Plasma-generated barrier for packaging

Abstract

In a first aspect, the invention relates to a coated substrate, wherein the coating is obtained or obtainable from a reaction product of a fluorine-free compound selected from the group consisting of lactams having 4 to 8 ring atoms, lactones having 4 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone, or a mixture thereof, deposited on the surface of the substrate by a plasma assisted deposition method. A C5 to C8 alkyne and a mixture of two or more of these compounds. A second aspect of the invention relates to a plasma-assisted deposition method for applying a coating based on a reaction product of a fluorine-free compound onto a surface of a substrate. A third aspect of the invention relates to the use of a coated substrate according to a first aspect or a coated substrate obtained or obtainable by a plasma-assisted deposition method of a second aspect for the packaging, storage and / or transportation of an article selected from the group consisting of a food, a beverage and a chemical, where the article is preferably a chemical, wherein the chemical is preferably a hazardous substance (transported as a hazardous article) or an agrochemical, more preferably an agrochemical.

Description

[0001] In a first aspect, the present invention relates to a coated substrate, wherein the coating is obtained or obtainable by depositing on the surface of the substrate by a plasma assisted deposition process a reaction product of a fluorine-free compound selected from the group consisting of: lactams having 4 to 8 ring atoms, lactones having 4 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone, C5 to C8 alkynes and mixtures of two or more of these compounds.

[0002] A second aspect of the present invention relates to a plasma-assisted deposition method for applying a coating based on a reaction product of a fluorine-free compound to a surface of a substrate.

[0003] A third aspect of the present invention relates to the use of a coated substrate according to the first aspect or a coated substrate obtained or obtainable by the plasma assisted deposition method of the second aspect for packaging, storing and / or transporting an article selected from the group consisting of food, beverages and chemicals, wherein the article is preferably a chemical, more preferably an agrochemical.

[0004] State-of-the-art containers for packaging plant protection products (PPP) (so-called agrochemicals) are usually designed in such a way that the walls of the container do not allow the agrochemicals, solvents and / or other formulation components to penetrate during transport, storage and application. This requires that the commonly used packaging materials such as polyethylene (PE) be equipped with barrier technology. The main established industrial methods for achieving this rely on (i) compounding or coextruding PE with less permeable polymers like polyamide (PA) or ethylene-vinyl alcohol (EVOH) copolymers, for example in the form of thick (multi-μm) surface or interphase layers, or (ii) coating the inner surface of the container with a thin (typically <1 μm) layer of a (per)fluorinated compound. The latter (per)fluorinated coating is classically obtained by gas phase fluorination or, more recently, can also be achieved by plasma-assisted deposition of gaseous fluorine compounds (so-called "plasma enhanced chemical vapor deposition", PECVD). This plasma-based technology (disclosed by Isytech (WO 2007 / 072120 A1), at low pressure) has been shown to produce coatings with excellent properties (high barrier effect, little mechanical deformation of the container during coating, easier recyclability) at relatively low cost (in-line process).

[0005] However, both approaches, compounding or coextrusion with PA or EVOH and coating with reaction products of (per)fluorinated compounds, have serious disadvantages:

[0006] On the one hand, coatings based on (per)fluorinated compounds may be subject to future restrictions on the use of perfluorinated alkyl substances (PFAS) in the US and EU27, and may therefore need to be replaced by alternative technologies. On the other hand, existing fluorine-free technologies for achieving adequate barrier properties often require laborious and cost-intensive methods such as coextrusion, in which PA or EVOH are coextruded with a substrate material (e.g. PE). In addition, the thickness of the PA or EVOH domain required for adequate barrier to the transmission of solvents and chemicals makes the container a multi-material, which poses a challenge for recycling and circular economy. Therefore, in order to recycle both types of current state-of-the-art barrier technologies, a large number of pretreatment steps are required to separate the main container material (e.g. PE) from the barrier components (e.g. large amounts of PA or EVOH, or trace amounts of substances of very high concern (SVHC) such as perfluorinated alkyl substances (PFAS)).

[0007] The problem underlying the present invention is therefore to provide a coating (and a corresponding coating method) for packaging materials used as containers for chemicals, in particular agrochemicals, which coating meets the following requirements: (i) a fluorine-free component that addresses regulatory issues; (ii) a coating thickness that is much lower than established PA or EVOH barrier technologies to facilitate recycling; and (iii) a barrier performance that is at least comparable to existing fluorine-containing coatings and PA or EVOH coextruded multimaterials for functional competitiveness.

[0008] Aspect 1 - Coated Substrate

[0009] The problem is solved by a coated substrate, wherein the coating is obtained or obtainable by depositing on the surface of the substrate by a plasma assisted deposition method a reaction product of a fluorine-free compound selected from the group consisting of: lactams having 4 to 8 ring atoms, lactones having 4 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone, C5 to C8 alkynes and mixtures of two or more of these compounds.

[0010] Surprisingly, it was found that coatings based on the compounds identified above allow for a significant improvement in the barrier properties, as shown by a significant reduction in the interaction of toluene vapor with the coated container wall, even though the coating is only a few tens of nanometers thick. Toluene is considered a representative solvent for testing the barrier properties of coatings against the transmission of harmful compounds present, for example, in agrochemical formulations. The interaction of toluene vapor with coated and uncoated HDPE substrates was detected by reverse phase gas chromatography and evaluated within the framework of the Brunauer-Emmett-Teller (BET) theory, which gives the monolayer capacity (q) for toluene binding. BET , expressed as the molar amount of toluene molecules adsorbed per unit surface area explored, in μmol / cm 2) and the corresponding dimensionless BET constant (C BET ) as a measure of the strength of the interaction. The high barrier to toluene vapor is given by q BET and / or C BET It was found that the q of the coating obtained by plasma-assisted deposition of the fluorine-free compound according to the present invention is BET q compared to comparative coatings made from fluorochemicals and HDPE / PA coextrudates by plasma deposition or gas phase fluorination BET Compared with the uncoated HDPE substrate, by coating with the fluorine-free compound according to the present invention, q BET The improvement is at least 20%. The C of the fluorine-free compound according to the present invention BET Compared with the comparative coating made of fluorochemical and HDPE / PA coextrudate BET The values ​​are in the same range.

[0011] Due to the use of plasma-based technology, coatings with reaction products of fluorine-free components allow for easier application of coatings than established (HD)PE / PA coextrusion technologies; these coatings are therefore (much) cheaper to produce. The use of fluorine-free components avoids the formation and subsequent potential release of (per)fluorinated species. Due to the low amount of applied coating material - as indicated above, the layer thickness required for an adequate barrier to toluene is only a few tens of nanometers - the coated substrate still qualifies as a single material and can therefore be recycled with much less effort.

[0012] In some preferred embodiments of the coated substrate, the compound used to deposit the coating on the surface of the substrate by a plasma assisted deposition method is selected from the group consisting of: lactams having 4 to 8 ring atoms (excluding vinyl pyrrolidone), lactones having 4 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone, C5 to C8 alkynes, and mixtures of two or more of these compounds.

[0013] In some preferred embodiments of the coated substrate, the compound used to deposit the coating on the surface of the substrate by a plasma assisted deposition method is selected from the group consisting of: lactams having 4 to 8 ring atoms (excluding vinyl pyrrolidone), lactones having 4 to 8 ring atoms, vinyl acetate, C5 to C8 alkynes, and mixtures of two or more of these compounds.

[0014] In some preferred embodiments of the coated substrate, the compound used to deposit the coating on the surface of the substrate by a plasma-assisted deposition method is selected from the group consisting of lactams having 4 to 8 ring atoms (excluding vinyl pyrrolidone), lactones having 4 to 8 ring atoms, vinyl acetate, and mixtures of two or more of these compounds, preferably selected from the group consisting of lactones having 4 to 8 ring atoms, vinyl acetate, and mixtures of two or more of these compounds.

[0015] In some preferred embodiments of the coated substrate, the lactam having 4 to 8 ring atoms has the formula (I)

[0016]

[0017] in

[0018] R 1 It's vinyl.

[0019] x is 0 or 1, and

[0020] n is an integer in the range of 2 to 5, preferably in the range of 2 to 4, more preferably n is 4 and x is 0 (ε-caprolactam) and / or n is 2 and x is 1, wherein R 1 It is a vinyl group replacing a hydrogen atom on the nitrogen of the ring structure (vinyl pyrrolidone).

[0021] R 1 represents vinyl and the residue R 1 (if present) on a nitrogen atom of a ring structure, where it replaces a hydrogen atom, or on a carbon atom of a ring structure, including the group -[CH2] n - any C atom of. Vinylpyrrolidone (which is also a lactam) is N-vinyl-2-pyrrolidone, ie the nitrogen atom of the five-membered lactam ring (γ-lactam) bears a vinyl group as a substituent instead of a hydrogen atom at that position.

[0022] In some preferred embodiments of the coated substrate, the lactone having 4 to 8 ring atoms, preferably 6 to 8 ring atoms, has the formula (II)

[0023]

[0024] in

[0025] R 2 selected from methyl and vinyl,

[0026] y is 0 or 1, and

[0027] m is an integer in the range of 1 to 5, preferably in the range of 3 to 4, wherein the lactone is more preferably selected from the group consisting of δ-valerolactone, γ-valerolactone, ε-caprolactone and a mixture of two or more of these lactones, more preferably the lactone contains at least γ-valerolactone, more preferably γ-valerolactone. R 2 represents a methyl group or a vinyl group and the residue R 2 (if present) located on a carbon atom of a ring structure, including the group -[CH2] n - any C atom. For example, δ-valerolactone is a six-membered ring with 5 carbon atoms (y=0), while γ-valerolactone is a five-membered ring with four carbon atoms and as R 2 The methyl group is located on the C atom adjacent to the oxygen atom of the -O- bond (y = 1 and R 2 =CH3), also known as 5-methyloxolane-2-one.

[0028] In some preferred embodiments of the coated substrate, the vinyl acetate has the formula (III)

[0029]

[0030] In some preferred embodiments of the coated substrate, the polyvinyl pyrrolidone has a weight average molecular weight of ≥ 222 g / mol, more preferably in the range of 2,500 to 2,500,000 g / mol, more preferably in the range of 6,000 to 40,000 g / mol.

[0031] In some preferred embodiments of the coated substrate, the C5 to C8 alkyne is a linear or branched C5 to C8 alkyne, more preferably a linear C5 to C8 alkyne, which more preferably has formula (V)

[0032]

[0033] wherein r is an integer in the range of 2 to 5, preferably r is 5.

[0034] In some preferred embodiments of the coated substrate, at least 80 weight-%, more preferably at least 90 weight-%, more preferably at least 95 weight-% of the compounds used to deposit the coating, based on the total weight of all compounds used to deposit the coating, are compounds from one of the groups as defined above, i.e. at least 80 weight-%, preferably at least 90 weight-%, more preferably at least 95 weight-% of the coating consists of the reaction product of compounds from one of the groups as described above.

[0035] In some embodiments, wherein the coating is made of vinyl acetate, wherein preferably at least 80 wt-%, preferably at least 90 wt-%, more preferably at least 95 wt-% of the compounds used to deposit the coating are vinyl acetate, based on the total weight of all compounds used to deposit the coating, i.e. at least 80 wt-%, preferably at least 90 wt-%, more preferably at least 95 wt-% of the coating consists of reaction products of vinyl acetate, then in these embodiments, the reaction products are at least partially hydrolyzed to obtain a vinyl alcohol copolymer. In some embodiments, the hydrolysis is performed by exposing the coating comprising the reaction product of vinyl acetate to a moist ammonia-containing atmosphere in a subsequent step, i.e. after the step in which the plasma-assisted deposition method is performed, preferably after step (d) as described below. For example, an aqueous solution of NH3 based on a 100 wt-% aqueous solution having a concentration of ammonia in water in the range of 0.1 to 50 wt-%, preferably in the range of 0.5 to 25 wt-% is provided at a temperature of 50°C (and at a pressure of 1013 mbar), and the coating is exposed to the resulting atmosphere.

[0036] Copolymer

[0037] In some preferred embodiments of the coated substrate, the additional compound is used to deposit the coating on the surface of the substrate by a plasma assisted deposition method, the additional compound is selected from the group consisting of C2 to C4 olefins, C2 to C4 alkynes and mixtures thereof, more preferably selected from the group consisting of C3 to C4 olefins, C2 to C4 alkynes and mixtures thereof, preferably the compound used to deposit the coating on the surface of the substrate by a plasma assisted deposition method contains at least vinyl acetate and the additional compound is acetylene, more preferably the compound used to deposit the coating on the surface of the substrate by a plasma assisted deposition method is vinyl acetate and the additional compound is acetylene.

[0038] In some preferred embodiments of the coated substrate, based on the total weight of all compounds used to deposit the coating, in the range of 50 to 90 wt-%, more preferably in the range of 80 to 90 wt-%, of the compounds used to deposit the coating are compounds of one of the groups as described above, and in the range of 10 to 50 wt-%, preferably in the range of 10 to 20 wt-%, are additional compounds as defined above. In some embodiments where additional compounds are used, the copolymer is formed from vinyl acetate and one or more additional compounds selected from C2 to C4 olefins, C2 to C4 alkynes, and mixtures thereof. The copolymer is then, in some embodiments, at least partially hydrolyzed to convert the vinyl acetate-based portion of the copolymer into vinyl alcohol. In those embodiments in which additional compounds are used, at least 80 wt-%, preferably at least 90 wt-%, more preferably at least 95 wt-% of the compounds used to deposit the coating, based on the total weight of all compounds used to deposit the coating, are compounds from one of the groups identified above and additional compounds, preferably vinyl acetate and one or more additional compounds selected from C2-C4 olefins, C2-C4 alkynes and mixtures thereof, i.e. at least 80 wt-%, preferably at least 90 wt-%, more preferably at least 95 wt-% of the coating consists of the reaction products of compounds from one of the groups identified above and additional compounds, more preferably at least 90 wt-%, more preferably at least 95 wt-% of the coating consists of the reaction products of vinyl acetate and one or more additional compounds selected from C2-C4 olefins, C2-C4 alkynes and mixtures thereof. In some embodiments, the hydrolysis is performed by exposing the coating comprising the reaction product of vinyl acetate and one or more additional compounds selected from C2-C4 alkenes, C2-C4 alkynes and mixtures thereof to a moist ammonia-containing atmosphere in a subsequent step, i.e., after the step of completing the plasma-assisted deposition method, preferably after step (d) as described below. For example, an aqueous solution of NH3 having a concentration of ammonia in water in the range of 0.1 to 50 wt-%, preferably in the range of 0.5 to 25 wt-%, based on a 100 wt-% aqueous solution is provided at a temperature of 50°C (and at a pressure of 1013 mbar), and the coating is exposed to the resulting atmosphere.

[0039] The state of the precursor

[0040] In some preferred embodiments of the coated substrate, the fluorine-free compound is used as a precursor in the plasma assisted deposition process in the form of a liquid phase comprising a single compound in a liquid state or a homogeneous solution in a liquid medium, wherein liquid means a liquid at 25° C. and 1013 mbar. The liquid medium is a polar organic solvent other than water. In some embodiments, the liquid medium is selected from the group consisting of C1-C5 alkanols and mixtures thereof, preferably at least 95 wt-%, more preferably at least 98 wt-%, more preferably at least 99 wt-%, more preferably at least 99.5 wt-%, more preferably at least 99.9 wt-%, more preferably at least 99.95 wt-%, more preferably at least 99.99 wt-% of the liquid medium is a polar organic solvent other than water and mixtures thereof.

[0041] No fluorine

[0042] In some preferred embodiments of the coated substrate, the coating is substantially free of fluorine, more preferably the coating comprises less than 1 wt-%, more preferably less than 0.1 wt-% fluorine based on the total weight of the coating (100 wt-%).

[0043] Additional properties of the coating

[0044] In some preferred embodiments of the coated substrate, the retention time of toluene vapor is in the range of 30 to 250 minutes, more preferably in the range of 35 to 200 minutes, more preferably in the range of 40 to 175 minutes, as determined by inverse gas chromatography (iGC) according to Reference Example 5.

[0045] In some preferred embodiments of the coated substrate, the monolayer binding capacity q BET 0.3 to 1.3 μmol / cm 2 In the range of 0.4 to 1.1 μmol / cm 2 In the range of 0.5 to 0.8 μmol / cm 2 In the range of 5, the BET constant C is determined by inverse gas chromatography (iGC) for toluene vapor according to Reference Example 5, and / or BET In the range of 50 to 300, preferably in the range of 50 to 200, more preferably in the range of 70 to 175, as determined by inverse phase gas chromatography (iGC) of toluene vapor according to Reference Example 5. BET The monolayer binding capacity, i.e. the number of binding sites for toluene on the investigated surface, is described and expressed as the molar amount of toluene molecules adsorbed per unit explored surface area (in μmol / cm 2 Calculation), and C BET Indicates the bonding strength. The strong barrier to toluene vapor is indicated by q BET and / or C BETThe low value of q of the fluorine-free compound according to the present invention reflects BET Compared with the comparative coating made of fluorine-containing compounds (such as Freon R-134a or F2 gas), the BET In the same range, the comparative coating has a value of about 0.5 μmol / cm 2 Q BET Compared with the uncoated substrate (which has a value of about 1.6 μmol / cm 2 Q BET ), the monolayer capacity is improved (i.e. further reduced) by at least 20%, preferably at least 30%, by coating with the fluorine-free compound according to the present invention. BET Compared with the C of the comparative coating made of fluorine-containing compounds (such as Freon R-134a or F2 gas), BET In the same range, the comparative coating has a C in the range of 70 to 90. BET It must also be noted that the monolayer binding capacity q of plasma-assisted coatings based on ε-caprolactam, for example BET (q BET =0.53 μmol / cm 2 ) and conventional barrier technology obtained by coextrusion of HDPE and PA-6 (q BET =0.50 μmol / cm 2 ) are completely comparable. C BET Also comparable: The plasma-assisted coating based on ε-caprolactam has a C of 74 BET Value, while PE / PA co-extrudate has a C value of 80 BET value.

[0046] In some preferred embodiments of the coated substrate, the static contact angle of the fluorine-free compound (which is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinyl pyrrolidone) relative to water is in the range of 10 to 46° (measured according to Reference Example 2), and the static contact angle of C5 to C8 alkynes relative to water is in the range of 90 to 120° (measured according to Reference Example 2), and / or the static contact angle of the fluorine-free compound (which is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinyl pyrrolidone) relative to diiodomethane is 1. The static contact angle of C5 to C8 alkynes relative to diiodomethane is in the range of 10 to 40° (measured according to Reference Example 2), and the static contact angle of C5 to C8 alkynes relative to diiodomethane is in the range of 40 to 55° (measured according to Reference Example 2), and / or the static contact angle of the fluorine-free compound (which is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinyl pyrrolidone) relative to formamide is in the range of 8 to 15° (measured according to Reference Example 2), and the static contact angle of C5 to C8 alkynes relative to formamide is in the range of 70 to 80° (measured according to Reference Example 2).

[0047] In some preferred embodiments of the coated substrate, for the fluorine-free compound (which is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinyl pyrrolidone), the surface free energy obtained from the static contact angles of water, formamide, and diiodomethane according to Reference Example 2 is in the range of 48 to 73 mN / m, and for C5 to C8 alkynes, the surface free energy obtained from the static contact angles of water, formamide, and diiodomethane according to Reference Example 2 is in the range of 30 to 40 mN / m.

[0048] In some preferred embodiments of the coated substrate, the coating has a thickness in the range of 20 to 500 nm, preferably in the range of 50 to 350 nm, preferably determined by transmission electron microscopy (TEM) according to Reference Example 6.

[0049] In some preferred embodiments of the coated substrate, the coating comprising the reaction product of the fluorine-free compound is present on at least a portion of the surface of the substrate, preferably having a surface coverage of at least 10%, more preferably at least 20%, more preferably at least 25%, and more preferably at least 30% of the surface area of ​​the substrate that has been treated with the plasma-assisted deposition method as determined by X-ray photoelectron spectroscopy (XPS) according to Reference Example 3.

[0050] In some preferred embodiments of the coated substrate, the reaction product of the fluorine-free compound contained in the coating is a free radical polymerization product (compared to condensation) as determined by time-of-flight secondary ion mass spectrometry (ToF-SIMS) according to Reference Example 4, characterized in that the nominal mass of the secondary ions generated from such a surface is offset by 2 amu compared to the nominal mass of the fragments produced by measuring the polymer produced by condensation.

[0051] Middle acetylene-based layer

[0052] In some preferred embodiments of the coated substrate, the layer comprising the reaction product of acetylene is present between the surface of the substrate and the coating comprising the reaction product of the fluorine-free compound. In some preferred embodiments of the coated substrate, the layer comprising the reaction product of acetylene is obtained or obtainable by plasma-assisted deposition of acetylene.

[0053] Substrate

[0054] In some preferred embodiments of the coated substrate, the substrate comprises a material selected from the group consisting of an organic material and a mixture of an organic material and an inorganic material, wherein the organic material is preferably one or more organic polymers and the inorganic material is preferably selected from the group consisting of glass, silica, ceramic and steel.

[0055] In some preferred embodiments of the coated substrate, the substrate comprises an organic polymer selected from the group consisting of: polyolefins, preferably polyethylene (PE) or polypropylene (PP); polyamides (PA); polyurethanes (PU); fluorinated polymers; silicones; polycarbonates (PC); polymethyl methacrylate (PMMA); polyacrylates; polyesters, especially polyethylene terephthalate (PET); cellulose; cellulose-derived polymers like cellulose acetate, lignin, including lignin-based composites of wood; and mixtures of two or more of these organic polymers.

[0056] In some preferred embodiments of the coated substrate, the substrate comprises an organic polymer selected from the group consisting of polyolefins, polyamides, polyesters and mixtures of two or more thereof, more preferably the substrate comprises an organic polymer selected from the group consisting of polyethylene, polyamides and mixtures of polyethylene and polyamides, more preferably the substrate comprises at least polyethylene (PE), more preferably high-density polyethylene (HDPE), more preferably at least 80 wt-%, more preferably at least 90 wt-%, more preferably at least 95 wt-%, more preferably at least 98 wt-% of the substrate consists of HDPE. The high-density polyethylene (HDPE) preferably has a density of 940 to 970 kg / m 3 density within the range of .

[0057] In some preferred embodiments of the coated substrate, the substrate is a package suitable for storing and transporting an article selected from the group consisting of food, beverages and chemicals, wherein the chemical is preferably a hazardous substance (transported as dangerous goods) or an agrochemical, wherein the coating is present on at least one surface of the substrate facing or intended to face the article. Hazardous substances are substances that must be transported as dangerous goods according to ADR / RID (ADR=Agreement on the International Carriage of Dangerous Goods by Road, RID=Regulations for the International Carriage of Dangerous Goods by Rail) and / or IMDG (International Maritime Dangerous Goods Regulations) and / or IATA (International Air Transport Association). The article is more preferably an agrochemical, and the substrate is more preferably an (agro)chemical container, wherein the coating is present on at least one surface of the substrate facing or intended to face the (agro)chemical. For example, if the substrate is a container in which the (agro)chemical is to be filled, the coating is present on at least a portion of the inner surface of the container. In some preferred embodiments of the coated substrate, the coated substrate is an agrochemical container.

[0058] Method steps and parameters - atmospheric pressure plasma

[0059] In some preferred embodiments of the coated substrate, the plasma assisted deposition method comprises

[0060] (a) providing a substrate having a surface;

[0061] (b) generating plasma by passing a carrier gas through an excitation region under plasma generating conditions and by applying a high frequency alternating current to an electrode positioned in the excitation region to generate a dielectric barrier discharge to generate plasma;

[0062] (c) generating an aerosol comprising a fluorine-free compound as defined above by using a nebulizer gas;

[0063] (d) treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (b) and the aerosol containing the fluorine-free compound generated according to (c), thereby depositing a reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0064] In some preferred embodiments of the coated substrate, in the plasma assisted deposition method, the plasma is generated in (a) at a pressure in the range of 0.5 to 1.5 bar, more preferably in the range of 0.8 to 1.2 bar (atmospheric pressure or near atmospheric pressure conditions, indirect atmospheric pressure plasma processing), i.e. the plasma generated in (b) and used in (d) is an atmospheric pressure plasma.

[0065] "Carrier gas" generally means a gas suitable for generating and maintaining a dielectric barrier discharge (DBD) plasma. In particular, the carrier gas is selected from the group consisting of N2, Ar, He, CO2, O2, N2O or a mixture of two or more of these gases. The term "atomizer gas" generally means a gas used for atomization or for generating an aerosol in an atomizer and for transporting the aerosol to and into the plasma. In particular, the atomizer gas is selected to be the same as the carrier gas.

[0066] In some embodiments, the plasma assisted deposition method is preferably an indirect plasma process, for example, as in wherein the plasma is blown out from the region between the electrodes generating the plasma. wherein the plasma according to (b) is preferably generated in the first region, more preferably in a plasma discharge chamber; wherein preferably, the plasma is generated under plasma generation conditions by passing a carrier gas through an excitation zone consisting of a ground electrode and a high voltage electrode and by applying a high frequency alternating current to the high voltage electrode to generate a dielectric barrier discharge to generate an atmospheric pressure plasma. the aerosol comprising at least one fluorine-free compound is preferably generated in the second region (atomizer region) according to (c), and the treatment according to (d) is preferably carried out in the third region, which is more preferably a so-called afterglow chamber, which is positioned downstream of the plasma discharge chamber and is in fluid communication with the outlet of the plasma discharge chamber. The establishment of an apparatus for such an indirect plasma treatment is known to the skilled person and is described, for example, in WO 2006 / 081637A1 (Vito) or in Vangeneugden et al., "Atmospheric DBD plasma processes for production of lightweight composites", published at the 21st International Conference on Plasma Chemistry (https: / / www.ispc-conference.org / ispcproc / ispc21 / ID287.pdf). Typically, a conveying device is provided for continuously conveying the substrate through the afterglow chamber and for keeping the substrate away from the plasma discharge chamber while being processed by the plasma-activated substance in the afterglow chamber. Alternatively, the plasma-assisted deposition method is (often referred to as plasma jet) method, which also uses indirect plasma treatment.

[0067] In some preferred embodiments of the coated substrate, step (c) of the plasma assisted deposition method comprises

[0068] (c.1) providing a fluorine-free compound in liquid form in a container having an outlet;

[0069] (c.2) passing a nebulizer gas through a nozzle so that the nebulizer gas contacts the fluorine-free compound at an outlet of the container, thereby generating an aerosol containing the fluorine-free compound.

[0070] Wherein provide at least one fluorine-free compound container in liquid form about its size and / or its shape is not particularly limited.In certain embodiments, container is a reservoir with capillary therein, wherein capillary contacts with liquid and protrudes from container.Capillary forms outlet at the opening of its side protruding from container.In these embodiments, the atomizer gas from the nozzle with specific diameter passes through along the outlet of capillary almost horizontally, i.e., roughly vertical relative to capillary ("roughly vertical" means that the flow direction of atomizer gas before passing through capillary and capillary form an angle in the range of 45 to 135 °, preferably in the range of 75 to 105 °, more preferably in the range of 80 to 100 °, more preferably in the range of 85 to 95 °, more preferably in the range of 88 to 92 °), thereby causing negative pressure (Venturi effect) in outlet, liquid is sucked in atomizer gas stream from nozzle thus.Atomizer gas preferably exists in compressed form before passing through nozzle and expands after passing through nozzle. In some embodiments, the tube is arranged approximately vertically relative to the flow of the nebulizer gas, and the nebulizer gas enters it through the opening after passing through the outlet of the capillary ("approximately vertical" means that the flow direction of the nebulizer gas before entering the tube through the opening and the tube form an angle in the range of 45 to 135°, preferably in the range of 75 to 105°, more preferably in the range of 80 to 100°, more preferably in the range of 85 to 95°, more preferably in the range of 88 to 92°). The nebulizer gas containing at least one fluorine-free compound in the form of droplets of different sizes then collides with the inner wall of the tube, which is opposite to the opening. Thereby, the larger droplets are removed, preferably by falling into the tube, while the aerosol containing smaller droplets preferably passes further through the tube in an upward direction. Preferably, the aerosol passing upward through the tube contains at least one fluorine-free compound in the form of droplets having a specific size in the range of 1 to 1000 nm, preferably in the range of 5 to 400 nm, more preferably in the range of 10 to 200 nm.

[0071] The fluorine-free compound in the embodiment with atmospheric pressure plasma is preferably as defined above.More preferably, the fluorine-free compound is ε-caprolactam.

[0072] In embodiments involving atmospheric pressure plasma variants, the plasma according to (a) is preferably heated at less than 40 kW / m 2 The power per electrode area is preferably between 7.5 and 38 kW / m 2 The power in the range of 8 to 30 kW / m 2In an embodiment relating to an atmospheric pressure plasma variant, one or more atomizers, preferably at least two atomizers, are used, wherein the atomizer gas according to (c) or (c.2) is preferably provided to the second region at a flow rate of more than 0.5 slm (standard liters per minute) per atomizer, more preferably at a flow rate per atomizer in the range of 0.5 to 5 slm, more preferably in the range of 0.8 to 3 slm, more preferably in the range of 1 to 2 slm. In an embodiment relating to an atmospheric pressure plasma variant, the amount of fluorine-free compound delivered to the plasma as an aerosol and entering the plasma each time is preferably in the range of 0.045 to 0.5 g / min per atomizer, more preferably in the range of 0.045 to 0.3 g / min per atomizer, more preferably in the range of 0.05 to 0.2 g / min per atomizer, more preferably in the range of 0.08 to 0.12 g / min per atomizer.

[0073] The amount of at least one fluorine-free compound delivered to the plasma and into the plasma each time as an aerosol is also referred to as the mass flow rate of the at least one fluorine-free compound delivered to the plasma and into the plasma as an aerosol. The mass flow rate is determined by determining the amount of the at least one fluorine-free compound present in the second region, preferably in the container in the second region, at a time t0 before the nebulizer gas according to (c) is provided into the second region, and determining the amount of the at least one fluorine-free compound in the second region, preferably in the container in the second region, again after a time t1 during which the nebulizer gas according to (c) is provided into the second region. The mass flow rate (mf) is determined according to the following

[0074] mf = [amount (t0) - amount (t1)] / [t1 - t0]]

[0075] The mass flow rate can be further normalized to the applied plasma power to obtain a value between 0.001 and 0.02 (g*m 2 ) / (kW*min), preferably in the range of 0.003 to 0.015(g*m 2 ) / (kW*min), more preferably in the range of 0.005 to 0.012(g*m 2 ) / (kW*min) range, which is related to the mass flow rate of power density.

[0076] In embodiments relating to atmospheric pressure plasma variants, the outlet of the excitation zone is preferably at a distance from the substrate surface according to (a) in the range of 0.5 to 10 mm, more preferably in the range of 0.5 to 5 mm, more preferably in the range of 2 to 4 mm, more preferably in the range of 2.5 to 3.5 mm. In embodiments relating to atmospheric pressure plasma variants, in the plasma assisted deposition method, the carrier gas is preferably provided to the excitation zone at a flow rate in the range of 50 to 500 l / min, more preferably in the range of 150 to 450 l / min, more preferably in the range of 200 to 300 l / min.

[0077] The plasma used in the atmospheric pressure plasma variant is a non-equilibrium plasma such as produced by an alternating current (AC) discharge. Alternatively, the plasma is another non-equilibrium plasma such as those produced by radio frequency (RF) excitation, microwave (MW) excitation or direct current (DC) discharge.

[0078] In embodiments involving atmospheric pressure plasma variants, an AC voltage of up to 100 kV is preferably applied, wherein the AC voltage is more preferably in the range of 10 to 40 kV. In embodiments involving atmospheric pressure plasma variants, the discharge frequency is preferably in the range of 50 to 100 kHz, more preferably in the range of 60 to 100 kHz, more preferably in the range of 70 to 95 kHz, more preferably in the range of 80 to 90 kHz.

[0079] Preferably, the substrate passes through the third zone (afterglow chamber) more than once (number of passes>1); preferably, the number of passes is in the range of 5 to 100, more preferably in the range of 10 to 50. The speed at which the substrate passes is preferably in the range of 0.1 to 10 m / min, more preferably in the range of 1 to 3 m / min. In other embodiments, the substrate is passed through one or more substantially identical third zones (afterglow chambers); preferably through x substantially identical third zones, wherein x is an integer in the range of 5 to 100, more preferably in the range of 10 to 50. The speed at which the substrate passes through each of the one or more or x substantially identical third zones is preferably in the range of 0.1 to 10 m / min, more preferably in the range of 1 to 3 m / min. In embodiments involving atmospheric pressure plasma variants, the plasma-assisted deposition method is preferably carried out for a total time in the range of 30 seconds to 10 minutes, more preferably in the range of 1 to 2 minutes.

[0080] In embodiments involving atmospheric pressure plasma variants, the plasma assisted deposition process is preferably carried out at a temperature in the range of 10°C to 80°C.

[0081] Process steps and parameters - low pressure plasma

[0082] In some alternative preferred embodiments of the coated substrate, in a plasma assisted deposition method, the plasma is generated at a pressure of <0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, preferably in the range of 0.001 to 0.05 mbar (low pressure plasma).

[0083] Preferably, in these alternative preferred embodiments relating to low pressure plasma, the plasma assisted deposition method comprises

[0084] (a) providing a substrate having a surface;

[0085] (b') generating an aerosol comprising the fluorine-free compound as defined above, preferably by using a nebulizer gas;

[0086] (c') converting the precursor aerosol produced in (b') into a plasma state by a combination of excitations including primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of discharge of an alternating voltage having a frequency between 1 kHz and 15 MHz, thereby producing plasma;

[0087] (d') treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (c'), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0088] As indicated above, the plasma generated in (c') is a low pressure plasma. Preferably, the alternating voltage has a frequency between 10 and 200 kHz. Microwaves are electromagnetic waves with a frequency between 300 and 3000 MHz, preferably between 915 and 2450 MHz.

[0089] Preferably, in these alternative preferred embodiments, step (c') of the plasma assisted deposition method comprises

[0090] (c'.a) providing a fluorine-free compound in liquid form in a container having an outlet, optionally under applied heat;

[0091] (c'.b) passing an atomizer gas through the nozzle so that the atomizer gas contacts the fluorine-free compound at the outlet of the container, thereby generating an aerosol containing the fluorine-free compound.

[0092] In these alternative preferred embodiments involving low pressure plasma, the plasma assisted deposition method comprises

[0093] (a) providing a substrate having a surface;

[0094] (b") providing an atmosphere comprising the fluorine-free compound in gaseous form or in aerosol form, optionally under applied heating;

[0095] (c") generating plasma from the atmosphere comprising the fluorine-free compound according to (b") under plasma generating conditions by a combination of excitations including primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of discharge of an alternating voltage having a frequency between 1 kHz and 15 MHz, thereby generating plasma;

[0096] (d") treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (c"), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0097] The atmosphere comprises the fluorine-free compound and optionally one or more gases, preferably selected from the group consisting of N2, Ar, He, CO2, O2, N2O or a mixture of two or more of these gases. For example, an atmosphere comprising the fluorine-free compound in gaseous form or in aerosol form is provided, in that the fluorine-free compound is partially gaseous due to its vapor pressure in its liquid form and the gas phase is transferred into the container for plasma generation and treatment, in combination with a carrier gas or alone, or a liquid fluorine-free compound or a solution of the liquid fluorine-free compound in a solvent is injected into the container for plasma generation and treatment.

[0098] For embodiments involving low-pressure variants that do not use a nebulizer gas (and do not use an aerosol), reference is made to US 2022 / 0112595 A1, in which the method is described in detail, which is incorporated herein by reference, especially paragraphs

[0010] to

[0020] ,

[0024] to

[0028] . US 2022 / 0112595 A1 describes a suitable device in paragraphs

[0031] to

[0060] , which are also incorporated herein by reference.

[0099] In all embodiments where low pressure plasma is used, the substrate to be coated may be the inner surface of a hollow container having an opening or a portion thereof, preferably the substrate is placed in a housing adapted to maintain a specific pressure therein and the entire housing is evacuated.

[0100] In these embodiments related to the low-pressure plasma variant, the fluorine-free compound is preferably selected from the group consisting of lactams having 4 to 8 ring atoms, lactones having 4 to 8, preferably 6 to 8, ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams having 4 to 8 ring atoms (excluding caprolactam), lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams having 4 to 8 ring atoms (excluding caprolactam), lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams having 4 to 8 ring atoms (excluding caprolactam). amides and excluding vinylpyrrolidone), lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate and mixtures of two or more of these compounds, more preferably the fluorine-free compound is a lactone having 4 to 8, preferably 6 to 8 ring atoms.

[0101] In some preferred embodiments of the coated substrate associated with the low-pressure plasma variant, the additional compound is used to deposit the coating on the surface of the substrate by a plasma-assisted deposition method, the additional compound is selected from the group consisting of C2 to C4 olefins, C2 to C4 alkynes and mixtures thereof, more preferably selected from the group consisting of C3 to C4 olefins, C2 to C4 alkynes and mixtures thereof, preferably the compound used to deposit the coating on the surface of the substrate by a plasma-assisted deposition method contains at least vinyl acetate and the additional compound is acetylene, more preferably the compound used to deposit the coating on the surface of the substrate by a plasma-assisted deposition method is vinyl acetate and the additional compound is acetylene.

[0102] In some preferred embodiments of the coated substrates associated with the low pressure plasma variant, based on the total weight of all compounds used to deposit the coating, the compounds used to deposit the coating are in the range of 50 to 90 wt-%, more preferably in the range of 80 to 90 wt-%, of compounds from one of the groups as described above, and in the range of 10 to 50 wt-%, preferably in the range of 10 to 20 wt-%, of additional compounds as defined above. In some embodiments where additional compounds are used, the copolymer is formed from vinyl acetate and one or more additional compounds selected from C2 to C4 olefins, C2 to C4 alkynes, and mixtures thereof. The copolymer is then, in some embodiments, at least partially hydrolyzed to convert the vinyl acetate-based portion of the copolymer into vinyl alcohol. In those embodiments in which additional compounds are used, at least 80 wt-%, preferably at least 90 wt-%, more preferably at least 95 wt-% of the compounds used to deposit the coating, based on the total weight of all compounds used to deposit the coating, are compounds from one of the groups identified above and additional compounds, preferably vinyl acetate and one or more additional compounds selected from C2-C4 olefins, C2-C4 alkynes and mixtures thereof, i.e. at least 80 wt-%, preferably at least 90 wt-%, more preferably at least 95 wt-% of the coating consists of the reaction products of compounds from one of the groups identified above and additional compounds, more preferably at least 90 wt-%, more preferably at least 95 wt-% of the coating consists of the reaction products of vinyl acetate and one or more additional compounds selected from C2-C4 olefins, C2-C4 alkynes and mixtures thereof. In some embodiments, the hydrolysis is performed by exposing the coating comprising the reaction product of vinyl acetate and one or more additional compounds selected from C2-C4 alkenes, C2-C4 alkynes and mixtures thereof to a moist ammonia-containing atmosphere in a subsequent step, i.e., after the step of completing the plasma-assisted deposition method, preferably after step (d) as described below. For example, an aqueous solution of NH3 having a concentration of ammonia in water in the range of 0.1 to 50 wt-%, preferably in the range of 0.5 to 25 wt-%, based on a 100 wt-% aqueous solution is provided at a temperature of 50°C (and at a pressure of 1013 mbar), and the coating is exposed to the resulting atmosphere.

[0103] In some preferred embodiments of the coated substrate associated with the low pressure plasma variant, the layer comprising the reaction product of acetylene is present between the surface of the substrate and the coating comprising the reaction product of the fluorine-free compound. In some preferred embodiments of the coated substrate associated with the low pressure plasma variant, the layer comprising the reaction product of acetylene is obtained or obtainable by plasma-assisted deposition of acetylene.

[0104] In these embodiments related to the low-pressure plasma variant, the power density of the electromagnetic wave is between 0.01 and 1 W / cm3 The range is and / or the power of the discharge is in the range of 4 to 30 W and the frequency is in the range of 20 to 200 kHz.

[0105] In embodiments involving low-pressure plasma variants, the plasma-assisted deposition method is preferably carried out at a temperature in the range of 10° C. to 80° C. That is, "under applied heating" means that a temperature in the range of 10° C. to 80° C. is established by suitable means, so that the fluorine-free compound can be provided in liquid form or in gaseous form.

[0106] Regardless of whether the atmospheric pressure plasma variant or the low pressure plasma variant is used in the plasma assisted deposition process, preferably no water is added in steps (a), (b), (c), (d), more preferably at least no water is added in step (d), and / or the plasma assisted deposition process, preferably at least step (d) thereof, is carried out in an atmosphere containing at most as much water as the atmosphere would contain based on a relative humidity (RH) of 100% at the corresponding process temperature.

[0107] Second Aspect of the Invention - Method

[0108] In a second aspect, the present invention relates to a plasma assisted deposition method for applying a coating to a surface of a substrate, the method comprising:

[0109] (a) providing a substrate having a surface;

[0110] (b) generating plasma by passing a carrier gas through an excitation region under plasma generating conditions and by applying a high frequency alternating current to an electrode positioned in the excitation region to generate a dielectric barrier discharge to generate plasma;

[0111] (c) generating an aerosol comprising a fluorine-free compound as defined in any one of the embodiments described above for the first aspect of the invention by using a nebulizer gas;

[0112] (d) treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (b) and the aerosol containing the fluorine-free compound generated according to (c), thereby depositing a reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0113] In some preferred embodiments of the plasma assisted deposition method for applying a coating to a surface of a substrate, step (c) of the plasma assisted deposition method comprises

[0114] (c.1) providing a fluorine-free compound in liquid form in a container having an outlet;

[0115] (c.2) passing a nebulizer gas through a nozzle so that the nebulizer gas contacts the fluorine-free compound at an outlet of the container, thereby generating an aerosol containing the fluorine-free compound.

[0116] Atmospheric pressure plasma

[0117] In some preferred embodiments of the plasma-assisted deposition method for applying a coating to a surface of a substrate, the plasma is generated in (a) at a pressure in the range of 0.5 to 1.5 bar, preferably in the range of 0.8 to 1.2 bar (atmospheric pressure or near-atmospheric pressure conditions, indirect atmospheric pressure plasma processing).

[0118] In those embodiments involving plasma-assisted deposition methods using atmospheric pressure plasma, the plasma according to (a) is preferably heated at less than 40 kW / m 2 The power per electrode area is preferably between 7.5 and 38 kW / m 2 The power in the range of 8 to 30 kW / m 2In these embodiments involving plasma-assisted deposition methods using atmospheric pressure plasma, one or more atomizers, preferably at least two atomizers, are used, wherein the atomizer gas according to (c) or (c.2) is preferably provided to the second region at a flow rate of more than 0.5 slm (standard liters per minute) per atomizer, more preferably at a flow rate per atomizer in the range of 0.5 to 5 slm, more preferably in the range of 0.8 to 3 slm, more preferably in the range of 1 to 2 slm. In these embodiments involving plasma-assisted deposition methods using atmospheric pressure plasma, the amount of fluorine-free compound delivered to the plasma as an aerosol and entering the plasma each time is in the range of 0.045 to 0.5 g / min per atomizer, more preferably in the range of 0.045 to 0.3 g / min per atomizer, more preferably in the range of 0.05 to 0.2 g / min per atomizer, more preferably in the range of 0.08 to 0.12 g / min per atomizer. In these embodiments involving plasma-assisted deposition methods using atmospheric pressure plasma, the outlet of the excitation zone is preferably at a distance from the substrate surface according to (a) in the range of 0.5 to 10 mm, more preferably in the range of 0.5 to 5 mm, more preferably in the range of 2 to 4 mm, more preferably in the range of 2.5 to 3.5 mm. In these embodiments involving plasma-assisted deposition methods using atmospheric pressure plasma, the carrier gas is preferably provided to the excitation zone at a flow rate in the range of 50 to 500 l / min, more preferably in the range of 150 to 450 l / min, more preferably in the range of 200 to 300 l / min. In these embodiments involving plasma-assisted deposition methods using atmospheric pressure plasma, an AC voltage of up to 100 kV is preferably applied, wherein the AC voltage is more preferably in the range of 10 to 40 kV. In these embodiments involving plasma-assisted deposition methods using atmospheric pressure plasma, the discharge frequency is preferably in the range of 50 to 100 kHz, preferably in the range of 60 to 100 kHz, more preferably in the range of 70 to 95 kHz, more preferably in the range of 80 to 90 kHz. In these embodiments involving plasma-assisted deposition methods using atmospheric pressure plasma, the plasma-assisted deposition method is preferably carried out at a temperature in the range of 10° C. to 80° C. In these embodiments involving plasma-assisted deposition methods using atmospheric pressure plasma, the plasma-assisted deposition method is preferably carried out for a total time in the range of 30 seconds to 10 minutes, more preferably in the range of 1 to 2 minutes.

[0119] Low pressure plasma

[0120] In some alternative preferred embodiments of the plasma-assisted deposition method for applying a coating to a surface of a substrate, the plasma is generated at a pressure of <0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, preferably in the range of 0.001 to 0.05 mbar (low pressure plasma).

[0121] In these alternative preferred embodiments involving low-pressure plasma, the plasma-assisted deposition method according to one variant preferably comprises

[0122] (a) providing a substrate having a surface;

[0123] (b') generating an aerosol comprising a fluorine-free compound as defined in any one of the embodiments described above in relation to the first aspect of the invention by using a nebulizer gas;

[0124] (c') converting the precursor aerosol produced in (b') into a plasma state by a combination of excitations including primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of discharge of an alternating voltage having a frequency between 1 kHz and 15 MHz, thereby producing plasma;

[0125] (d') treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (c'), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0126] As indicated above, the plasma generated in (c) is a low pressure plasma. Preferably, the alternating voltage has a frequency between 10 and 200 kHz. Microwaves are electromagnetic waves with a frequency between 300 and 3000 MHz, preferably between 915 and 2450 MHz.

[0127] In these alternative preferred embodiments involving low-pressure plasma, step (c) of the plasma-assisted deposition method according to one variant comprises

[0128] (c'.a) providing a fluorine-free compound in liquid form in a container having an outlet, optionally under applied heat;

[0129] (c'.b) passing an atomizer gas through the nozzle so that the atomizer gas contacts the fluorine-free compound at the outlet of the container, thereby generating an aerosol containing the fluorine-free compound.

[0130] In an alternative preferred embodiment involving a low-pressure plasma, a plasma-assisted deposition method according to another variant comprises

[0131] (a) providing a substrate having a surface;

[0132] (b") providing an atmosphere comprising the fluorine-free compound in gaseous form or in aerosol form, optionally under applied heating;

[0133] (c") generating plasma from the atmosphere comprising the fluorine-free compound according to (b.1) by a combination of excitations under plasma generating conditions, the excitation comprising primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of a discharge of an alternating voltage having a frequency between 1 kHz and 15 MHz, thereby generating plasma;

[0134] (d") treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (c"), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0135] The atmosphere comprises the fluorine-free compound and optionally one or more gases, preferably selected from the group consisting of N2, Ar, He, CO2, O2, N2O or a mixture of two or more of these gases. For example, an atmosphere comprising the fluorine-free compound in gaseous form or in aerosol form is provided, in that the fluorine-free compound is partially gaseous due to its vapor pressure in its liquid form and the gas phase is transferred into the container for plasma generation and treatment, in combination with a carrier gas or alone, or a liquid fluorine-free compound or a solution of the liquid fluorine-free compound in a solvent is injected into the container for plasma generation and treatment.

[0136] For embodiments involving low-pressure variants that do not use a nebulizer gas (and do not use an aerosol), reference is made to US 2022 / 0112595 A1, in which the method is described in detail, which is incorporated herein by reference, especially paragraphs

[0010] to

[0020] ,

[0024] to

[0028] . US 2022 / 0112595 A1 describes a suitable device in paragraphs

[0031] to

[0060] , which are also incorporated herein by reference.

[0137] In all embodiments where low pressure plasma is used, the substrate to be coated may be the inner surface of a hollow container having an opening or a portion thereof, preferably the substrate is placed in a housing adapted to maintain a specific pressure therein and the entire housing is evacuated.

[0138] In all embodiments in which low-pressure plasma is used, the fluorine-free compound is preferably selected from the group consisting of lactams having 4 to 8 ring atoms, lactones having 4 to 8, preferably 6 to 8, ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams having 4 to 8 ring atoms (excluding caprolactam), lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams having 4 to 8 ring atoms (excluding caprolactam), lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams having 4 to 8 ring atoms (excluding caprolactam). amides and excluding vinylpyrrolidone), lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate and mixtures of two or more of these compounds, more preferably the fluorine-free compound is a lactone having 4 to 8, preferably 6 to 8 ring atoms.

[0139] In all embodiments where low pressure plasma is used, the power density of the electromagnetic wave is between 0.01 and 1 W / cm 3 The range is and / or the power of the discharge is in the range of 4 to 30 W and the frequency is in the range of 20 to 200 kHz.

[0140] “Under application of heat” means that a temperature in the range of 10° C. to 80° C. is established by suitable means so that the fluorine-free compound can be provided in a liquid form or a gaseous form.

[0141] Regardless of whether an atmospheric pressure plasma or a low pressure plasma is used in the plasma-assisted deposition process for applying a coating to a surface of a substrate, preferably no water is added in steps (a), (b), (c), (d), more preferably at least no water is added in step (d), and / or the plasma-assisted deposition process, preferably at least step (d) thereof, is carried out in an atmosphere containing at most as much water as the atmosphere would contain based on a relative humidity (RH) of 100% at the corresponding process temperature.

[0142] Whether atmospheric pressure plasma or low pressure plasma is used in the plasma assisted deposition method for applying the coating to the surface of the substrate, the substrate comprises a material selected from the group consisting of organic materials and mixtures of organic materials and inorganic materials, wherein the organic material is preferably one or more organic polymers and the inorganic material is preferably selected from the group consisting of glass, silica, ceramics and steel. The organic polymer is preferably selected from the group consisting of polyolefins, preferably polyethylene (PE) or polypropylene (PP); polyamides (PA); polyurethanes (PU); fluorinated polymers; silicones; polycarbonates (PC); polymethyl methacrylate (PMMA); polyacrylates; polyesters, especially polyethylene terephthalate (PET); cellulose; cellulose-derived polymers like cellulose acetate, lignin, including lignin-based composites of wood; and mixtures of two or more of these organic polymers.

[0143] Whether atmospheric pressure plasma or low pressure plasma is used in the plasma-assisted deposition method for applying the coating to the surface of the substrate, the substrate more preferably comprises an organic polymer selected from the group consisting of polyolefins, polyamides, polyesters and mixtures of two or more thereof, more preferably the substrate comprises an organic polymer selected from the group consisting of polyethylene, polyamides and mixtures of polyethylene and polyamides, more preferably the substrate comprises at least polyethylene (PE), more preferably high density polyethylene (HDPE).

[0144] With regard to the properties of the obtained coated substrate, reference is made to the disclosure above in relation to the first aspect of the invention, i.e. the properties of the obtained coated substrate are as disclosed in detail in the above section for the first aspect. In addition, preferred embodiments of the method and process parameters are as disclosed in detail above with regard to the first aspect. Furthermore, the details disclosed above with regard to the first aspect, for example, about atmospheric pressure plasma variants and low pressure variants, also apply to the plasma assisted deposition method of the second aspect.

[0145] The third aspect of the present invention - use

[0146] A third aspect of the present invention relates to the use of a coated substrate as described above in relation to the first aspect or a coated substrate obtained or obtainable by the plasma assisted deposition method of the second aspect as described above for packaging, storing and / or transporting items selected from the group consisting of food, beverages and chemicals, wherein the items are preferably chemicals, wherein the chemicals are preferably hazardous substances (transported as dangerous goods) or agrochemicals, more preferably agrochemicals.

[0147] The present invention is further illustrated by the following examples and combinations of the examples as indicated by the corresponding dependencies and back references. In particular, it should be noted that in each case where a series of embodiments is mentioned, for example in the context of a term such as "as any one of embodiments 1 to 4 ...", each embodiment in this series is intended to be disclosed explicitly to the skilled person, i.e. the wording of this term should be understood by the skilled person as being synonymous with "as any one of embodiments 1, 2, 3 and 4 ...".

[0148] 1. A coated substrate, wherein the coating is obtained or obtainable by depositing on the surface of the substrate by a plasma assisted deposition process a reaction product of a fluorine-free compound selected from the group consisting of: lactams having 4 to 8 ring atoms, lactones having 4 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone, C5 to C8 alkynes and mixtures of two or more of these compounds.

[0149] 2. The coated substrate of embodiment 1, wherein the compound used to deposit the coating on the surface of the substrate by a plasma assisted deposition method is selected from the group consisting of lactams having 4 to 8 ring atoms (excluding vinyl pyrrolidone), lactones having 4 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone, C5 to C8 alkynes, and mixtures of two or more of these compounds.

[0150] 3. The coated substrate of embodiment 1 or 2, wherein the compound used to deposit the coating on the surface of the substrate by a plasma assisted deposition method is selected from the group consisting of lactams having 4 to 8 ring atoms (excluding vinyl pyrrolidone), lactones having 4 to 8 ring atoms, vinyl acetate, C5 to C8 alkynes, and mixtures of two or more of these compounds.

[0151] 4. The coated substrate of any one of embodiments 1 to 3, wherein the compound used to deposit the coating on the surface of the substrate by a plasma assisted deposition method is selected from the group consisting of lactams having 4 to 8 ring atoms (excluding vinyl pyrrolidone), lactones having 4 to 8 ring atoms, vinyl acetate, and mixtures of two or more of these compounds, preferably selected from the group consisting of lactones having 4 to 8 ring atoms, vinyl acetate, and mixtures of two or more of these compounds.

[0152] 5. The coated substrate of any one of embodiments 1 to 4, wherein the lactam having 4 to 8 ring atoms has formula (I)

[0153]

[0154] in

[0155] R 1 It's vinyl.

[0156] x is 0 or 1, and

[0157] n is an integer in the range of 2 to 5, preferably in the range of 2 to 4, more preferably n is 4 and x is 0 (ε-caprolactam) and / or n is 2 and x is 1, wherein R 1 It is a vinyl group replacing a hydrogen atom on the nitrogen of the ring structure (vinyl pyrrolidone).

[0158] 6. The coated substrate of any one of embodiments 1 to 5, wherein the lactone having 4 to 8 ring atoms, preferably 6 to 8 ring atoms, has the formula (II)

[0159]

[0160] in

[0161] R 2 selected from methyl and vinyl,

[0162] y is 0 or 1, and

[0163] m is an integer in the range of 1 to 5, preferably in the range of 3 to 4, wherein the lactone is more preferably selected from the group consisting of: δ-valerolactone, γ-valerolactone, ε-caprolactone and a mixture of two or more of these lactones, more preferably the lactone contains at least γ-valerolactone, more preferably γ-valerolactone.

[0164] 7. The coated substrate of any one of embodiments 1 to 6, wherein the vinyl acetate has the formula (III)

[0165]

[0166] 8. The coated substrate of any of embodiments 1 to 7, wherein the polyvinylpyrrolidone has a weight average molecular weight of ≥222 g / mol, preferably in the range of 2,500 to 2,500,000 g / mol, more preferably in the range of 6,000 to 40,000 g / mol.

[0167] 9. The coated substrate of any one of embodiments 1 to 8, wherein the C5 to C8 alkyne is a linear or branched C5 to C8 alkyne, preferably a linear C5 to C8 alkyne, which more preferably has formula (V)

[0168]

[0169] wherein r is an integer in the range of 2 to 5, preferably r is 5.

[0170] 10. The coated substrate of any one of embodiments 1 to 9, wherein at least 80 wt.-%, preferably at least 90 wt.-%, more preferably at least 95 wt.-% of the compounds used to deposit the coating, based on the total weight of all compounds used to deposit the coating, are compounds according to one of the groups of embodiments 1 to 9, i.e. at least 80 wt.-%, preferably at least 90 wt.-%, more preferably at least 95 wt.-% of the coating consists of reaction products of compounds according to one of the groups of embodiments 1 to 9.

[0171] 11. The coated substrate of any one of embodiments 1 to 10, wherein the additional compound is used to deposit the coating on the surface of the substrate by a plasma assisted deposition method, the additional compound is selected from the group consisting of C2 to C4 olefins, C2 to C4 alkynes and mixtures thereof, more preferably selected from the group consisting of C3 to C4 olefins, C2 to C4 alkynes and mixtures thereof, preferably the compound used to deposit the coating on the surface of the substrate by a plasma assisted deposition method comprises at least vinyl acetate and the additional compound is acetylene, more preferably the compound used to deposit the coating on the surface of the substrate by a plasma assisted deposition method is vinyl acetate and the additional compound is acetylene.

[0172] 12. The coated substrate according to embodiments 1 to 11, wherein the compound used to deposit the coating comprises, in a range of 50 to 90 wt.-%, preferably in a range of 80 to 90 wt.-%, a compound according to one of the groups of embodiments 1 to 9, and in a range of 10 to 50 wt.-%, preferably in a range of 10 to 20 wt.-%, a further compound according to embodiment 11, based on the total weight of all compounds used to deposit the coating.

[0173] 13. The coated substrate of any one of embodiments 1 to 12, wherein the fluorine-free compound is used as a precursor in the plasma-assisted deposition method in the form of a liquid phase comprising a single compound in a liquid state or a homogeneous solution in a liquid medium.

[0174] 14. The coated substrate of any one of embodiments 1 to 13, wherein the coating is substantially free of fluorine, preferably the coating comprises less than 1 wt-%, more preferably less than 0.1 wt-% fluorine based on the total weight of the coating (100 wt-%).

[0175] 15. The coated substrate of any one of embodiments 1 to 14, wherein the monolayer binding capacity (q BET ) between 0.3 and 1.3 μmol / cm 2 In the range of 0.4 to 1.1 μmol / cm 2 In the range of 0.5 to 0.8 μmol / cm2 Within the range of , it was determined by inverse gas chromatography (iGC) for toluene vapor according to Reference Example 5.

[0176] 16. The coated substrate of any one of embodiments 1 to 15, wherein the retention time of toluene vapor (t R，结束 ) is in the range of 30 to 250 minutes, more preferably in the range of 35 to 200 minutes, more preferably in the range of 40 to 175 minutes, as determined by inverse gas chromatography (iGC) according to Reference Example 5.

[0177] 17. The coated substrate of any one of embodiments 1 to 16, wherein the BET constant (C BET ) is in the range of 50 to 300, preferably in the range of 50 to 200, more preferably in the range of 70 to 175, as determined by inverse gas chromatography (iGC) for toluene vapor according to Reference Example 5.

[0178] 18. A coated substrate as described in any one of embodiments 1 to 17, wherein the static contact angle of the fluorine-free compound (which is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinyl pyrrolidone) relative to water is in the range of 10 to 46° (measured according to Reference Example 2), and the static contact angle of C5 to C8 alkynes relative to water is in the range of 90 to 120° (measured according to Reference Example 2), and / or the fluorine-free compound (which is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinyl pyrrolidone) relative to The static contact angle of C5 to C8 alkynes with respect to diiodomethane is in the range of 10 to 40° (measured according to Reference Example 2), and the static contact angle of C5 to C8 alkynes with respect to diiodomethane is in the range of 40 to 55° (measured according to Reference Example 2), and / or the static contact angle of the fluorine-free compound (which is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinyl pyrrolidone) with respect to formamide is in the range of 8 to 15° (measured according to Reference Example 2), and the static contact angle of C5 to C8 alkynes with respect to formamide is in the range of 70 to 80° (measured according to Reference Example 2).

[0179] 19. A coated substrate as described in any of Examples 1 to 18, wherein for the fluorine-free compound (which is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinyl pyrrolidone), the surface free energy obtained from the static contact angles of water, formamide, and diiodomethane according to Reference Example 2 is in the range of 48 to 73 mN / m, and for C5 to C8 alkynes, the surface free energy obtained from the static contact angles of water, formamide, and diiodomethane according to Reference Example 2 is in the range of 30 to 40 mN / m.

[0180] 20. The coated substrate of any one of embodiments 1 to 19, wherein the coating has a thickness in the range of 20 to 500 nm, preferably in the range of 50 to 350 nm, preferably determined by transmission electron microscopy (TEM) according to Reference Example 6.

[0181] 21. A coated substrate as described in any of Examples 1 to 20, wherein the coating comprising the reaction product of the fluorine-free compound is present on at least a portion of the surface of the substrate, preferably having a surface coverage of at least 10%, more preferably at least 20%, more preferably at least 25%, more preferably at least 30% of the surface area of ​​the substrate that has been treated with the plasma-assisted deposition method as determined by X-ray photoelectron spectroscopy (XPS) according to Reference Example 3.

[0182] 22. A coated substrate as described in any of Examples 1 to 21, wherein the reaction product of the fluorine-free compound contained in the coating is a free radical polymerization product (compared to polycondensation) as determined by time-of-flight secondary ion mass spectrometry (ToF-SIMS) according to Reference Example 4, characterized in that the nominal mass of the secondary ions generated from this surface is offset by 2 amu compared to the nominal mass of the fragments generated by measuring the polymer produced by the polycondensation.

[0183] 23. The coated substrate of any of embodiments 1 to 22, wherein a layer comprising a reaction product of acetylene is present between the surface of the substrate and the coating comprising a reaction product of the fluorine-free compound.

[0184] 24. The coated substrate of embodiment 23, wherein the layer comprising a reaction product of acetylene is obtained or obtainable by plasma-assisted deposition of acetylene.

[0185] 25. The coated substrate of any one of embodiments 1 to 24, wherein the substrate comprises a material selected from the group consisting of an organic material and a mixture of an organic material and an inorganic material, wherein the organic material is preferably one or more organic polymers and the inorganic material is preferably selected from the group consisting of glass, silicon dioxide, ceramics, and steel.

[0186] 26. A coated substrate as described in any of embodiments 1 to 25, wherein the substrate comprises an organic polymer selected from the group consisting of: polyolefins, preferably polyethylene (PE) or polypropylene (PP); polyamides (PA); polyurethanes (PU); fluorinated polymers; silicones; polycarbonates (PC); polymethyl methacrylate (PMMA); polyacrylates; polyesters, especially polyethylene terephthalate (PET); cellulose; cellulose-derived polymers like cellulose acetate, lignin, including lignin-based composites of wood; and mixtures of two or more of these organic polymers.

[0187] 27. A coated substrate as described in any of embodiments 1 to 26, wherein the substrate comprises an organic polymer selected from the group consisting of polyolefins, polyamides, polyesters and mixtures of two or more thereof, more preferably the substrate comprises an organic polymer selected from the group consisting of polyethylene, polyamides and mixtures of polyethylene and polyamides, more preferably the substrate comprises at least polyethylene (PE), more preferably high-density polyethylene (HDPE), more preferably at least 80 wt-%, more preferably at least 90 wt-%, more preferably at least 95 wt-%, more preferably at least 98 wt-% of the substrate consists of HDPE.

[0188] 28. A coated substrate as described in any one of embodiments 1 to 27, wherein the substrate is a packaging suitable for storing and transporting an article selected from the group consisting of food, beverages and chemicals, wherein the chemical is preferably a hazardous substance (transported as dangerous goods) or an agrochemical, wherein the coating is present on at least one surface of the substrate facing or intended to face the article, wherein the article is more preferably an agrochemical, and the substrate is more preferably an (agro)chemical container, wherein the coating is present on at least one surface of the substrate facing or intended to face the (agro)chemical.

[0189] 29. The coated substrate of any of embodiments 1 to 28 which is an agrochemical container.

[0190] 30. The coated substrate of any one of embodiments 1 to 29, wherein in the plasma assisted deposition method, the plasma is generated in (a) at a pressure in the range of 0.5 to 1.5 bar, preferably in the range of 0.8 to 1.2 bar (atmospheric or near atmospheric conditions, indirect atmospheric pressure plasma processing).

[0191] 31. The coated substrate of any one of Embodiment 30, wherein the plasma assisted deposition method comprises

[0192] (a) providing a substrate having a surface;

[0193] (b) generating plasma by passing a carrier gas through an excitation region under plasma generating conditions and by applying a high frequency alternating current to an electrode positioned in the excitation region to generate a dielectric barrier discharge to generate plasma;

[0194] (c) generating an aerosol comprising a fluorine-free compound as defined in any one of embodiments 1 to 11 by using a nebulizer gas;

[0195] (d) treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (b) and the aerosol containing the fluorine-free compound generated according to (c), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0196] 32. The coated substrate of embodiment 30 or 31, wherein step (c) of the plasma assisted deposition method comprises

[0197] (c.1) providing a fluorine-free compound in liquid form in a container having an outlet;

[0198] (c.2) passing a nebulizer gas through a nozzle so that the nebulizer gas contacts the fluorine-free compound at an outlet of the container, thereby generating an aerosol containing the fluorine-free compound.

[0199] 33. The coated substrate of any one of embodiments 1 to 29, wherein in the plasma-assisted deposition method, the plasma is generated at a pressure of <0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, preferably in the range of 0.001 to 0.05 mbar (low-pressure plasma).

[0200] 34. The coated substrate of embodiment 33, wherein the plasma assisted deposition method comprises

[0201] (a) providing a substrate having a surface;

[0202] (b') generating an aerosol comprising a fluorine-free compound as defined in any one of embodiments 1 to 11, preferably by using a nebulizer gas;

[0203] (c') converting the precursor aerosol produced in (b') into a plasma state by a combination of excitations including primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of discharge of an alternating voltage having a frequency between 1 kHz and 15 MHz, thereby producing plasma;

[0204] (d') treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (c'), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0205] 35. The coated substrate of embodiment 34, wherein step (c.1) of the plasma assisted deposition method comprises

[0206] (c'.a) providing a fluorine-free compound in liquid form in a container having an outlet, optionally under applied heat;

[0207] (c'.b) passing an atomizer gas through the nozzle so that the atomizer gas contacts the fluorine-free compound at the outlet of the container, thereby generating an aerosol containing the fluorine-free compound.

[0208] 36. The coated substrate of embodiment 33, wherein the plasma assisted deposition method comprises

[0209] (a) providing a substrate having a surface;

[0210] (b") providing an atmosphere comprising the fluorine-free compound in gaseous form or in aerosol form, optionally under applied heating;

[0211] (c") generating plasma from the atmosphere comprising the fluorine-free compound according to (b") under plasma generating conditions by a combination of excitations including primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of discharge of an alternating voltage having a frequency between 1 kHz and 15 MHz, thereby generating plasma;

[0212] (d") treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (c"), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0213] 37. A coated substrate as described in any one of embodiments 33 to 36, wherein the fluorine-free compound is preferably selected from the group consisting of lactams with 4 to 8 ring atoms, lactones with 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams with 4 to 8 ring atoms (excluding caprolactam), lactones with 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams with 4 to 8 ring atoms (excluding caprolactam), lactones with 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams with 4 to 8 ring atoms (excluding caprolactam). The fluorine-free compound is preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate and mixtures of two or more of these compounds, more preferably the fluorine-free compound is a lactone having 4 to 8, preferably 6 to 8 ring atoms.

[0214] 38. The coated substrate of any one of embodiments 30 to 32, wherein in the plasma-assisted deposition method, the plasma according to (a) is heated at a speed of less than 40 kW / m 2 The power per electrode area is preferably between 7.5 and 38 kW / m 2 The power in the range of 8 to 30 kW / m 2 power generation within the range of .

[0215] 39. A coated substrate as described in any of Examples 30 to 32 and 38, wherein in the plasma assisted deposition method, one or more atomizers, preferably at least two atomizers, are used, wherein the atomizer gas according to (c) or (c.2) is provided to the second region at a flow rate of greater than 0.5 slm (standard liters per minute) per atomizer, preferably at a flow rate per atomizer in the range of 0.5 to 5 slm, more preferably in the range of 0.8 to 3 slm, more preferably in the range of 1 to 2 slm.

[0216] 40. The coated substrate of any one of embodiments 30 to 32 and 38 to 39, wherein in the plasma assisted deposition method, the amount of the fluorine-free compound delivered to the plasma and entering the plasma as an aerosol at each time is in the range of 0.045 to 0.5 g / min per atomizer, preferably in the range of 0.045 to 0.3 g / min per atomizer, more preferably in the range of 0.05 to 0.2 g / min per atomizer, more preferably in the range of 0.08 to 0.12 g / min per atomizer.

[0217] 41. A coated substrate as described in any of Examples 30 to 32 and 38 to 40, wherein in the plasma assisted deposition method, the distance between the outlet of the excitation zone and the substrate surface according to (a) is in the range of 0.5 to 10 mm, preferably in the range of 0.5 to 5 mm, more preferably in the range of 2 to 4 mm, more preferably in the range of 2.5 to 3.5 mm.

[0218] 42. A coated substrate as described in any of Examples 30 to 32 and 38 to 41, wherein in the plasma assisted deposition method, the carrier gas is provided to the excitation zone at a flow rate in the range of 50 to 500 l / min, preferably in the range of 150 to 450 l / min, more preferably in the range of 200 to 300 l / min.

[0219] 43. The coated substrate of any one of embodiments 30 to 32 and 38 to 42, wherein in the plasma assisted deposition method, an AC voltage of up to 100 kV is applied, wherein the AC voltage is preferably in the range of 10 to 40 kV.

[0220] 44. A coated substrate as described in any of embodiments 30 to 32 and 38 to 43, wherein in the plasma assisted deposition method, the discharge frequency is in the range of 50 to 100 kHz, preferably in the range of 60 to 100 kHz, more preferably in the range of 70 to 95 kHz, more preferably in the range of 80 to 90 kHz.

[0221] 45. The coated substrate of any one of embodiments 30 to 32 and 38 to 44, wherein the plasma assisted deposition process is performed for a total time in the range of 30 seconds to 10 minutes, preferably in the range of 1 to 2 minutes.

[0222] 46. ​​A coated substrate as described in any one of embodiments 33 to 37, wherein the power density of the electromagnetic wave is between 0.01 and 1 W / cm 3 The range is and / or the power of the discharge is in the range of 4 to 30 W and the frequency is in the range of 20 to 200 kHz.

[0223] 47. The coated substrate of any of embodiments 30 to 46, wherein the plasma assisted deposition process is performed at a temperature in the range of 10°C to 80°C.

[0224] 48. A coated substrate as described in any of embodiments 30 to 47, wherein in the plasma-assisted deposition method, preferably no water is added in any of steps (a), (b), (c), (d), more preferably at least no water is added in step (d), and / or wherein the plasma-assisted deposition method, preferably at least its step (d), is carried out in an atmosphere containing at most as much water as the atmosphere based on 100% relative humidity (RH) at the corresponding process temperature.

[0225] 49. A plasma assisted deposition method for applying a coating to a surface of a substrate, the method comprising:

[0226] (a) providing a substrate having a surface;

[0227] (b) generating plasma by passing a carrier gas through an excitation region under plasma generating conditions and by applying a high frequency alternating current to an electrode positioned in the excitation region to generate a dielectric barrier discharge to generate plasma;

[0228] (c) generating an aerosol comprising a fluorine-free compound as defined in any one of embodiments 1 to 11, preferably by using a nebulizer gas;

[0229] d) treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (b) and the aerosol containing the fluorine-free compound generated according to (c), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0230] 50. The plasma-assisted deposition method for applying a coating to a surface of a substrate according to embodiment 49, wherein step (c) of the plasma-assisted deposition method comprises

[0231] (c.1) providing a fluorine-free compound in liquid form in a container having an outlet;

[0232] (c.2) passing a nebulizer gas through a nozzle so that the nebulizer gas contacts the fluorine-free compound at an outlet of the container, thereby generating an aerosol containing the fluorine-free compound.

[0233] 51. A plasma-assisted deposition method for applying a coating to a surface of a substrate according to embodiment 49 or 50, wherein the plasma is generated in (a) at a pressure in the range of 0.5 to 1.5 bar, preferably in the range of 0.8 to 1.2 bar (atmospheric pressure or near atmospheric pressure conditions, indirect atmospheric pressure plasma processing).

[0234] 52. The plasma-assisted deposition method for applying a coating to a surface of a substrate according to any one of embodiments 49 to 51, wherein the plasma according to (a) is heated at a speed of less than 40 kW / m 2 The power per electrode area is preferably between 7.5 and 38 kW / m 2 The power in the range of 8 to 30 kW / m 2 power generation within the range of .

[0235] 53. A plasma-assisted deposition method for applying a coating to a surface of a substrate according to any one of embodiments 49 to 52, wherein one or more atomizers, preferably at least two atomizers, are used, wherein the atomizer gas according to (c) or (c.2) is provided to the second region at a flow rate of greater than 0.5 slm (standard liters per minute) per atomizer, preferably at a flow rate per atomizer in the range of 0.5 to 5 slm, more preferably in the range of 0.8 to 3 slm, and more preferably in the range of 1 to 2 slm.

[0236] 54. A plasma-assisted deposition method for applying a coating to a surface of a substrate according to any one of embodiments 49 to 53, wherein the amount of the fluorine-free compound delivered to the plasma and entering the plasma as an aerosol at each time is in the range of 0.045 to 0.5 g / min per atomizer, preferably in the range of 0.045 to 0.3 g / min per atomizer, more preferably in the range of 0.05 to 0.2 g / min per atomizer, and more preferably in the range of 0.08 to 0.12 g / min per atomizer.

[0237] 55. A plasma-assisted deposition method for applying a coating to a surface of a substrate according to any one of embodiments 49 to 54, wherein the distance between the outlet of the excitation zone and the surface of the substrate according to (a) is in the range of 0.5 to 10 mm, preferably in the range of 0.5 to 5 mm, more preferably in the range of 2 to 4 mm, and more preferably in the range of 2.5 to 3.5 mm.

[0238] 56. A plasma-assisted deposition method for applying a coating to a surface of a substrate according to any one of embodiments 49 to 55, wherein the carrier gas is provided to the excitation zone at a flow rate in the range of 50 to 500 l / min, preferably in the range of 150 to 450 l / min, more preferably in the range of 200 to 300 l / min.

[0239] 57. The plasma-assisted deposition method for applying a coating to a surface of a substrate according to any one of embodiments 49 to 56, wherein an AC voltage of up to 100 kV is applied, wherein the AC voltage is preferably in the range of 10 to 40 kV.

[0240] 58. A plasma-assisted deposition method for applying a coating to a surface of a substrate according to any one of embodiments 49 to 57, wherein the discharge frequency is in the range of 50 to 100 kHz, preferably in the range of 60 to 100 kHz, more preferably in the range of 70 to 95 kHz, more preferably in the range of 80 to 90 kHz.

[0241] 59. The plasma-assisted deposition method for applying a coating to a surface of a substrate according to any one of embodiments 49 to 58, wherein the plasma-assisted deposition method is performed at a temperature in the range of 10°C to 80°C.

[0242] 60. The plasma-assisted deposition method for applying a coating to a surface of a substrate according to any one of embodiments 49 to 59, wherein the plasma-assisted deposition method is performed for a total time in the range of 30 seconds to 10 minutes, preferably in the range of 1 to 2 minutes.

[0243] 61. A plasma-assisted deposition method for applying a coating to a surface of a substrate, wherein the plasma is generated at a pressure of <0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, preferably in the range of 0.001 to 0.05 mbar (low-pressure plasma).

[0244] 62. The plasma-assisted deposition method for applying a coating to a surface of a substrate according to embodiment 61, wherein the plasma-assisted deposition method comprises

[0245] (a) providing a substrate having a surface;

[0246] (b') generating an aerosol comprising a fluorine-free compound as defined in any one of Examples 1 to 11 by using a nebulizer gas;

[0247] (c') converting the precursor aerosol produced in (b') into a plasma state by a combination of excitations including primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of discharge of an alternating voltage having a frequency between 1 kHz and 15 MHz, thereby producing plasma;

[0248] (d') treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (c'), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0249] 63. The plasma-assisted deposition method for applying a coating to a surface of a substrate according to embodiment 62, wherein step (c) of the plasma-assisted deposition method comprises

[0250] (c'.a) providing a fluorine-free compound in liquid form in a container having an outlet, optionally under applied heat;

[0251] (c'.b) passing an atomizer gas through the nozzle so that the atomizer gas contacts the fluorine-free compound at the outlet of the container, thereby generating an aerosol containing the fluorine-free compound.

[0252] 64. A plasma assisted deposition method for applying a coating to a surface of a substrate, wherein the plasma assisted deposition method comprises

[0253] (a) providing a substrate having a surface;

[0254] (b") providing an atmosphere comprising a fluorine-free compound as defined in any one of embodiments 1 to 11 in gaseous form or in aerosol form, optionally under applied heating;

[0255] (c") generating plasma from the atmosphere comprising the fluorine-free compound according to (b") under plasma generating conditions by a combination of excitations including primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of discharge of an alternating voltage having a frequency between 1 kHz and 15 MHz, thereby generating plasma;

[0256] (d") treating at least a portion of the surface of the substrate provided according to (a) with the plasma generated according to (c"), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the substrate surface, thereby obtaining a coated substrate.

[0257] 65. A plasma-assisted deposition method for applying a coating to a surface of a substrate as described in any of embodiments 49 or 50 or 61 to 64, wherein the fluorine-free compound is preferably selected from the group consisting of lactams having 4 to 8 ring atoms, lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams having 4 to 8 ring atoms (excluding caprolactam), lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of lactams having 4 to 8 ring atoms (excluding caprolactam), lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinyl pyrrolidone and mixtures of two or more of these compounds, more preferably selected from the group consisting of The fluorine-free compound is selected from the group consisting of lactams having 4 to 8 ring atoms (excluding caprolactam and excluding vinylpyrrolidone), lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone and a mixture of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone and a mixture of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone and a mixture of two or more of these compounds, more preferably selected from the group consisting of lactones having 4 to 8, preferably 6 to 8 ring atoms, vinyl acetate and a mixture of two or more of these compounds, more preferably the fluorine-free compound is a lactone having 4 to 8, preferably 6 to 8 ring atoms.

[0258] 66. A plasma-assisted deposition method for applying a coating to a surface of a substrate as described in any one of embodiments 61 to 65, wherein the power density of the electromagnetic wave is between 0.01 and 1 W / cm 3 The range is and / or the power of the discharge is in the range of 4 to 30 W and the frequency is in the range of 20 to 200 kHz.

[0259] 67. A plasma-assisted deposition method for applying a coating to a surface of a substrate as described in any of embodiments 49 to 66, wherein in the plasma-assisted deposition method, preferably no water is added in any of steps (a), (b), (c), (d), more preferably at least no water is added in step (d), and / or wherein the plasma-assisted deposition method, preferably at least its step (d), is carried out at the corresponding process temperature in an atmosphere containing at most as much water as the atmosphere contains based on a relative humidity (RH) of 100%.

[0260] 68. A plasma-assisted deposition method for applying a coating to a surface of a substrate as described in any of Examples 49 to 67, wherein the substrate comprises an organic polymer selected from the group consisting of: polyolefins, preferably polyethylene (PE) or polypropylene (PP); polyamides (PA); polyurethanes (PU); fluorinated polymers; silicones; polycarbonates (PC); polymethyl methacrylate (PMMA); polyacrylates; polyesters, especially polyethylene terephthalate (PET); cellulose; cellulose-derived polymers like cellulose acetate, lignin, including lignin-based composites of wood; and mixtures of two or more of these organic polymers.

[0261] 69. A plasma-assisted deposition method for applying a coating to a surface of a substrate as described in any of Examples 49 to 68, wherein the substrate comprises an organic polymer selected from the group consisting of polyolefins, polyamides, polyesters and mixtures of two or more thereof, more preferably the substrate comprises an organic polymer selected from the group consisting of polyethylene, polyamides and mixtures of polyethylene and polyamides, more preferably the substrate comprises at least polyethylene (PE), more preferably high-density polyethylene (HDPE).

[0262] 70. Use of the coated substrate according to any one of embodiments 1 to 48 or the coated substrate obtained or obtainable by the plasma assisted deposition method according to any one of embodiments 49 to 69 for packaging, storing and / or transporting items selected from the group consisting of food, beverages and chemicals, wherein the items are preferably chemicals, wherein the chemicals are preferably hazardous substances (transported as dangerous goods) or agrochemicals, more preferably agrochemicals.

[0263] The present invention is further illustrated by the following Reference Examples and Examples.

[0264] Examples

[0265] Reference Example 1: Plasma coating method at atmospheric pressure

[0266] In the first coating step, A cast high-density polyethylene (HDPE) plate of 20 cm × 25 cm in size (cleaned by flushing with isopropanol and blowing dry in air) was pretreated with a plasma generated using an argon carrier gas at a flow rate of 250 slm in a reactor (product of VITO), into which pure acetylene gas was fed at a flow rate of 2 × 2.5 slm (i.e., 2.5 slm per atomizer, because The reactor comprises two gas inlets connected to two atomizers). The gaseous mixture is fed into the afterglow region of the plasma, the HDPE plate is moved 30 times (hereinafter referred to as the number of passes) at a speed of 2 m / min and thereby coated with the reaction product of acetylene. During this first coating step, the frequency of the DC current driving the plasma is set to 85 kHz, using a power of 150 W. The distance between the outlet of the excitation zone and the surface of the substrate is kept constant at 3 mm. The resulting HDPE plate has a coating with the reaction product of acetylene on its surface and is referred to as a "pretreated substrate". In the second coating step, the reaction product of ε-caprolactam is deposited on the pretreated substrate obtained by the first coating step. For this purpose, the pretreated substrate is exposed to another plasma generated using an argon carrier gas at a flow rate of 250 slm, into which ε-caprolactam is fed in the form of an aerosol obtained by evaporating a solution of 1000 g / L of a precursor in methanol with Ar gas at a flow rate of 1.5 slm per atomizer in two atomizers. The pretreated substrate was passed through the afterglow region 30 times at a speed of 2 m / min and was thus coated with the reaction product of the fluorine-free compound. During this second coating step, the frequency of the DC current driving the plasma was set to 85 kHz, using a power of 150 W. Based on the known surface area (100 cm2) of the high-voltage electrode used, the 2 ), the power density applied during the coating process was 15 kW / m 2 or 1.5W / cm 2 The distance between the outlet of the excitation zone and the substrate surface was kept constant at 3 mm. Thus, a substrate having the reaction product of acetylene and the reaction product of ε-caprolactam deposited thereon on its surface was obtained by a plasma-assisted coating process at atmospheric pressure.

[0267] Reference Example 2: Plasma coating method at low pressure

[0268] A standard 1L bottle consisting of HDPE was introduced into a low-pressure plasma reactor developed and described by ISYTECH (US2022 / 112595A1). The reactor includes a vacuum chamber placed in a microwave coupler. The pressure in the vacuum chamber inside and around the bottle was reduced to <0.1 mbar and 20 mbar, respectively, by using a vacuum pump. Subsequently, the inner surface of the HDPE bottle was treated with an argon plasma for a period of 5 s, which was generated by adding Ar gas to the inner volume of the bottle at a flow rate of 120 sccm (standard cubic centimeters) and introducing the energy required for plasma ignition by a microwave generator with a frequency of 2.45 GHz and a power of 350 W. The resulting HDPE container is called a "pre-cleaned bottle" and is used for continuous plasma-assisted coating at low pressure. In the first coating step, gaseous acetylene is fed into the inner volume of the pre-cleaned bottle at 100 sccm and activated into a plasma state by electromagnetic waves provided by a microwave generator with a power of 400 W. This resulted in partial decomposition of the reaction gases and deposition of the reaction products of the acetylene on the inner surface of the pre-cleaned bottle for a period of 1 second, resulting in a "pre-treated bottle". In a second step, gaseous 1-octyne obtained from the head space above the liquid 1-octyne was introduced into the inner volume of the pre-treated bottle by means of an argon carrier gas and was heated by a power of 500 W (which corresponds to 0.5 W / cm 3 The pretreated bottle was activated into a plasma state by electromagnetic waves provided by a microwave generator having an effective power density of 100 Å (0.1 Å). The treatment with the obtained plasma for a period of 3 s resulted in the deposition of the reaction product of 1-octyne on the inner surface of the pretreated bottle. Thus, a substrate having the reaction product of acetylene and the reaction product of 1-octyne deposited on its surface was obtained by a plasma-assisted coating process under low pressure.

[0269] Reference Example 3: Static Contact Angle Measurement

[0270] The wetting behavior of the coated substrates and untreated references (e.g. blank HDPE) was investigated by conventional contact angle measurements using three standard solvents (water as a highly polar liquid, diiodomethane as a highly nonpolar liquid, and formamide as a moderately polar liquid). 8-10 drops (volume: 0.5-2 μl) of these liquids were deposited on the substrate and the contact angles were measured after 10 s by shape analysis (sessile drop method, fitting the droplet profile with the aid of an ellipsoid or a circle) using a Krüss DSA100 instrument under ambient conditions (23° C.). The resulting contact angles were averaged and quoted as averages with the corresponding standard deviations. In addition, the surface energy of the substrate (with polar and dispersive components) was calculated using the contact angles obtained for water, formamide and diiodomethane, based on the theory of Owens and Wendt (D. Owens & R. Wendt, J. Appl. Polym. Sci. [Journal of Applied Polymer Science] 1969, Vol. 13, p. 1741).

[0271] Reference Example 4: X-ray Photoelectron Spectroscopy (XPS) Analysis

[0272] XPS analysis was performed with a Kratos Axis Nova XPS-spectrometer using monochromatic Al Kα radiation (120 W) with a spot size of 800 μm×300 μm in standard configuration. The XPS system is calibrated according to ISO 15472.2001. The binding energy of Au 4f7 / 2 is 84.00 eV and the binding energy of Cu2p3 / 2 is 932.62 eV. All samples were mounted insulated from the ground and neutralized with a built-in charge neutralizer during the measurement. The measurement scan analysis was performed with a pass energy of 160 eV and an energy step size of 0.5 eV. High-resolution analysis was performed on the same analysis area with a pass energy of 40 eV and an energy step size of 0.1 eV. The spectral charge was corrected to the main line of the carbon 1s spectrum, set to 284.8 eV, as a typical value quoted for the peak energy of exogenous hydrocarbons. All spectra were analyzed using standard XPS analysis software like CasaXPS (version 2.3.20) and applying Shirley background subtraction to the main peaks of the elements of interest (F1s, N1s, O1s, C 1s, Si 2p). Quantification was performed using the relative sensitivity factors and transmission functions provided by the instrument manufacturer.

[0273] The surface coverage was calculated from the collected XPS spectra in three different ways, based on the type of substrate and precursor used:

[0274] (i) In cases where the substrate contains significant concentrations of elements not present in the precursor, the surface coverage after plasma-assisted coating can be estimated by the following formula:

[0275] Coverage (in percentage) = 100*(1-C 样品 / C 参考 ) equation (XPS I)

[0276] Among them C 样品 is the atomic concentration of the substrate-specific element in at-% after plasma treatment and C 参考 is the atomic concentration of the substrate-specific element in at-% on an untreated clean reference. Thus, a sample with the same concentration of the substrate-specific element will result in zero percent coverage, while a sample with no detectable substrate-specific element will result in 100% coverage.

[0277] (ii) In cases where the precursor contains significant concentrations of elements not present on the substrate, if there is strong experimental evidence that the precursor is deposited in this defined molecular form, the surface coverage can be estimated based on the theoretical composition of the precursor used in the method. Here, the surface coverage after plasma-assisted coating can be calculated as:

[0278] Coverage (in percentage) = 100*(C 样品 / C 理论 ) equation (XPS II)

[0279] Among them C 样品 is the atomic concentration of the coating-specific element in at-% after plasma treatment and C 理论 is the atomic concentration of an element specific to the precursor in at-%, calculated based on the stoichiometry of the precursor. Thus, a sample with the same concentration of an element as in the theoretical composition will result in 100% coverage, while a sample with no detectable specific precursor element will result in zero percent coverage.

[0280] (iii) In cases where the substrate contains elements that are also present in the precursor but in different binding states and therefore exhibit different chemical shifts in the XPS spectrum, the coverage can be derived by using the relative fractions of the relevant elements in the precursor-specific binding state as obtained from a peak fitting procedure.

[0281] Coverage (in percentage) = 100*(C 样品 / C 理论前体 ) equation (XPS III)

[0282] For samples obtained by plasma-assisted coating of HDPE with reaction products of fluorine-free compounds, the surface coverage is calculated according to equation (XPS II) or equation (XPS III), while equation (XPS II) is used to calculate the coverage of the comparative sample (Comp2 in Table 2) obtained by plasma-assisted deposition of reaction products of tetramethylsilane. Here and hereinafter, the comparative sample is abbreviated as CompX, where "X" is a placeholder for the corresponding number of the comparative sample. For the analysis according to equation (XPS III), the carbon 1s spectrum of the coated substrate is fitted with components present on the substrate and therefore in the precursor, representing carbon atoms in various possible forms combined with nitrogen or oxygen (for example, COOR for vinyl acetate, CN in C(=O)-NR for lactams, and CN, CO for lactams, lactones and vinyl acetate). The parameters used for this type of evaluation are shown in Table 1.

[0283] Table 1

[0284] Parameters used to evaluate the XPS spectra and calculate the surface coverage in the case of lactam, lactone and vinyl acetate precursors (samples 2-10).

[0285]

[0286] To estimate the surface coverage of the comparative samples (Comp3 and Comp4) carrying fluorine-rich surface coatings, the carbon 1s spectra of the coated substrates were fitted with components representing carbon atoms bound to fluorine in different stoichiometries (i.e., CF3, CF2, CHF) and fluorine-free functional groups present in the HDPE substrate (like CH2). The parameters used for such evaluation are shown in Table 2.

[0287] Table 2

[0288] Parameters used to evaluate XPS spectra and calculate surface coverage of fluorinated HDPE surfaces (Comp3, Comp4).

[0289]

[0290] The coverage is then calculated by the following equation:

[0291]

[0292] Where R CFi is the percentage of the binding state of interest in the detailed spectrum of the carbon 1s signal of carbon atoms bound to 1, 2, or 3 fluorine atoms, respectively, and C F and C C denote respectively the total concentrations of fluorine and carbon on the surface (in atom-%) as obtained from the measured spectra.

[0293] In the case of alkynes such as 1-octyne, it was not possible to determine by XPS due to the lack of chemical differentiation compared to the HDPE substrate. Here, the presence of the reaction products of the precursors on the substrate after plasma-assisted deposition can be independently verified by TEM imaging (as described in Reference Example 7) and atomic force microscopy (as described in Reference Example 8).

[0294] Finally, the surface coverage of the comparative sample consisting of coextruded HDPE and polyamide (Comp5), ie the amount of PA at the surface, could not be reliably determined by XPS due to the presence of strongly adhering surface contaminants.

[0295] Reference Example 5: Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) Analysis

[0296] Static ToF-SIMS spectra were recorded using a ToF.SIMS 5 spectrometer (IonTOF GmbH, Münster, Germany). 50 keV singly charged tri-bismuth clusters (Bi3 2+ ) was used to record the spectrum of secondary electrons over an area of ​​500 μm × 500 μm in positive ion detection mode. To prevent charging of the sample surface, a low electron energy immersion electron gun (about 20 eV) was used. The mass resolution was limited by the surface roughness to the range of M / ΔM ~ 1000 at 55 u and by using the hydrocarbon peak CH3 + (15u), C2H3 + (27u), C3H5 + (41u), C3H7 + (43u) and C4H7 + After (55u) mass calibration, improved by using "Advanced ToF-Correction" as provided by SurfaceLab 7.2, the obtained spectra were compared with reference spectra of polymers synthesized by polycondensation.

[0297] Reference Example 6: Inverse Gas Chromatography (iGC)

[0298] The barrier effect of the coated substrate and the untreated reference (e.g. blank HDPE) on organic solvents was evaluated by inverse gas chromatography (iGC) using toluene vapor as the test permeate (see chapter "Surface Properties Characterization by Inverse Gas Chromatography (IGC) Applications", Eric Brendlé, Eugène Papirer's book "Powders and Fibers", 1st edition, 2006, Imprint CRC Press, page 76). For this purpose, the substrate was cut into strips with a length of 14 cm and a width of 1 cm and mounted on a plate such as Figure 1 The sample cell is shown. The cell consists of two 14 cm × 14 cm aluminum plates. On the bottom surface of the upper plate, a linear notch with a length of 12.8 cm, a width of 1 mm and a depth of 0.25 mm is printed as a chromatographic path (see Figure 1 a). At each end of the notch, drill 1 / 16" holes to allow for gas inlet and outlet. Place the sample strip along the notch (as shown in Figure 1 b) and sandwiched between the upper and lower plates, which are then securely connected by several screws to ensure airtightness (see Figure 1 c). Use appropriate Swagelok connectors and PEEK fittings to connect the outer ends of the inlet and outlet holes on the top of the upper plate to PEEK capillaries (1 / 16", 10 cm long), through which the entire assembly is connected to the chromatograph.

[0299] The iGC experiments were performed on a Thermo Fisher Trace 1310 gas chromatograph equipped with a flame ionization detector (FID) and a PAL3 RSI injection system. The system was operated with Neuronics 2.2.3 and InPulse 2.3.5 software provided by Adscientis SARL. After the sample cell was assembled and connected to the GC instrument, the cell was placed in the oven of the GC and conditioned at 40° C. in dry helium (Nippon Gases, 6.0 quality) at a flow rate of 18 ml / min for 4 hours to remove any volatile contaminants from the surface of the coated substrate.

[0300] Subsequently, liquid toluene (Honeywell, PA quality) was injected into the He carrier gas at a constant rate of 0.02 μl / s for a period of about 9 minutes at a calibrated carrier gas flow rate of 5.4 ml / min and a temperature of 40°C. In this way, the surface of the coated substrate (or uncoated reference) in the chromatographic channel of the cell was exposed to a constant relative toluene pressure of p / p0=0.64 (where p0 is the saturation pressure of toluene at 40°C). After the initial adsorption of toluene on the sample surface, stable FID readings were established during the injection period in all cases, indicating that the surface was saturated with toluene under the given experimental conditions. Subsequently, the injection was stopped and the substrate was purged with pure He carrier gas, resulting in a gradual desorption of toluene. Once 10 pA (corresponding to p / p0=4.5·10 -5 The FID signal of the relative toluene pressure) is stopped and the corresponding time (t R，结束 , which refers to the time point when toluene injection is stopped and pure He purge is started) is recorded as the first parameter characterizing the barrier effect (where the higher t R，结束 According to the procedure described in the literature (see chapter "Surface Properties Characterization by Inverse Gas Chromatography (IGC) Applications", Eric Brendlé, Eugène Papirer's book "Powders and Fibers", 1st edition, 2006, Imprint CRC Press, page 76), from the obtained desorption curve, q ads =f(p / p0) in the form of adsorption isotherm, where q ads is the amount of toluene adsorbed at any given p / p0 during desorption. For the relative pressure regime of 0.01≤p / p0≤0.05, the obtained isotherms are then evaluated using the Brunauer-Emmett-Teller (BET) theory (see Brunauer, Stephen; Emmett, PH; Teller, Edward (1938). "Adsorption of Gases in Multimolecular Layers". Journal of the American Chemical Society. 60(2):309-319), giving the monolayer binding capacity q BET and the corresponding BET constant C BETAs two other parameters to characterize the barrier effect (note that q BET describes the number of binding sites for toluene on the investigated surface and is expressed as the molar amount of adsorbed toluene molecules per unit surface area explored (in μmol / cm 2 Calculation), and C BET Indicates bonding strength). The strong barrier to toluene vapor is given by q BET and / or C BET reflects the low value of .

[0301] Reference Example 7: Transmission Electron Microscope (TEM) Analysis

[0302] The thin fluorine-free layer present on the HDPE surface after a successful plasma-assisted coating process is visible in cross-section by TEM imaging. For sample preparation, the plasma-treated surface was first coated with a platinum layer (thickness: about 50 nm) and then embedded in epoxy resin. Ultrathin sections were prepared by cryo-ultramicrotomy using a Leica UC 7 microtome. Thin sections of the resulting samples were examined on a Zeiss Libra 120 microscope equipped with an Ω filter and operated in elastic and inelastic mode at an accelerating voltage of 120 kV.

[0303] Reference Example 8: Determination of surface roughness by atomic force microscopy (AFM)

[0304] The surface roughness of the coated substrates and the uncoated reference was characterized by AFM using a Dimension ICON instrument from Bruker under ambient conditions. Topographic height images covering 2 μm×2 μm, 5 μm×5 μm and 50 μm×50 μm surface areas were collected in tapping mode. From the 2 μm×2 μm images, the roughness values ​​Ra and Rq were obtained. Ra roughness is defined as the arithmetic mean of the absolute values ​​of the surface height deviations (Z) measured from the corresponding mean plane for each analysis point in the image (i), where the total number of analysis points is N:

[0305]

[0306] Rq represents the root mean square (RMS) surface roughness calculated as follows:

[0307]

[0308] Reference Example 9: Mechanical Characterization by Nanoindentation

[0309] The mechanical properties of HDPE substrates and fluorine-free coatings applied to such substrates were investigated by nanoindentation experiments using a Nano Indenter G200 instrument from KLA equipped with a DCMII head and a diamond tip with Berkovich geometry. In a first step, cross sections of the samples were prepared by cryosectioning at -80 °C using a Leica EMUC 7 microtome and a DiATOME diamond knife. The microstructure and morphology of the obtained cross sections were then examined by atomic force microscopy under ambient conditions using a DimensionICON instrument from Bruker in order to locate the outer coating and the underlying bulk HDPE material. Topographic height and phase contrast images were collected with a 160AC-NA cantilever in tapping mode over a surface area of ​​2 μm × 2 μm. Subsequently, the mechanical properties of the bulk HDPE substrates were determined by nanoindentation in quasi-static mode at a maximum load of 1 mN. In the second step, the surface of the intact coated sample is nanoindented using the continuous stiffness mode (CSM, see L. Xiaodong et al., Materials Characterization, Vol. 48, No. 1, 02 / 2022, pp. 11-36) with a maximum displacement of 500 nm into the surface. This method provides values ​​for the elastic modulus and hardness as a function of depth (i.e., the distance from the coated surface into the bulk material).

[0310] Example 1: Plasma treatment of HDPE sheet at atmospheric pressure

[0311] Prior to plasma-assisted coating, all HDPE substrates were cleaned by rinsing with isopropanol and subsequently blow-dried. For each selected chemical precursor and set of process parameters, at least two HDPE plates were independently coated by plasma-enhanced chemical vapor deposition according to Reference Example 1. The precursors were provided in pure liquid form or as solutions in organic solvents. The selected precursors and their respective coating conditions are summarized in Table 3. The following process parameters were the same for all samples listed in Table 3:

[0312]

[0313] In all cases, the HDPE plates were pretreated as described in Reference Example 1 by coating with acetylene plasma.

[0314] For comparison, the HDPE substrate was analyzed in the same manner as in Reference Example 1 without coating (Comp1) and after coating by plasma enhanced chemical vapor deposition using tetramethylsilane (Comp2) as precursor compound.

[0315] For further comparison, commercially available HDPE containers were purchased and analyzed exactly like the samples prepared by plasma-assisted deposition as described above. The following types of containers were included in the analysis (all 5 l cans, manufactured according to state-of-the-art methods established in the packaging industry and characterized on their respective inner surfaces): (i) HDPE coated by plasma treatment with the fluorine-containing precursor Freon R-134a (referred to as "Plasma-F", Comp3, having a fluorine-rich layer on its inner surface with a thickness of 50-60 nm, as determined by TEM analysis on cross-sections), (ii) HDPE coated with F2 gas (referred to as "Direct-F", Comp4, having a fluorine-rich layer on its inner surface with a thickness of about 200 nm, as determined by TEM analysis on cross-sections), and (iii) HDPE coextruded with polyamide-6 (referred to as "PE / PA Coex", Comp5, having a polyamide-rich layer on its inner surface with a thickness of 50-60 μm, as determined by AFM analysis on cross-sections).

[0316] Table 3

[0317] Plasma process conditions for preparing fluorine-free coatings (Samples 1-10) on HDPE according to the present invention at atmospheric pressure (Reference Example 1), with uncoated HDPE (Comp 1) and silane-based coatings (Comp 2) as comparative samples (n / a: not applicable).

[0318]

[0319]

[0320] Example 2: Plasma treatment of HDPE bottles at low pressure

[0321] For plasma-assisted coating of HDPE substrates with fluorine-free precursors at low pressure, a complete bottle made of HDPE with a nominal volume of 1 liter was used. According to Reference Example 2, the inner surface of the bottle was treated in successive steps using a low-pressure plasma generated by electromagnetic waves provided by a microwave generator. In the final coating step, 1-octyne or 1-pentyne was applied as a gaseous precursor, as given in Table 4. For comparison, a 1 liter HDPE bottle of the same type without any coating or plasma treatment was included as a reference for further analysis.

[0322] Table 4

[0323] Conditions for preparing fluorine-free coatings (Samples 1-10) on the inner surface of HDPE bottles according to the present invention under low pressure (Reference Example 2), wherein an uncoated HDPE bottle (Comp 6) served as a comparative sample (n / a: not applicable).

[0324]

[0325] Example 3: Surface coverage of HDPE substrate after plasma assisted coating

[0326] The surface coverage of the samples prepared as described in Example 1 was analyzed by XPS according to Reference Example 4. The results are listed in Table 5. For Sample 1 and Comp 5, the surface coverage could not be determined by XPS, as explained in Reference Example 4.

[0327] Table 5

[0328] Surface coverage (average) determined by XPS analysis according to Reference Example 4 for HDPE substrates before and after plasma-assisted coating at atmospheric pressure (np: not determinable by XPS; n / a: not applicable).

[0329] Sample No. Surface coverage in % Comp1 not applicable Comp2 15.4 Comp3 72.4 Comp4 76.8 Comp5 np 1 np 2 76.4 3 22.2 4 79.5 5 31.5 6 17.1 7 45.7 8 91.2 9 27.5 10 28.5

[0330] The data show that the nominal surface coverage of the samples prepared according to the invention varies in a wide range (17% - 92%), depending on the type of precursor used, even if the selected process conditions for the plasma assisted deposition are similar. Furthermore, relatively high surface coverages (72% - 77%) are obtained for the fluorinated reference materials (i.e. Comp3, Comp4). However, several fluorine-free coatings of the invention can be comparable to these reference materials (as well as the PE / PA-COEX material, Comp5) in terms of barrier properties measured against toluene vapor, as described in Example 5, despite their low thickness. This shows that a certain minimum coverage is required for strong barrier properties, but the specific threshold depends on the type of precursor used.

[0331] XPS analysis of samples prepared by plasma-assisted coating with the reaction products of 1-octyne (Sample 11) and 1-pentyne (Sample 12) at low pressure (as described in Example 2) gave a surface composition very similar to that of the octyne-based coating (Sample 1) formed by plasma-assisted deposition at atmospheric pressure. The C-1s spectrum can be fitted by the same model and shows that the major part of the carbon signal (about 75%) comes from the CH2 chemical group at 284.8 eV.

[0332] Example 4: ToF-SIMS characterization of polyamide obtained by plasma assisted coating compared to conventional polyamide-6

[0333] The coating obtained by plasma-assisted deposition of ε-caprolactam (Sample 4, hereinafter referred to as "plasma-polyamide") at atmospheric pressure as described in Example 1 was analyzed in comparison with a bulk polyamide-6 sample (wherein the PA-6 was made by classical polycondensation) (Comp5). The analysis was performed by ToF-SIMS according to Reference Example 5. The results are shown in Table 6, while the corresponding ToF-SIMS spectra (cation detection mode) in the range of 5-300 amu are shown in Figure 2 middle.

[0334] Table 6

[0335] Nominal masses of selected peaks of plasma-polyamide compared to conventional polyamide-6 were detected by ToF-SIMS.

[0336] Plasma-polyamide (Sample 4) Polyamide-6 (Comp5) 30(H2N+=CH2) 30(H2N+=CH2) 56(H2N+=CH-CH=CH2) 56(H2N+=CH-CH=CH2) 112(MH)+ 114(M+H+) 207(2M-H-H2O)+ 209(2M+H-H2O)+ 225(2M-2H)+ 227(2M+H)+ 318(3M-3H-H2O)+ 322(3M+H-H2O)+ 336(3M-3H)+ 340(3M+H)+ 449(4M-4H)+ 453(4M+H)+

[0337] The data in Table 6 show that for polyamide-6 produced by conventional polycondensation, monomer +H + ions, while for the coating obtained by plasma-assisted deposition of the reaction product of ε-caprolactam, the fragment appears with a nominal mass of 112. This indicates the formation of the polyamide material by hydrogen abstraction and subsequent free radical polymerization. The same pattern is found for all other characteristic fragments, and the deviations between plasma-polyamide and conventional PA-6 become more significant with higher masses, due to the difference of one nominal mass unit per monomer in the two types of polymers.

[0338] Example 5: Wetting behavior of HDPE substrate after plasma assisted coating

[0339] The effect of coating a HDPE substrate (prepared as described in Example 1) with the reaction products of different precursors by plasma-assisted deposition at atmospheric pressure on the wetting behavior was evaluated by static contact angle measurements using water, formamide and diiodomethane as test liquids. For comparison, several commercially available HDPE containers with different barrier technologies (Comp3, Comp4, Comp5) as well as an uncoated HDPE material (Comp1) were also analyzed.

[0340] The results are Figure 3 The values ​​are shown as bar graphs in FIG. 7 and listed in Table 7 as average values ​​(AVG) and corresponding standard deviations (SdDev).

[0341] Table 7

[0342] Static contact angles (mean values ​​and corresponding standard deviations) of water, formamide and diiodomethane on HDPE determined according to Reference Example 3 after plasma-assisted deposition of different precursors at atmospheric pressure according to the invention (Sample) and selected comparative samples (CompX).

[0343]

[0344] It was observed that the plasma-assisted deposition of the reaction products of the fluorine-free polar compounds at atmospheric pressure on the HDPE substrate according to the invention (Samples 2-10) resulted in an increase in wettability (reduced contact angle after coating) for all three test liquids used. The static contact angles measured relative to water ranged from 10 to 66°, compared to 97.1° for the uncoated HDPE and 85-108° for Comp2-Comp5. This indicates that the coating with the polar (i.e. more hydrophilic) fluorine-free precursor was successful. Similar trends of increased wettability were also observed for the non-polar test liquids diiodomethane (15-42° for Samples 2-10 compared to >45° for all comparative samples) and for the medium-polar formamide (8-36° for Samples 2-9 and 50.2° for Sample 10, except Comp4, due to the non-polar co-reactant, compared to 70-80° for Comp1, Comp2, Comp3 and Comp5). The only different inventive example is Sample 1, i.e. the coating obtained by plasma-assisted deposition of the reaction product of 1-octyne. However, this is reasonable since alkynes are non-polar compounds in contrast to lactams, lactones and vinyl acetate. In fact, the wetting behavior observed for sample 1 is quite similar to that of uncoated HDPE, which is expected given the chemical similarity of the reaction products of polyethylene and 1-octyne.

[0345] Based on the measured static contact angles of water, formamide and diiodomethane, the surface free energies of the uncoated and coated HDPE as well as their polar and dispersive components were calculated according to Reference Example 3, giving the values ​​listed in Table 8 and in Figure 3 Displayed in a bar graph.

[0346] Table 8

[0347] Surface free energy (with dispersive and polar components) determined from static contact angles measured on HDPE for water, formamide and diiodomethane according to Reference Example 3 after plasma-assisted deposition of different precursors at atmospheric pressure according to the invention (Sample) and selected comparative samples (CompX).

[0348]

[0349] Consistent with the single static contact angle, the calculated surface free energies indicate that plasma-assisted deposition of the reaction products of the fluorine-free polar compounds on HDPE substrates results in a significant increase in surface energy (48-73 mN / m for samples 2-10 compared to <35 mN / m for Comp1-Comp5), which is primarily due to an increase in the polar component of the surface energy (10-35 mN / m for samples 2-10 compared to <5 mN for Comp1-Comp5). Again, the coating formed from the reaction product of 1-octyne (Sample 1) is a reasonable exception, with a surface energy profile very similar to that of the uncoated HDPE (Comp1).

[0350] Example 6: Barrier properties of HDPE substrate after plasma assisted coating

[0351] The effect of coating HDPE substrates with reaction products of different fluorine-free precursors by plasma-assisted deposition at atmospheric pressure (i.e., samples of Example 1) and at low pressure (i.e., samples of Example 2) on the barrier properties against toluene vapor was evaluated by reversed-phase gas chromatography as described in Reference Example 6. For comparison, the corresponding uncoated HDPE substrates (Comp1 for atmospheric pressure and Comp6 for low pressure), HDPE coated with silane precursors by plasma-assisted deposition at atmospheric pressure (Comp2) and commercial HDPE containers with different barrier technologies (Comp3, Comp4, Comp5) were also analyzed.

[0352] The values ​​obtained for the three physical parameters characterizing the barrier properties (as described in Reference Example 6) of the selected coatings according to the invention (Sample) and different comparative samples (CompX) are listed in Table 9. The corresponding bar graphs of the three parameters are shown in Figure 5 , 6 and 7.

[0353] Table 9

[0354] The monolayer binding capacity (q) of toluene vapor interaction with uncoated and coated HDPE was determined by reverse phase gas chromatography according to Reference Example 6. BET ), BET constant (C BET ) and characteristic retention time (t R，结束 ). The relative pressure range used to evaluate the adsorption isotherm according to the BET theory is 0.01≤p / p0≤0.05.

[0355]

[0356]

[0357] The data collected show that the monolayer capacity for toluene binding is reduced to a similar extent by coating with the fluorine-free compound according to the invention at atmospheric pressure (Samples 1-10) relative to untreated HDPE (e.g. (for the ε-caprolactam based coating q BET =0.53 μmol / cm 2 , sample 4) and for a comparative coating made of a fluorine-containing compound such as Freon R-134a (q BET =0.47 μmol / cm 2 , Comp3) or F2 gas (q BET =0.50 μmol / cm 2 , Comp4) and HDPE packaging materials with PA-based barrier technology (q BET =0.50 μmol / cm 2 , Comp5). Compared with the uncoated substrate (Comp1) (which has 2.02 μmol / cm 2 Q BET By coating with the fluorine-free compound according to the invention, the monolayer capacity is improved (i.e. further reduced) by at least 30%, preferably at least 50%, compared to the C value of the coating made of the fluorine-free compound according to the invention at atmospheric pressure. BET The values ​​are compared with comparative coatings made from fluorine-containing compounds (such as Freon R-134a or F2 gas) (which have a C in the range of 70 to 90 BET Value) and HDPE packaging materials with PA-based barrier technology (C BET =80) BET The values ​​are in the same range. Again, these values ​​are significantly lower than those observed for the corresponding uncoated HDPE (220) or substrates treated with TMS at atmospheric pressure (495), with the exception of samples 5 and 8. Similar trends and conclusions can also be inferred from the characteristic retention times, which are significantly shorter for coatings made from fluorine-free compounds according to the invention at atmospheric pressure (except samples 5 and 8 with γ-butyrolactone and PVP as precursors, respectively) as well as fluorine-containing and PA-based barrier layers compared to uncoated and TMS-treated HDPE.

[0358] The coatings obtained with the fluorine-free compound according to the invention at low pressure (Samples 11 and 12) provide essentially the same beneficial effects when compared to the corresponding uncoated HDPE bottle (Comp 6): the monolayer capacity of toluene binding increased from 1.45 μmol / cm 2 Reduced to 0.53 μmol / cm 2 and 0.52 μmol / cm 2 (this corresponds to an improvement of about 63%), while for C BETSimilar strong decreases are observed for the values ​​of α and the characteristic retention times. This indicates that comparable levels of barrier properties can be achieved according to the present invention by plasma-assisted deposition of reaction products of different fluorine-free compounds at both atmospheric and low pressures.

[0359] Example 7: Thickness of coatings obtained by plasma assisted deposition on HDPE

[0360] The thickness of the coatings formed by plasma-assisted deposition of reaction products of different fluorine-free compounds (i.e., selected samples of Example 1) on HDPE substrates at atmospheric pressure was evaluated by TEM analysis as described in Reference Example 7. Representative TEM images of cross sections prepared from HDPE substrates coated with 1-octyne, ε-caprolactam, vinyl acetate, and δ-valerolactone are shown in Figure 8 These images demonstrate that a closed and dense layer of the reaction product of the fluorine-free compound is formed with all selected precursors, resulting in coatings with a thickness in the range of 20 to 500 nm, preferably in the range of 50 to 350 nm, more preferably in the range of 50 to 200 nm.

[0361] Example 8: Roughness of coatings obtained by plasma assisted deposition on HDPE

[0362] The roughness of the coatings formed by plasma-assisted deposition of reaction products of different fluorine-free compounds (i.e., selected samples of Example 1) on HDPE substrates at atmospheric pressure was measured by AFM according to Reference Example 8. The obtained arithmetic mean roughness (Ra) and root mean square (RMS) roughness (Rq) values ​​are listed in Table 10, and the corresponding topographic images are shown in Fig. 9 For comparison, the roughness values ​​of selected comparative samples are also included in Table 10.

[0363] Table 10

[0364] The arithmetic mean roughness (Ra) and root mean square (RMS) roughness (Rq) values ​​of the surfaces of the present invention and comparative samples (obtained by plasma assisted deposition under atmospheric conditions) were measured by atomic force microscopy as described in Reference Example 8.

[0365]

[0366]

[0367] Fig. 9The AFM images in show that plasma assisted deposition results in the formation of a closed nanostructured coating consisting of multiple particle domains with individual sizes in the typical range of 50-150 nm. This structure results in Ra values ​​ranging from 17 to 73 nm and Rq values ​​ranging from 24 to 125 nm, which are significantly higher than the uncoated HDPE reference (Comp1). The comparative samples with surface coating (Comp2-Comp5) show slightly lower roughness, with Ra values ​​ranging from 20 to 57 nm and Rq values ​​ranging from 25 to 72 nm.

[0368] Example 9: Mechanical properties of coatings obtained by plasma assisted deposition on HDPE

[0369] The elastic modulus and hardness of the coating formed by plasma-assisted deposition of the reaction product of 1-octyne (i.e., Sample 1 of Example 1) on a pretreated HDPE substrate at atmospheric pressure were measured by nanoindentation according to Reference Example 9. For comparison, an HDPE substrate coated with only the reaction product of acetylene on its surface (i.e., the "pretreated substrate" described in Reference Example 1) was studied in the same manner. AFM images obtained from the cross-sections of the two samples are shown in Fig.10 , where the surface coating and bulk HDPE material are clearly visible on the left and right sides respectively. Nanoindentation measurements on the bulk material in the cross section gave typical values ​​for elastic modulus and hardness of (1.18 ± 0.08) GPa and (0.036 ± 0.002) GPa, respectively, as expected for HDPE – for expected data refer to SK Sahu et al., Materials Chemistry and Physics, Vol. 203, 1 January 2018, pp. 173-184. Fig.11 and Fig.12Depth dependence curves of elastic modulus and hardness determined by nanoindentation measurements in CSM mode for Sample 1 and the pretreated substrate in its intact state are shown, respectively, as described in Reference Example 9. The collected data reveal that neither the elastic modulus nor the hardness at the coated surface changes significantly (within the given experimental error limits) compared to the HDPE bulk material. This demonstrates that the coating obtained according to the invention is soft and elastic and therefore fundamentally different from other carbon-containing coatings described in the literature, in particular films of “diamond-like carbon” (DLC), which exhibit much higher elastic moduli (50-250 GPa) and hardnesses (10-40 GPa) in nanoindentation measurements (see Q. Wei et al., Composites Part B: Engineering, Vol. 30, No. 7, October 1999, pp. 675-684 or N. Savvides et al. Thin Solid Films, Vol. 228, No. 1-2, May 15, 1993, pp. 289-292). BRIEF DESCRIPTION OF THE DRAWINGS

[0370] Figure 1 : Shows the experimental setup for iGC measurements of the barrier effect on toluene vapor.

[0371] (a) Bottom view of the upper plate of the sample cell, with holes for gas inlet and outlet on both ends of a linear recess serving as a chromatographic path.

[0372] (b) Bottom view of the upper plate of the cell after installation of the sample strips.

[0373] (c) Top view of the assembled sample cell with PEEK capillaries installed on the inlet and outlet ports for connection to the GC instrument.

[0374] Figure 2 : Tof-SIMS spectra of plasma-polyamide (Sample 4) and conventional polyamide-6 reference (Comp 5) (cationic detection mode) in the range of 0-500 atomic mass units (amu) are shown.

[0375] Figure 3 Shown is a bar graph comparing the mean values ​​(with the corresponding standard deviations) of the static contact angles of water, formamide and diiodomethane measured on uncoated and coated HDPE according to Reference Example 3 (for individual values ​​see Table 7).

[0376] Figure 4Shown is a bar graph comparing the surface free energy values ​​obtained according to Reference Example 3 for the static contact angles of water, formamide and diiodomethane on uncoated and coated HDPE with their polar and dispersion contributions (see Table 8 for individual values).

[0377] Figure 5 A comparison of the monolayer capacity (q) available for adsorption of toluene on uncoated and coated HDPE as obtained by reverse phase gas chromatography according to Reference Example 6 is shown. BET ) values. BET The values ​​were obtained by evaluation in the relative pressure range 0.01≤p / p0≤0.05 (for the individual values ​​see Table 9).

[0378] Figure 6 The BET constant (C BET ) values, i.e., a bar graph of the affinity for adsorption of toluene on uncoated and coated HDPE. BET The values ​​were obtained by evaluation in the relative pressure range 0.01≤p / p0≤0.05 (for the individual values ​​see Table 9).

[0379] Figure 7 The characteristic retention times (t) of the interaction of toluene vapor with uncoated and coated HDPE determined by reverse phase gas chromatography according to Reference Example 6 are shown. R，结束 ) values ​​(see Table 9 for individual values).

[0380] Figure 8 TEM images of cross sections prepared from HDPE substrates after plasma-assisted coating at atmospheric pressure with reaction products of selected fluorine-free compounds are shown: 1-octyne (sample 1), ε-caprolactam (sample 4), vinyl acetate (sample 9) and δ-valerolactone (sample 7). These samples were coated with a layer of platinum (for comparison reasons) and embedded in resin before sectioning. The outer layer deposited by the plasma process is clearly visible in all cases and can be used to quantify the thickness of the coating.

[0381] Fig. 9 AFM height images of the surface of a HDPE substrate after plasma-assisted coating at atmospheric pressure with the reaction products of selected fluorine-free compounds are shown: 1-octyne (sample 1), ε-caprolactam (sample 4), vinyl acetate (sample 9) and δ-valerolactone (sample 7). For comparison, an image of the HDPE substrate before plasma-assisted deposition is also shown (Comp 1). From the topographic information contained in the images, Ra and Rq values ​​(reported in Table 10) were derived as a measure of the surface.

[0382] Fig.10 AFM phase contrast images of cross sections prepared by plasma-assisted coating of HDPE substrates (all at atmospheric pressure) with acetylene (pretreated substrate defined in Reference Example 1) or the reaction product of acetylene and 1-octyne (Sample 1) in sequence. Arrows indicate coatings present on the original surface of the material.

[0383] Fig.11 Shown are the depth dependence curves of the elastic modulus determined by nanoindentation measurements in CSM mode according to Reference Example 9 for sample 1 (coating with a reaction product of 1-octyne obtained by plasma-assisted deposition at atmospheric pressure, black squares) and the corresponding pretreated substrate without 1-octyne coating (grey circles). The symbols represent the average of eight independent determinations and their corresponding standard deviations.

[0384] Fig.12 Shown are the depth dependence curves of the hardness determined by nanoindentation measurements in CSM mode according to Reference Example 9 for sample 1 (coating with a reaction product of 1-octyne obtained by plasma-assisted deposition at atmospheric pressure, black squares) and the corresponding pretreated substrate without 1-octyne coating (grey circles). The symbols represent the average of eight independent determinations and their corresponding standard deviations.

[0385] References

[0386] - WO 2007 / 072120 A1

[0387] -US2022 / 0112595 A1

[0388] - Chapter "Surface Properties Characterization by Inverse Gas Chromatography (IGC) Applications", Eric Brendlé, Eugène Papirer, book "Powders and Fibers", 1st edition, 2006, CRC Press, page 76

[0389] -S. Brunauer, PH Emmett, E. Teller, Journal of the American Chemical Society, Vol. 60, No. 2, 1938, pp. 309-319

[0390] - WO 2006 / 081637 A1

[0391] - Vangeneugden et al., “Atmospheric DBD plasma processes for production of lightweight composites”, presented at the 21st International Conference on Plasma Chemistry (https: / / www.ispc-conference.org / ispcproc / ispc21 / ID287.pdf)

[0392] -US2022 / 112595 A1

[0393] -L. Xiaodong et al., Materials Characterization, Vol. 48, No. 1, February 2022, pp. 11-36

[0394] -Q. Wei et al., Composites Part B: Engineering, Vol. 30, No. 7, October 1999, pp. 675-684

[0395] - N. Savvides et al., Thin Solid Films, Vol. 228, No. 1-2, May 15, 1993, pp. 289-292

[0396] -SK Sahu et al., Materials Chemistry and Physics, Vol. 203, 1 January 2018, pp. 173-184

Claims

1. A coated polyolefin substrate, wherein the coating is obtained or obtainable by depositing on the surface of the polyolefin substrate by a plasma assisted deposition process a reaction product of a fluorine-free compound selected from the group consisting of: lactams having 4 to 8 ring atoms, lactones having 4 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone, C5 to C8 alkynes and mixtures of two or more of these compounds, in The lactam having 4 to 8 ring atoms has the formula (I) in n is an integer in the range of 2 to 5; The lactone having 4 to 8 ring atoms has the formula (II) in R 2 It is methyl. y is 0 or 1, and m is an integer in the range of 1 to 5; The vinyl acetate has the formula (III) The polyvinyl pyrrolidone has a weight average molecular weight of ≥222 g / mol; and The C5 to C8 alkyne is a linear or branched C5 to C8 alkyne.

2. The coated polyolefin substrate according to claim 1, wherein in the lactam of formula (I) having 4 to 8 ring atoms, n is an integer in the range of 2 to 4, preferably n is 4.

3. The coated polyolefin substrate of claim 1, wherein the lactone of formula (II) has 6 to 8 ring atoms and / or m is an integer in the range of 3 to 4 and / or wherein the lactone is selected from the group consisting of δ-valerolactone, γ-valerolactone, ε-caprolactone and a mixture of two or more of these lactones, preferably the lactone comprises at least γ-valerolactone, more preferably γ-valerolactone.

4. The coated polyolefin substrate of claim 1, wherein the polyvinyl pyrrolidone has a weight average molecular weight in the range of 2,500 to 2,500,000 g / mol, preferably in the range of 6,000 to 40,000 g / mol.

5. The coated polyolefin substrate of claim 1, wherein the C5 to C8 alkyne is a linear C5 to C8 alkyne, preferably having formula (V) wherein r is an integer in the range of 2 to 5, preferably r is 5.

6. The coated polyolefin substrate of any one of claims 1 to 5, wherein the polyolefin of the substrate is polyethylene (PE) or polypropylene (PP).

7. The coated polyolefin substrate according to any one of claims 1 to 6, wherein at least 80 wt.-%, preferably at least 90 wt.-%, more preferably at least 95 wt.-% of the compounds used to deposit the coating, based on the total weight of all compounds used to deposit the coating, are compounds according to one of the groups of claims 1 to 5.

8. The coated polyolefin substrate according to any one of claims 1 to 7, wherein the additional compound for depositing the coating on the surface of the substrate by a plasma assisted deposition process is selected from the group consisting of C2 to C4 olefins, C2 to C4 alkynes and mixtures thereof, more preferably selected from the group consisting of C3 to C4 olefins, C2 to C4 alkynes and mixtures thereof, preferably the compound for depositing the coating on the surface of the substrate by a plasma assisted deposition process comprises at least vinyl acetate and the additional compound is acetylene, more preferably the compound for depositing the coating on the surface of the substrate by a plasma assisted deposition process is vinyl acetate and the additional compound is acetylene.

9. A coated polyolefin substrate as claimed in claims 1 to 8, wherein in the range of 50 to 90 wt.-%, preferably in the range of 80 to 90 wt.-%, of the compounds used for depositing the coating are compounds according to one of the groups of claims 1 to 5, and in the range of 10 to 50 wt.-%, preferably in the range of 10 to 20 wt.-%, of further compounds according to claim 8, based on the total weight of all compounds used for depositing the coating.

10. The coated polyolefin substrate of any one of claims 1 to 9, wherein the monolayer binding capacity (q BET ) between 0.3 and 1.3 μmol / cm 2 In the range of 0.4 to 1.2 μmol / cm 2 In the range of 0.5 to 1.1 μmol / cm 2 In the range of , measured by inverse gas chromatography (iGC) of toluene vapor according to Reference Example 5, and / or the BET constant (C BET ) is in the range of 50 to 300, preferably in the range of 50 to 200, more preferably in the range of 70 to 175, as determined by inverse gas chromatography (iGC) of toluene vapor according to Reference Example 5.

11. The coated polyolefin substrate according to any one of claims 1 to 10, wherein a layer comprising a reaction product of acetylene is present between the surface of the substrate and the coating comprising the reaction product of the fluorine-free compound, wherein the layer comprising a reaction product of acetylene is preferably obtained or obtainable by plasma-assisted deposition of acetylene.

12. A plasma assisted deposition method for applying a coating to a surface of a polyolefin substrate, the method comprising: (a) providing a polyolefin substrate having a surface; (b) generating plasma by passing a carrier gas through an excitation region under plasma generating conditions and by applying a high frequency alternating current to an electrode positioned in the excitation region to generate a dielectric barrier discharge to generate plasma; (c) generating an aerosol comprising a fluorine-free compound as defined in any one of claims 1 to 5 by using a nebulizer gas; (d) treating at least a portion of the surface of the polyolefin substrate provided according to (a) with the plasma generated according to (b) and the aerosol containing the fluorine-free compound generated according to (c), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the polyolefin substrate surface, thereby obtaining a coated polyolefin substrate, wherein the plasma is preferably generated in (a) at a pressure in the range of 0.5 to 1.5 bar, preferably in the range of 0.8 to 1.2 bar (atmospheric pressure or near atmospheric pressure conditions, indirect atmospheric pressure plasma processing), and wherein the plasma according to (a) is generated at a pressure of less than 40 kW / m 2 of power produced per electrode area.

13. A plasma assisted deposition method for applying a coating to a surface of a polyolefin substrate, the method comprising: (a) providing a polyolefin substrate having a surface; (b') generating an aerosol comprising a fluorine-free compound as defined in any one of claims 1 to 5, preferably by using a nebulizer gas; (c') converting the precursor aerosol produced in (b') into a plasma state by a combination of excitations including primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of discharge of an alternating voltage having a frequency between 1 and 15 MHz, thereby producing plasma; (d') treating at least a portion of the surface of the polyolefin substrate provided according to (a) with the plasma generated according to (c'), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the surface of the polyolefin substrate, thereby obtaining a coated polyolefin substrate; The plasma is generated at a pressure of <0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, preferably in the range of 0.001 to 0.05 mbar (low-pressure plasma), wherein the power density of the electromagnetic waves is between 0.01 and 1 W / cm 3 within the range.

14. A plasma assisted deposition method for applying a coating to a surface of a polyolefin substrate, wherein the plasma assisted deposition method comprises (a) providing a polyolefin substrate having a surface; (b") providing an atmosphere comprising a fluorine-free compound as defined in any one of claims 1 to 5 in gaseous form or in aerosol form, optionally under applied heating; (c") generating plasma from the atmosphere containing the fluorine-free compound according to (b") under plasma generating conditions by a combination of excitations including primary excitation by means of microwave-type electromagnetic waves and secondary excitation by means of discharge of an alternating voltage having a frequency between 1 and 15 MHz, thereby generating plasma; (d") treating at least a portion of the surface of the polyolefin substrate provided according to (a) with the plasma generated according to (c"), thereby depositing the reaction product of the fluorine-free compound on the treated portion of the surface of the polyolefin substrate, thereby obtaining a coated polyolefin substrate; The plasma is generated at a pressure of <0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, preferably in the range of 0.001 to 0.05 mbar (low-pressure plasma), wherein the power density of the electromagnetic waves is between 0.01 and 1 W / cm 3 within the range.

15. Use of the coated polyolefin substrate according to any one of claims 1 to 11 or the coated polyolefin substrate obtained or obtainable by the plasma assisted deposition method according to any one of claims 12 to 14 for packaging, storing and / or transporting articles selected from the group consisting of food, beverages and chemicals, wherein the articles are preferably chemicals, wherein the chemicals are preferably hazardous substances (transported as dangerous goods) or agrochemicals, more preferably agrochemicals.

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