Plasma-produced barrier for packaging

Abstract

In a first aspect, the present invention relates to a coated substrate, wherein the coating is obtained or can be obtained by depositing on the surface of the substrate by plasma-assisted vapor deposition 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-C8 alkynes, and mixtures of two or more of these compounds. A second aspect of the present invention relates to a plasma-assisted vapor deposition method for applying a coating based on a reaction product of a fluorine-free compound to the surface of a substrate. A third aspect of the present invention is the use of a coated substrate according to the first aspect, or a coated substrate obtained or obtainable from the plasma-assisted vapor 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, and the chemical is preferably a hazardous substance (transported as a dangerous good) or a pesticide, more preferably a pesticide.

Description

Technical Field

[0001] In a first aspect, the present invention relates to a coated substrate, wherein the coating is obtained or can be obtained by depositing 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-C8 alkynes, and mixtures of two or more of these compounds on the surface of the substrate by plasma-assisted vapor deposition.

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

[0003] A third aspect of the present invention is the use of a coated substrate according to the first aspect, or a coated substrate obtained or obtainable from the plasma-assisted vapor 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 a pesticide.

Background Art

[0004] The latest containers for packaging plant protection products (PPPs), so-called pesticides, are usually designed so that the walls of the container do not permit the penetration of pesticides, solvents, and / or other formulation components during transport, storage, and application. This requires incorporating barrier technology into commonly used packaging materials such as polyethylene (PE). The main industrial processes established to achieve this are: (i) compounding or co-extruding PE with a relatively low-permeability polymer such as polyamide (PA) or ethylene vinyl alcohol (EVOH) copolymer, for example in the form of a thick (several μm) surface layer or an interfacial layer, or (ii) coating the inner surface of the container with a thin (usually less than 1 μm) layer of (per)fluorinated compound. The latter (per)fluorocoating is classically obtained by gaseous fluorination or, more recently, can also be achieved by plasma-assisted vapor deposition of gaseous fluorochemicals (so-called "plasma-enhanced chemical vapor deposition", PECVD). This plasma-based technology, published by Isytech at low pressure (WO 2007 / 072120 A1 pamphlet), has been proven to yield coatings with relatively low costs (in-line process) and excellent properties (high barrier effect, little mechanical deformation of the container during coating, ease of recycling).

[0005] However, both methods, namely compounding or co-extruding with PA or EVOH and coating with the reaction product of (per)fluorinated compounds, have the following major drawbacks:

[0006] On the one hand, (per)fluorinated compound-based coatings may be subject to future regulations regarding the use of perfluoroalkyl substances (PFAS) in the United States and the 27 European countries, and thus may need to be replaced with alternative technologies. On the other hand, existing fluorine-free technologies for achieving sufficient barrier properties often require laborious and costly processes such as coextrusion in which PA or EVOH is coextruded with a base material such as PE. Furthermore, the thickness of the PA or EVOH domains required for a sufficient barrier against the permeation of solvents and chemicals makes the container multi-material, which poses problems from the perspective of recycling and the circular economy. As a result, in order to recycle both of the latest barrier technologies, a large-scale pretreatment process is required to separate the main container material (e.g., PE) from the barrier components (e.g., large amounts of PA or EVOH, or substances of very high concern (SVHC) such as trace amounts of perfluoroalkyl species (PFAS)).

Summary of the Invention

Problems to be Solved by the Invention

[0007] Therefore, the underlying problem of the present invention was to provide a coating (and corresponding coating process) for packaging materials used as containers for chemicals, particularly pesticides, that satisfies the following requirements: (i) a fluorine-free component to address regulatory concerns, (ii) a coating thickness much smaller than that of existing PA or EVOH barrier technologies to facilitate recycling, and (iii) barrier performance at least comparable to that of existing fluorine-containing coatings and PA or EVOH coextruded multi-materials for functional competitiveness.

Means for Solving the Problems

[0008] First Aspect - Coating Substrate This problem is solved by a coated substrate, wherein the coating is obtained or can be obtained by depositing 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-C8 alkynes, and mixtures of two or more of these compounds on the surface of the substrate by plasma-assisted vapor deposition.

[0009] Surprisingly, coatings based on the compounds identified above enable a significant improvement in barrier properties, as demonstrated by a substantial reduction in the interaction between toluene vapor and the coated container walls, even when the coating is only a few tens of nanometers thick. Toluene is considered, for example, a representative solvent for testing the barrier properties of coatings against the permeation of harmful compounds present in pesticide formulations. The interaction between toluene vapor and coated and uncoated HDPE substrates was investigated by inverse gas chromatography and evaluated within the framework of the Brunauer-Emmett-Teller (BET) theory, thereby obtaining the monolayer capacity of toluene binding (q BET , expressed as the molar amount of adsorbed toluene molecules per unit of investigated surface area (μmol / cm 2 ), and the corresponding dimensionless BET constant (C BET ) as a measure of the strength of the interaction. A high barrier property against toluene vapor is reflected in low values of q BET and / or C BET . The q BET of the coatings obtained by plasma-assisted vapor deposition of the fluorine-free compounds according to the invention was found to be in the same range as the q BET values of comparative coatings made from fluorine-containing compounds by plasma vapor deposition or gas-phase fluorination, and HDPE / PA coextrudates. Compared to the uncoated HDPE substrate, q BET is improved by at least 20% by the coating using the fluorine-free compound according to the invention. The C BET of the fluorine-free compound according to the inventionis in the same range as the C value of the comparative coating made from the fluorine-containing compound and the HDPE / PA co-extrudate. BET It is in the same range.

[0010] Coatings using the reaction product of non-fluorine-containing components can apply the coating much more easily than the existing (HD)PE / PA co-extrusion technology because they use plasma-based technology, and thus it is much cheaper to produce these coatings. The use of non-fluorine-containing components can avoid the generation of (per)fluorinated substances and their subsequent potential release. Since the amount of the coating material applied as described above is small, the layer thickness required for a sufficient barrier against toluene is only a few tens of nanometers, and the coating substrate is still qualified as a single material and can thus be recycled with much less effort.

Brief Description of the Drawings

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Mode for Carrying Out the Invention

[0012] In some preferred embodiments of the coated substrate, the compound used to deposit the coating on the surface of the substrate by plasma-assisted vapor deposition is selected from the group consisting of lactams having 4 to 8 ring atoms excluding vinylpyrrolidone, lactones having 4 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone, C5-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 plasma-assisted vapor deposition is selected from the group consisting of lactams having 4 to 8 ring atoms excluding vinylpyrrolidone, lactones having 4 to 8 ring atoms, vinyl acetate, C5-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 plasma-assisted vapor deposition is selected from the group consisting of lactams having 4 to 8 ring atoms excluding vinylpyrrolidone, 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).

Chemical formula

[0016] R 1 represents a vinyl group, and when the residue R 1 is present, it is located at a nitrogen atom replacing a hydrogen atom in the ring structure, or at a carbon atom in the ring structure containing any one of the C atoms of the group -[CH2] n -. Vinyl pyrrolidone, which is also a lactam, is N-vinyl-2-pyrrolidone, that is, the nitrogen atom of a 5-membered lactam ring (γ-lactam) has a vinyl group as a substituent instead of a hydrogen atom at this position.

[0017] In some preferred embodiments of the coating substrate, the lactone having 4 to 8 ring atoms, preferably 6 to 8 ring atoms, has the formula (II).

Chemical formula

[0018] In some preferred embodiments of the coating substrate, vinyl acetate has the formula (III).

Chemical formula

[0019] In some preferred embodiments of the coating substrate, polyvinylpyrrolidone has a weight average molecular weight of 222 g / mol or more, more preferably in the range of 2,500 to 2,500,000 g / mol, and even more preferably in the range of 6,000 to 40,000 g / mol.

[0020] In some preferred embodiments of the coating substrate, the C5 - C8 alkyne is a straight-chain or branched-chain C5 - C8 alkyne, more preferably a straight-chain C5 - C8 alkyne, and even more preferably has the formula (V).

Chemical formula

[0021] In some preferred embodiments of the coating substrate, based on the total weight of all the compounds used to deposit the coating, at least 80% by weight, more preferably at least 90% by weight, and even more preferably at least 95% by weight of the compounds used to deposit the coating are one of the groups defined above, that is, at least 80% by weight, preferably at least 90% by weight, and more preferably at least 95% by weight of the coating consists of the reaction product of one of the compounds of the groups defined above.

[0022] The coating is made from vinyl acetate, and based on the total weight of the compounds used to deposit the coating, preferably at least 80 wt%, preferably at least 90 wt%, more preferably at least 95 wt% of the compounds used to deposit the coating is vinyl acetate, i.e., in some embodiments, at least 80 wt%, preferably at least 90 wt%, more preferably at least 95 wt% of the coating consists of the reaction product of vinyl acetate. In some embodiments, the reaction product is at least partially hydrolyzed in these embodiments to yield a vinyl alcohol copolymer. The hydrolysis is carried out in some embodiments by exposing the coating containing the reaction product of vinyl acetate to a moist ammonia-containing atmosphere after a subsequent step, i.e., after completion of the steps of the plasma-assisted vapor deposition method, preferably after step (d) described below. For example, based on an aqueous solution having 100 wt%, an NH3 aqueous solution having an ammonia concentration in the range of 0.1 to 50 wt%, preferably in the range of 0.5 to 25 wt% in water, is brought to a temperature of 50 °C (and a pressure of 1013 mbar), and the coating is exposed to the resulting atmosphere.

[0023] Copolymer In some preferred embodiments of the coating substrate, a further compound is used to deposit a coating on the surface of the substrate by a plasma-assisted vapor deposition method, and this further compound is selected from the group consisting of C2-C4 alkenes, C2-C4 alkynes and mixtures thereof, more preferably from the group consisting of C3-C4 alkenes, C2-C4 alkynes and mixtures thereof. Preferably, the compound used to deposit the coating on the surface of the substrate by the plasma-assisted vapor deposition method contains at least vinyl acetate, and the further compound is acetylene. More preferably, the compound used to deposit the coating on the surface of the substrate by the plasma-assisted vapor deposition method is vinyl acetate, and the further compound is acetylene.

[0024] In some preferred embodiments of the coating substrate, 50 to 90% by weight, more preferably 80 to 90% by weight, of the compounds used to deposit the coating is one of the above groups of compounds based on the total weight of all the compounds used to deposit the coating, and 10 to 50% by weight, preferably 10 to 20% by weight, is a further compound as defined above. In some embodiments where a further compound is used, a copolymer is formed from vinyl acetate and one or more further compounds selected from C2-C4 alkenes, C2-C4 alkynes and mixtures thereof. Then, in some embodiments, the copolymer is at least partially hydrolyzed to convert the vinyl acetate-based moiety in the copolymer to vinyl alcohol. In these embodiments where a further compound is used, based on the total weight of all the compounds used to deposit the coating, at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight of the compounds used to deposit the coating is one of the compounds of the above-specified groups and a further compound, preferably vinyl acetate, and one or more further compounds selected from C2-C4 alkenes, C2-C4 alkynes and mixtures thereof, i.e., at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight of the coating consists of the reaction product of one of the compounds of the groups defined above and a further compound, more preferably, more preferably at least 90% by weight, more preferably at least 95% by weight of the coating consists of the reaction product of vinyl acetate and one or more further compounds selected from C2-C4 alkenes, C2-C4 alkynes and mixtures thereof. Hydrolysis is carried out in some embodiments by exposing a coating containing the reaction product of vinyl acetate and one or more further compounds selected from C2-C4 alkenes, C2-C4 alkynes and mixtures thereof to a moist ammonia-containing atmosphere after a subsequent step, i.e., after completion of the steps of the plasma-assisted vapor deposition process, preferably after step (d) described below.For example, based on an aqueous solution having 100% by weight, an aqueous solution of NH3 having an ammonia concentration in the range of 0.1 to 50% by weight, preferably in the range of 0.5 to 25% by weight in water, is brought to a temperature of 50 °C (and a pressure of 1013 mbar) and exposed to the atmosphere in which the coating is obtained.

[0025] State of the precursor In some preferred embodiments of the coating substrate, the fluorine-free compound is used as a precursor in a plasma-assisted vapor deposition process in liquid phase form, which liquid phase is composed of either a single compound in liquid state or a homogeneous solution in a liquid medium, where liquid means a liquid at 25 °C and 1013 mbar. The liquid medium is a polar organic solvent excluding water. In some embodiments, the liquid medium is selected from the group consisting of C1-C5 alkanols and mixtures thereof, preferably at least 95% by weight, more preferably at least 98% by weight, more preferably at least 99% by weight, more preferably at least 99.5% by weight, more preferably at least 99.9% by weight, more preferably at least 99.95% by weight, more preferably at least 99.99% by weight of the liquid medium is a polar organic solvent excluding water and mixtures thereof.

[0026] Fluorine-free In some preferred embodiments of the coating substrate, the coating is substantially free of fluorine, more preferably the coating contains less than 1% by weight, more preferably less than 0.1% by weight of fluorine based on the total weight of the 100% by weight coating.

[0027] Further properties of the coating In some preferred embodiments of the coating substrate, the retention time of toluene vapor, when measured by inverse gas chromatography (iGC) according to Reference Example 5, 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.

[0028] In some preferred embodiments of the coating substrate, the monolayer binding capacity qBET When measured for toluene vapor by inverse gas chromatography (iGC) according to Reference Example 5, it is in the range of 0.3 to 1.3 μmol / cm 2 Preferably in the range of 0.4 to 1.1 μmol / cm 2 More preferably in the range of 0.5 to 0.8 μmol / cm 2 And / or the BET constant C BET When measured for toluene vapor by inverse gas chromatography (iGC) according to Reference Example 5, it 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. q BET Is the monolayer binding capacity, that is, the number of binding sites for toluene on the investigated surface, and is represented by the molar amount of adsorbed toluene molecules per unit surface area in μmol / cm 2 While C BET Indicates the binding strength. A strong barrier against toluene vapor is reflected in the low value of q BET And / or C BET The q of the fluorine-free compound according to the present invention BET Is in the same range as the q BET Of a comparative coating made from a fluorine-containing compound such as Freon R-134a or F2 gas where the value of q is about 0.5 μmol / cm 2 When compared with the uncoated substrate where q is about 1.6 μmol / cm BET , the coating with the fluorine-free compound according to the present invention improves the monolayer capacity by at least 20%, preferably at least 30% (i.e., further reduced). The C of the fluorine-free compound according to the present invention BET Is in the same range as the C 2 Of a comparative coating made from a fluorine-containing compound such as Freon R-134a or F2 gas where the C value is in the range of 70 to 90. Also, for example, the monolayer binding capacity q of a plasma-assisted coating based on ε-caprolactam BET (q BET = 0.53 μmol / cm BET = 0.53 μmol / cm BET (q BET = 0.53 μmol / cm 2) is exactly equivalent to the conventional barrier technology (q) obtained by coextrusion of HDPE and PA-6 BET = 0.50 μmol / cm 2 ) and this must also be noted. Also, C BET is equivalent: Plasma-assisted coating based on ε-caprolactam has a C BET value of 74, while the PE / PA coextrudate has a C BET value of 80.

[0029] In some preferred embodiments of the coating substrate, the static contact angle of a fluorine-free compound that is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinylpyrrolidone with respect to water is in the range of 10 to 46° when measured according to Reference Example 2, while the static contact angle of a C5-C8 alkyne with respect to water is in the range of 90 to 120° when measured according to Reference Example 2, and / or the static contact angle of a C5-C8 alkyne with respect to diiodomethane is in the range of 40 to 55° when measured according to Reference Example 2, and / or the static contact angle of a fluorine-free compound that is a lactam having 4 to 8 ring atoms, a lactone having 4 to 8 ring atoms, vinyl acetate, or polyvinylpyrrolidone with respect to formamide is in the range of 8 to 15° when measured according to Reference Example 2, while the static contact angle of a C5-C8 alkyne with respect to formamide is in the range of 70 to 80° when measured according to Reference Example 2.

[0030] In some preferred embodiments of the coating substrate, the surface free energy derived 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 for fluorine-free compounds that are lactams having 4 to 8 ring atoms, lactones having 4 to 8 ring atoms, vinyl acetate, or polyvinylpyrrolidone, while the surface free energy derived from the static contact angles of water, formamide, and diiodomethane for C5-C8 alkynes according to Reference Example 2 is in the range of 30 to 40 mN / m.

[0031] In some preferred embodiments of the coating substrate, the coating preferably has a thickness in the range of 20 to 500 nm, preferably in the range of 50 to 350 nm, when determined by transmission electron microscopy (TEM) according to Reference Example 6.

[0032] In some preferred embodiments of the coating substrate, the coating containing the reaction product of the fluorine-free compound is present on at least a part of the substrate surface, and preferably, the surface coverage rate determined by X-ray photoelectron spectroscopy (XPS) according to Reference Example 3 is at least 10%, more preferably at least 20%, more preferably at least 25%, more preferably at least 30% of the area of the substrate surface treated by the plasma-assisted vapor deposition method.

[0033] In some preferred embodiments of the coating substrate, the reaction product of the fluorine-free compound contained in the coating is a radical polymerization product (as opposed to polycondensation) determined by time-of-flight secondary ion mass spectrometry (ToF-SIMS) according to Reference Example 4 so as to be characterized by the nominal mass shift of secondary ions of 2 amu generated from such a surface compared to the nominal mass of the fragments resulting from the measurement of the polymer produced by polycondensation.

[0034] Acetylene-based layer as an intermediate In some preferred embodiments of the coated substrate, the layer containing the reaction product of acetylene is present between the surface of the substrate and a coating containing the reaction product of a fluorine-free compound. In some preferred embodiments of the coated substrate, the layer containing the reaction product of acetylene can be obtained from, or can be obtained by, plasma-assisted vapor deposition of acetylene.

[0035] substrate In some preferred embodiments of the coated substrate, the substrate comprises a material selected from the group consisting of organic materials and mixtures of organic 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.

[0036] 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); fluoropolymers; silicones; polycarbonates (PC); polymethyl methacrylate (PMMA); polyacrylates; polyesters; particularly polyethylene terephthalate (PET); cellulose; cellulose-derived polymers such as cellulose acetate, lignin, lignin-based composites containing wood; and mixtures of two or more of these organic polymers.

[0037] In some preferred embodiments of the coating substrate, the substrate comprises an organic polymer selected from the group consisting of polyolefins, polyamides, polyesters, and mixtures of two or more thereof. More preferred substrates comprise an organic polymer selected from the group consisting of polyethylene, polyamide, and mixtures of polyethylene and polyamide. 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. High-density polyethylene (HDPE) preferably has a density in the range of 940-970 kg / m 3 .

[0038] In some preferred embodiments of the coating substrate, the substrate is a packaging suitable for storing and transporting articles selected from the group consisting of food, beverages, and chemicals. The chemicals are preferably hazardous substances (substances transported as dangerous goods) or pesticides. The coating is present at least on the surface of the substrate that faces or is intended to face the article. Hazardous substances are substances that must be transported as dangerous goods in accordance with ADR / RID (ADR = International Agreement on the International Carriage of Dangerous Goods by Road, RID = Regulations Concerning the International Carriage of Dangerous Goods by Rail) and / or IMDG (International Maritime Dangerous Goods Code) and / or IATA (International Air Transport Association). The article is more preferably a pesticide, the substrate is more preferably a (agro)chemical container, and the coating is present at least on the surface of the substrate that faces or is intended to face the (agro)chemical. For example, when the substrate is a container filled with (agro)chemicals, the coating is present on at least a part of the inner surface of the container. In some preferred embodiments of the coating substrate, the coating substrate is a pesticide container.

[0039] Process steps and parameters - Atmospheric pressure plasma In some preferred embodiments of the coating substrate, the plasma-assisted vapor deposition method is (a) Providing a substrate having a surface; (b) Generating plasma under plasma generation conditions by passing a carrier gas through an excitation zone and applying a high-frequency alternating current to an electrode disposed in the excitation zone to generate a dielectric barrier discharge, thereby generating plasma; (c) Using an atomizer gas to generate an aerosol containing a fluorine-free compound as defined above; (d) Treating at least a part 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 part of the substrate surface, thereby obtaining a coated substrate comprising.

[0040] In some preferred embodiments of the coated substrate, in the plasma-assisted vapor deposition method, the plasma is generated 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 conditions close to atmospheric pressure, indirect atmospheric pressure plasma treatment) in (a), that is, the plasma generated in (b) and used in (d) is atmospheric pressure plasma.

[0041] The term "carrier gas" typically means a gas suitable for the generation and maintenance of 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" typically means a gas used to atomize or generate an aerosol in an atomizer and to transport the aerosol to the plasma. In particular, the atomizer gas is selected to be the same as the carrier gas.

[0042] In some embodiments, the plasma-assisted vapor deposition method is preferably an indirect plasma treatment such as PlasmaLine (registered trademark), and the plasma is blown out from a zone where plasma is generated between electrodes. Therein, the plasma according to (b) is preferably generated in a first zone, more preferably in a plasma discharge chamber; preferably, the plasma is passed through a carrier gas into an excitation zone composed of a ground electrode and a high-voltage electrode, and a high-frequency alternating current is applied to the high-voltage electrode to generate a dielectric barrier discharge, thereby generating atmospheric pressure plasma, and generating under plasma generation conditions. An aerosol containing at least one fluorine-free compound is preferably generated according to (c) in a second zone (atomizer zone), and the treatment according to (d) is preferably located downstream of the plasma discharge chamber and is in fluid communication with the outlet of the plasma discharge chamber, and more preferably is carried out in a third zone which is a so-called afterglow chamber. The construction of a device for such an indirect plasma treatment is known to those skilled in the art, for example, as described in WO 2006 / 081637A1 pamphlet (Vito) or Vangeneugden et al. "Atmospheric DBD plasma processes for production of lightweight composites" published in the 21st International Symposium on Plasma Chemistry (https: / / www.ispc-conference.org / ispcproc / ispc21 / ID287.pdf). Usually, the transport means is provided to continuously transport the substrate through the afterglow chamber, and while the substrate is being treated by plasma active species in the afterglow chamber, the substrate is kept away from the plasma discharge chamber. Alternatively, the plasma-assisted vapor deposition method is a PlasmaSpot (registered trademark) (often called a plasma jet) method, which also uses an indirect plasma treatment.

[0043] In some preferred embodiments of the coated substrate, step (c) of the plasma-assisted vapor deposition method is (c.1) supplying a fluorine-free compound in liquid form to a container having an outlet; (c.2) Pass the atomizing gas through the nozzle such that the atomizing gas contacts the fluorine-free compound at the outlet of the container, thereby producing an aerosol containing the fluorine-free compound and comprises.

[0044] A container for supplying at least one fluorine-free compound in liquid form is not particularly limited with respect to its dimensions and / or its shape. In some embodiments, the container is a reservoir having a capillary therein, the capillary being in contact with the liquid and protruding from the container. The opening of the capillary on the side protruding from the container forms an outlet. In these embodiments, an atomizing gas coming out of a nozzle having a specific diameter passes substantially horizontally along the outlet of the capillary, i.e., substantially perpendicular to the capillary (by "substantially perpendicular" is meant that the flow direction of the atomizing gas before passing through the capillary and the 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°), thus creating a sub-atmospheric pressure inside the outlet (Venturi effect), whereby the liquid is sucked into the flow of the atomizing gas from the nozzle. The atomizing gas preferably exists in a compressed state before passing through the nozzle and expands after passing through the nozzle. In some embodiments, the tube is arranged substantially perpendicular to the atomizing gas flow entering through the opening after the atomizing gas has passed through the outlet of the capillary (by "substantially perpendicular" is meant that the flow direction of the atomizing 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°). Then, an atomizing gas containing at least one fluorine-free compound in the form of droplets of various sizes impinges on the inner wall on the side opposite to the opening of the tube. Thereby, the larger droplets are preferably removed by falling within the tube, while the aerosol containing the smaller droplets further passes through the tube, preferably in the upward direction. The aerosol passing through the tube, preferably in the upward direction, contains at least one fluorine-free compound in the form of droplets, and these droplets have a size ratio 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.

[0045] In the embodiment using atmospheric pressure plasma, the fluorine-free compound is preferably as defined above. More preferably, the fluorine-free compound is ε-caprolactam.

[0046] In embodiments related to the atmospheric pressure plasma modification, the plasma according to (a) is preferably at a power per electrode area of less than 40 kW / m 2 and more preferably is generated at a power in the range of 7.5 - 38 kW / m 2 and even more preferably is generated at a power in the range of 8 - 30 kW / m 2 In embodiments related to the atmospheric pressure plasma modification, one or more atomizers, preferably at least two atomizers, are used, and the atomizer gas according to (c) or (c.2) is preferably supplied to the second zone at a flow rate per atomizer exceeding 0.5 slm (standard liters per minute), more preferably in the range of 0.5 - 5 slm, even more preferably in the range of 0.8 - 3 slm, and even more preferably in the range of 1 - 2 slm. In embodiments related to the atmospheric pressure plasma modification, the amount of the fluorine-free compound transported to the plasma as an aerosol per unit time is preferably in the range of 0.045 - 0.5 g / min per atomizer, more preferably in the range of 0.045 - 0.3 g / min per atomizer, even more preferably in the range of 0.05 - 0.2 g / min per atomizer, and even more preferably in the range of 0.08 - 0.12 g / min per atomizer.

[0047] The amount of at least one fluorine-free compound transported as an aerosol into the plasma per unit time is also referred to as the mass flow rate of at least one fluorine-free compound transported as an aerosol into the plasma. The mass flow rate is measured at time t0 before the atomizing gas according to (c) is supplied to the second zone, where the amount of at least one fluorine-free compound present in the second zone, preferably in the vessel of the second zone, is measured, and the amount of at least one fluorine-free compound present in the second zone, preferably in the vessel of the second zone, is measured again after time t1 when the atomizing gas according to (c) has been supplied to the second zone. The mass flow rate (mf) is determined according to the following. mf = [amount(t0) - amount(t1)] / [t1 - t0]

[0048] The mass flow rate can furthermore be normalized to the applied plasma power, and a mass flow rate related to a power density in the range of 0.001 to 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) is obtained.

[0049] In embodiments related to the atmospheric pressure plasma variant, the outlet of the excitation zone is at a distance in the range of preferably 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 from the substrate surface according to (a). In embodiments related to the atmospheric pressure plasma variant, in the plasma-assisted vapor deposition method, the carrier gas is supplied to the excitation zone at a flow rate in the range of preferably 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.

[0050] The plasma used in the atmospheric pressure plasma variant is a non-equilibrium plasma such as generated by alternating current (ac) discharge. Alternatively, the plasma is another non-equilibrium plasma such as a plasma generated by radio frequency (rf) excitation, microwave (mw) excitation, or direct current (dc) discharge.

[0051] In embodiments related to the atmospheric pressure plasma modification example, an AC voltage of up to 100 kV is preferably applied, and the AC voltage is more preferably in the range of 10 to 40 kV. In embodiments related to the atmospheric pressure plasma modification example, 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, and more preferably in the range of 80 to 90 kHz.

[0052] Preferably, the substrate is passed through the third zone (afterglow chamber) two or more times (number of passes > 1); preferably, the number of passes is in the range of 5 to 100 times, and more preferably in the range of 10 to 50 times. The speed at which the substrate is passed is preferably in the range of 0.1 to 10 m / min, and 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, it is passed through x substantially identical third zones, where x is an integer in the range of 5 to 100, and 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, and more preferably in the range of 1 to 3 m / min. In embodiments related to the atmospheric pressure plasma modification example, the plasma-assisted vapor deposition method is preferably carried out for a total time in the range of 30 seconds to 10 minutes, and more preferably in the range of 1 minute to 2 minutes.

[0053] In embodiments related to the atmospheric pressure plasma modification example, the plasma-assisted vapor deposition method is preferably carried out at a temperature in the range of 10 to 80 °C.

[0054] Process steps and parameters - low pressure plasma In some alternative preferred embodiments of the coated substrate, in the plasma-assisted vapor deposition method, the plasma is generated at a pressure of less than 0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, and more preferably in the range of 0.001 to 0.05 mbar (low pressure plasma).

[0055] Preferably, in these alternative preferred embodiments related to low-pressure plasma, the plasma-assisted vapor deposition method comprises: (a) providing a substrate having a surface; (b’) generating an aerosol containing a fluorine-free compound as defined above, preferably using an atomizing gas; (c’) converting the precursor aerosol produced in (b’) into a plasma state by a combination of excitation consisting of primary excitation by microwave-type electromagnetic waves and secondary excitation by discharge of an alternating voltage having a frequency of 1 kHz to 15 MHz, thereby generating a plasma; (d’) treating at least a part of the substrate surface provided according to (a) with the plasma generated according to (c’), thereby depositing a reaction product of the fluorine-free compound on the treated part of the substrate surface, thereby obtaining a coated substrate and comprising.

[0056] As shown above, the plasma generated in (c’) is a low-pressure plasma. Preferably, the alternating voltage has a frequency of 10 to 200 kHz. The microwave is an electromagnetic wave having a frequency of 300 to 3000 MHz, preferably 915 to 2450 MHz.

[0057] Preferably, in these alternative preferred embodiments, step (c’) of the plasma-assisted vapor deposition method comprises: (c’.a) supplying a fluorine-free compound in liquid form to a container having an outlet while optionally heating; (c’.b) passing an atomizing gas through a nozzle such that the atomizing gas contacts the fluorine-free compound at the outlet of the container, thereby generating an aerosol containing the fluorine-free compound and comprising.

[0058] In these alternative preferred embodiments related to low-pressure plasma, the plasma-assisted vapor deposition method comprises: (a) providing a substrate having a surface; (b”) providing an atmosphere containing a fluorine-free compound in gaseous or aerosol form, optionally while heating; (c”) generating a plasma from the atmosphere containing the fluorine-free compound according to (b”) under plasma generation conditions by a combination of main excitation by electromagnetic waves of the microwave type and secondary excitation by discharge of an alternating voltage having a frequency of 1 kHz to 15 MHz, thereby generating a plasma; (d”) treating at least a part of the substrate surface provided according to (a) with the plasma generated according to (c”), thereby depositing a reaction product of the fluorine-free compound on the treated part of the substrate surface, thereby obtaining a coated substrate comprising.

[0059] The atmosphere contains a fluorine-free compound and optionally one or more gases, preferably a gas selected from the group consisting of N2, Ar, He, CO2, O2, N2O, or a mixture of two or more of these gases. The atmosphere containing the fluorine-free compound in gaseous or aerosol form is, for example, such that the fluorine-free compound is partially gaseous due to the vapor pressure of the fluorine-free compound in liquid form, and the gas phase is transferred to the container used for plasma generation and treatment in combination with a carrier gas or alone, or a liquid fluorine-free compound, or a solution in a solvent of a liquid fluorine-free compound is provided so as to be injected into the container used for plasma generation and treatment.

[0060] Regarding embodiments related to a low-pressure variant that does not use an atomizing gas (and does not use an aerosol), the process is described in detail in U.S. Patent Application Publication No. 2022 / 0112595A1, which is incorporated herein by reference, particularly paragraphs

[0010] to

[0020] ,

[0024] to

[0028] . Suitable devices are described in paragraphs

[0031] to

[0060] of U.S. Patent Application Publication No. 2022 / 0112595A1, which is also incorporated herein by reference.

[0061] In all embodiments in which low-pressure plasma is used, the substrate to be coated may be the inner surface of a hollow container having an opening or a part thereof, and the substrate is preferably placed in a sealed container suitable for maintaining a specific pressure therein, and the entire sealed container is evacuated.

[0062] 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, polyvinylpyrrolidone, and mixtures of two or more of these compounds, more preferably 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, polyvinylpyrrolidone, and mixtures of two or more of these compounds, more preferably excluding caprolactam and polyvinylpyrrolidone, 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, polyvinylpyrrolidone, and mixtures of two or more of these compounds, more preferably 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 from the group consisting of lactones having 4 to 8 ring atoms, vinyl acetate, and mixtures of two or more of these compounds, and more preferably the fluorine-free compound is a lactone having 4 to 8, preferably 6 to 8 ring atoms.

[0063] In some preferred embodiments of the coating substrate related to the low-pressure plasma modification example, a further compound is used to deposit a coating on the surface of the substrate by plasma-assisted vapor deposition. This further compound is selected from the group consisting of C2-C4 alkenes, C2-C4 alkynes, and mixtures thereof. More preferably, it is selected from the group consisting of C3-C4 alkenes, C2-C4 alkynes, and mixtures thereof. Preferably, the compound used to deposit a coating on the surface of the substrate by plasma-assisted vapor deposition contains at least vinyl acetate, and the further compound is acetylene. More preferably, the compound used to deposit a coating on the surface of the substrate by plasma-assisted vapor deposition is vinyl acetate, and the further compound is acetylene.

[0064] In some preferred embodiments of the coating substrate related to the low-pressure plasma modification example, in the range of 50 to 90% by weight, more preferably in the range of 80 to 90% by weight, of the compounds used to deposit the coating, based on the total weight of all the compounds used to deposit the coating, it is one of the above-mentioned groups of compounds, and in the range of 10 to 50% by weight, preferably in the range of 10 to 20% by weight, is the additional compound defined above. In some embodiments where an additional compound is used, a copolymer is formed from vinyl acetate and one or more additional compounds selected from C2-C4 alkenes, C2-C4 alkynes, and mixtures thereof. Then, in some embodiments, the copolymer is at least partially hydrolyzed to convert the vinyl acetate-based portion in the copolymer to vinyl alcohol. In these embodiments where an additional compound is used, based on the total weight of all the compounds used to deposit the coating, at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight of the compounds used to deposit the coating are one of the compounds of the groups specified above and the additional compound, preferably vinyl acetate and one or more additional compounds selected from C2-C4 alkenes, C2-C4 alkynes, and mixtures thereof, that is, at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight of the coating consists of the reaction product of one of the compounds of the groups defined above and the additional compound, more preferably, more preferably at least 90% by weight, more preferably at least 95% by weight of the coating consists of the reaction product of vinyl acetate and one or more additional compounds selected from C2-C4 alkenes, C2-C4 alkynes, and mixtures thereof. Hydrolysis is carried out in some embodiments by exposing the coating containing 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 after a subsequent step, i.e., after completion of the steps of the plasma-assisted vapor deposition method, preferably after step (d) described below.For example, based on an aqueous solution having 100% by weight, an aqueous solution of NH3 having an ammonia concentration in the range of 0.1 to 50% by weight, preferably in the range of 0.5 to 25% by weight, in water is brought to a temperature of 50 °C (and a pressure of 1013 mbar) and exposed to the atmosphere in which the coating has been obtained.

[0065] In some preferred embodiments of the coating substrate related to the low-pressure plasma modification example, the layer containing the reaction product of acetylene is present between the surface of the substrate and a coating containing the reaction product of a fluorine-free compound. In some preferred embodiments of the coating substrate related to the low-pressure plasma modification example, the layer containing the reaction product of acetylene is obtained from or can be obtained from plasma-assisted vapor deposition of acetylene.

[0066] In these embodiments related to the low-pressure plasma modification, the power density of the electromagnetic wave is in the range of 0.01 to 1 W / cm 3 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.

[0067] In embodiments related to the low-pressure plasma modification example, the plasma-assisted vapor deposition method is preferably carried out at a temperature in the range of 10 to 80 °C. That is, "while heating" means that the temperature is established by appropriate means in the range of 10 to 80 °C so that the fluorine-free compound can be provided in liquid form or gas form.

[0068] Regardless of whether the atmospheric pressure plasma modification example or the low-pressure plasma modification example is used in the plasma-assisted vapor deposition method, preferably it is not carried out in any of steps (a), (b), (c), (d), more preferably not carried out in at least step (d), but water is added and / or the plasma-assisted vapor deposition method, preferably at least step (d) thereof, is carried out in an atmosphere containing at most the same amount of water as contained in the atmosphere, based on 100% relative humidity (RH) at the respective process temperature.

[0069] Second Aspect of the Invention - Process In a second aspect, the present invention is a plasma-assisted vapor deposition method for applying a coating to the surface of a substrate, comprising: (a) providing a substrate having a surface; (b) generating a plasma under plasma generation conditions by passing a carrier gas through an excitation zone and applying a high-frequency alternating current to an electrode disposed in the excitation zone to generate a dielectric barrier discharge, thereby generating a plasma; (c) using an atomizer gas to generate an aerosol containing a fluorine-free compound defined in any one of the above embodiments for the first aspect of the present invention; (d) treating at least a part of the substrate surface 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 part of the substrate surface, thereby obtaining a coated substrate relates to a plasma-assisted vapor deposition method.

[0070] In some preferred embodiments of the plasma-assisted vapor deposition method for applying a coating to the surface of a substrate, step (c) of the plasma-assisted vapor deposition method comprises (c.1) supplying a fluorine-free compound in liquid form to a container having an outlet; (c.2) passing an atomizer gas through a nozzle such that the atomizer gas contacts the fluorine-free compound at the outlet of the container, thereby generating an aerosol containing the fluorine-free compound including.

[0071] Atmospheric Pressure Plasma In some preferred embodiments of the plasma-assisted vapor deposition method for applying a coating to the 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 conditions close to atmospheric pressure, indirect atmospheric pressure plasma treatment).

[0072] In these embodiments of the plasma-assisted vapor deposition method related to the use of atmospheric pressure plasma, the plasma according to (a) is preferably at a power per electrode area of less than 40 kW / m 2 and more preferably in the range of 7.5 to 38 kW / m 2 of power, and more preferably in the range of 8 to 30 kW / m 2It is generated with power in the range of. In these embodiments of the plasma-assisted vapor deposition method related to the use of atmospheric pressure plasma, one or more atomizers, preferably at least two atomizers, are used, and the atomizer gas according to (c) or (c.2) is preferably at a flow rate per atomizer exceeding 0.5 slm (standard liters per minute), more preferably in the range of 0.5 - 5 slm per atomizer, more preferably in the range of 0.8 - 3 slm per atomizer, and more preferably in the range of 1 - 2 slm per atomizer, and is supplied to the second zone. In these embodiments of the plasma-assisted vapor deposition method related to the use of atmospheric pressure plasma, the amount of the fluorine-free compound transported to the plasma as an aerosol per unit time is in the range of 0.045 - 0.5 g / min per atomizer, more preferably in the range of 0.045 - 0.3 g / min per atomizer, more preferably in the range of 0.05 - 0.2 g / min per atomizer, and more preferably in the range of 0.08 - 0.12 g / min per atomizer. In these embodiments of the plasma-assisted vapor deposition method related to the use of atmospheric pressure plasma, the outlet of the excitation zone is at a distance in the range of preferably 0.5 - 10 mm, more preferably in the range of 0.5 - 5 mm, more preferably in the range of 2 - 4 mm, and more preferably in the range of 2.5 - 3.5 mm from the substrate surface according to (a). In these embodiments of the plasma-assisted vapor deposition method related to the atmospheric pressure plasma modification, the carrier gas is preferably supplied to the excitation zone at a flow rate in the range of 50 - 500 l / min, more preferably in the range of 150 - 450 l / min, and more preferably in the range of 200 - 300 l / min. In these embodiments of the plasma-assisted vapor deposition method related to the use of atmospheric pressure plasma, an AC voltage of preferably up to 100 kV is applied, and the AC voltage is more preferably in the range of 10 - 40 kV. In these embodiments related to the atmospheric pressure plasma modification, the discharge frequency is preferably in the range of 50 - 100 kHz, more preferably in the range of 60 - 100 kHz, preferably in the range of 70 - 95 kHz, and more preferably in the range of 80 - 90 kHz. In these embodiments of the plasma-assisted vapor deposition method related to the use of atmospheric pressure plasma, the plasma-assisted vapor deposition method is preferably carried out at a temperature in the range of 10 - 80 °C.In these embodiments of the plasma-assisted vapor deposition method related to the use of atmospheric pressure plasma, the plasma-assisted vapor deposition method is preferably carried out for a total time in the range of 30 seconds to 10 minutes, more preferably for a total time in the range of 1 minute to 2 minutes.

[0073] Low-pressure plasma In some alternative preferred embodiments of the plasma-assisted vapor deposition method for applying a coating to the surface of a substrate, the plasma is generated at a pressure of less than 0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, more preferably in the range of 0.001 to 0.05 mbar (low-pressure plasma).

[0074] In these alternative preferred embodiments related to low-pressure plasma, in one variant, the plasma-assisted vapor deposition method preferably comprises: (a) providing a substrate having a surface; (b’) using an atomizing gas to generate an aerosol containing a fluorine-free compound as defined in any one of the embodiments related to the first aspect of the present invention above; (c’) converting the precursor aerosol generated in (b’) into a plasma state by a combination of excitation consisting of primary excitation by microwave-type electromagnetic waves and secondary excitation by discharge of an alternating voltage having a frequency in the range of 1 kHz to 15 MHz, thereby generating a plasma; (d) treating at least a part of the substrate surface provided according to (a) with the plasma generated according to (c’), thereby depositing a reaction product of the fluorine-free compound on the treated part of the substrate surface, thereby obtaining a coated substrate and includes.

[0075] As shown above, the plasma generated in (c) is a low-pressure plasma. Preferably, the alternating voltage has a frequency in the range of 10 to 200 kHz. The microwave is an electromagnetic wave having a frequency in the range of 300 to 3000 MHz, preferably in the range of 915 to 2450 MHz.

[0076] In these alternative preferred embodiments related to low-pressure plasma, in one variant, step (c) of the plasma-assisted vapor deposition method comprises (c’.a) Supplying a fluorine-free compound in liquid form to a container having an outlet while optionally heating it; (c’.b) Passing an atomizing gas through a nozzle such that the atomizing gas contacts the fluorine-free compound at the outlet of the container, thereby generating an aerosol containing the fluorine-free compound and including.

[0077] In these alternative preferred embodiments related to low-pressure plasma, in another variant, the plasma-assisted vapor deposition method comprises (a) Providing a substrate having a surface; (b”) Providing an atmosphere containing a fluorine-free compound in gaseous or aerosol form while optionally heating it; (c”) Generating a plasma from the atmosphere containing the fluorine-free compound according to (b.1) under plasma generation conditions by a combination of primary excitation by microwave-type electromagnetic waves and secondary excitation by discharge of an alternating voltage having a frequency of 1 kHz to 15 MHz, thereby generating a plasma; (d”) Treating at least a part of the substrate surface provided according to (a) with the plasma generated according to (c”), thereby depositing a reaction product of the fluorine-free compound on the treated part of the substrate surface, thereby obtaining a coated substrate and including.

[0078] The atmosphere contains a fluorine-free compound and optionally one or more gases, preferably a gas selected from the group consisting of N2, Ar, He, CO2, O2, N2O, or a mixture of two or more of these gases. An atmosphere containing a fluorine-free compound in gaseous form or aerosol form is, for example, such that the fluorine-free compound is partially gaseous due to its vapor pressure in liquid form, and the gas phase is transferred to a container used for plasma generation and treatment in combination with a carrier gas or alone, or a liquid fluorine-free compound, or a solution in a solvent of a liquid fluorine-free compound, is provided to be injected into a container used for plasma generation and treatment.

[0079] Regarding embodiments related to a low-pressure variant that does not use an atomizing gas (and does not use an aerosol), the process is described in detail in U.S. Patent Application Publication No. 2022 / 0112595A1, which is incorporated herein by reference, particularly paragraphs

[0010] -

[0020] ,

[0024] -

[0028] . Suitable devices are described in paragraphs

[0031] -

[0060] of U.S. Patent Application Publication No. 2022 / 0112595A1, which is also incorporated herein by reference.

[0080] In all embodiments where low-pressure plasma is used, the substrate to be coated may be the inner surface or a part of the inner surface of a hollow container having an opening, but the substrate is preferably placed in a sealed container suitable for maintaining a specific pressure therein, and the entire sealed container is evacuated.

[0081] In all embodiments where 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, polyvinylpyrrolidone, and mixtures of two or more of these compounds. More preferably, it is 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, polyvinylpyrrolidone, and mixtures of two or more of these compounds. More preferably, excluding caprolactam and polyvinylpyrrolidone, it is 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, polyvinylpyrrolidone, and mixtures of two or more of these compounds. More preferably, it is 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, it is selected from the group consisting of lactones having 4 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.

[0082] In all embodiments where low-pressure plasma is used, the power density of the electromagnetic wave is in the range of 0.01 to 1 W / cm 3 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.

[0083] "While heating" means that the temperature is established by appropriate means in the range of 10 to 80 °C so that the fluorine-free compound can be provided in liquid or gaseous form.

[0084] Regardless of whether atmospheric pressure plasma or low-pressure plasma is used in a plasma-assisted vapor deposition method for applying a coating to the surface of a substrate, preferably it is not performed in any of steps (a), (b), (c), (d), more preferably it is not performed in at least step (d), but water is added and / or the plasma-assisted vapor deposition method, preferably at least step (d) thereof, is carried out in an atmosphere containing at most the same amount of water as is contained in the atmosphere based on 100% relative humidity (RH) at the respective process temperature.

[0085] Regardless of whether atmospheric pressure plasma or low-pressure plasma is used in a plasma-assisted vapor deposition method for applying a coating to the surface of a substrate, the substrate comprises a material selected from the group consisting of organic materials and mixtures of organic 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); fluoropolymers; silicones; polycarbonates (PC); polymethyl methacrylate (PMMA); polyacrylates; polyesters; especially polyethylene terephthalate (PET); cellulose; cellulose-derived polymers such as cellulose acetate, lignin, lignin-based composites containing wood; and mixtures of two or more of these organic polymers.

[0086] Regardless of whether atmospheric pressure plasma or low-pressure plasma is used in a plasma-assisted vapor deposition method for applying a coating to the surface of a 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, polyamide, and mixtures of polyethylene and polyamide, more preferably the substrate comprises at least polyethylene (PE), more preferably high-density polyethylene (HDPE).

[0087] Regarding the properties of the obtained coated substrate, refer to the disclosure in this specification related to the first aspect of the present invention, that is, the properties of the obtained coated substrate are as disclosed in detail in the above section related to the first aspect. Further, the preferred embodiments of the present method, as well as the process parameters, are as disclosed in detail above with respect to the first aspect. Furthermore, the details disclosed above regarding the first aspect, for example, the atmospheric pressure plasma modification example and the low pressure modification example, are also applicable to the plasma-assisted vapor deposition method of the second aspect.

[0088] The third aspect of the present invention - Use The third aspect of the present invention relates to the use of the above-mentioned coated substrate according to the first aspect, or a coated substrate obtained from or obtainable by the plasma-assisted vapor 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, and the chemical is preferably a harmful substance (transported as a dangerous good) or a pesticide, more preferably a pesticide.

[0089] The present invention will be further described by the following embodiments and the combinations of the embodiments shown by their respective dependencies and backward references. Specifically, in each example referring to the scope of the embodiments in association with terms such as "any one of Embodiments 1 to 4", it should be noted that all embodiments included in this scope are explicitly disclosed to those skilled in the art, that is, the syntax of this term should be understood by those skilled in the art as being synonymous with "any one of Embodiments 1, 2, 3, and 4".

[0090] 1. A coated substrate, wherein the coating is obtained or can be obtained by depositing 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-C8 alkynes, and mixtures of two or more of these compounds on the surface of the substrate by plasma-assisted vapor deposition. 2. The compound used for depositing the coating on the surface of the substrate by plasma-assisted vapor deposition is selected from the group consisting of lactams having 4 to 8 ring atoms excluding vinylpyrrolidone, lactones having 4 to 8 ring atoms, vinyl acetate, polyvinylpyrrolidone, C5-C8 alkynes, and mixtures of two or more of these compounds, and is the coated substrate according to Embodiment 1. 3. The compound used for depositing the coating on the surface of the substrate by plasma-assisted vapor deposition is selected from the group consisting of lactams having 4 to 8 ring atoms excluding vinylpyrrolidone, lactones having 4 to 8 ring atoms, vinyl acetate, C5-C8 alkynes, and mixtures of two or more of these compounds, and is the coated substrate according to Embodiment 1 or 2. 4. The compound used for depositing the coating on the surface of the substrate by plasma-assisted vapor deposition is selected from the group consisting of lactams having 4 to 8 ring atoms excluding vinylpyrrolidone, lactones having 4 to 8 ring atoms, vinyl acetate, and mixtures of two or more of these compounds, and preferably is selected from the group consisting of lactones having 4 to 8 ring atoms, vinyl acetate, and mixtures of two or more of these compounds, and is the coated substrate according to any one of Embodiments 1 to 3. 5. The lactam having 4 to 8 ring atoms has the formula (I), and is the coated substrate according to any one of Embodiments 1 to 4. [Chemical formula] (In the formula, R 1 is a vinyl group, x is 0 or 1, n is an integer in the range of 2 to 5, preferably in the range of 2 to 4, more preferably n is 4, x is 0 (ε-caprolactam), and / or n is 2, x is 1, R 1 is a vinyl group that replaces a hydrogen atom with nitrogen in the ring structure (vinylpyrrolidone)) The lactam having 6.4 to 8 ring atoms, preferably 6 to 8 ring atoms, is the coating substrate according to any one of Embodiments 1 to 5 having the formula (II).

Chemical formula

Chemical formula

Chemical formula

[0091] The present invention is further illustrated by the following reference examples and examples.

Examples

[0092] Reference Example 1: Plasma coating method at atmospheric pressure A 20 cm × 25 cm sized cast high-density polyethylene (HDPE) plate (rinsed with isopropanol and blow-dried in air for cleaning) was pretreated in a first coating process using a plasma generated by an argon carrier gas with a flow rate of 250 slm in a PlasmaLine200® reactor (product of VITO), and pure acetylene gas with a flow rate of 2 × 2.5 slm (i.e., since the PlasmaLine200® reactor has two gas inlets connected to two atomizers, a supply of 2.5 slm per atomizer) was supplied thereto. This gaseous mixture was supplied to the afterglow region of the plasma, and the HDPE plate was moved through it 30 times (hereinafter referred to as the number of passes) at a speed of 2 m / min and coated with the reaction product of acetylene. In this first coating process, the frequency of the DC current driving the plasma was set to 85 kHz using 150 W of power. The distance from the outlet of the excitation zone to the substrate surface was kept constant at 3 mm. The surface of the obtained HDPE plate was coated with the reaction product of acetylene and was called the "pretreated substrate". In the second coating process, the reaction product of ε-caprolactam was vapor-deposited on the pretreated substrate obtained in the first coating process. For this purpose, the pretreated substrate was exposed to another plasma generated using an argon carrier gas with a flow rate of 250 slm, and ε-caprolactam was supplied in the form of an aerosol obtained by vaporizing a 1000 g / L solution of the precursor in methanol using Ar gas at a flow rate of 1.5 slm / atomizer with two atomizers. The pretreated substrate was passed through the afterglow region 30 times at a speed of 2 m / min and coated with the reaction product of a fluorine-free compound. During this second coating process, the frequency of the DC current driving the plasma was set to 85 kHz using 150 W of power. Based on the known surface area (100 cm 2 ) of the high-voltage electrode used, the power density applied in this coating process was 15 kW / m 2 or 1.5 W / cm 2It was. The distance from the exit of the excitation zone to the substrate surface was kept constant at 3 mm. In this way, a substrate on which a reaction product of acetylene and a reaction product of ε-caprolactam were deposited on its surface was obtained by a plasma-assisted coating process at atmospheric pressure.

[0093] Reference Example 2: Plasma Coating Method at Low Pressure A standard 1 L bottle made of HDPE was introduced into a low-pressure plasma reactor developed and described by ISYTECH (U.S. Patent Application Publication No. 2022 / 112595A1). The reactor had a vacuum chamber placed inside a microwave coupler. The pressure inside the bottle was reduced to less than 0.1 mbar and the pressure inside the vacuum chamber surrounding the bottle was reduced to less than 20 mbar using a vacuum pump. Then, the inner surface of the HDPE bottle was treated with argon plasma for 5 seconds. The argon plasma was generated by adding Ar gas at a flow rate of 120 sccm (standard cubic centimeters) to the inner volume of the bottle and introducing the energy required for plasma ignition with a microwave generator operating at a frequency of 2.45 GHz and a power of 350 W. The resulting HDPE container was called a "pre-cleaned bottle" and was used for continuous plasma-assisted coating at low pressure. In the first coating step, gaseous acetylene was supplied to the inner volume of the pre-cleaned bottle at 100 sccm and activated into a plasma state by electromagnetic waves supplied by a microwave generator with a power of 400 W. This partially decomposed the reaction gas and deposited the reaction product of acetylene on the inner surface of the pre-cleaned bottle for 1 second, obtaining a "pre-treated bottle". In the second step, gaseous 1-octyne obtained from the headspace of liquid 1-octyne was introduced into the inner volume of the pre-treated bottle by an argon carrier gas, and 0.5 W / cm 3It was activated to a plasma state by electromagnetic waves supplied from a microwave generator with a power of 500 W corresponding to the effective power density. When the obtained plasma was treated for 3 seconds, the reaction product of 1-octyne was deposited on the inner surface of the pretreated bottle. In this way, a substrate with the reaction product of acetylene and the reaction product of 1-octyne deposited on its surface was obtained by a plasma-assisted coating process at low pressure.

[0094] Reference Example 3: Static Contact Angle Measurement Using three types of standard solvents (water as a highly polar liquid, diiodomethane as a highly non-polar liquid, and formamide as a liquid with intermediate polarity), the wetting behavior of the coated substrate and the untreated reference sample (e.g., blank HDPE) was examined by ordinary contact angle measurement. These liquids were deposited on the substrate as 8 - 10 droplets (volume: 0.5 - 2 μl), and the contact angle after 10 seconds was measured by shape analysis (droplet method of fitting the contour of the droplet with an ellipse or a circle) using a Kruess DSA100 instrument under ambient conditions (23 °C). The obtained contact angles were averaged, and the average value was obtained using the corresponding standard deviation. Furthermore, based on the theory of Owens and Wendt (D. Owens & R. Wendt, J. Appl. Polym. Sci. 1969, vol. 13, pp. 1741), the surface energy (including polar and dispersive components) of the substrate was calculated using the contact angles obtained for water, formamide, and diiodomethane.

[0095] Reference Example 4: X-ray Photoelectron Spectroscopy (XPS) Analysis XPS analysis was performed using a Kratos Axis Nova XPS-Spectrometer with a standard configuration of monochromatic Al Kα line (120 W) and a spot size of 800 μm x 300 μm. The XPS system was calibrated according to ISO15472.2001. 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 installed insulated from ground and neutralized with a built-in charge neutralizer during measurement. The survey scan analysis was performed with a pass energy of 160 eV and an energy step size of 0.5 eV. The high-resolution analysis was performed in the same analysis region with a pass energy of 40 eV and an energy step size of 0.1 eV. The spectra were charge-corrected, and the main line of the carbon 1s spectrum was set to a representative value of 284.8 eV as the energy of the peak of adventitious hydrocarbon. All spectra were analyzed using standard XPS analysis software such as CasaXPS (version 2.3.20) by applying the Shirley background subtraction method to the main peaks of the target elements (F1s, N1s, O1s, C1s, Si2p). For quantification, the relative sensitivity factors and transmission functions provided by the instrument manufacturer were used.

[0096] Based on the types of substrates and precursors used, the surface coverage was calculated in three ways from the collected XPS spectra: (i) When the substrate contains a significant concentration of an element that is not present in the precursor, the surface coverage after plasma-assisted coating can be estimated by the following equation: Coverage (percent) = 100 * (1 - C sample / C ref ) Equation (XPS I) where C sample is the atomic concentration (% unit) of the substrate-specific element after plasma treatment, and C ref is the atomic concentration (% unit) of the substrate-specific element in the untreated clean reference sample. Therefore, samples with the same concentration of a specific substrate element have a coverage of 0%, and samples in which a specific substrate element is not detected have a coverage of 100%. (ii) When the precursor contains a significant concentration of elements that are not present on the substrate, if there is conclusive experimental evidence that the precursor has been deposited in this defined molecular form, the surface coverage can be estimated based on the theoretical composition of the precursor used in this process. Here, the surface coverage after plasma-assisted coating can be calculated as follows: Coverage (percent) = 100 * (C sample / C theor ) Equation (XPS II) where C sample is the atomic concentration (% units) of the element specific to the coating after plasma treatment, and C theor is the atomic concentration (% units) of the element specific to the precursor calculated based on the stoichiometry of the precursor. Therefore, a sample with the same element concentration as the theoretical composition will have a coverage of 100%, and a sample in which a specific precursor element is not detected will have a coverage of 0%. (iii) When the substrate contains an element that is also present in the precursor but in a different bonding state and therefore shows a different chemical shift in the XPS spectrum, the coverage can be derived using the relative fraction of the element in the bonding state specific to the precursor obtained from the peak fitting procedure. Coverage (percent) = 100 * (C sample / C theor.precursor ) Equation (XPS III)

[0097] For samples obtained by plasma-assisted coating of HDPE with reaction products of fluorine-free compounds, the surface coverage was calculated according to formula (XPS II) or formula (XPS III). For comparative samples obtained by plasma-assisted vapor deposition of the reaction product of tetramethylsilane (comparison 2 in Table 2), the coverage was calculated using formula (XPS II). Here, and hereinafter, the comparative samples are abbreviated as Comparative X, where "X" is a placeholder representing the respective number of the comparative sample. For analysis according to formula (XPS III), the carbon 1s spectrum of the coated substrate was fitted with components representing carbon atoms bonded to either nitrogen or oxygen in various possible forms present on the substrate and accordingly in the precursor (e.g., COOR of vinyl acetate, C-N in C(=O)-N-R of lactam, and C-N, C-O of lactam, lactone, and vinyl acetate). The parameters used for this type of evaluation are shown in Table 1.

[0098]

Table 1

[0099] To estimate the surface coverage of comparative samples having fluorine-rich surface coatings (comparisons 3 and 4), the carbon 1s spectrum of the coated substrate was fitted with components representing carbon atoms bonded to fluorine with different stoichiometries (i.e., CF3, CF2, CHF) and fluorine-free functional groups (such as CH2) as present in the HDPE substrate. The parameters used for this type of evaluation are shown in Table 2.

[0100]

Table 2

[0101] The coverage was calculated by the following formula:

Equation

[0102] In the case of alkynes such as 1-octyne, since there was no chemical difference when compared with the HDPE substrate, measurement by XPS was impossible. Here, the presence of the reaction product of the precursor on the substrate after plasma-assisted deposition could be independently verified by TEM imaging (described in Reference Example 7) and atomic force microscopy (described in Reference Example 8).

[0103] Finally, the surface coverage of the comparative sample (Comparison 5) composed of co-extruded HDPE and polyamide, that is, the amount of PA on the surface, could not be reliably measured by XPS due to the presence of strongly adhering surface contamination.

[0104] Reference Example 5: Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) Analysis Static ToF-SIMS spectra were recorded using a ToF.SIMS 5 spectrometer (IonTOF GmbH, Münster, Germany). To record the spectrum of secondary electrons over a 500 μm x 500 μm area in the positive ion detection mode, a pulsed mass-filtered primary ion beam of 50 keV single-charged triple bismuth clusters (Bi3 2+ ) was used. To prevent charging of the sample surface, a low electron energy flood gun (about 20 eV) was used. The mass resolution was limited to a range of about M / ΔM 1000 with 55 u depending on the surface roughness, and hydrocarbon peaks CH3 + (15 u), C2H3 + (27 u), C3H5 + (41 u), C3H7 + (43 u), and C4H7 +After mass calibration using (55u), it was improved by using "Advanced ToF-Correction" provided by SurfaceLab 7.2. The obtained spectrum was compared with the reference spectrum of the polymer synthesized by polycondensation.

[0105] Reference Example 6: Inverse Gas Chromatography (iGC) The barrier effects of the coated substrate and the untreated standard sample (such as blank HDPE) against organic solvents were evaluated by inverse gas chromatography (iGC) using toluene vapor as the test permeate (see the chapter "Surface Properties Characterization by Inverse Gas Chromatography (IGC) Applications" in the book "Powders and Fibers" by Eric Brendle and Eugene Papirer, 1st Edition, 2006, Imprint CRC Press, page 76). For this purpose, the substrate was cut into stripes 14 cm long and 1 cm wide and placed in the sample cell shown in Figure 1. The cell consisted of two 14 cm × 14 cm aluminum plates. A linear notch 12.8 cm long, 1 mm wide, and 0.25 mm deep was engraved on the bottom surface of the upper plate as the chromatography path (see Figure 1a). At both ends of the notch, 1 / 16-inch bores were drilled to allow for the inlet and outlet of the gas. The sample stripe was placed along the notch (as shown in Figure 1b), sandwiched between the upper plate and the lower plate, and these were firmly connected with several screws to ensure gas tightness (see Figure 1c). Appropriate Swagelok connectors and PEEK joints were used to connect the outer ends of the inlet bore and the outlet bore on the upper surface of the upper plate with PEEK capillaries (1 / 16 inch, 10 cm long), and the entire assembly was connected to the chromatograph through this.

[0106] The iGC experiments were carried out on a Thermo Fisher Trace1310 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 assembling the sample cell and connecting it to the GC instrument, the cell was placed in the GC oven and conditioned at a flow rate of 18 ml / min in dry helium (Nippon Gases, grade 6.0) at 40 °C for 4 h to remove all volatile contaminants from the surface of the coated substrate.

[0107] Thereafter, liquid toluene (Honeywell, p.a. grade) was injected at a constant rate of 0.02 μl / s for approximately 9 min into a He carrier gas with a calibration 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 sample) 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 measurements were obtained during the injection period in all cases, indicating that the surface was saturated with toluene under the given experimental conditions. Thereafter, the injection was stopped and the substrate was purged with pure He carrier gas to gradually desorb the toluene. Collection was stopped when the FID signal reached 10 pA (corresponding to a relative toluene pressure p / p0 = 4.5·10 -5 ), and each time point (t R,end which means the time point when the injection of toluene was stopped and the purge with pure He was started) was recorded as the first parameter characterizing the barrier effect (the larger t R,end the weaker the barrier, and vice versa). From the obtained desorption profiles, the adsorption isotherm was calculated in the form of q ads = f(p / p0), where q adsis the amount of toluene adsorbed at a given p / p0 during desorption, following the procedure described in the literature (see the chapter "Surface Properties Characterization by Inverse Gas Chromatography (IGC) Applications" in the book "Powders and Fibers" by Eric Brendle and Eugene Papirer, 1st Edition, 2006, Imprint CRC Press, page 76). The obtained isotherm was evaluated using the Brunauer-Emmett-Teller (BET) theory (see Brunauer, Stephen; Emmett, P.H.; Teller, Edward (1938). "Adsorption of Gases in Multimolecular Layers" Journal of the American Chemical Society. 60(2):309-319). For the relative pressure range of 0.01 ≤ p / p0 ≤ 0.05, as two additional parameters for characterizing the barrier effect, the monolayer binding capacity q BET and the corresponding BET constant C BET were obtained (q BET represents the number of binding sites for toluene on the investigated surface and is expressed as the molar amount of adsorbed toluene molecules per square centimeter of the investigated surface area in μmol / cm 2 , while C BET should be noted to indicate the binding strength). The strong barrier properties against toluene vapor are reflected in the low values of q BET and / or C BET .

[0108] Reference Example 7: Transmission Electron Microscope (TEM) Analysis The thin fluorine-free layer present on the HDPE surface after successful plasma-assisted coating process was visualized in cross-section by TEM imaging. In sample preparation, first the plasma-treated surface was coated with a platinum layer (thickness: about 50 nm) and embedded in an epoxy resin. Ultra-thin sections were prepared by cryo-ultramicrotomy using a Leica UC 7 microtome. Thin sections of the obtained samples were observed with a Zeiss Libra 120 microscope equipped with an omega filter and operating in elastic and inelastic modes at an accelerating voltage of 120 kV.

[0109] Reference Example 8: Measurement of surface roughness by atomic force microscope (AFM) The surface roughness of the coated substrate and the uncoated reference sample was characterized by AFM under ambient conditions using a Bruker Dimension ICON instrument. Three-dimensional height images were collected in tapping mode covering surface areas of 2 μm × 2 μm, 5 μm × 5 μm, and 50 μm × 50 μm. From the 2 μm × 2 μm images, the roughness values Ra and Rq were derived. The roughness Ra is defined as the arithmetic mean of the absolute values of the surface height deviations (Z) measured from the respective mean planes at each analysis point in the image (i), and the total number of analysis points is N:

Equation

Equation

[0110] Reference Example 9: Evaluation of mechanical properties by nanoindentation The mechanical properties of the HDPE substrate and the fluorine-free coating applied to such a substrate were investigated by nanoindentation experiments using a KLA Nano Indenter G200 instrument equipped with a DCM II head and a Berkovich-shaped diamond tip. As a first step, sample sections were prepared by cryosectioning at -80 °C using a Leica EM UC 7 microtome and a DiATOME diamond knife. Next, the microstructure and morphology of the obtained sections were observed by atomic force microscopy under ambient conditions using a Bruker Dimension ICON instrument to identify the outer coating and the underlying bulk HDPE material. Three-dimensional height images and phase contrast images were collected in tapping mode using a 160AC-NA cantilever over a 2 μm × 2 μm surface area. Thereafter, the mechanical properties of the HDPE bulk substrate were measured by nanoindentation in quasi-static mode with a maximum load of 1 mN. As a second step, the nanoindentation measurements were performed on the surface of the as-coated samples with a maximum displacement of 500 nm to the surface using the continuous stiffness mode (CSM, see L. Xiaodong et al, Materials Characterization, vo.48, issue 1, 02 / 2022, pages 11-36). In this method, values of elastic modulus and hardness are obtained as a function of depth (i.e., the distance from the coating surface to the bulk material).

[0111] Example 1: Plasma treatment of HDPE plates at atmospheric pressure Prior to plasma-assisted coating, all HDPE substrates were cleaned by rinsing with isopropanol and then blow-drying. For each set of selected chemical precursors and process parameter settings, at least two HDPE plates were independently coated by plasma-enhanced chemical vapor deposition according to Reference Example 1. The precursors were supplied either in pure liquid form or as solutions in organic solvents. The selected precursors used for each coating condition are summarized in Table 3. The following process parameters were the same for all samples listed in Table 3: - Type of carrier gas: argon - Carrier gas flow rate: 250 l / min - Type of atomizing gas: Argon - Frequency of DC current: 85 kHz - Distance from the outlet of the excitation zone to the substrate: 3 mm - Moving speed of the substrate through the afterglow region: 2 m / min - Substrate: HDPE

[0112] In all cases, the HDPE plates were pretreated by plasma coating with acetylene as described in Reference Example 1.

[0113] For comparison, HDPE substrates were analyzed without coating (Comparison 1) and after coating by plasma-enhanced chemical vapor deposition using tetramethylsilane as the precursor compound and then performing the same process as in Reference Example 1 (Comparison 2).

[0114] For further comparison, commercially available HDPE containers were purchased and analyzed in exactly the same manner as the samples prepared by the above plasma-assisted vapor deposition method. The following types of containers (all 5-liter containers, manufactured according to the latest processes established in the packaging industry, and the inner surfaces of each having been characterized) were included in the analysis: (i) HDPE plasma-treated with Freon R-134a of a fluorine-containing precursor (referred to as "Plasma-F", Comparison 3, having a fluorine-rich layer 50 - 60 nm thick on its inner surface as measured by TEM analysis of the cross-section), (ii) HDPE coated with F2 gas (referred to as "Direct-F", Comparison 4, having a fluorine-rich layer approximately 200 nm thick on its inner surface as measured by TEM analysis of the cross-section), and (iii) HDPE coextruded with polyamide-6 (referred to as "PE / PA Coex", Comparison 5, having a polyamide-rich layer 50 - 60 nm thick on its inner surface as measured by AFM analysis of the cross-section), (ii).

[0115]

Table 3

[0116] Example 2: Plasma Treatment of HDPE Bottles at Low Pressure For plasma-assisted coating of an HDPE substrate with a fluorine-free precursor at low pressure, an as-received bottle made of HDPE with a nominal volume of 1 l was used. The inner surface of the bottle was treated in a continuous process using low-pressure plasma generated by electromagnetic waves supplied from a microwave generator according to Reference Example 2. In the final coating step, 1-octyne or 1-pentyne was applied as a gaseous precursor as shown in Table 4. For comparison, an uncoated and untreated 1 l HDPE bottle of the same type was included as a reference sample for further analysis.

[0117] [Table 4]

[0118] Example 3: Surface Coverage of HDPE Substrate after Plasma-Assisted Coating The surface coverage of the samples prepared as in Example 1 was analyzed by XPS according to Reference Example 4. The results are shown in Table 5. As explained in Reference Example 4, the surface coverage could not be measured by XPS for Sample 1 and Comparative 5.

[0119] [Table 5]

[0120] This data showed that even when the selected process conditions for plasma-assisted deposition were similar, the nominal surface coverage of the samples prepared according to the present invention varied widely (17 - 92%) depending on the type of precursor used. On the other hand, for the fluorinated reference materials (i.e., Comparative 3, Comparative 4), relatively high surface coverages (72 - 77%) were obtained. Nevertheless, some of the fluorine-free coatings of the present invention, despite their small thickness, were able to compete with these reference materials (and the PE / PA-COEX material, Comparative 5) in terms of barrier properties against toluene vapor, as described in Example 5. This indicates that a certain minimum coverage is required to obtain strong barrier performance, but the specific threshold depends on the type of precursor used.

[0121] XPS analysis of samples prepared by plasma-assisted coating at low pressure (described in Example 2) with the reaction products of 1-octyne (Sample 11) and 1-pentyne (Sample 12) showed 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 could be fitted with the same model, and it was shown that the major part of the carbon signal (about 75%) originated from the CH2 chemical group at 284.8 eV.

[0122] Example 4: Evaluation of ToF-SIMS Characteristics of Polyamide Obtained from Plasma-Assisted Coating Compared with Conventional Polyamide-6 The coating obtained by plasma-assisted deposition of ε-caprolactam at atmospheric pressure described in Example 1 (Sample 4, hereinafter referred to as "plasma-polyamide") was analyzed in comparison with a bulk polyamide-6 sample (Comparative 5) in which PA-6 was produced by classical condensation polymerization. The analysis was performed by ToF-SIMS according to Reference Example 5. The results are shown in Table 6, and the corresponding ToF-SIMS spectra (cation detection mode) in the range of 5 - 300 amu are shown in Figure 2.

[0123]

Table 6

[0124] The data in Table 6 show that in polyamide-6 produced by conventional polycondensation, monomer + H + ions were detected at 114 amu, whereas in the coating obtained from the reaction product of ε-caprolactam by plasma-assisted vapor deposition, fragments appeared at a nominal mass of 112. This indicates that the polyamide material was formed by hydrogen abstraction followed by radical polymerization. The same pattern appears for all other characteristic fragments, and the deviation between plasma-polyamide and conventional PA-6 becomes more pronounced with increasing mass due to the difference in a certain nominal mass unit per monomer in the two polymers.

[0125] Example 5: Wettability Behavior of HDPE Substrate after Plasma-Assisted Coating The effect of the reaction products of various precursors by plasma-assisted vapor deposition at atmospheric pressure (prepared as described in Example 1) on the wettability behavior of HDPE coatings was evaluated by static contact angle measurements using water, formamide, and diiodomethane as test liquids. For comparison, several commercially available HDPE containers (Comparative 3, Comparative 4, Comparative 5) with different barrier technologies and uncoated HDPE material (Comparative 1) were also analyzed.

[0126] The results are shown as a bar graph in Figure 3, and the average values (AVG) and corresponding standard deviations (SdDev) are shown in Table 7.

[0127] [Table 7]

[0128] When the reaction product of a fluorine-free polar compound is plasma-assisted vapor deposited onto an HDPE substrate (Samples 2 to 10) under atmospheric pressure according to the present invention, it was observed that the wettability was improved (the contact angle after coating became smaller) for all three types of test liquids used. The static contact angle measured with respect to water was in the range of 10 to 66°, whereas it was 97.1° for uncoated HDPE and 85 to 108° for Comparative Examples 2 to 5. This indicates that the coating with a polar (i.e., more hydrophilic) fluorine-free precursor was successful. A similar tendency of improved wettability was also observed for the non-polar test liquid diiodomethane (Samples 2 to 10 were 15 to 42° while all comparative samples were over 45°) and the mid-polar formamide (Samples 2 to 9 were 8 to 36°, Sample 10 was 50.2° while Comparative 1, Comparative 2, Comparative 3 and Comparative 5 were 70 to 80° with the exception of Comparative 4). The only different inventive example was the coating obtained by plasma-assisted vapor deposition of the reaction product of Sample 1, i.e., 1-octyne. However, this was reasonable since alkyne is a non-polar compound in contrast to lactam, lactone and vinyl acetate. In fact, the wetting behavior observed for Sample 1 was rather similar to that of uncoated HDPE, which was expected from the point of chemical similarity between polyethylene and the reaction product of 1-octyne.

[0129] Based on the static contact angles measured for water, formamide and diiodomethane, the surface free energy and its polar and dispersive components were calculated for uncoated HDPE and coated HDPE according to Reference Example 3, and the values shown in Table 8 were obtained and displayed as a bar graph in Figure 3.

[0130]

Table 8

[0131] Consistent with the individual static contact angles, the calculated surface free energy shows that when the reaction products of fluorine-free polar compounds are plasma-assisted vapor deposited onto the HDPE substrate, the surface energy increases significantly (48 - 73 mN / m for Samples 2 - 10 compared to less than 35 mN / m for Comparisons 1 - 5), which was mainly caused by an increase in the polar component of the surface energy (10 - 35 mN / m for Samples 2 - 10 compared to less than 5 mN / m for Comparisons 1 - 5). Here too, the coating formed from the reaction product of 1-octyne (Sample 1) was a valid exception, and the surface energy profile was very similar to that of uncoated HDPE (Comparison 1).

[0132] Example 6: Barrier Properties of HDPE Substrate after Plasma-Assisted Coating The influence of the barrier properties of the HDPE substrate coated with the reaction products of various fluorine-free precursors by plasma-assisted vapor deposition at atmospheric pressure (i.e., the samples of Example 1) and low pressure (i.e., the samples of Example 2) on toluene vapor was evaluated by inverse gas chromatography as described in Reference Example 6. For comparison, each uncoated HDPE substrate (Comparison 1 at atmospheric pressure and Comparison 6 at low pressure), HDPE coated with a silane precursor by plasma-assisted vapor deposition at atmospheric pressure (Comparison 2), and commercially available HDPE containers using various barrier technologies (Comparisons 3, 4, 5) were also analyzed.

[0133] The values obtained for three physical parameters (described in Reference Example 6) characterizing the barrier performance are shown in Table 9 for the selected coatings (samples) according to the present invention and various comparative samples (Comparison X). Bar graphs corresponding to the three parameters are shown in Figures 5, 6, and 7.

[0134]

Table 9

[0135] The data collected showed that the monolayer capacity of toluene bonds was reduced by coating with the non-fluorine-containing compounds according to the invention (samples 1-10) at atmospheric pressure to the same extent as untreated HDPE (e.g., q for ε-caprolactam-based coatings). BET =0.53μmol / cm 2 , sample 4), and Freon R-134a (q BET =0.47μmol / cm 2 , Comparative 3) or F2 gas (q BET = 0.50 μmol / cm 2 Comparative coatings made from fluorine-containing compounds such as fluorine-containing ... BET = 0.50 μmol / cm 2 The same was true for comparison 5). BET The value is 2.02 μmol / cm 2 The monolayer capacity is improved (i.e., further reduced) by at least 30%, preferably at least 50%, by coating with a fluorine-free compound according to the present invention, compared to the uncoated substrate (Comparative 1) at atmospheric pressure. BET Values ​​range from 70 to 90 C, such as Freon R-134a or F2 gas. BET Comparison coatings made from fluorine-containing compounds with different values ​​and HDPE packaging materials with PA-based barrier technology (C BET =80)C BET The values ​​are in the same range as those observed for uncoated HDPE (220) or TMS treated substrates (495) at atmospheric pressure, with the exception of samples 5 and 8. Similar trends and conclusions could also be inferred from the significantly shorter property retention times for coatings made from non-fluorine containing compounds at atmospheric pressure according to the present invention (except for sample 5, which used γ-butyrolactone as a precursor, and sample 8, which used PVP), as well as for fluorine containing compounds and PA based barriers, compared to uncoated HDPE and TMS treated HDPE.

[0136] At low pressure, the coatings obtained using the fluorine-free compounds according to the invention (Samples 11 and 12) brought about essentially the same beneficial effects when compared to the corresponding uncoated HDPE bottles (Comparison 6): the monolayer capacity for toluene binding decreased from 1.45 μmol / cm 2 to 0.53 μmol / cm 2 and 0.52 μmol / cm 2 (which corresponds to an improvement of about 63%), while a similarly strong decrease was also observed for the C BET value and the retention time of the properties. This shows that according to the invention, comparable levels of barrier performance can be achieved by plasma-assisted deposition of reaction products of various fluorine-free compounds at atmospheric pressure and low pressure.

[0137] Example 7: Thickness of the coatings obtained by plasma-assisted deposition on HDPE The thicknesses of the coatings formed on HDPE substrates with reaction products of various fluorine-free compounds by the plasma-assisted deposition method at atmospheric pressure, i.e., the selected samples of Example 1, were evaluated by TEM analysis as described in Reference Example 7. Representative TEM images of sections prepared from HDPE substrates coated with 1-octyne, ε-caprolactam, vinyl acetate, and δ-valerolactone are shown in Figure 8. These images show that closed and dense layers of reaction products of fluorine-free compounds were formed with all the selected precursors, and coatings with thicknesses in the range of 20 - 500 nm, preferably in the range of 50 - 350 nm, more preferably in the range of 50 - 200 nm were obtained.

[0138] Example 8: Roughness of the coatings obtained by plasma-assisted deposition on HDPE The roughness of the coatings formed on the HDPE substrate from the reaction products of various fluorine-free compounds by plasma-assisted vapor deposition at atmospheric pressure, i.e., the selected samples of Example 1, was measured by AFM as described in Reference Example 8. The values of the arithmetic mean roughness (Ra) and the root mean square (RMS) roughness (Rq) obtained as a result are shown in Table 10, and the corresponding three-dimensional images are shown in Figure 9. For comparison, the roughness values of the selected comparative samples are also included in Table 10.

[0139]

Table 10

[0140] The AFM image of Figure 9 shows that a closed nanostructured coating consisting of a plurality of particle domains with individual sizes in the typical range of 50 - 150 nm was formed by plasma-assisted vapor deposition. As a result of this structure, the Ra value was 17 - 73 nm and the Rq value was 24 - 125 nm, which was significantly higher than that of the uncoated HDPE reference sample (Comparison 1). The comparative samples with surface coatings (Comparisons 2 - 5) showed slightly lower roughness, with Ra values in the range of 20 - 57 nm and Rq values in the range of 25 - 72 nm.

[0141] Example 9: Mechanical Properties of Coatings Obtained by Plasma-Assisted Vapor Deposition on HDPE The elastic modulus and hardness of the coating formed on the HDPE substrate pretreated with the reaction product of 1-octyne by plasma-assisted vapor deposition at atmospheric pressure (i.e., Sample 1 of Example 1) were measured by nanoindentation according to Reference Example 9. For comparison, an HDPE substrate coated only with the reaction product of acetylene on its surface (i.e., the "pretreated substrate" described in Reference Example 1) was also examined in the same manner. AFM images obtained from the cross-sections of these two samples are shown in FIG. 10, where the surface coating and the bulk HDPE material can be clearly seen on the left and right sides, respectively. In the nanoindentation measurements performed on the bulk material in the cross-section, typical values of an elastic modulus of (1.18 ± 0.08) GPa and a hardness of (0.036 ± 0.002) GPa were obtained as expected for HDPE. For the expected data, see S.K. Sahu et al, Materials Chemistry and Physics, Vol. 203, 1 January 2018, pages 173-184. FIGS. 11 and 12 show the depth-dependent profiles of the elastic modulus and hardness obtained by nanoindentation measurements in the CSM mode for Sample 1 and the pretreated substrate as they are, as described in Reference Example 9. From the collected data, it became clear that neither the elastic modulus nor the hardness changed significantly at the coating surface (within the limits of the given experimental error) compared to the HDPE bulk material. This demonstrates that the coating obtained according to the present invention is flexible and elastic, and thus is fundamentally different from other carbonaceous coatings described in the literature, particularly the "diamond-like carbon" (DLC) films that 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, Issue 7, October 1999, Pages 675-684, or N. Savvides et al. Thin Solid Films, Vol. 228, Issues 1-2, 15 May 1993, Pages 289-292).

[0142] Cited References: - International Publication No. WO 2007 / 072120 A1 Pamphlet - US Patent Application Publication No. 2022 / 0112595 A1 Specification - Chapter “Surface Properties Characterization by Inverse Gas Chromatography(IGC)Applications”, by Eric Brendle, Eugene Papirer, Book “Powders and Fibers”, 1 st Edition, 2006, CRC Press, Page 76 - S. Brunauer, P. H. Emmett, E. Teller, Journal of the American Chemical Society, Vol. 60, Issue 2, 1938, Pages 309 - 319 - International Publication No. WO 2006 / 081637 A1 Pamphlet - Vangeneugden et al, “Atmospheric DBD plasma processes for production of lightweight omposites” published at the 21 st International Symposium on Plasma Chemistry(https: / / www.ispc - conference.org / ispcproc / ispc21 / ID287.pdf) - US Patent Application Publication No. 2022 / 112595 A1 Specification - L. Xiaodong et al., Materials Characterization, Vol. 48, issue 1, February 2022, Pages 11 - 36 - Q. Wei et al., Composites Part B: Engineering, Vol. 30, Issue 7, October 1999, Pages 675 - 684 - N.Savvides et al.Thin Solid Films,Vol.228,Issues 1-2,15 May 1993,Pages 289-292 - S.K.Sahu et al.,Materials Chemistry and Physics,Vol.203,1 January 2018,pages 173-184

Claims

1. A coated polyolefin substrate, wherein the coating is obtained, or can be obtained, by depositing 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 onto the surface of the polyolefin substrate by plasma-assisted deposition. (In the formula, The lactam having 4 to 8 ring atoms has formula (I), 【Chemistry 1】 During the ceremony, n is an integer in the range of 2 to 5; The lactone having 4 to 8 ring atoms has formula (II), 【Chemistry 2】 During the ceremony, R ２ It is a methyl group, y is either 0 or 1, m is an integer in the range of 1 to 5; The vinyl acetate has formula (III) 【Transformation 3】 ； The polyvinylpyrrolidone has a weight-average molecular weight of 222 g / mol or more; The C5-C8 alkynes mentioned above are either linear or branched C5-C8 alkynes.

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

3. The coating polyolefin substrate according to 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 the lactone is selected from the group consisting of δ-valerolactone, γ-valerolactone, ε-caprolactone, and mixtures of two or more of these lactones, preferably the lactone comprises at least γ-valerolactone, and more preferably γ-valerolactone.

4. The coated polyolefin substrate according to claim 1, wherein the polyvinylpyrrolidone 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 according to claim 1, wherein the C5-C8 alkyne is a linear C5-C8 alkyne, preferably having formula (V). 【Chemistry 4】 (In the formula, r is an integer in the range of 2 to 5, preferably r is 5.)

6. The coated polyolefin substrate according to claim 1, wherein the polyolefin of the substrate is polyethylene (PE) or polypropylene (PP).

7. The coated polyolefin substrate according to claim 1, wherein, based on the total weight of all compounds used to deposit the coating, at least 80% by weight, preferably at least 90% by weight, and more preferably at least 95% by weight of the compounds used to deposit the coating is one of the compounds of the group described in claim 1.

8. A further compound is used to deposit the coating onto the surface of the substrate by plasma-assisted vapor deposition, wherein the further compound is selected from the group consisting of C2-C4 alkenes, C2-C4 alkynes and mixtures thereof, more preferably from the group consisting of C3-C4 alkenes, C2-C4 alkynes and mixtures thereof, preferably the compound used to deposit the coating onto the surface of the substrate by plasma-assisted vapor deposition comprises at least vinyl acetate, the further compound is acetylene, and more preferably the compound used to deposit the coating onto the surface of the substrate by plasma-assisted vapor deposition is vinyl acetate and the further compound is acetylene, according to claim 1.

9. The coated polyolefin substrate according to claim 1, wherein, based on the total weight of all compounds used to deposit the coating, 50 to 90% by weight, preferably 80 to 90% by weight, of the compounds used to deposit the coating is one of the groups described in claim 1, and 10 to 50% by weight, preferably 10 to 20% by weight, is a further compound described in claim 8.

10. Monolayer bond capacity (q ＢＥＴ The concentration (%) was measured for toluene vapor by reverse gas chromatography (iGC) according to Reference Example 5, and was 0.3–1.3 μmol / cm³. ２ A range of preferably 0.4 to 1.2 μmol / cm³ ２ range, more preferably 0.5 to 1.1 μmol / cm² ２ The range is and / or the BET constant (C ＢＥＴ The coated polyolefin substrate according to claim 1, wherein the coefficient of toluene vapor is measured by reverse gas chromatography (iGC) according to Reference Example 5, and is in the range of 50 to 300, preferably 50 to 200, and more preferably 70 to 175.

11. The coated polyolefin substrate according to claim 1, wherein a layer containing the reaction product of acetylene exists between the surface of the substrate and the coating containing the reaction product of the fluorine-free compound, and the layer containing the reaction product of acetylene is preferably obtained or can be obtained from plasma-assisted deposition of acetylene.

12. A plasma-assisted deposition method for applying a coating to the surface of a polyolefin substrate: (a) To provide a polyolefin substrate having a surface; (b) Generating plasma under plasma generation conditions by passing a carrier gas through an excitation zone and applying a high-frequency alternating current to electrodes placed in the excitation zone to generate a dielectric barrier discharge, thereby generating plasma; (c) Using an atomizer gas to generate an aerosol containing the fluorine-free compound as defined in claim 1; (d) Treating at least a portion of the surface of the polyolefin substrate provided in accordance with (a) with the aerosol containing the plasma generated in accordance with (b) and the fluorine-free compound generated in accordance with (c), thereby depositing the reaction product of the fluorine-free compound onto the treated portion of the polyolefin substrate surface, thereby obtaining a coated polyolefin substrate. Includes, The plasma is generated in (a) at a pressure preferably 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, indirect atmospheric pressure plasma treatment), and the plasma generated in (a) is 40 kW / m³ ２ A plasma-assisted deposition method for applying coatings to the surface of polyolefin substrates, generated with power per electrode area of ​​less than [value missing].

13. A plasma-assisted deposition method for applying a coating to the surface of a polyolefin substrate: (a) To provide a polyolefin substrate having a surface; (b') Preferably using an atomizer gas to generate an aerosol containing the fluorine-free compound as defined in claim 1; The precursor aerosol generated in (c') and (b') is converted into a plasma state by a combination of excitations consisting of primary excitation by microwave-type electromagnetic waves and secondary excitation by discharge of an AC voltage having a frequency of 1 to 15 MHz, thereby generating plasma; (d') The method includes 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 onto the treated portion of the surface of the polyolefin substrate, thereby obtaining a coated polyolefin substrate. The plasma is generated at a pressure of less than 0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, and more preferably in the range of 0.001 to 0.05 mbar (low-pressure plasma), and the power density of the electromagnetic waves is 0.01 to 1 W / cm². ３ A plasma-assisted deposition method for applying a coating to the surface of a polyolefin substrate, within the specified range.

14. A plasma-assisted deposition method for applying a coating to the surface of a polyolefin substrate: (a) To provide a polyolefin substrate having a surface; (b) Providing an atmosphere containing a fluorine-free compound in gaseous or aerosol form as defined in claim 1, while optionally heating it; (c") Plasma is generated from the atmosphere containing the fluorine-free compound according to (b) under plasma generation conditions by a combination of excitations consisting of primary excitation by microwave-type electromagnetic waves and secondary excitation by discharge of an AC voltage having a frequency of 1 to 15 MHz; (d") The method includes treating at least a portion of the surface of the polyolefin substrate provided in accordance with (a) with the plasma generated in accordance with (c), thereby depositing the reaction product of the fluorine-free compound onto the treated portion of the surface of the polyolefin substrate, thereby obtaining a coated polyolefin substrate. The plasma is generated at a pressure of less than 0.1 mbar, preferably in the range of 0.0001 to 0.09 mbar, more preferably in the range of 0.001 to 0.05 mbar (low-pressure plasma), and the power density of the electromagnetic wave is in the range of 0.01 to 1 W / cm ３ A plasma-assisted vapor deposition method for applying a coating to the surface of a polyolefin substrate, which is in the range of.

15. Use of a coated polyolefin substrate according to any one of claims 1 to 11, or a coated polyolefin substrate obtained or obtainable by a 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, and the chemicals are preferably hazardous substances (transported as hazardous materials) or pesticides, more preferably pesticides.

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