chamber.
    Preferably, when applied in a pulsed manner in a 12000 liter plasma chamber, the pretreatment takes place at a power of 25 to 10000 W, more preferably 50 to 9000 W, more preferably 100 to 8000 W, such as 200 to 7500 W, such as 300 to 7000 W, e.g. 7000, 6750, 6500, 6250, 5750, 5500, 5250, 5000, 4750, 4500, 4250, 4000, 3750, 3500, 3250, 3000, 2750, 2500, 2250, 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350 or 300 W. In plasma chambers of a different volume, preferably, a power density equivalent to the above Intervals for a 12000 liter plasma chamber is used.
    When applied in pulsed power, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching time of about 0.05 to 50%, with the optimal parameters depending on the gas or gas mixture used.
    For systems of other dimensions, with a different volume and / or a different electrode arrangement than in the embodiments of the examples or the preferred embodiments, the power, operating pressure and pretreatment time are varied in such a way that the best process parameters for the pretreatment be used, bearing in mind the previous explanation.
    When a pretreatment is used, the polymeric coating is applied in a next step, which can be done in the same machine.
    The pretreatment and the deposition step are preferably performed in the same chamber without opening the chamber in between the steps, to avoid deposition of additional contamination between the pretreatment step and the atmospheric deposition step.
    In a further embodiment, a post-treatment step can be performed after the low pressure plasma polymerization process. Whether or not this post-treatment step
    BE2015 / 5507 will not be carried out depending on the deposited polymers and the design of the substrate.
    A post-treatment can allow to obtain a denser polymer structure, or a polymer structure with improved orientation of the functional groups. Both a denser polymer structure and an improved orientation of the functional groups greatly contribute to a better performance of the coating in terms of water repellency, in particular in a better resistance to washing and dry cleaning.
    In a first embodiment, the after-treatment is a low-pressure plasma process.
    In a second embodiment, the aftertreatment is a low pressure process without ignition of the plasma.
    The post-treatment, when carried out, is preferably carried out in the same chamber as the low pressure plasma polymerization without opening the chamber between the steps, to exclude the influence of the atmosphere between the two steps.
    When an aftertreatment is carried out as low pressure plasma processes, this aftertreatment is preferably carried out with inert gases, such as Ar, N 2 or He, but reactive gases, such as H 2 or O 2 , or etching gases such as CF 4 , can also be used . Mixtures of previous gases can also be used.
    The pretreatment is preferably carried out with He or Ar.
    The post-treatment, when performed in a batch process to treat finished textile products such as clothing (3D), preferably lasts 10 seconds to 15 minutes, for example 15 seconds to 10 minutes, more preferably 30 seconds to
    7.5 minutes, e.g. 7.5, 7, 6, 5, 4, 3, 2, or 1 minutes, or 45 or 30 seconds. The duration of the post-treatment depends on the deposited polymer and the design of the substrate.
    The power of the post-treatment can be applied in a continuous manner or in a pulsed manner. The average power applied during post-treatment is preferably lower than the average power during low-pressure plasma pretreatment, thereby avoiding partial damage to the deposited polymeric coating. This is particularly preferable when
    BE2015 / 5507 the same gas or gas mixture is used for the pre-treatment step as the post-treatment step.
    Preferably, when applied in a continuous manner in an 1836 liter plasma chamber, designed with 4 vertical spaces to accommodate 8 to 12 coats, the post-treatment takes place at a power of 5 to 1000 W, more preferably 10 to 750 W, more preferably 15 up to 500 W, such as 20 to 250 W, such as 25 to 200 W, e.g. 200, 175, 150, 125, 100, 90, 80, 75, 70, 60, 50, 40, 30 or 25 W. In plasma chambers of a different volume, a power density equivalent to the Intervals mentioned above is preferably used. for an 1836 liter plasma chamber.
    Preferably, when applied in a pulsed manner in an 1836 liter plasma chamber, designed with 4 vertical spaces to accommodate 8 to 12 coats, the post-treatment takes place at a power of 5 to 2000 W, more preferably 10 to 1500 W, more preferably 15 up to 1000 W, such as 20 to 750 W, such as 25 to 500 W, e.g. 500, 450, 400, 350, 300, 250, 200, 175, 150, 125, 100, 90, 80, 75, 70, 60, 50, 40, 30 or 25 W. In plasma chambers of a different volume, preferably uses a power density equivalent to the above Intervals for an 1836 liter plasma chamber.
    When applied in pulsed power, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching time of about 0.05 to 50%, with the optimal parameters depending on the gas or gas mixture used.
    When performed in a roll-to-roll process to treat textiles and fabrics on rolls (2D), the low pressure plasma post-treatment is carried out at a speed of 1 to 30 m / min, e.g. 2 to 20 m / min, such as 3 m / min to 15 m / min, preferably about 5 to 10 m / min. The rate of post-treatment depends on the deposited polymer and the design of the substrate.
    The power of the post-treatment can be applied in a continuous manner or in a pulsed manner. The average power is preferably lower than the average power during a low pressure plasma pretreatment, since the deposited polymeric coating should not be damaged.
    Preferably, when applied in a continuous manner in a 12000 liter plasma chamber, the post-treatment takes place at a power of 10 to 5000 W,
    BE2015 / 5507
    Never 20 to 4000 W, never 25 to 3000 W, such as 50 to 2500 W, such as 75 to 2000 W, e.g. 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 275, 250, 225, 175, 150, 125, 100, 90, 80 or 75 W. In plasma chambers of a different volume, preferably use a power density equivalent to the above mentioned Intervals for a 12000 liter plasma chamber.
    Preferably, when applied in a pulsed manner in a 12000 liter plasma chamber, the after-treatment takes place at a power of 20 to 10000 W, Never 25 to 7500 W, Never 50 to 5000 W, such as 75 to 4000 W, such as 100 to 3000 W, e.g. 3000, 2750, 2500, 2250, 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 275, 250, 225, 175, 150, 125 or 100 W. In plasma chambers of a different volume, preferably use a power density equivalent to the above Intervals for a 12000 liter plasma chamber.
    When applied in pulsed power, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching time of about 0.05 to 50%, with the optimal parameters depending on the gas or gas mixture used.
    When a post-treatment is carried out as a low pressure process without ignition of a plasma, this post-treatment is preferably carried out with an inert gas, such as Ar, N 2 or He, but also reactive gases, such as H 2 and O 2 , and etching gases like CF 4 can be used. Mixture requirement of previous gases can also be used.
    The post-treatment without ignition of a plasma is preferably carried out with He, Ar or O 2 .
    The post-ignition without plasma ignition, when performed in a batch process to treat finished textile products such as clothing (3D), preferably lasts 10 seconds to 15 minutes, e.g. 15 seconds to 10 minutes, Never 30 seconds to 7.5 minutes, e.g. 7.5, 7, 6, 5, 4, 3, 2, or 1 minutes, or 45 or 30 seconds. The duration of the post-treatment depends on the deposited polymer and the design of the substrate.
    BE2015 / 5507
    When performed in a roll-to-roll process to treat textiles and fabrics on rolls (2D), the low pressure plasma aftertreatment without ignition of a plasma is carried out at a speed of 1 to 30 m / min, for example 2 to 20 m / min, such as 3 m / min to 15 m / min, most preferably about 5 to 10 m / min. The rate of post-treatment depends on the deposited polymer and the design of the substrate.
    The method of the present invention includes the step of applying a low pressure plasma polymer coating with a thickness of 50 nm to 1000 nm, more preferably from 75 to 500 nm, such as 500, 475, 450, 425, 400, 375, 350 , 325, 300, 275, 250, 225, 200, 175, 150, 125, 100 or 75 nm.
    In the present invention, with organosilane monomers of Formula (I) to (V) hydrophobic surfaces are obtained with water contact angles of more than 90 °, even more than 100 °, even more than 110 ° or even 120 °, according to ASTM D5946-04 .
    The method comprises depositing polymeric coatings with preferably a variation in water uniformity contact angles of less than 10 ° according to ASTM D5946-04.
    In the present invention, hydrophobic surfaces are obtained with organosilane monomers of Formula (I) to (V) with a spray test rating of 3 or more, such as 4 or 5, according to AATCC 22-2010, or ISO 9073 - section 17 and ISO 4920 .
    The obtained water contact angle and spray test quotation depend on the monomers used, any additional gases, on the process parameters used, but also on the substrate on which the nano coating is deposited, the complexity of the design, etc.
    The best performance of the coatings is measured by water contact angles, spray test, before and after washing and dry cleaning.
    Examples
    In order that the invention may be more readily understood, it will now be described by means of some examples which do not impose any limitation in scope of protection.
    2015/5507
    BE2015 / 5507
    Example 1: Influence of pre-treatment
    To investigate the influence of a pre-treatment for low-pressure plasma polymerization, 4 different low-pressure plasma pre-treatments were performed on a hydrophilic, 100% recycled PES textile (details in Table 2), followed by the same low-pressure plasma polymerization processes (Table 1). ). Performance was evaluated with water contact angle measurement and spray test rating, before and after washing. Details of the washing procedure are shown in Table 3.
    Parameter Value Plasma chamber Dimensions 600 x 600 x 600 mm Temperature wall 30-60 ° C Electrodes RF / grounded Pretreatment Details Table 2 Coating Monomer Hexamethyldisiloxane Flow 75 - 125 seem Extra gas Oxygen (O 2 ) Flow (% of monomer flow) 5-20% Basic pressure 10 - 30 mTorr Operating pressure 20 - 75 mTorr Power 150 - 250 W. Frequency 13.56 MHz Frequency mode cw
    Table 1: Process parameters in a 600 liter chamber according to Example 1
    Gas None Ar O 2 Hey N 2 Flow - 100-300 seem 100-300 seem 100-300 seem 100-300 seem Power - 200-400 W. 200-400 W. 200-400 W. 200-400 W. Frequency - 13.56 MHz 13.56 MHz 13.56 MHz 13.56 MHz Frequency mode - cw cw cw cw Time - 2-10 min 2-10 min 2-10 min 2-10 min
    Table 2: Process parameters for pretreatments according to Example 1
    2015/5507
    BE2015 / 5507
    Temperature 40 ° C Washing cycle duration lu30 Detergent 66 g of standard washing powder Ballast loading 2 kg PES ballast according to ISO 6330 Drying method Line drying Duration of drying At least 12h
    Table 3: Details of the washing procedure
    Figure 1 shows the spray test results and Figure 2 shows the water contact angle measurements for the different pre-treatments, before and after washing. It is clear from Figure 1 that only the samples treated without pretreatment give a spray test rating higher than 0 after 1 and 2 wash cycles. It is also clear from Figure 2 that the samples without pretreatment and a coating according to Table 1 give a water contact angle higher than 0 ° after 3 wash cycles. The conclusion is that for the monomer tested the best performance in terms of resistance to washing is obtained without plasma pretreatment. For washing, there is no clear difference between the pretreatments.
    Example 2: Influence of extra gas
    To investigate the influence of the additional gas used in the process, a low pressure plasma process according to Table 4 is performed (no pretreatment). The additional gas or gas mixture was varied according to the three variations in Table 5. Spray test and water contact angle were measured before and after washing according to the washing details in Table 3.
    Parameter Value Plasmakmaer Dimensions 600 x 600 x 600 mm Temperature wall 30-60 ° C Electrodes RF / grounded Pretreatment No Coating Monomer Hexamethyldisiloxane Flow 75 - 125 seem
    2015/5507
    Extra gas
    Basic pressure
    Operating pressure
    Power
    Frequency
    Frequency mode
    I BE2015 / 5507
    See Table 5
    - 30 mTorr
    - 75 mTorr
    150 - 250 W.
    13.56 MHz cw
    Table 4: Process parameters in a 600 liter chamber according to Example 2
    Gas o 2 O 2 + Ar O 2 + Hey Flow (% of monomer flow) 10% 10% + 10% 10% + 10%
    Table 5: Process parameters for additional gases according to Example 2
    Figure 3 shows the spray test quotations for different additional gas mixtures as a function of the number of wash cycles. Figure 4 shows the water contact angles for different additional gas mixtures as a function of the number of washing cycles. Obviously, no significant improvement was obtained in terms of resistance to washing.
    The conclusion is that a wide range of additional gas mixtures can be used with the monomer used in this example.
    Example 3: Influence of monomer
    Different monomers allow the deposition of halogen-free water-repellent nano coatings on textiles. To this end, processes were carried out with 2 different monomers, and the water contact angle was subsequently measured. The coating according to Table 6 gives a water contact angle of 128 °, and the coating according to Table 7 gives a water contact angle of 92 °.
    Parameter Value Plasma chamber Dimensions 500 x 400 x 250 mm Temperature wall 30-60 ° C Electrodes RF / grounded
    Pretreatment
    No
    2015/5507
    30 Coating Monomer Hexamethyldisiloxane Flow 5-15 seem Extra gas o 2 Flow (% of monomer flow) 5-20% of monomer flow Basic pressure 10 - 30 mTorr Operating pressure 15 - 75 mTorr Power 100-275 W. Frequency 13.56 MHz Frequency mode cw el 6: Process parameters in a 50 liter chamber according to Example 3 Parameter Value Plasma chamber Dimensions 500 x 400 x 250 mm Temperature wall 50 - 80 ° C Electrodes RF / grounded Pretreatment No Coating Monomer 3- (trimethoxysilyl) propyl methacrylate Flow 5-30 seem Basic pressure 10 - 30 mTorr Operating pressure 15 - 75 mTorr Power 10 - 100 W. Frequency 13.56 MHz Frequency mode cw
    BE2015 / 5507
    Table 7: Process parameters in a 50 liter chamber according to Example 3
    BE2015 / 5507
    权利要求:
    Claims (11)
    [1]
    CONCLUSIONS
    1. Method of depositing a halogen-free durable water-repellent (DWR) nano-coating on a textile product via a low-pressure plasma polymerization process with an organosilane monomer, thereby obtaining a DWR nano-coating that is resistant to repeated washings.
    [2]
    The method according to any one of the preceding claims, wherein the organosilane monomer is an organosilane according to
    Y1-X-Y2, where X is, O or NH, Yi is -Si (Y 3 ) (Y 4 ) Y 5 and Y 2 is Si (Y 3 ) (Y 4 ) Y 5 'where Y 3 , Y 4 , Y 5 , Y 3 -, Y 4 ', and Y 5 - are independently H or an alkyl group up to 10 carbon atoms; wherein at most one of Y 3 , Y 4 and Y 5 'is H, and at most one of Y 3 -, Y 4 ' and Y 5 'is H; and the total number of carbon atoms is not more than 20;
    - [Si (CH 3 ) q (H) 2 -qX-] n -, which is cyclic, where n is 2 to 10, where q is 0 to 2, and the total number of carbon atoms is not more than 20;
    CH 2 = C (R 1) -Si (R 2 ) (R 3 ) -R 4 , where R 1 is H or an alkyl group, e.g. CH 3 , and wherein R 1, R 2 and R 3 are independently H, or an alkyl group up to 10 carbon atoms long or an alkoxy group -OZ, wherein Z is preferably -C t H 2t + i, where t is 1 to 10 ;
    R5-Si (Rs) (R7) -R8, where Rs is H or an alkyl group, e.g. -CH 3 , and where Re, R and R 8 are each, independently of one another are H or an alkyl group up to 10 carbon atoms, or an alkoxy group -OZ, wherein Z is preferably C t H 2t + i, wherein t is 1 to 10; or
    CH 2 = C (R9) C (0) -0- (CH 2 ) p-Si (Rio) (Rn) -Ri 2 , where Rg is H or an alkyl group, e.g. -CH 3 , where p is from 0 to 10, and wherein R 1, R 1 and R 12 are each independently H or an alkyl group up to 10 carbon atoms or an alkoxy group-O 2, where Z is preferably -C t H 2t + i, where t is 1 to 10.
    [3]
    A method according to any preceding claim, wherein the textile product is a 3D finished textile product, after confection, such as a garment or accessory, treated in a batch process.
    [4]
    A method according to any preceding claim, wherein the textile product is a textile on a roll (2D) treated in a roll-to-roll process.
    [5]
    The method according to any one of the preceding claims, wherein the low pressure plasma polymerization process is preceded by an outgassing of the textile product.
    [6]
    The method of any preceding claim, wherein the low pressure plasma polymerization process is preceded by a low pressure plasma pretreatment.
    2015/5507
    BE2015 / 5507
    [7]
    The method of claim 6, wherein the low pressure plasma pretreatment process is performed with an inert and / or a reactive gas.
    [8]
    The method of any preceding claim, wherein the low pressure plasma polymerization process is followed by a post-treatment process comprising the step of exposing the treated fabric to a low-pressure post-treatment gas.
    [9]
    Method according to Claim 8, wherein the after-treatment process is carried out with an inert and / or a reactive gas.
    [10]
    A method according to Claims 8 or 9, wherein the post-treatment gas is provided with a post-treatment ability that is at least 10% and at most 190% of a plasma polymerization applied during the low pressure plasma polymerization process to ignite the organosilane monomer.
    [11]
    A method according to any preceding claim, wherein an additional gas or an additional gas mixture is used during the low pressure plasma polymerization processes, wherein the additional gas or gas mixture is a carrier gas, a functional gas, and / or a functional carrier gas is.
    2015/5507
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    同族专利:
    公开号 | 公开日
    WO2016193486A1|2016-12-08|
    BE1024821A1|2018-07-06|
    EP3101170A1|2016-12-07|
    DK3101170T3|2018-10-08|
    EP3101170B1|2018-08-22|
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    法律状态:
    2018-09-05| FG| Patent granted|Effective date: 20180713 |
    2021-05-26| MM| Lapsed because of non-payment of the annual fee|Effective date: 20200831 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP15170410.3|2015-06-03|
    EP15170410.3A|EP3101170B1|2015-06-03|2015-06-03|Surface coatings|
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