Film-forming compositions for preparing monolayers with improved adhesive strength on metallized surfaces

Abstract

The present application relates to a composition comprising a fluoropolymer, a silicon-sulfur compound, an ethylene-based polymer consisting of carbon and hydrogen atoms and optionally oxygen and / or nitrogen atoms, and a solvent or a mixture of solvents, a method for preparing the same, and a method for preparing a coated substrate by applying the composition.

Description

[0001] This application relates to a composition comprising a combination of specific components for preparing a monolayer that has improved durable adhesive strength to a substrate, particularly a metallized substrate.

[0002] Fluoropolymers, such as those containing polyvinylidene fluoride (PVDF), are particularly known for their excellent durability and dielectric and / or piezoelectric properties. They are used in a wide range of applications, especially in electronics. In many applications, they are used in the form of coatings or printed layers, where good adhesion is required.

[0003] However, fluoropolymers have very weak adhesion to metals, which is detrimental to their use in electronic applications, thus requiring a metal surface as a substrate.

[0004] To address this problem, several solutions have been developed. One method to promote adhesion between fluoropolymers and metal substrates is to add a combination of a sulfur-containing adhesion promoter and the fluoropolymer. For example, EP 3638733 and WO 1982 / 000606A1 disclose a composition comprising a fluoropolymer and a silane agent in methyl ethyl ketone, wherein the fluoropolymer comprises units derived from vinylidene fluoride and units derived from trifluoroethylene. JP 2010 / 182994 describes an organic piezoelectric material suitable for high-frequency and broadband ultrasonic transducers, comprising a layer obtained from a composition of an organic piezoelectric material in methyl ethyl ketone, wherein the organic piezoelectric material comprises a fluoropolymer and a material capable of forming covalent bonds with an electrode metal, the electrode metal comprising thiol groups as functional groups.

[0005] US2020 / 0239724 also describes a composition for manufacturing a passivation layer comprising a fluorinated copolymer and a thiol-based adhesion promoter.

[0006] However, these existing layers exhibit insufficient adhesion to metal substrates, especially after immersing the layer and substrate assembly in aqueous solutions. This issue is critical for end-use applications in harsh environments, particularly in outdoor applications or water-contact applications such as medical devices.

[0007] Furthermore, as mentioned above, fluoropolymers are typically used in the form of layers applied to a substrate. Several techniques exist for coating polymers onto substrates: one route involves melting and processing the polymer, while another involves dissolving the polymer in a solvent to obtain a liquid composition. Liquid compositions, unlike melt-processable compositions, offer advantages at room temperature, enabling global energy savings. Moreover, liquid compositions can be used in a variety of coating technologies. Therefore, printed or patterned coatings can be performed using liquid compositions. Finally, in molten processes such as hot melt molding, melt-processable compositions exhibit high viscosity, typically requiring high shear rates. When thin coatings are intended to achieve high dielectric properties, the resulting coating film may lack thickness uniformity and surface coverage.

[0008] In the literature, many solvents are readily used with fluoropolymers. However, the literature lacks precision, listing the solvents used among various chemical substances. Therefore, it is difficult to directly select a solvent. Furthermore, existing compositions are not easy to prepare, especially because the solvents cannot adequately dissolve the components. Therefore, existing solutions do not provide an easy-to-operate method to obtain such compositions that can be obtained through standard equipment, compact industrial plants, open-air operations, and are environmentally friendly to operators.

[0009] Therefore, there is a need for a composition for producing a layer containing a fluoropolymer that provides a good compromise between the final dry layer thickness, the drying time to obtain the dry layer, the preparation time to produce the composition at room temperature, and the possibility of coating the composition in one step using conventional coating / printing techniques.

[0010] There is a need for a composition comprising a fluoropolymer that can be readily prepared in a compact industrial plant using standard equipment in an open-air operation, and / or is environmentally friendly to operators, while obtaining a single layer with very high adhesive strength to substrates, particularly metal or metallized substrates.

[0011] A composition comprising a fluoropolymer is also needed, which allows for the production of a monolayer exhibiting very high adhesive strength to a substrate, particularly a metal substrate, while also being active, especially when the component is used in devices that come into contact with fluids such as water. A monolayer exhibiting electroactive properties is particularly needed, particularly electrical or electronic or piezoelectric or thermoelectric dielectric or electrostrictive properties.

[0012] An electroactive or passivated monolayer that can be obtained from this composition is also needed.

[0013] Therefore, this application relates to a composition comprising:

[0014] - Fluoropolymers,

[0015] -Silicon-sulfur compounds,

[0016] - Ethylene polymers composed of carbon and hydrogen atoms, and optionally oxygen and / or nitrogen atoms, and

[0017] - A solvent or a mixture of solvents.

[0018] In fact, the inventors discovered that fluoropolymers and silicon-sulfur compounds should be combined with ethylene polymers to achieve very good adhesive strength on monolayer metal substrates that can be obtained from the composition, especially to withstand contact in aqueous solutions, while maintaining the active properties of interest of the fluoropolymers.

[0019] In particular, the inventors were surprised to find that adding silicon-sulfur compounds and ethylene-based polymers to fluoropolymers could maintain electroactive properties. Indeed, certain applications require high levels of dielectric properties, such as dielectric constant. Such performance levels can be achieved using fluoropolymers, but performance is expected to decline once adhesive accelerators are added. Conversely, this application allows for the use of non-dielectric adhesive accelerators to improve the adhesion of the layer to the substrate while maintaining electroactive properties, such as dielectric properties.

[0020] Composition

[0021] Preferably, the sum of the mass contents of the fluoropolymer, the silicon sulfide compound, and the ethylene polymer relative to the total mass of the composition is 5% to 30%, more preferably 7% to 30%, more preferably 10% to 28%, more preferably 13% to 25%, and more preferably 14% to 20%.

[0022] Preferably, the composition contains 70% to 95% by mass, more preferably 70% to 93% by mass, more preferably 72% to 90% by mass, more preferably 75% to 87% by mass, and even more preferably 80% to 86% by mass of solvent relative to the total mass of the composition.

[0023] Specifically, the viscosity of the composition of this application is 10 to 20,000 cP, preferably 100 to 10,000 cP.

[0024] The viscosity of the composition was measured at 23°C using a standard laboratory method with a cone-plate rheometer.

[0025] Preferably, the composition contains no surfactants and / or no foaming agents.

[0026] In fact, several parameters, such as the properties of the solvent or the sum of the mass contents of fluoropolymers, silicone-sulfur compounds, and ethylene polymers, can be optimized to achieve the desired properties of the composition and monolayer. These parameters affect several factors, such as viscosity, drying time, film thickness, adhesive strength, compliance with known coating or printing processes, and overall performance. Generally, high solids content results in thick coatings or strong adhesion. However, for a specific end use, the film must exhibit a thin thickness to achieve suitable properties. For example, this is a necessary condition for producing high-efficiency dielectric films. The thickness of the film depends on the coating process, as well as the solids content, viscosity, and surface energy. In fact, the solids content of the coating composition drives its tendency to completely cover the surface as a film. The uniformity of the film applied to the substrate is crucial to quality: higher solids content may result in higher coverage. However, higher solids content also makes the composition more expensive and increases viscosity.

[0027] Fluoropolymers

[0028] The compositions of this application comprise at least one fluoropolymer.

[0029] Fluoropolymers are polymers based on fluorocarbon compounds, meaning they contain several carbon-fluorine bonds.

[0030] Fluoropolymers contain units derived from fluorinated monomers (fluorinated monomers). Fluorinated monomers contain at least one carbon-fluorine bond.

[0031] These fluorinated monomers are preferably selected from:

[0032] Fluorinated monomers of formula (I)

[0033] C(X1)(X2)=C(X3)(X4)(I),

[0034] X1, X2, X3 and X4 are each independently selected from: H, Cl, Br, F, I and C1-C6 straight-chain or branched alkyl, preferably methyl or ethyl, and the C1-C6 straight-chain or branched alkyl is optionally partially or completely halogenated, provided that at least one of X1, X2, X3 and X4 contains at least one fluorine atom.

[0035] - Perfluoro(alkyl vinyl ether) of the formula Rx-O-CF=CF2, where Rx is C1-C8, preferably C1-C4 straight-chain or branched alkyl, such as perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE).

[0036] A perfluoro(meth)acrylate of the formula Ry-O-(O)C-CF=CF2, wherein Ry is H or C1-C8, preferably C1-C4 straight-chain or branched alkyl.

[0037] A fluoro(meth)acrylate of the formula Rz-O-(O)C-CH=CH2, wherein Ry is a C1-C8, preferably C1-C4, straight-chain or branched alkyl group, and has at least one, preferably three, fluorine atoms.

[0038] -C3-C6 perfluorocycloolefins (tetrafluorocyclopropylene, hexafluorocyclobutene, octafluorocyclopentene, decafluorocyclohexene),

[0039] - Perfluorinated (1,3-dioxacyclopentene);

[0040] - Perfluoro(2,2-dimethyl-1,3-dioxacyclopentene) (PDD)

[0041] - A fluorinated monomer of the formula CF2=C(F)O-CF2CF(CF3)-O-CF2CF2-X, wherein X is CO2H, CH2OH, CO2CH3, SO2F, CH2OPO3H or CH2OCN.

[0042] Fluorine-containing monomers of the formula CF2=C(F)-O-CF2CF2SO2F,

[0043] A fluorinated monomer of the formula R-CH2-O-CF=CF2, where R is H or F(CF2). m - and m is 1, 2, or 3.

[0044] - A fluorinated monomer of the formula R'-O-CF=CH2, where R' is F(CF2). n - and n is 1, 2, 3, or

[0045] -Equation F(CF2) z A fluorinated monomer of CH2-O-CF=CF2, where z is 1, 2, 3, 4 or 5.

[0046] Fluoropolymers preferably contain units of fluorinated monomers derived from formula (I).

[0047] Preferably, in formula (I), X1, X2, X3 and X4 are each independently selected from: H, F, Cl, I, Br, or optionally contain one or more methyl groups with substituents selected from F, Cl, I and Br, more preferably independently selected from: H, F, Cl, Br or optionally contain one or more methyl groups with substituents selected from F, Cl and Br, even more preferably independently selected from: H, F, Cl or optionally contain one or more methyl groups with substituents selected from F and Cl, advantageously independently selected from: H, F and methyl groups optionally containing one or more F, provided that at least one of X1, X2, X3 and X4 contains at least one fluorine atom.

[0048] According to one embodiment, X1, X2, X3 and X4 are each independently selected from H, F, Cl, I and Br, preferably independently selected from H, F, Cl and Br, more preferably independently selected from H, F and Cl, and even more preferably independently selected from H and F, provided that at least one of X1, X2, X3 and X4 contains at least one fluorine atom.

[0049] According to another embodiment, one and only one of X1, X2, X3 and X4 is selected from: Cl, I and Br, preferably Cl, while the others of X1, X2, X3 and X4 are independently selected from: H, F or C1-C3 alkyl, preferably C1-C2 alkyl, more preferably methyl, wherein the alkyl or methyl group optionally has one or more fluorine substituents, provided that at least one of X1, X2, X3 and X4 contains at least one fluorine atom.

[0050] Examples of fluorinated monomers of formula (I) are: ethylene fluoride (ethylene fluoride), vinylidene fluoride (VDF), 1,2-difluoroethylene, trifluoroethylene (TrFE), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), trifluoropropylene such as 3,3,3-trifluoropropylene, tetrafluoropropylene such as 2,3,3,3-tetrafluoropropylene or 1,3,3,3-tetrafluoropropylene, pentafluoropropylene such as 1,1,3,3,3-pentafluoropropylene or 1,2,3,3,3-5-pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene, 3,3-3-trifluoro-2-(trifluoromethyl)propene, perfluorobutylethylene (PFBE), bromofluoroethylene (1-bromo-1-fluoroethylene or 1-bromo-2-fluoroethylene), bromodifluoroethylene (1-bromo-2,2-difluoroethylene or 1-bromo-1,2-difluoroethylene), bromotrifluoroethylene (cis or trans form 1... 1-Bromo-3,3,3-trifluoropropene or 2-Bromo-3,3,3-trifluoropropene), chlorofluoroethylene (CFE) (1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene), dichlorofluoroethylene (1-chloro-2,2-difluoroethylene or 1-chloro-1,2-difluoroethylene), chlorotrifluoroethylene (CTFE) (cis or trans form of 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene). -trifluoropropylene), bromotrifluoropropylene, chlorotrifluoropropylene, (1 or 2 or 3 or 4)-bromo-(1 or 2)-fluorobutene, (1 or 2 or 3 or 4)-chloro-(1 or 2)-fluorobutene, (2 or 3 or 4)-chloro-1,1-difluorobutene, (2 or 3 or 4)-bromo-1,1-difluorobutene, (3 or 4)-bromo-1,1,2-trifluorobutene, (3 or 4)-chloro-1,1,2-trifluorobutene.

[0051] Fluoropolymers can be homopolymers of fluorinated monomers, or they can be obtained by copolymerizing fluorinated monomers with one or more other fluorinated monomers and / or non-fluorinated monomers to form copolymers.

[0052] A copolymer is a polymer derived from multiple monomers. The copolymers of this application are in particular comonomers of two monomers (dimers) or three different monomers (terpolymers).

[0053] Preferably, the total molar content of fluorinated monomers in the fluorinated polymer is 40% to 100% relative to the total molar content of the fluorinated polymer monomers, more preferably 50% to 95%, and more preferably 60% to 90%.

[0054] The monomers that are non-fluorinated and can be copolymerized with fluorinated monomers are preferably selected from non-fluorinated olefin monomers.

[0055] An alkene monomer is a molecule containing at least one carbon-carbon double bond. Preferably, the nonfluorinated alkene monomer is as described in formula C(R1)(R2)=C(R3)(R4), wherein R1, R2, R3 and R4 are independently selected from: hydrogen atoms, aryl (preferably phenyl), C1-C10 (preferably C1-C4) straight-chain or branched or cyclic saturated or unsaturated hydrocarbon groups, optionally also containing ether, ester, nitrile, carboxyl, amine and / or amide groups, including the possibility that two of the groups in R1, R2, R3 and R4 form a 5, 6 or 7-membered ring.

[0056] Advantageously, the nonfluorinated olefin monomers are selected from: ethylene, propylene, methyl or ethyl vinyl ethers, vinyl esters, allyl glycidyl ethers, (meth)acrylic acid, (m)ethyl (meth)acrylic acid and vinyl acetate.

[0057] Preferably, the molar content (or molar ratio) of the first fluorinated monomer (especially when the first fluorinated monomer is vinylidene fluoride) in the fluoropolymer is 40% to 98%, more preferably 50% to 90%, more preferably 60% to 80%, and even more preferably 60% to 70%. Preferably, the molar content of the second fluorinated monomer in the fluoropolymer is 2% to 60% relative to the total molar content of the fluoropolymer monomers, more preferably 10% to 50%, more preferably 20% to 40%, and even more preferably 30% to 40%.

[0058] According to one embodiment, the fluoropolymer is a dimer of two different fluorinated monomers, namely a first fluorinated monomer and a second fluorinated monomer. The fluorinated monomers are each described independently as described above.

[0059] Preferably, the fluoropolymer is a terpolymer of at least three different fluorinated monomers, namely a first fluorinated monomer, a second fluorinated monomer, and a third fluorinated monomer. Each fluorinated monomer is independently as described above.

[0060] Ternary copolymers are particularly advantageous because they allow for high electroactive properties, especially high dielectric properties, as well as exceptionally high piezoelectric properties.

[0061] Fluoropolymers may comprise a first fluorinated monomer unit and a second fluorinated monomer unit, or may be composed of a first fluorinated monomer unit and a second fluorinated monomer unit. Fluoropolymers may also comprise a first fluorinated monomer unit, a second fluorinated monomer unit, and a third fluorinated monomer unit, or may be composed of a first fluorinated monomer unit, a second fluorinated monomer unit, and a third fluorinated monomer unit.

[0062] Specifically, the fluoropolymer is a copolymer of vinylidene fluoride (as the first fluorinated monomer) and at least one second fluorinated monomer, wherein the second fluorinated monomer is a fluorinated monomer as described above, provided that it is different from vinylidene fluoride. More preferably, the fluoropolymer is a terpolymer of vinylidene fluoride (as the first fluorinated monomer) with a second fluorinated monomer and a third fluorinated monomer, provided that the second fluorinated monomer and the third fluorinated monomer are different from vinylidene fluoride and are distinct from each other.

[0063] Fluoropolymers may comprise vinylidene fluoride units and second fluorinated monomer units (and third fluorinated monomer units, if present), or may consist of vinylidene fluoride units and second fluorinated monomer units (and third fluorinated monomer units, if present).

[0064] The second fluorinated monomer is preferably a fluorinated monomer of formula (I) as described above.

[0065] If present, the third fluorinated monomer is preferably a fluorinated monomer of formula (I) as described above.

[0066] Preferably, the fluoropolymer is a copolymer of vinylidene fluoride and (at least) a second fluorinated monomer of formula (I), preferably a dimer, wherein X1, X2, X3 and X4 are each independently selected from: H, F, Cl, I, Br or optionally contain one or more methyl groups selected from F, Cl, I and Br, preferably independently selected from: H, F, Cl, Br or optionally contain one or more methyl groups selected from F, Cl and Br, provided that at least one of X1, X2, X3 and X4 contains at least one fluorine atom, and provided that the second fluorinated monomer is different from vinylidene fluoride.

[0067] More preferably, the fluoropolymer is a copolymer of vinylidene fluoride and (at least) a second fluorinated monomer of formula (I), preferably a dimer, wherein X1, X2, X3 and X4 are each independently selected from: H, Cl, F or optionally a methyl group containing one or more F or Cl, preferably selected from H, F or optionally a methyl group containing one or more F, provided that at least one of X1, X2, X3 and X4 contains at least one fluorine atom, and provided that the second fluorinated monomer is different from vinylidene fluoride.

[0068] According to one embodiment, the fluoropolymer is a copolymer of vinylidene fluoride and (at least) a second fluorinated monomer of formula (I), preferably a dimer, wherein X1, X2, X3 and X4 are each independently selected from: H, F, Cl, I or Br, preferably from H, F, Cl or Br, more preferably from H, F and Cl, provided that at least one of X1, X2, X3 and X4 contains at least one fluorine atom, and provided that the second fluorinated monomer is different from vinylidene fluoride.

[0069] According to another embodiment, the fluoropolymer is a copolymer of vinylidene fluoride and (at least) a second fluorinated monomer of formula (I), preferably a dimer, wherein one and only one of X1, X2, X3 and X4 is selected from Cl, I and Br, preferably Cl and Br, and the others of X1, X2, X3 and X4 are independently selected from: H, F or C1-C3 alkyl, preferably C1-C2 alkyl, more preferably methyl, said alkyl or methyl optionally having one or more fluorine substituents, advantageously the others of X1, X2, X3 and X4 are independently selected from H and F, provided that at least one of X1, X2, X3 and X4 contains at least one fluorine atom, and provided that the second fluorinated monomer is different from vinylidene fluoride.

[0070] Preferably, the fluoropolymer is a copolymer of vinylidene fluoride and (at least) a second fluorinated monomer, preferably a dimer, wherein the second fluorinated monomer is selected from: vinylidene fluoride (vinyl fluoride), vinylidene fluoride (VDF), 1,2-difluoroethylene, trifluoroethylene (TrFE), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), trifluoropropylene such as 3,3,3-trifluoropropylene, tetrafluoropropylene such as 2,3,3,3-tetrafluoropropylene or 1,3,3,3-tetrafluoropropylene, pentafluoropropylene such as 1,1,3,3,3-pentafluoropropylene or 1,2,3,3,3-pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene, 3,3-3-trifluoro-2-(trifluoromethyl)propene, perfluorobutylethylene (PFBE), bromofluoroethylene (1-bromo-1-fluoroethylene or 1-bromo-2-fluoroethylene), bromodifluoroethylene (1-bromo-2,2-difluoroethylene or 1-bromo-1,2-difluoroethylene), bromo... Trifluoroethylene (cis or trans form of 1-bromo-3,3,3-trifluoropropene or 2-bromo-3,3,3-trifluoropropene), chlorofluoroethylene (CFE) (1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene), dichlorofluoroethylene (1-chloro-2,2-difluoroethylene or 1-chloro-1,2-difluoroethylene), chlorotrifluoroethylene (CTFE) (cis or trans form of 1-chloro-3,3,3-trifluoropropene or 2-... Chloro-3,3,3-trifluoropropene), bromotrifluoropropene, chlorotrifluoropropene, (1 or 2 or 3 or 4)-bromo-(1 or 2)-fluorobutene, (1 or 2 or 3 or 4)-chloro-(1 or 2)-fluorobutene, (2 or 3 or 4)-chloro-1,1-difluorobutene, (2 or 3 or 4)-bromo-1,1-difluorobutene, (3 or 4)-bromo-1,1,2-trifluorobutene or (3 or 4)-chloro-1,1,2-trifluorobutene.

[0071] According to the most preferred embodiment, the fluoropolymer is a copolymer of vinylidene fluoride and (at least) a fluorinated monomer, preferably a dimer, wherein the fluorinated monomer is selected from hexafluoropropylene, chlorofluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene and trifluoroethylene, preferably selected from chlorofluoroethylene, chlorotrifluoroethylene and trifluoroethylene.

[0072] According to a preferred embodiment, the fluoropolymer is a terpolymer of vinylidene fluoride, a second fluorinated monomer of formula (I), and a third fluorinated monomer of formula (I), wherein X1, X2, X3, and X4 are each independently selected from H, F, Cl, I, Br, or optionally contain one or more methyl groups selected from F, Cl, I, and Br, preferably independently selected from H, F, Cl, Br, or optionally contain one or more methyl groups selected from F, Cl, and Br, provided that at least one of X1, X2, X3, and X4 contains at least one fluorine atom, and provided that the second and third fluorinated monomers are different from vinylidene fluoride and are different from each other.

[0073] More preferably, the fluoropolymer is a terpolymer of vinylidene fluoride, a second fluorinated monomer of formula (I), and a third fluorinated monomer of formula (I), wherein X1, X2, X3, and X4 are each independently selected from: H, Cl, F, or optionally a methyl group containing one or more F or Cl, preferably selected from: H, F, or optionally a methyl group containing one or more F, provided that at least one of X1, X2, X3, and X4 contains at least one fluorine atom, and provided that the second fluorinated monomer and the third fluorinated monomer are different from vinylidene fluoride and different from each other.

[0074] According to one embodiment, the fluoropolymer is a terpolymer of vinylidene fluoride, a second fluorinated monomer of formula (I), and a third fluorinated monomer of formula (I), wherein X1, X2, X3, and X4 are each independently selected from: H, F, Cl, I, or Br, preferably from H, F, Cl, or Br, more preferably from H, F, and Cl, provided that at least one of X1, X2, X3, and X4 contains at least one fluorine atom, and provided that the second and third fluorinated monomers are different from vinylidene fluoride and are different from each other.

[0075] According to another embodiment, the fluoropolymer is a terpolymer of vinylidene fluoride, a second fluorinated monomer of formula (I), and a third fluorinated monomer of formula (I), wherein one and only one of X1, X2, X3, and X4 is selected from Cl, I, and Br, preferably Cl and Br, and the others of X1, X2, X3, and X4 are independently selected from H, F, or C1-C3 alkyl, preferably C1-C2 alkyl, more preferably methyl, wherein the alkyl or methyl may optionally have one or more fluorine substituents, advantageously, the others of X1, X2, X3, and X4 are independently selected from H and F, provided that at least one of X1, X2, X3, and X4 contains at least one fluorine atom, and provided that the second and third fluorinated monomers are different from vinylidene fluoride and are different from each other.

[0076] Preferably, the fluoropolymer is a terpolymer of vinylidene fluoride, a second fluorinated monomer, and a third fluorinated monomer, wherein the second and third fluorinated monomers are independently selected from: ethylene fluoride (vinyl fluoride), vinylidene fluoride (VDF), 1,2-difluoroethylene, trifluoroethylene (TrFE), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), trifluoropropylene such as 3,3,3-trifluoropropylene, tetrafluoropropylene such as 2,3,3,3-tetrafluoropropylene or 1,3,3,3-tetrafluoropropylene, pentafluoropropylene such as 1,1,3,3,3-pentafluoropropylene or 1,2,3,3,3-pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene, 3,3-3-trifluoro-2-(trifluoromethyl)propene, perfluorobutylethylene (PFBE), bromofluoroethylene (1-bromo-1-fluoroethylene or 1-bromo-2-fluoroethylene), bromodifluoroethylene (1-bromo-2,2-difluoroethylene or 1-bromo-1,2-difluoroethylene) Ethylene), bromotrifluoroethylene (cis or trans form of 1-bromo-3,3,3-trifluoropropene or 2-bromo-3,3,3-trifluoropropene), chlorofluoroethylene (CFE) (1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene), dichlorofluoroethylene (1-chloro-2,2-difluoroethylene or 1-chloro-1,2-difluoroethylene), chlorotrifluoroethylene (CTFE) (cis or trans form of 1-chloro-3,3,3-trifluoropropene or... 2-Chloro-3,3,3-trifluoropropene), bromotrifluoropropene, chlorotrifluoropropene, (1 or 2 or 3 or 4)-bromo-(1 or 2)-fluorobutene, (1 or 2 or 3 or 4)-chloro-(1 or 2)-fluorobutene, (2 or 3 or 4)-chloro-1,1-difluorobutene, (2 or 3 or 4)-bromo-1,1-difluorobutene, (3 or 4)-bromo-1,1,2-trifluorobutene or (3 or 4)-chloro-1,1,2-trifluorobutene.

[0077] According to the most preferred embodiment, the fluoropolymer is a terpolymer of vinylidene fluoride, a second fluorinated monomer, and a third fluorinated monomer, wherein the second and third fluorinated monomers are independently selected from hexafluoropropylene, chlorofluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, and trifluoroethylene, preferably from chlorofluoroethylene, chlorotrifluoroethylene, and trifluoroethylene.

[0078] Preferably, the terpolymer is a polymer of vinylidene fluoride, trifluoroethylene (as the second fluorinated monomer), and chlorotrifluoroethylene (P(VDF-TrFE-CTFE)) (as the third fluorinated monomer), or a terpolymer of vinylidene fluoride, trifluoroethylene (as the second fluorinated monomer), and chlorofluoroethylene (P(VDF-TrFE-CFE)) (as the third fluorinated monomer).

[0079] Preferably, the molar content (or molar ratio) of vinylidene fluoride in the fluoropolymer is 40% to 98%, more preferably 50% to 80%, more preferably 60% to 75%, and even more preferably 60% to 70%. Preferably, the molar content of the second fluorinated monomer in the fluoropolymer is 15% to 45% relative to the total molar content of the fluoropolymer monomers, more preferably 20% to 40%, and even more preferably 25% to 30%. Preferably, the molar content of the third fluorinated monomer in the fluoropolymer is 1% to 15% relative to the total molar content of the fluoropolymer monomers, more preferably 3% to 12%, and even more preferably 5% to 10%.

[0080] The weight-average molar mass Mw of the fluoropolymer is preferably at least 100,000 g·mol⁻¹. -1 Preferably at least 200,000 g / mol -1 More preferably at least 300,000 g·mol -1 Even more preferred is at least 400,000 g·mol⁻¹ -1 Preferably, the concentration is 200,000 to 1,000,000 g·mol⁻¹ -1 Molecular weight distribution can be determined by size exclusion chromatography (SEC).

[0081] The compositions of this application preferably contain 3% to 30% by mass, more preferably 5% to 25% by mass, more preferably 7% to 20% by mass, and more preferably 8% to 18% by mass of a fluoropolymer relative to the total mass of the composition.

[0082] silicon sulfide compounds

[0083] The composition of this application contains at least one silicon-sulfur compound.

[0084] A silicon-sulfur compound is a compound containing at least one silicon atom and at least one sulfur atom, preferably at least one silyl group and / or at least one silazyl group, and at least one sulfur atom, more preferably at least one silyl group and at least one sulfur atom.

[0085] The silane group is preferably a group of the formula -Si(Ra)(Rb)(Rc), wherein Ra, Rb and Rc are each independently selected from: H, OH, Alk and -O-Alk, and Alk is a C1-C8 straight-chain or branched alkyl group, preferably selected from OH, Alk and -O-Alk.

[0086] The silazane group contains at least a Si-N bond, and preferably contains at least one nitrogen atom covalently bonded to a hydrogen atom and two silicon atoms (-Si-NH-Si- group).

[0087] Preferably, Ra, Rb, and Rc are each independently selected from Alk and -O-Alk.

[0088] Preferably, Alk (or Alk that is independently a -O-Alk group) is a C1-C4 straight-chain or branched alkyl group, more preferably methyl or ethyl, and even more preferably methyl.

[0089] Preferably, in the silicon-sulfur compound, the sulfur atom of the thiol functional group is not directly connected to the silicon atom.

[0090] More preferably, the sulfur compound of the silicon-sulfur compound exists in the form of a -S-(Rd) group, wherein (Rd) is selected from H and an organic moiety comprising 1-30 carbon atoms and at least one nitrogen atom and / or at least one oxygen atom. Preferably, (Rd) is selected from H and an organic moiety comprising 1 to 30 carbon atoms, hydrogen atoms, and one or more nitrogen atoms and / or one or more oxygen atoms.

[0091] Preferably, the silicon-sulfur compound is as shown in formula (II):

[0092] (Rd)S–Rw–Si(Ra)(Rb)(Rc)(II)

[0093] Rw is a straight-chain, branched, or cyclic group comprising 1 to 18 carbon atoms and optionally one or more oxygen and / or nitrogen atoms, and Ra, Rb, Rc, and Rd are as described above according to any embodiment. More preferably, Rw is C1-C12, preferably C1-C8, preferably C1-C6, preferably C1-C4, more preferably C2-C4, straight-chain or branched, preferably straight-chain alkyl or alkylene, preferably alkyl.

[0094] According to a preferred embodiment, Rd is H. According to this embodiment, the silane-sulfur compound is a mercaptosilane, i.e., a compound containing at least one silane group and at least one thiol functional group (-SH).

[0095] Preferably, the silicon-sulfur compound is not a polymer.

[0096] Preferably, the molecular weight of silicon-sulfur is less than 800 g·mol⁻¹. -1 Preferably less than 600 g·mol⁻¹ -1 Preferably less than 400 g·mol⁻¹ -1 Preferably less than 250 g·mol⁻¹ -1 Preferably 80 g·mol -1 Up to 800g.mol -1 .

[0097] Non-limiting examples of silicon-sulfur compounds are:

[0098] The reaction product of thiooctanoic acid S-[3-(triethoxysilyl)propyl] ester with 2-methyl-1,3-propanediol and 3-(triethoxysilyl)-1-propanethiol (EC No.: 485-270-1);

[0099] 3-(triethoxysilyl)propanethiol (CAS No. 14814-09-6);

[0100] 3-(dimethoxymethylsilyl)-2-methylpropanethiol (CAS No. 14857-92-2);

[0101] -3-(methoxydimethylsilyl)propanethiol (CAS No. 14857-97-7);

[0102] - The reaction product of hexamethylene diisocyanate oligomer with 3-aminopropylmethylamine, trimethylacetaldehyde and 3-trimethoxysilylpropane-1-thiol (CAS No. 161278-26-8);

[0103] -The reaction product of propoxylated pentaerythritol with 3-isocyanate-3,5,5-trimethylcyclohexyl isocyanate and 3-trimethoxysilylpropane-1-thiol (CAS No. 161308-00-5);

[0104] - The reaction product of hexamethylene diisocyanate trimer with (3-aminopropyl)methylamine, benzaldehyde and 3-trimethoxysilylpropane-1-thiol (CAS No. 162491-90-9);

[0105] 2-Methyl-3-(triethoxysilyl)propanethiol (CAS No. 17980-28-8);

[0106] -2-(triethoxysilyl)ethanethiol (CAS No. 18236-15-2);

[0107] -(trimethylsilyl)methyl thiocyanate (CAS No. 18293-51-1);

[0108] - Trimethylsilyl isothiocyanate (CAS No. 2290-65-5);

[0109] -3-(dimethoxymethylsilyl)propanethiol (CAS No. 31001-77-1);

[0110] -1-Allyl-3-[3-(triethoxysilyl)propyl]thiourea (CAS No. 42168-36-5);

[0111] -3-Trimethoxysilylprop-1-thiol (CAS No. 4420-74-0);

[0112] -4-(triethoxysilyl)but-2-thiol (CAS No. 57640-10-5);

[0113] -2-[3-(trimethoxysilyl)propyl]isothiourea ammonium chloride (CAS No. 58505-58-1);

[0114] -3-[tris(2-ethoxyethoxy)silyl]propanethiol (CAS No. 67724-41-8);

[0115] -2-(trimethoxysilyl)ethanethiol (CAS No. 7538-45-6);

[0116] A mixture of -S-(3-trimethoxysilyl)propyl19-isocyanate-11-(6-isocyanohexyl)-10,12-dioxo-2,9,11,13-tetraazanonadecane sulfate; and S-(3-(trimethoxysilyl)propyl17-isocyanate-9-(isocyanohexyl-aminocarbonyl)-10-oxo-2,9,11-triazaheptadecane sulfate) (CAS No. 85702-90-5);

[0117] -1,3-Dibutyl-2-[3-(triethoxysilyl)propyl]isothiourea ammonium chloride (CAS No. 90210-34-7);

[0118] -1,3-Diphenyl-2-[3-(triethoxysilyl)propyl]isothiourea monohydrochloride (CAS No. 90210-35-8);

[0119] -3-[tris(decoxy)silyl]propanethiol (CAS No. 93777-94-7);

[0120] 1-Methyl-3-(triethoxysilyl)propyl thiocyanate (CAS No. 94087-37-3);

[0121] 2-Methyl-3-(triethoxysilyl)propyl thiocyanate (CAS No. 94087-38-4);

[0122] -3-[tris(octyloxy)silyl]propanethiol (CAS No. 94291-66-4).

[0123] Advantageous examples of silicon-sulfur compounds include:

[0124] -3-(triethoxysilyl)propanethiol (CAS No. 14814-09-6);

[0125] 3-(dimethoxymethylsilyl)-2-methylpropanethiol (CAS No. 14857-92-2);

[0126] -3-(methoxydimethylsilyl)propanethiol (CAS No. 14857-97-7);

[0127] 2-Methyl-3-(triethoxysilyl)propanethiol (CAS No. 17980-28-8);

[0128] -2-(triethoxysilyl)ethanethiol (CAS No. 18236-15-2);

[0129] -3-(dimethoxymethylsilyl)propanethiol (CAS No. 31001-77-1);

[0130] -3-Trimethoxysilylpropane-1-thiol (CAS No. 4420-74-0);

[0131] -4-(triethoxysilyl)but-2-thiol (CAS No. 57640-10-5);

[0132] -3-[tris(2-ethoxyethoxy)silyl]propanethiol (CAS No. 67724-41-8);

[0133] -2-(trimethoxysilyl)ethanethiol (CAS No. 7538-45-6);

[0134] -3-[tris(decoxy)silyl]propanethiol (CAS No. 93777-94-7);

[0135] -3-[tris(octyloxy)silyl]propanethiol (CAS No. 94291-66-4).

[0136] The composition of this application preferably contains 0.05% to 0.3% by mass, more preferably 0.08% to 0.25% by mass, more preferably 0.1% to 0.2% by mass, and more preferably 0.12% to 0.18% by mass of a silicon-sulfur compound relative to the total mass of the composition.

[0137] The composition of this application preferably contains 0.1% to 5% by mass, more preferably 0.3% to 3% by mass, more preferably 0.5% to 2% by mass, and more preferably 0.8% to 1.5% by mass of a silicon-sulfur compound relative to the mass of the fluoropolymer.

[0138] Ethylene polymers

[0139] The compositions of this application comprise at least one ethylene polymer consisting of carbon and hydrogen atoms, and optionally oxygen and / or nitrogen atoms.

[0140] Ethylene polymers contain units derived from one or more vinyl monomers.

[0141] Vinyl monomers are small organic molecules that contain at least one carbon-carbon double bond.

[0142] Preferably, the vinyl monomer has the following formula: C(X)(X')=C(X”)(X”'), wherein X, X', X” and X”' are independently selected from: hydrogen atom, OH group, COOH group, CN group, aryl (preferably phenyl), saturated or unsaturated hydrocarbon group containing 1-10 carbon atoms (preferably 2-10 carbon atoms), wherein the aryl or hydrocarbon group optionally further comprises OH group, ester group, carboxyl group, amino group, nitrile group and / or amide group.

[0143] The vinyl monomer is preferably selected from alkenyl monomers in C2-C8 (preferably C2-C4), diene monomers in C4-C12, acrylate monomers, styrene monomers, vinyl alcohol, vinyl acetate, acrylamide monomers, maleic acid, and acrylonitrile.

[0144] Ethylene polymers can also be elastomers, such as, but not limited to, copolymers of acrylonitrile and ethylene, or terpolymers of ethyl monomers, acrylate monomers and other vinyl monomers.

[0145] Ethylene polymers can also be PVA copolymers, copolymers of vinyl acetate and acrylic acid, or polyacrylamide.

[0146] Preferably, the ethylene polymer is an acrylate polymer.

[0147] Acrylic polymers are polymers based on acrylic acid or acrylic acid derivatives (or obtained from acrylic acid or acrylic acid derivatives), and therefore are polymers containing units derived from acrylate monomers.

[0148] Acrylic ester monomers are molecules containing at least one ester functional group and an unsaturated C=C double bond with a carbon atom directly attached to the acid or ester functional group. In other words, acrylate monomers contain an ester group, which is a vinyl monomer consisting of two carbon atoms in a double bond directly attached to a carbonyl group. Acrylic ester polymers belong to the vinyl polymer family.

[0149] According to this application, acrylic acid is included in the definition of acrylate monomers.

[0150] Preferably, the acrylate polymer comprises units of acrylate monomers derived from formula (III).

[0151]

[0152] Xa and Xb are independently selected from: H, -CN groups, and C1-C8 straight-chain, branched, or cyclic saturated or unsaturated groups containing 1-8 carbon atoms, and Xc is selected from: H, benzyl, and straight-chain, branched, or cyclic saturated or unsaturated aliphatic or aromatic groups containing 1-24 carbon atoms, wherein the aliphatic or aromatic groups are optionally substituted by at least one OH group and / or one COOH group, and / or optionally interrupted by at least one -O- atom.

[0153] Preferably, Xa and Xb are independently selected from H and C1-C8 straight-chain or branched alkyl groups.

[0154] Preferably, Xa = H.

[0155] Preferably, Xb = H, -CN group or C1-C2 alkyl, preferably H or C1-C2 alkyl, more preferably H or methyl.

[0156] Preferably, Xc is selected from:

[0157] -C1-C24, preferably C1-C16, more preferably C1-C8, even more preferably C1-C4 saturated, straight-chain or branched alkyl groups, advantageously methyl or ethyl; and

[0158] -–A–O–Rx group, wherein A is –CH2CH(OH)CH2– or –CH2CH(CH2OH)–, and Rx is a straight-chain or branched alkyl group of C10-C22.

[0159] More preferably, Xc is a saturated, straight-chain or branched alkyl group of C1-C24, preferably C1-C16, more preferably C1-C8, or even more preferably C1-C4, and advantageously is methyl or ethyl.

[0160] The acrylate monomer can be an acrylate having an additional methyl group linked to (Xb), where Xc is a methyl group. The acrylate monomer can also be a methacrylate. One of the most common methacrylate polymers is polymethyl methacrylate (PMMA).

[0161] Acrylic ester monomers, particularly ethyl acrylate, ethyl methacrylate, butyl acrylate, ethylhexyl acrylate or their derivatives.

[0162] The acrylate polymer can be a homopolymer of the preferred acrylate monomer (III), or it can be obtained by copolymerizing the acrylate monomer with one or more other acrylate monomers and / or other non-acrylate monomers to form a copolymer.

[0163] For example, acrylate polymers can be copolymers of methyl acrylate and methyl methacrylate, ethyl acrylate and methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.

[0164] The acrylate polymer can also be an acrylonitrile-styrene (meth)acrylate terpolymer, a styrene-acrylonitrile copolymer with a grafted acrylic elastomer, or a copolymer of styrene and acrylate monomers. Non-acrylate monomers and monomers that can copolymerize with acrylate monomers are preferably selected from the vinyl monomers described above, provided that these vinyl monomers are non-acrylate monomers.

[0165] The non-acrylate monomers that can be copolymerized with acrylate monomers can be C2-C8 (preferably C2-C4) alkenyl monomers, C4-C12 diene monomers, styrene monomers, vinyl alcohol, vinyl acetate, acrylamide monomers, maleic acid, and acrylonitrile.

[0166] The acrylic monomer can be ethyl acrylate, butyl acrylate, ethylhexyl acrylate or their derivatives.

[0167] The vinyl (co)monomer is preferably as shown in the formula C(X)(X')=C(X”)(X”'), where X, X', X” and X”' are as described above.

[0168] Preferably, X = X' = H.

[0169] According to one embodiment, X = X' = H, X” is H or a C1-C2 alkyl group, preferably H, and X”' is –C6H5, –CN, –C(O)NH2, –NC4H6O, -C(O)NHC(CH3)3, -C(O)N(CH3)2, -C(O)NHC(CH3)2(CH2)4CH3 and -C(O)NHC(CH3)2CH2S(O)(O)OH.

[0170] According to another embodiment, X = X' = H, X” = H or C1-C2 alkyl, preferably H, and X”' is -OC(O)-Xm, wherein Xm is a straight-chain or branched C1-C18 alkyl.

[0171] According to another embodiment, X = X' = H, X” = H or C1-C2 alkyl, preferably H, and X”' is -OC(O)-Xm, wherein Xm is a straight-chain or branched C1-C18 alkyl.

[0172] Preferably, the ethylene polymers are not fluorinated; this means that the ethylene polymers do not contain any fluorine atoms.

[0173] According to one embodiment, the vinyl polymer is not sodium poly(meth)acrylate. In particular, the vinyl polymer is not a superabsorbent polymer. Specifically, the vinyl monomer is not a basic salt of acrylic acid or acrylate monomers.

[0174] The composition of this application preferably contains 0.05% to 0.3% by mass, more preferably 0.08% to 0.25% by mass, more preferably 0.1% to 0.2% by mass, and more preferably 0.12% to 0.18% by mass of ethylene polymer relative to the total mass of the composition.

[0175] The compositions of this application preferably contain 0.1% to 5%, more preferably 0.3% to 3%, more preferably 0.5% to 2%, and more preferably 0.8% to 1.5% by mass of an ethylene polymer relative to the mass of the fluoropolymer.

[0176] solvent

[0177] The composition of this application comprises at least one solvent. The composition may comprise a blend of at least two solvents. The ratio between the solvents can be determined based on their respective miscibility, boiling point, and toxicity characteristics. The solvent blend can be adjusted according to the target thickness of a wet and / or dry monolayer containing the composition. The solvent blend can also be adjusted according to industry standards for environmentally friendly zones.

[0178] In the case of a blend of at least two solvents, each solvent is preferably as described below.

[0179] Preferably, the solvent has a boiling point of 95°C to 180°C at atmospheric pressure, more preferably 100°C to 150°C.

[0180] In fact, to minimize the energy required for drying after coating the composition onto the substrate, it is preferable to use solvents with relatively low boiling points. On the other hand, excessively low boiling points can pose safety concerns (e.g., high flammability).

[0181] Preferably, the solvent is an oxyhydrocarbonated solvent, preferably containing 3-7 carbon atoms, more preferably 4-6 carbon atoms, and preferably containing at least one ester or ketone functional group, advantageously selected from cyclopentanone, propyl acetate and propylene glycol methyl ether acetate.

[0182] Oxyhydrocarbon solvents are solvents composed of carbon, hydrogen, and oxygen atoms.

[0183] This solvent offers a good trade-off between its ability to readily dissolve (for short periods and at room temperature) fluoropolymers, silicon-sulfur compounds, and ethylene polymers in total weight contents of 12% to 30%, while yielding compositions with appropriate viscosity that can be coated onto substrates and good safety (flammability and toxicity).

[0184] This application also relates to a method for preparing the composition of this application, comprising mixing a fluoropolymer, a silicon-sulfur compound, and an ethylene polymer in a solvent.

[0185] The method preferably includes a first step of preparing a fluoropolymer solution by mixing a fluoropolymer and a solvent, and a subsequent step of adding a silicon-sulfur compound and an ethylene polymer to the fluoropolymer solution.

[0186] Preferably, all mixing steps are carried out at a temperature of 15°C to 30°C.

[0187] This application also relates to a method for preparing a coated substrate, comprising the steps of applying the composition of this application to the surface of the substrate or a portion thereof, followed by the step of evaporating a solvent.

[0188] The substrate can be, in particular, glass, silicon, quartz, polymer materials, metals, or a mixture of several of these materials.

[0189] Preferably, the substrate is or includes metal, particularly selected from gold, stainless steel, copper and aluminum, chromium and silver.

[0190] Preferably, the substrate comprises a metal surface, particularly gold, stainless steel, copper, aluminum, chromium, or silver, and more particularly copper or gold. Preferably, a monolayer is applied to and in contact with said metal surface.

[0191] According to one embodiment, the substrate includes a gold surface, preferably composed of gold.

[0192] According to another embodiment, the substrate includes a copper surface, preferably composed of copper.

[0193] The substrate can be of any shape. It can be flat or undulating, smooth or rough, linear or curved, porous or non-porous. Attached Figure Description

[0194] Figure 1 This is a circuit diagram used to measure the capacitance and loss factor of a polymer monolayer.

[0195] The following examples illustrate this application, but do not limit it. Example

[0196] Example 1—The Influence of the Presence and Properties of Compounds

[0197] Several compositions were prepared on a laboratory scale according to the following protocol (each step was performed at room temperature):

[0198] 1 / Weigh the solvent in the vial;

[0199] 2 / Weigh the fluoropolymer in the same vial, stir the mixture for 30 minutes, and then let it stand for 1 hour;

[0200] 3 / Weigh the silicon-sulfur compound and ethylene polymer and add them to the vial. Then, stir the mixture for 10 minutes, and then let it stand until all bubbles disappear. The total content of the "active ingredients" (fluoropolymer, silicon-sulfur compound, and ethylene polymer) is 15% by mass.

[0201] Each composition is then applied to the metallized substrate by screen printing, and the solvent is evaporated by heating.

[0202] Use transparent tape to assess the adhesion of each layer according to the following method:

[0203] Tape type: 3M 2525

[0204] Bond strength of steel: 75 N / 100 mm

[0205] step:

[0206] 1 / Cut a piece of adhesive about 3 cm long and fold one end over.

[0207] 2 / Apply adhesive to the sample by applying controlled and uniform pressure (finger pressure) to the sample surface.

[0208] 3 / Use medium, constant force (by hand) to peel off the adhesive at a 180° angle.

[0209] 4 / Visually inspect the test area on the sample to identify any delamination of the film on the substrate.

[0210] Scoring criteria:

[0211] 5. No delamination; all layers on the substrate remain intact.

[0212] 4: In the area where the tape is applied, less than 5% of the layer (surface) delaminates.

[0213] 3: In the area where the tape is applied, 5% to 15% of the layer (surface) delaminates.

[0214] 2: In the area where the tape is applied, 15% to 35% of the layer (surface) should be delaminated.

[0215] 1: In the area where the tape is applied, 35% to 65% of the layer (surface) is delaminated.

[0216] 0: More than 65% of the layer (surface) delaminates on the area where the tape is applied.

[0217] The horizontal adhesive strength of each monolayer after immersion in the aqueous solution was also evaluated according to the following scheme:

[0218] Soaking delay: 3 days, 7 days, 10 days, 14 days

[0219] step:

[0220] 1 / Prepare an aqueous bath

[0221] 2 / Immerse each sample completely in the aqueous solution, carefully avoiding contact with or friction against the layer (this may damage it).

[0222] 3 / Close the container to prevent the aqueous solution from evaporating.

[0223] 4 / Take samples after soaking for x days.

[0224] 5. Carefully wipe away any remaining aqueous solution from the layer with a lint-free cloth, ensuring the layer remains, and allow it to dry.

[0225] 6 / Perform a peel test using the steps and standards described above.

[0226] Table 1 contains detailed information on each layer composition and the test results for each layer, where the ethylene polymer content and adhesive accelerator content are calculated relative to the weight of the fluoropolymer:

[0227]

[0228] *:Compare

[0229] Table 1: Composition and Experimental Results of Each Layer in MPTMS

[0230]

[0231] MPMDMS:

[0232]

[0233] Pentaerythritol tetra(3-mercaptopropionate):

[0234]

[0235] These results indicate that even after immersion in aqueous solution for 14 days, the presence of adhesion promoters and vinyl polymers is necessary to obtain fluoropolymer layers exhibiting high adhesion properties.

[0236] They also showed that even after soaking in aqueous solution for 14 days, sulfur compounds without any silicon could not effectively produce fluoropolymer layers exhibiting high adhesion properties.

[0237] The dielectric properties of the adhesion-improving layer were compared with those of a single-layer fluoropolymer. Test samples were prepared according to the following protocol:

[0238] 1. Coat the polymer layer onto the metal foil and cure it as described above.

[0239] 2. Place a mask containing several circular holes over the polymer film.

[0240] 3. By placing the stack within the metallized device, vapor-deposited gold can be applied onto a thin film not covered by the mask to create conductive pads of a predetermined surface area.

[0241] 4. Then, the actual surface area of ​​each pad is measured using a microscope.

[0242] 5. The capacitance C and loss factor tanδ of each pad were measured at different frequencies (1, 10, 50, and 100 kHz) using a GWIntek LCR-819 device (see [link to 5]). Figure 1 ).

[0243] The dielectric constant ε represents a material's tendency to store electrical energy in an electric field. It essentially defines how a material responds to an electric field and describes the polarizability of a dielectric material: materials with high dielectric constants respond more strongly to an applied electric field than those with low dielectric constants, thus storing more energy within the material. It is a fundamental property of electromagnetism and plays a crucial role in the design of capacitors, insulators, and other electronic devices.

[0244] The loss factor tanδ quantifies the energy loss of a dielectric material under an alternating electric field. It represents the dissipative effects within the material, such as energy loss caused by dielectric conductivity and dipole orientation.

[0245] Relative permittivity ε r Calculate using the following formula:

[0246]

[0247] Where C = capacitance, t = film thickness, and A s = Pad surface area, ε0 = Vacuum dielectric constant.

[0248] Each measurement was repeated 15 to 18 times, and the average values ​​of the dielectric constant and loss factor were calculated. The results are summarized in the table below, showing the average values:

[0249]

[0250] These results indicate that all these layers exhibit remarkably identical dielectric properties, regardless of whether they consist solely of fluoropolymers, mixtures of fluoropolymers and silicon-sulfur compounds, or mixtures of fluoropolymers, silicon-sulfur compounds, and vinyl compounds. Surprisingly, the presence of silicon-sulfur compounds and vinyl compounds does not alter the dielectric properties of the fluoropolymers, even though they themselves possess no dielectric properties.

[0251] These results indicate that the adhesion promoter not only provides better adhesion and avoids delamination after immersion in water, but also limits the decrease in dielectric constant.

[0252] Therefore, this single layer can withstand humidity, water immersion or other liquid contact, and can still perform responses in electronic applications such as actuators (devices that convert electrical energy into mechanical motion), sensors (devices that detect changes in the environment and convert them into electrical signals), or energy storage devices (electrodes and membranes in batteries and supercapacitors).

[0253] Example 2—Influence of Solvent Properties

[0254] Several compositions were prepared according to the following scheme (each step was carried out at room temperature):

[0255] 1 / Weigh the solvent in a vial (its properties may vary; the volume may be 125 mL or 250 mL);

[0256] 2 / Weigh the fluoropolymer (P(VDF-TrFE-CTFE)) in the same vial, stir the mixture for 30 minutes, and then let it stand for 1 hour;

[0257] 3 / Weigh the silane-sulfur compound (MPMDMS) and ethylene polymer (PMMA) in a vial, stir the mixture for 10 minutes, and then let it stand until all bubbles disappear. The total content of the "active ingredients" (fluoropolymer, silane coupling compound, and ethylene polymer) is 10 or 15% by mass. The solid content of the non-solvent compound relative to the solvent mass is expressed as wt% in MS.

[0258] For each composition, its solubility was visually evaluated after mixing the composition components in a planetary mixer for 1.5 hours.

[0259] The viscosity of some of the compositions was also evaluated at 23°C using standard laboratory methods, with a cone-plate rheometer and a shear rate of 10 s⁻¹.

[0260] The solvent properties and related results for each composition are summarized in Table 2:

[0261]

[0262]

[0263] Table 2: Solvent properties, solubility, and viscosity results for each composition.

Claims

1. A composition comprising: - Fluoropolymers, -Silicon-sulfur compounds, - Ethylene polymers composed of carbon and hydrogen atoms, and optionally oxygen and / or nitrogen atoms, and - A solvent or a mixture of solvents.

2. The composition according to claim 1, wherein the sum of the mass contents of the fluoropolymer, the silicon-sulfur compound, and the ethylene polymer is 5% to 30% relative to the total mass of the composition.

3. The composition according to claim 1, wherein the fluoropolymer comprises units of a fluorine monomer derived from formula (I): C(X1)(X2)=C(X3)(X4)(I), X1, X2, X3 and X4 are each independently selected from H, Cl, Br, F, I and C1-C6 straight-chain or branched alkyl groups, wherein the C1-C6 straight-chain or branched alkyl groups are optionally partially or completely halogenated, provided that at least one of X1, X2, X3 and X4 contains at least one fluorine atom.

4. The composition according to claim 1, wherein the fluoropolymer is a terpolymer of vinylidene fluoride with a second fluorinated monomer and a third fluorinated monomer, provided that the second fluorinated monomer and the third fluorinated monomer are different from vinylidene fluoride and are distinct from each other, and wherein the second fluorinated monomer and the third fluorinated monomer are as shown in formula (I): C(X1)(X2)=C(X3)(X4)(I), X1, X2, X3, and X4 are each independently selected from: H, Cl, Br, F, I, and C1-C6 straight-chain or branched alkyl groups, wherein the C1-C6 straight-chain or branched alkyl groups are optionally partially or completely halogenated. The condition is that at least one of X1, X2, X3 and X4 contains at least one fluorine atom.

5. The composition according to claim 1, comprising 3% to 30% by mass of a fluoropolymer relative to the total mass of the composition.

6. The composition according to claim 1, wherein the silicon-sulfur compound is as shown in formula (II): (Rd)S–Rw–Si(Ra)(Rb)(Rc)(II), Rw is a straight-chain, branched, or cyclic group comprising 1 to 18 carbon atoms and optionally one or more oxygen atoms and / or nitrogen atoms, Ra, Rb, and Rc are each independently selected from: H, OH, Alk, and -O-Alk, Alk being a C1-C8 straight-chain or branched alkyl group, and Rd is selected from: H and an organic moiety comprising 1 to 30 carbon atoms, at least one nitrogen atom, and / or at least one oxygen atom.

7. The composition according to claim 1, comprising 0.05% to 0.3% by mass of a silicon-sulfur compound relative to the total mass of the composition.

8. The composition of claim 1, wherein the vinyl polymer comprises a vinyl unit derived from the formula C(X)(X')=C(X”)(X”'), wherein X, X', X” and X”' are independently selected from: hydrogen atom, OH group, COOH group, CN group, aryl group, and saturated or unsaturated hydrocarbon group comprising 1 to 10 carbon atoms, wherein the aryl or hydrocarbon group optionally further comprises OH group, ester group, carboxyl group, amino group, nitrile group and / or amide group.

9. The composition according to claim 1, wherein the ethylene polymer is an acrylate polymer comprising units of an acrylate monomer derived from formula (III): Xa and Xb are independently selected from: H, -CN groups, and C1-C8 straight-chain, branched, or cyclic saturated or unsaturated groups containing 1 to 8 carbon atoms, and Xc is selected from: H, benzyl, and straight-chain, branched, or cyclic saturated or unsaturated aliphatic or aromatic groups containing 1 to 24 carbon atoms, wherein the aliphatic or aromatic groups are optionally substituted by at least one OH group and / or one COOH group, and / or optionally interrupted by at least one -O- atom.

10. The composition according to claim 1, comprising 0.05% to 0.3% by mass of an ethylene polymer relative to the total mass of the composition.

11. The composition according to claim 1, wherein the solvent has a boiling point of 95°C to 180°C at atmospheric pressure.

12. The composition according to claim 1, wherein the solvent is an oxyalkylating solvent, preferably containing 3-7 carbon atoms.

13. The composition of claim 1, wherein the solvent comprises at least one ester or ketone functional group.

14. The composition according to claim 1, wherein the viscosity is 10 to 20,000 cP, preferably 100 to 10,000 cP.

15. A method for preparing the composition of any one of claims 1-14, comprising mixing a fluoropolymer, a silicon-sulfur compound, and an ethylene polymer in a solvent.

16. A method for preparing a coated substrate, comprising the step of applying the composition of any one of claims 1-14 to a surface or a portion thereof of a substrate, followed by the step of evaporating a solvent.

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