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    • 专利摘要:
    The present invention relates to hydrophilic, multifunctional ultra-thin coatings deposited on substrates for various applications, with excellent performance in terms of stability and durability. The present invention also describes improved methods for depositing the hydrophilic, multifunctional ultra-thin coatings of the present invention. The coatings are applied by means of a low-pressure plasma polymerization. The present invention also includes substrates coated according to a method and a coating as described in the present invention.
    公开号:BE1025053B1
    申请号:E2017/0041
    申请日:2017-04-04
    公开日:2018-10-12
    发明作者:Filip Legein；Eva Rogge；Samir Loulidi
    申请人:Europlasma Nv；
    IPC主号:
    专利说明:

    (30) Priority data:
    09/11/2016 EP 16198015.6 (73) Holder (s):
    EUROPLASMA NV 9700, OUDENAARDE Belgium (72) Inventor (s):
    EMPTY Filip
    9700 PARENTAL
    Belgium
    RYE Eva
    9700 PARENTAL
    Belgium
    LOULIDI Samir
    9700 PARENTAL
    Belgium (54) HYDROFILE, MULTIFUNCTIONAL, ULTRA-THIN COATINGS WITH EXCELLENT STABILITY AND DURABILITY (57) The present invention relates to hydrophilic, multifunctional ultra-thin coatings deposited on substrates for various applications, with excellent performance in terms of stability and durability. The present invention also describes improved methods of depositing the hydrophilic, multifunctional ultra-thin coatings of the present invention. The coatings are applied by low pressure plasma polymerization. The present invention also includes substrates coated by a method and a coating as described in the present invention.
    BELGIAN INVENTION PATENT
    FPS Economy, K.M.O., Self-employed & Energy
    Publication number: 1025053
    Filing number: BE2017 / 0041
    Intellectual Property Office
    International classification: B05D 3/14 B05D 1/00
    Date of grant: 12/10/2018
    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 04/04/2017.
    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 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: HYDROFILE, MULTIFUNCTIONAL ULTRA-THIN COATERS WITH EXCELLENT STABILITY AND DURABILITY.
    INVENTOR (S):
    LEGEIN Filip, De Bruwaan 15, 9700, OUDENAARDE;
    RYE Eva, De Bruwaan 15, 9700, OUDENAARDE;
    LOULIDI Samir, De Bruwaan 15, 9700, OUDENAARDE;
    PRIORITY :
    09/11/2016 EP 16198015.6;
    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, 12/10/2018,
    With special authorization:
    BE2017 / 0041
    Hydrophilic, multi-functional ultra-thin coatings with excellent stability and durability
    Description of the invention
    Technical domain
    The present invention relates to hydrophilic, multi-functional ultra-thin coatings (nanoplays) deposited on substrates for various applications, with excellent performance in terms of stability and durability. The present invention also describes improved methods of depositing the hydrophilic, multifunctional ultra-thin coatings of the present invention. The coatings are applied by low pressure plasma polymerization, which is preferably used at low power. The present invention also includes substrates coated by such a method and a coating obtained by methods of the present invention.
    Background of the invention
    The present invention relates to methods of depositing hydrophilic, multifunctional ultra-thin coatings (nano coatings) on substrates wherein the coatings have excellent properties such as durability, e.g. against moisture, and stability, e.g. thermal stability. The nano coatings are deposited using a low pressure plasma polymerization process, preferably at low power.
    Target applications for the nano coatings of the present invention are medical applications - lenses, catheters, stents, bandages, blood filters, biochemical applications, e.g. cultivation plates, electrochemical applications, fuel cells, batteries and the like, and application to membranes and textiles, for example, used in filtration applications, e.g. blood filtration and separation applications, e.g. battery separator textile. The hydrophilic nature is often used to reduce bonding with organic materials and to achieve reduced coagulation. Furthermore, the hydrophilic nature is often used to obtain an increased bond with biomolecules, e.g. for analysis purposes, or to promote bone and tissue growth. Adhesion with water is also improved, resulting in excellent wettability.
    BE2017 / 0041
    Several hydrophilic treatments and processes already exist. One way to deposit hydrophilic coatings is by using a wet chemical process, which typically uses complex compounds of monomers and additives, leads to thicker coatings (thickness in the micrometer range), significant amounts requires water, chemicals and energy, and therefore has a high ecological footprint.
    WO2006019175 describes a curable composition for forming an anti-fog coating by means of a wet-chemical process, using a compound with chemicals, such as a urethane compound, an epoxy compound and (meth) acrylic acid.
    JP4698529 describes an anti-fog film obtained by a wet chemical coating process using (meth) acrylic acid and (meth) acrylic acid alkyl ester.
    It is clear, therefore, that the wet chemical methods require a complex composition consisting of different chemical products to make a good emulsion, dispersion or solution. The present invention overcomes these requirements by using a low pressure plasma polymerization using the monomer in its pure form and requiring no additives. The energy consumption of the plasma polymerization process can be kept low compared to these wet chemical processes, since there is no need for drying or curing at elevated temperatures.
    Another way to deposit hydrophilic coatings is through plasma graft polymerization. These processes, like all plasma processes, do not require water and use lower amounts of chemicals. However, in graft polymerization, the liquid monomer is typically sprayed onto the substrate or applied in the form of an aqueous solution and then cured to induce polymerization and cross-linking. This requires at least 2 steps and high power - thus high energy consumption - for the curing to induce polymerization and cross-linking. The reverse order of steps is also used in some priority documents.
    CN101890314 describes a method of hydrophilic treatment to polytetrafluoroethylene (PTFE) by graft polymerization. In a first step, a low pressure plasma pretreatment is performed without the
    BE2017 / 0041 presence of monomer to induce graft polymerization. In a second step, the polymerization is performed by contacting the plasma pretreated substrate with the liquid monomer.
    WO2012133154 also describes a plasma graft polymerization of acrylic acid to obtain a polyacrylic acid coating on a PMMA substrate. The process comprises 4 steps: atomization of liquid acrylic acid monomer, argon plasma for curing, atomization of liquid acrylic acid monomer again, and argon plasma for curing again.
    CN 102432905 describes a 3-step process in which a Corona (air) pretreatment is performed, followed by spraying the acrylic acid monomer via a nozzle on the substrate, followed by UV curing to obtain polymerization and cross-linking.
    US2014336758, EP2705859, EP2792380 and WO2015096876 all describe a 3-step method of applying hydrophilic coatings to medical device surfaces, the coatings exhibiting water contact angles of less than 10 °. The 3-step process consists of a plasma pretreatment, e.g. for roughening the substrate on a micro scale, followed by PECVD (Eng. plasma enhanced chemical vapor deposition, NI. plasma induced chemical vapor deposition) of acrylic acid, followed by a CVD (Eng. chemical vapor deposition, Ni. chemical vapor deposition) process of acrylic acid without a plasma present. These methods as described all require an additional step, the CVD step, to obtain a hydrophilic coating of acceptable performance. Obviously, this makes the process more complex and requires increased monomer consumption.
    EP0995762 discloses a method of anti-fouling coatings on biomedical devices such as stents, catheters and intraocular lenses, wherein a coating is applied via low pressure plasma polymerization, wherein the polymeric polymer coating is highly grafted onto the surface of the substrate. The polymer has hydrophilic properties that prevent the adhesion of proteins, cells and lipids.
    US2009069790 discloses a method of obtaining a higher surface energy, high adhesion coating, to increase material reactions of surrounding tissue devices, using a stacked method
    BE2017 / 0041 is implemented. A two-step cycle is repeated several times until the desired functionality is obtained. The two-step cycle includes an inert gas plasma treatment as the first step, and a low pressure plasma graft polymerization step as the second step.
    W003012893 describes a method of depositing a hydrophilic coating on a battery separating material in which the membrane is contacted with the monomer and the monomer is polymerized in a subsequent step by exposure to radiation.
    A third method described in the prior art to deposit hydrophilic coatings is with atmospheric pressure plasma, wherein the acrylic acid monomer is introduced into the deposition region by means of a carrier gas, for example an inert gas such as helium. To exclude the influence of the atmosphere, the electrodes are flat and placed close together (mm to cm range), which limits the use of the method for complex 3D substrates, such as for ski goggles and car headlights. The power between the electrodes is typically in the range of kW, e.g. 1 to 2 kW (1000 to 2000 W) over a distance between the flat electrodes in the mm range.
    The present invention improves the state of the art by providing a method of depositing hydrophilic, multifunctional ultra-thin coatings on substrates, the nanod coatings having excellent stability and durability, where the substrates can have a flat (2D) or complex shape (3D) -
    e.g. finished products, and where the method improves on the known methods by:
    Dry and clean process: no consumption of water
    Ultra-thin, invisible coatings
    Use of monomer, no mixtures and additives required. Low power, so low energy consumption
    Reduced complexity of the process steps
    Excellent stability and durability of the coatings
    Summary of the invention
    The present invention relates to hydrophilic, multifunctional ultra-thin coatings deposited on substrates for various target applications, with excellent performance in terms of stability and durability. The present invention also describes methods of hydrophilic,
    BE2017 / 0041 to sell multifunctional ultra-thin coatings of the present invention.
    The nano coatings are deposited by low pressure plasma polymerization. The present invention also includes substrates coated by a method and with a coating as described in the present invention.
    The present invention relates in particular to a method for depositing a hydrophilic, multifunctional ultra-thin coating on a substrate according to claim 1.
    The present invention also relates to a method of depositing a hydrophilic, multifunctional ultra-thin coating on a substrate, comprising the following steps:
    Optional performing a first pretreatment on the substrate; thereafter
    Optionally, providing an intermediate nano-coating on the substrate by exposing the substrate to a low pressure plasma polymerization process with a first precursor monomer;
    Optionally thereafter performing a second pretreatment on the substrate provided with the optional intermediate nanodeck; and then
    Providing a hydrophilic, multifunctional, ultra-thin coating on the substrate with the optional intermediate nanodecovery, by exposing the substrate with the optional intermediate nanodecovering to a low pressure and low power plasma polymerization process with a second precursor monomer different from said first precursor monomer wherein the second precursor monomer has the formula (I):
    CH 2 = CR 4 - CH 2 - O - R 5 (I), wherein R 4 is H or an alkyl group, eg -CH 3 , and wherein R s is H, an alkyl or an alkenyl. The alkyl or alkenyl groups of R 5 may contain 1 to 10 carbon atoms, and may be linear or branched. R 5 preferably contains one or more hydrophilic functional groups, such as hydroxyl groups and / or carbonyl groups.
    The plasma polymerization process herein refers to a process where the first or second monomer is introduced into the plasma chamber in which the substrate is located, and a plasma is ignited by electrical or electromagnetic discharge over the radiofreguent and the grounded electrodes that positioned in the plasma chamber to obtain a reactive first or second precursor from the monomer, the precursor being the monomer brought into the plasma state. The precursor then polymerizes on the exposed surface of the substrate, thereby forming a polymeric coating. The steps of monomer reactivity and subsequent polymerization all occur in the same plasma chamber in which the substrates to be treated are positioned. The electrical or electromagnetic discharge is obtained by creating a continuous (cw) radio frequency (RF) field in the plasma chamber, e.g. via a set of radio frequency and ground electrodes positioned in the chamber. The power input to generate the cw-RF field is non-zero at any time and is preferably kept constant for the second precursor at a preset value between 0.02 W / l and 2.50 W / l for plasma chambers of 50 I and above, because The Applicant has discovered that such low powers allow to obtain polymeric coatings with the best quality and optimal composition in terms of bonds and functional groups.
    This method provides a coating that is hydrophilic and has good adhesion to the substrate for a variety of substrates. This leads to a significant reduction in installation and production costs, since the method is preferably used largely irrespective of the type of substrate in a single plasma chamber.
    The Applicant has surprisingly discovered that the coating of the present invention has much better stability and durability in terms of e.g. thermal aging than the coatings described in the prior art, such as low pressure plasma coatings deposited from acrylic acid as a monomer. Without wishing to be bound by any particular theory, it is believed that the improvement is created by better hydrophilic functional groups in the monomer and the resulting coating, along with the presence of an ether function (R - O - R ') that allows hydrogen bonding are formed between the molecules in the polymer structure, thereby adding extra strength to the coating. In addition, these bonds are not covalent bonds, so in the event that they are broken in conditions such as high temperature and / or humidity, they will be reformed once the conditions stabilize,
    BE2017 / 0041 preserves the excellent hydrophilic properties, which guarantee excellent stability and durability in various conditions.
    In light of this, Applicant has discovered that the use of a continuous plasma polymerization process at low power, e.g. less than 2.5 W / l for the second precursor gives unexpectedly better results than other processes, especially pulsed plasma polymerization processes or higher power polymerization processes, with respect to the hydrophilic properties of the coating, and the stability and durability at an interval of conditions (temperature, humidity), and in terms of the process speed. Again, without wishing to be bound by any theory, the Applicant considers that this is due to the low power continuous plasma polymerization process which allows the coating to grow while most of the ether functional groups and the hydrophilic functional groups of the structure remain intact, combined with optimal cross-linking via covalent bonds, while a continuous high-power process can remove the hydrogen bond bonds between the ether functions, and a pulsed process, which may require peaks of up to 200 W / l to form a plasma igniting and where the peaks are separated by periods without energy supplied, may not provide enough energy to achieve cross-linking.
    Applicant has further discovered that the method of the present invention is more scalable than the methods described in the prior art, due to a combination of monomer selection and the continuous plasma polymerization step. Accordingly, the method of the present invention is preferably performed in a plasma chamber of 50 I or greater, more preferably 100 I or greater, more preferably 200 I or greater, more preferably 300 I or greater, 400 I or greater, 500 I or greater, such as 500 I, 600 I, 700 I, 800 I, 900 I, 1000 I, and any value in between, or even greater than 1000 I.
    The present invention also relates to coated substrates according to a method of the present invention.
    Brief description of the figures g BE2017 / 0041
    Figure 1 shows the thermal stability of the coatings of the present invention compared to a benchmark coat also deposited via low pressure plasma polymerization.
    Figure 2 shows a thermal cycling profile used in Example 2.
    Figure 3 shows the thermal cycling stability testing of the coatings of the present invention compared to a benchmark coat also deposited via low pressure plasma polymerization.
    Figure 4 shows the durability of the coatings of the present invention compared to a benchmark coat also deposited via low pressure plasma polymerization.
    Detected description of the invention
    As used herein, the following terms have the following meanings:
    One and the as used herein refers to both singular and plural unless the context clearly indicates otherwise. As an example, a compartment refers to one or more compartments.
    About ”as used herein refers to a measurable value such as a parameter, an amount, a time period, and the like, and is intended to include variations of +/- 20% or less, preferably +/- 10% or less, more preferably +/- 5% or less, even more preferably +/- 1% or less, and even more preferably +/- 0.1% or less from and from the specified value, to the extent that such changes are suitable for making in the described invention. It is to be understood, however, that the value to which the expression approximately refers to has also been specifically described.
    Includes, comprising and includes "and consisting of" as used herein is synonymous with consisting of "including, including" or consisting of, containing ", contains" and includes or excludes terms that specify and exclude the presence of what follows, for example, not eliminate the presence of other unlisted components, properties, elements, steps or members as known in the art or described herein.
    g BE2017 / 0041
    The term hydrophilic as used herein to denote the property of the coating indicates that a water contact angle of less than 90 ° is achieved. As will become apparent from the present specification, coatings with very small water contact angles can be achieved with the present invention, such as at most 30 °, at most 20 ° or even at most 10 °, such as 9 °, 8 °, 7 °, 6 °, 5 °, 4 °, 3 °, 2 °, 1 °, 0 ° or any value in between. According to the method of the present invention, coated surfaces can be obtained which have a substantially disappearing water contact angle, i.e. coated surfaces which can be completely wetted with water.
    The term multifunctional as used herein to denote the property of the coating indicates that the coating may have properties other than the hydrophilic property. The coating can also provide the substrate with protection against mechanical wear and friction or protection against environmental factors. The inventors have also surprisingly discovered that the coating may also have other unobvious properties, as described further in this document.
    Naming numerical ranges by endpoints includes all numbers and fractions that fall within that range, as well as the listed endpoints.
    The present invention improves the prior art by providing a method of depositing hydrophilic, multi-purpose radial coatings on substrates, the coatings having excellent stability and durability, where the substrates may have flat (2D) or complex shapes (3D) and wherein the method is a low pressure plasma polymerization, preferably at low power.
    It is a first aspect of the present invention to provide a method of depositing a hydrophilic, multi-purpose, radiopaque coating on a substrate, wherein the nano coating is deposited by low pressure plasma polymerization, preferably at low power.
    It is a second aspect of the present invention to provide a method of depositing a hydrophilic, multi-purpose radial coating on textile, the nanocoating having excellent stability and durability.
    BE2017 / 0041
    In a first embodiment, the low pressure low power plasma polymerization is a low pressure low power plasma polymerization of a precursor monomer which is introduced into the plasma chamber. In a gaseous state, the precursor monomer of formula (I) being:
    CH 2 = CR 4 - CH 2 - O - R s (I), wherein R 4 is H or an alkyl group, eg -CH 3 , and wherein R s is H, an alkyl or an alkenyl. The alkyl or alkenyl groups of R 5 may contain 1 to 10 carbon atoms, and may be linear or branched. R 5 preferably contains one or more hydrophilic functional groups, such as hydroxyl groups and / or carbonyl groups.
    In a particularly preferred embodiment, R 4 is H and R 5 is -CH 2 -CH (OH) 2 , ie 3-allyloxy-1,2-propanediol.
    Preferably, for coating 3D articles (e.g. finished products), the plasma polymerization time, expressed in the time that a power is applied to the electrode layers, is about 1 minute to about 20 minutes, more preferably about 2 minutes to about 15 minutes , such as about 5 minutes to about 10 minutes, such as 10, 9, 8, 7, 6, or 5 minutes.
    Applicants have surprisingly discovered that it is appropriate to conduct the plasma polymerization as a continuous plasma polymerization, applying a constant power strictly higher than 0 W during the plasma polymerization time. By applying an optimal, low, non-zero power, the plasma polymerization will give good quality coatings, with the fragmentation of the monomer well controlled, making the use of inert carrier gases superfluous, and in which the functional groups containing the hydrophilic properties are retained while good polymer cross-linking and good adhesion to the substrate are realized. An additional advantage of using a continuous plasma polymerization in which a constant power strictly above 0 W is applied is that the deposition rate is higher than with pulsed plasma polymerization, resulting in shorter coating times and shorter cycle times, and consequently reduced costs.
    Preferably, the plasma chamber comprises one or more electrode layers, which may be radio frequency electrode layers or grounded electrode layers, to generate an electromagnetic field.
    BE2017 / 0041
    Preferably, the or each radio-frequency electrode layer generates a high-frequency electric field at a frequency from 20 kHz to 2.45 GHz ; preferably from 40 kHz to 13.56 MHz, with 13.56 MHz the preferred value.
    Preferably, when used in a 280 liter 4 drawer plasma chamber to place the products to be treated, each drawer having electrode layers above and below the drawer for optimum uniformity throughout the chamber, the applied power for the deposition process, when applied to continuous plasma mode, about 5 to 600 W, more preferably about 10 to 250 W, even more preferably 15 to 100 W, say 100, 90, 80, 75, 70, 60, 50, 45, 35, 30, 25 , 20, or 15 W. In plasma chambers of other volumes, a power density equivalent to that for a 280 liter plasma chamber is applied.
    Preferably, the operational pressure (so-called working pressure) for the deposition step is about 10 to 500 mTorr, preferably about 15 to 200 mTorr, preferably about 20 to 150 mTorr, say 25 to 100 mTorr, say less than 100, 90, 80, 70, 60, 50, 40, 30, or 25 mTorr. For example, in a 280 liter plasma chamber, such pressure intervals are particularly preferred.
    Preferably, the thickness of the hydrophilic multifunctional nano-coating is about 50 to about 1000 nm, more preferably about 75 to about 750 nm, such as about 100 nm to about 500 nm, for example 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 95, 90, 85, 80, or 75 nm.
    A pretreatment can be performed before the low pressure plasma polymerization step is performed at low power. Preferably, the pretreatment is a low pressure plasma process. Whether or not a low pressure plasma pretreatment is carried out depends on the contamination of the substrates to be coated 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 hydrophilic, multifunctional ultra-thin coating is better when no pretreatment is performed. For other monomers, pre-treatment in the form of low pressure plasma cleaning and / or activation and / or etching can be advantageous.
    BE2017 / 0041
    In one embodiment, a pretreatment step in the form of an activation and / or cleaning and / or etching is performed prior to the plasma polymerization process. A pre-treatment step in the form of an activation and / or cleaning and / or etching can be advantageous for improving the adhesion and cross-linking of the polymeric coating.
    When a low pressure plasma pretreatment is performed, this pretreatment is preferably carried out with reactive gases, eg H 2 , O 2 , CO 2 and / or etching reagents such as CF 4 , but inert gases such as Ar, N 2 or He can also be used. Mixtures of the foregoing gases can also be used.
    Preferably, the pretreatment is carried out with O 2 , Ar or a mixture of O 2 and Ar.
    Preferably, when used in a batch process to treat complex 3D-molded products, the pretreatment is carried out for 15 seconds to 15 minutes, e.g. 30 seconds to 10 minutes, preferably 45 seconds to 5 minutes, e.g. 5, 4, 3, 2 or 1 minutes. The duration of the pretreatment depends on the precursor monomer, on the design and materials of the substrate to be coated, on the degree of contamination on the substrate to be coated, and on the low pressure plasma equipment.
    The pretreatment power can be applied in continuous mode or in pulsed mode.
    Preferably, when used in continuous mode in a 280 liter plasma chamber, the pretreatment takes place at powers from 10 to 1000 W, more preferably from 25 to 750 W, even more preferably from 50 to 600 W, such as 75 to 500 W , say 500, 450, 400, 350, 300, 250, 200, 150, 125, 100 or 75 W. In plasma chambers with other volumes, preferably a power density equivalent to the above-mentioned intervals for a 280 liter plasma chamber is used.
    Preferably, when used in pulsed mode in a 280 liter plasma chamber, the pretreatment takes place at a power of 10 to 2000 W, more preferably from 25 to 1500 W, even more preferably from 50 to 1000 W, say 75 to 750 W, such as 100 to 600 W, say 600, 550, 500, 450, 400, 350, 300, 250, 200,
    BE2017 / 0041
    175, 150, 125, or 100 W. In plasma chambers with other volumes, a power density equivalent to the above intervals for a 280 liter plasma chamber is preferably used.
    When applied in pulsed mode, the pulse frequency can be from 100 Hz to 10 kHz with a duty cycle of about 0.05 to 50%, with the optimal parameters depending on the gas or gas mixture used.
    Preferably, the or each radio frequency electrode layer generates a high frequency electric field at a frequency from 20 kHz to 2.45 GHz, more preferably from 40 kHz to 13.56 MHz, with 13.56 MHz being preferred.
    Preferably, the operating pressure (so-called working pressure) for the pretreatment step is about 10 to 500 mTorr, preferably about 20 to 250 mTorr, preferably about 25 to 200 mTorr, say 50 to 150 mTorr, say less than 150, 140, 130, 125, 120, 110, 100, 90, 80, 75, 70, 60 or 50 mTorr.
    When a pre-treatment is used, the hydrophilic, multifunctional ultra-thin polymeric coating is applied in a next step, which can be performed in the same machine.
    Preferably, the pretreatment and the deposition step are performed in the same chamber without opening the chamber between the steps to prevent deposition of additional atmospheric contamination in the period between the pretreatment and the deposition step.
    Applicants have also discovered that it may be advantageous to deposit an ultra-thin intermediate nanocover prior to the actual hydrophilic, multifunctional ultra-thin coating of the present invention being deposited. When a pretreatment is carried out, the ultra-thin intermediate nanopaper is preferably deposited after the pretreatment and before the low pressure plasma polymerization of the actual hydrophilic multifunctional nanod coat of the present invention, but can also be deposited before the pretreatment. Optionally, two pretreatments can be performed on the substrate: a first pretreatment before the intermediate nanodeposition is deposited and a second pretreatment after the intermediate nanodecover coating and before the hydrophilic coating is deposited.
    BE2017 / 0041
    Preferably, the ultra-thin intermediate nanodeposition is deposited by a low pressure plasma polymerization process. In one embodiment, the low pressure plasma polymerization is a low pressure plasma polymerization of an organosilane precursor monomer introduced into a plasma chamber, the organosilane of the formula (II) being:
    Y, -X ~ Y 2 (II) where X is O or NH, Yj is Si (Y 3 ) (Y 4 ) Y 5 and Y2 is Si (Y 3 ') (Y 4 ') Y5 'where Y 3 , Y 4 , Y 5 , Y 3 ', Y 4 ' and Y s , each independently is H or an alkyl group having up to 10 carbon atoms; wherein at most one of Y 3 , Y 4 and Y 5 is hydrogen, and at most one of Y 3 ', Y 4 and Y 5 - is hydrogen; and the total number of carbon atoms does not exceed 20.
    The organosilane monomer is preferably introduced into the plasma chamber in a gaseous state.
    For some substrates, in particular glass and glassy substrates such as polycarbonate (PC) and polymethyl methacrylate (PMMA), the application of an ultra-thin intermediate nanocover is particularly preferred. In glass and vitreous substrates such as PC and PMMA, in an even more preferred embodiment, the intermediate nanopaper precursor monomer is an organosilane precursor of formula (II). Without wishing to be bound by any theory, the excellent results of the use of an intermediate nanosurface based on an organosilane precursor monomer on glass or a vitreous substrate prior to the hydrophilic coating may be related to the semi-organic and semi-inorganic character of the organosilane monomer. This monomer has chemical properties, such as the bond type, which makes it adheres well to a wide range of substrates, especially glass and glass-like surfaces, while at the same time resulting in a layer with physicochemical properties such as interatomic distances, elasticity and in particular thermal expansion coefficient, these lie between the corresponding properties of the substrate and the hydrophilic, multifunctional coating.
    The present invention also relates to a method of depositing a hydrophilic, multifunctional ultra-thin coating on a substrate, comprising the following steps:
    - Possibly performing a first pretreatment on the substrate; thereafter
    BE2017 / 0041
    - Optionally providing an intermediate nano-coating on the substrate by exposing the substrate to a low-pressure plasma polymerization process with a first precursor monomer;
    - Possibly thereafter performing a second pretreatment on the substrate provided with the optional intermediate nanodeck; and then
    - Providing a hydrophilic, multifunctional, ultra-thin coating on the substrate with the optional intermediate nanoplastic, by exposing the substrate with the optional intermediate nanoplastic to a low pressure plasma polymerization process at low power with a second precursor monomer different from said first precursor monomer.
    In a preferred embodiment, the second precursor monomer of the formula (I) is:
    ch 2 - cr 4 - ch 2 - O - R s (I), wherein R 4 is H or an alkyl group, eg -CH 3 , and wherein R s is H, an alkyl or an alkenyl. The alkyl or alkenyl groups of R s may contain from 1 to 10 carbon atoms, and may be linear or branched. R 5 preferably contains one or more hydrophilic functional groups, such as hydroxyl groups and / or carbonyl groups.
    In a particularly preferred embodiment, R 4 is H and R 5 is -CH 2 -CH (OH) 2 , ie 3-allyloxy-1,2-propanediol.
    In one embodiment, the first precursor monomer contains one or more atoms equal to one or more atoms contained in the substrate. In a preferred embodiment, the first precursor monomer contains an atomic group equal to an atomic group present in the substrate. The term "atomic group" refers herein to a bonded group of at least two atoms.
    The monomers are preferably introduced into the gaseous plasma chamber.
    In a preferred embodiment, the first precursor monomer is an organosilane of the formula (II).
    Yi-XY 2 (II) where X is O or NH, Yj is -Si (Y 3 ) (Y 4 ) Ys and Y2 is Si (Y 3 ') (Y 4 ') Y 5 'where Y 3 , Y 4 , Y 5 , Y 3 ', Y 4 ' and Y 5 'are each independently H or an alkyl group having up to 10 carbon atoms; wherein at most one of Y 3 , Y 4 and Y 5 is hydrogen and
    BE2017 / 0041 at most one of Υ 3 ·, Y 4 - and Y 5 . is hydrogen; and the total number of carbon atoms does not exceed 20.
    In some embodiments, the method may include the step of introducing an additional gas into the plasma chamber in combination with the precursor monomer for the intermediate nanoplane. The additional gas must be viewed as a functional gas that contributes to the low pressure plasma polymerization reaction in terms of generating the plasma to ignite the plasma, or affecting the low pressure plasma polymerization reaction to provide higher performance coatings. to realise.
    The additional gas can be H 2 , N 2 , O 2 , N 2 O, CO 2 , CH 4 , He or Ar, or mixtures thereof, most preferably O 2 or CO 2 .
    Preferably, when an additional gas is used in the intermediate nano-coating step, the flow of additional gas introduced into the chamber is about 1 to about 75% of the monomer flow rate. Preferably, the flow rate of additional gas introduced into the chamber is about 5 to about 50% of the monomer flow rate, e.g. about 10 to 20% of the monomer.
    Preferably, the thickness of the intermediate nano-coating is about 5 to about 250 nm, more preferably about 10 to about 200 nm, such as from about 15 nm to about 150 nm, for example about 20 nm to about 100 nm, say 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, or 20 nm.
    The plasma polymerization can be a continuous plasma polymerization. The plasma polymerization can be a pulsed wave polymerization. Whether a continuous or a pulsed plasma is used for the polymerization depends on the chemistry used and on the volume and design of the plasma chamber.
    Preferably, when used in a 280 liter plasma chamber, the applied power for the deposition process, when used in a continuous mode, is about 5 to 1000 W, more preferably about 25 to 750 W, even more preferably 50 to 500 W, say 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 75, 70, 60 or 50 W. In plasma chambers of other volumes, a power density equivalent to that for a 280 liter plasma chamber is applied.
    BE2017 / 0041
    Preferably, when used in a 280 liter piano chamber, the applied power for the deposition process, when used in pulsed wave mode, is about 5 to 2000 W, more preferably about 25 to 1500 W, even more preferably 50 to 1000 W, such as 100 to 750 W, say 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 or 100 W. In plasma chambers of other volumes, a power density equivalent to that for a 280 liter plasma chamber is applied.
    Preferably, when in pulsed plasma mode, the pulse repetition frequency can be 100 Hz to 10 kHz with a duty cycle of about 0.05 to 50%, with the optimal parameters depending on the monomer used.
    Preferably, the piano chamber comprises one or more electrode layers, which may be radio frequency electrode layers or grounded electrode layers, to generate an electromagnetic field.
    Preferably, the or each radio-frequency electrode layer generates a high-frequency electric field at a frequency of 20 kHz to 2.45 GHz, more preferably from 40 kHz to 13.56 MHz, with 13.56 MHz the preferred value.
    Preferably, the operational pressure (so-called working pressure) of the intermediate nanodeposition step is about 10 to 500 mTorr, preferably about 15 to 200 mTorr, preferably about 20 to 150 mTorr, say 25 to 100 mTorr, say less than 100.90 , 80, 70, 60, 50, 40, 30 or 25 mTorr. In a 280 liter piano chamber, for example, such pressure intervals are particularly preferred.
    In a particularly preferred embodiment, the plasma chamber temperature is controlled, e.g. to prevent temperature differences from occurring within the chamber, and to avoid cold spots where the process gas, i.e. the monomer vapor or the monomer gas and possibly the additional gas, may condense. For example, the door and one or each wall of the vacuum chamber can be equipped with at least one temperature controller. Alternatively, or in parallel, one or more electrodes in the plasma chamber used to ignite a plasma may include temperature controllers, such as a body through which a liquid can flow at a controlled temperature. The piano chamber is preferably temperature controlled during
    BE2017 / 0041 the plasma polymerization step in which an ultra-thin hydrophilic, multifunctional coating is applied and / or in which an ultra-thin intermediate nanopaper is applied, in order to prevent condensation of the precursor monomer. Preferably, the plasma chamber is also temperature controlled during the pretreatment step prior to the plasma polymerization step in which an ultra-thin hydrophilic nano-coating is deposited and / or in which an ultra-thin intermediate nano-coating is provided.
    By introducing a gaseous precursor monomer into the plasma chambers and by controlling the temperature of the plasma chamber to avoid condensation of the monomer, the quality of the resulting coating can be significantly increased. Condensation of the monomer can lead to less polymerization and result in sticky products. In addition, contamination of the plasma chamber, in particular the walls or electrodes, with condensed monomer which may be partially polymerized can be avoided.
    Preferably, the temperature control maintains the temperature at room temperature up to 90 ° C, more preferably between 40 and 60 ° C.
    Preferably, when the electrode layers are radiofrequency electrode layers, they are also temperature controlled to ensure still further temperature uniformity in the plasma chamber.
    Preferably, the pump, the liquid monomer feed and all connections between these components and the plasma chamber are also temperature controlled to avoid cold spots where the process gas or gases can condense.
    Preferably, the method includes coating the polymer substrate to decrease the contact angle measured according to ASTM D5946 and to increase the surface energy measured according to ASTM D2578-04.
    The coating performance is measured by conducting a water contact angle test on the substrates, according to ASTM D5946.
    The coatings of the present invention, deposited by the method as described above, lead to water contact angles less than or equal to 30 °
    BE2017 / 0041 after treatment, even less than or equal to 20 °, more preferably approximately
    15 ° and below, for example 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0 °.
    The performance of the coatings of the present invention can also be evaluated in terms of stability and durability.
    Stability can be measured by performing an aging test in which the samples are exposed to an elevated temperature for a longer time, e.g. 4 hours at 150 ° C.
    Furthermore, the stability can also be tested in a thermal cycle test, where the temperature and relative humidity are varied according to a fixed schedule.
    Coating durability can be tested by repeated water contact angle measurements at the same spot of the coated substrate.
    By depositing the hydrophilic, multifunctional ultra-thin coatings of this invention, not only are hydrophilic properties obtained, but the following properties can also be significantly improved:
    Decreased coagulation, e.g. of components in blood;
    Resistance to acidic media;
    Increased surface tension:
    a Improved transport of liquids;
    * Improved absorption of aqueous liquids, e.g. improved wicking effect;
    Hence, the present invention also relates to the use of a coating obtained by a method according to the present description for all individual and all combinations of the following properties:
    For reducing coagulation;
    - To increase resistance to acidic media;
    For increasing the surface tension, preferably for improving transport of liquid and / or for improving the absorption of aqueous liquids, e.g. to promote wicking.
    BE2017 / 0041
    EXAMPLES
    In order that the invention may be more readily understood, it will now be described by the following non-limiting examples.
    Glass substrates, e.g. for biochemical analysis (culture growth plates), were treated with various processes according to the present invention.
    Evaluation of deposition processes and the influence of different parameters was done by measuring the water contact angle according to ASTM D5946, before and after testing. The untreated, uncoated substrate has a water contact angle of 45.2 °.
    The machine used to deposit the coatings was a 280 liter 4-drawer chamber on which the products to be treated can be placed, each drawer having an electrode positioned above the drawer and an electrode below the drawer.
    Applicants have discovered that hydrophilic coatings deposited with low pressure plasma polymerization with acrylic acid as a precursor monomer lead to problems in industrial environments as a result of the reactivity of the acrylic acid. Liquid acrylic acid is typically stored in bottles in which an inhibitor has been added and an atmosphere of about 20-25% oxygen is present above the liquid. Acrylic acid easily forms radicals, which in turn react with the acrylic acid, leading to rapid polymerization. The inhibitor and the oxygen-containing atmosphere reduce the formation of radicals and neutralize the radicals formed. However, in a low pressure plasma process, the oxygen-containing atmosphere is no longer present, and by evaporating the monomer for controlled introduction of monomer vapor into the chamber for the low pressure polymerization process, the inhibitor is no longer present in the vapor. Once the vapor reaches a cold spot (called a cold spot), it condenses and polymerizes with itself due to the absence of an oxygen-containing atmosphere and inhibitor, which leads to easy clogging of the plasma machine's pipes.
    The monomer of the present invention solves this problem in that it is much less reactive and does not polymerize with itself. In terms of industrial applicability and scaling-up, the monomer of the present invention is capable of addressing the problems with e.g. dissolve acrylic acid.
    BE2017 / 0041
    In addition, acrylic acid is a dangerous monomer, the vapor can cause severe burns when in contact with human skin, and the smell of acrylic acid is sharp and strong. The monomer of the present invention does not cause burns when it comes into contact with human skin - although direct skin contact should be avoided for all chemicals, using appropriate personal protective equipment
    - and the smell is also less sharp and more neutral.
    To do a comparative test, the existing acrylic acid coating was used as a benchmark for the coating of the present invention. The untreated surface has also been tested as a reference. Both coatings are deposited in a 130-liter volume plasma chamber.
    Example 1: Aging test - thermal stability
    The coatings were evaluated for thermal stability by conducting an aging test. The samples were placed in an oven at ambient relative humidity and kept at a temperature of 150 ° C for 4 hours. Then they were allowed to cool.
    1.1. Comparison with the benchmark coating
    The coating of the present invention was compared to the untreated substrate and to a benchmark coating. The benchmark coating is a hydrophilic coating that has also been deposited via low pressure plasma polymerization, with acrylic acid as the monomer. The benchmark coating was deposited according to the parameters in Table 1, and the inventive coating according to the parameters in Table 2.
    Parameter Value Plasma ChamberVolume 130 liters Temperature wall 40-60 ° C Electrode layers RF / grounded PretreatmentGas Oxygen Flow 200 sccm Power 200 W. Frequency 13.56 MHz Frequency mode Cw
    BE2017 / 0041
    Time 225 minutes CoatingMonomer Acrylic acid Flow 50 - 60 sccm Additional gas No Flow (% of monomer flow) - Basic pressure 10 - 20 mTorr Workload 30 - 50 mTorr Power 95 W. Frequency 13.56 MHz Frequency mode Cw el 1: Process parameters for the benchmark low pressure plasma coating Parameter Value Plasma ChamberVolume 130 liters Temperature wall 40-60 ° C Electrode layers RF / grounded PretreatmentGas Oxygen Flow 200 sccm Power 200 W. Frequency 13.56 MHz Frequenctle mode Cw Time 5 minutes CoatingMonomer 3-allyloxy-1,2-propanediol Flow 5-15 sccm Additional gas No Flow (% of monomer flow) - Basic pressure 10 - 20 mTorr Workload 30 - 50 mTorr Power 20 W. Frequency 13.56 MHz Frequency mode cw
    BE2017 / 0041
    Table 2: Process parameters for a second precursor monomer
    From Tables 1 and 2, it is readily apparent that the coating of the present invention is sold at a lower power than the benchmark coating: 20 W instead of 95 W, or 0.15 W / l instead of 0.73 W / l.
    Figure 1 shows the water contact angle values for the untreated substrate and the same substrate with the benchmark coating and with the coating of the present invention. For the aging test, the water contact angle values of both coatings are comparable, and are significantly lower than the untreated sample. After the aging test, it is clear that the best results are obtained with the coating of the present invention. It is much more stable than the benchmark coating, with a significant increase in water contact angle noted.
    Furthermore, the benchmark coating showed cracks and yellowing, which are clear indications of degradation and unwanted reactions. Such cracks and yellowing were not observed for the coatings of the present invention, which supports the data obtained, since the coatings of the present invention showed no clear indications of degradation or damage.
    Example 2: Thermal cycle test - thermal stability
    The coatings were evaluated for thermal stability via a profile thermal cycle test according to Figure 2. This cycle was repeated 5 times.
    2.1. Comparison with the benchmark coating
    The coating of the present invention was compared to the untreated substrate and to a benchmark coating. The benchmark coating is a hydrophilic coating that has also been deposited via low pressure plasma polymerization, with acrylic acid as the monomer. Both coatings were deposited in a 130 liter volume plasma chamber. The benchmark coating was deposited according to the parameters in Table 1, and the inventive coating according to the parameters in Table 2.
    Figure 3 shows the water contact angles of the untreated substrate, and the substrate treated with the benchmark coating and the coating of the present invention, before and after the thermal cycle test. Before the thermal cycle test, both coatings have similar water contact angles that are significantly lower than the water contact angle of the untreated substrate. After
    BE2017 / 0041 it is clear that the best results are obtained with the coating according to the present invention. The coating of this invention is much more stable than the benchmark coating, for which a significant increase in the water contact angle has been noted.
    Furthermore, the benchmark coating showed cracks and yellowing after the test, which are clear indications of degradation and unwanted reactions. Such cracks and yellowing were not observed for the coatings of the present invention, which supports the data obtained, since the coatings of the present invention showed no clear indications of degradation or damage.
    Example 3; Durability test
    The coatings were evaluated for durability by measuring the water contact angle according to ASTM D5946 before and after a drop of water was used to wet the surface, after which the water was removed by vacuuming with a soft cloth.
    3.1. Comparison with the benchmark coating
    The coating of the present invention was compared to the untreated substrate and to a benchmark coating. The benchmark coating is a hydrophilic coating also deposited via low pressure plasma polymerization, with acrylic acid as a monomer. Both coatings were deposited in a 130 liter volume plasma chamber. The benchmark coating was deposited according to the parameters in Table 1, and the inventive coating according to the parameters in Table 2.
    Figure 4 shows the water contact angles of the untreated substrate, and the substrate treated with the benchmark coating and the coating of the present invention, before and after the durability test.
    The water contact angles before the durability test show similar values for the benchmark coating and the coating of the present invention, which are significantly lower than that of the untreated substrate. After the test it is clear that the best results are obtained with the coating according to the present invention. The coating of this invention is much more stable than the benchmark coating, resulting in a lesser increase in the water contact angle.
    BE2017 / 0041
    权利要求:
    Claims (12)
    [1]
    CONCLUSIONS
    A method of depositing a hydrophilic nano coating on a substrate, wherein the coating is deposited by a continuous low pressure and low power plasma polymerization process in a plasma chamber, the power applied during the plasma polymerization process being essentially constant value has between 0.02 and 2.50 Watts per liter volume of the plasma chamber, and using a monomer according to
    CH 2 - CR 4 - CH 2 - O - R s ,
    Where R 4 is H or an alkyl, e.g. -CH 3 , and wherein R s is H, an alkyl or an alkenyl, and wherein R s preferably contains one or more hydrophilic functional groups, such as hydroxyl groups and / or carbonyl groups.
    [2]
    The method according to claim 1, wherein the applied power is selected so that a water contact angle of the hydrophilic nano coating is equal to or less than 20 °.
    [3]
    A method according to any one of the preceding Claims, wherein the low pressure plasma process is preceded by a low pressure plasma pretreatment, wherein the low pressure plasma pretreatment is performed with an inert gas and / or a reactive gas.
    [4]
    A method according to any one of the preceding Claims, wherein the low pressure plasma polymerization process is preceded by a low pressure plasma polymerization step in which an ultra-thin intermediate nano-coating is deposited.
    [5]
    The method of claim 4, wherein the intermediate nanodeposition is deposited prior to a low pressure plasma pretreatment.
    [6]
    A method according to Claim 4 or 5, wherein the intermediate nanodeposition is deposited after a low pressure plasma pretreatment process.
    [7]
    A method according to any one of Claims 4 to 6, wherein the intermediate nanocover is deposited from a monomer according to Yj-XY 2 , wherein X is O or NH, Y 1 is -Si (Y 3 ) (Y 4 ) Y 5 and Y 2 Si (Y 3 ) (Y 4 ) is Y 5 ', where Y 3 , Y 4 , ί 5ί Y 3 -, Y 4 -, Y 5 en each independently are H or an alkyl group having up to 10 carbon atoms; wherein at most one of Y 3 , Y 4 and Y 5 is hydrogen, at most one of Υ 3 -, Y 4 - and Y 5 - is hydrogen; and the total number of carbon atoms does not exceed 20.
    [8]
    The method of any preceding Claim, wherein the monomer or monomers used in a plasma polymerization process are introduced into the plasma chamber in a gaseous state.
    26 BE2017 / 0041
    [9]
    The method of claim 8, wherein the plasma chamber and / or a feed line to introduce the monomer in a gaseous state is temperature controlled to prevent condensation of the monomer or monomers.
    [10]
    Substrate comprising a hydrophilic, multifunctional coating applied by a method according to any one of claims 1 to 9, wherein the substrate is a medical consumable, a biochemical consumable, an electrochemical substrate, a membrane or a textile.
    [11]
    Use of a hydrophilic coating obtained by a method according to any one of claims 1 to 10 on a substrate for:
    reduction of coagulation;
    increasing resistance to acidic media;
    increasing the surface tension, preferably to improve liquid transport and / or to improve the absorption of aqueous liquids, e.g. to promote wicking.
    [12]
    Use of a method according to any one of claims 1 to 10 to obtain a hydrophilic coating, which is durable and thermally stable, on a substrate.
    BE2017 / 0041
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    同族专利:
    公开号 | 公开日
    BE1025053A1|2018-10-05|
    EP3320986B1|2020-07-01|
    WO2018087192A1|2018-05-17|
    CN110139719B|2022-03-08|
    KR20190082283A|2019-07-09|
    CN110139719A|2019-08-16|
    EP3320986A1|2018-05-16|
    US20190358668A1|2019-11-28|
    EP3538287A1|2019-09-18|
    US11167311B2|2021-11-09|
    JP2020512479A|2020-04-23|
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    法律状态:
    2018-11-29| FG| Patent granted|Effective date: 20181012 |
    2019-12-19| MM| Lapsed because of non-payment of the annual fee|Effective date: 20190430 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP16198015.6|2016-11-09|
    EP16198015.6A|EP3320986B1|2016-11-09|2016-11-09|Hydrophilic, multifunctional ultra-thin coatings with excellent stability and durability|
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