Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/54—Nitrogen-containing linkages
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

• the present invention relates to a process for obtaining an improved biocidal and virucidal coating.
• a coating created from epoxy resin, corresponding to a thermosetting liquid polymer is known.
• epoxy resin When epoxy resin is cured, often in the presence of a catalyst, it can be shaped to the needs of the user. For example, it can be smoothed, cut or perforated. It works in liquid form and is applicable in many areas such as jewelry, furniture or even flooring.
• this resin has the disadvantage of requiring several days of drying to be hardened and the hardness depends on the temperature or the time of treatment or the presence of catalysts. Another disadvantage of this resin is that it degrades over time.
• patent US8158191 discloses a two-step process: a first layer of polyurethane is applied to a surface of a polycarbonate or polyamide substrate, then a silane-type coating resistant to 'abrasion.
• US4345053 discloses a moisture-curable sealant composition for application to non-porous substrates.
• the sealing composition comprises a silicon-terminated polymer which is obtained by reaction between a polyurethane, polyether or polyethylene prepolymer carrying two OH (or amine) functions with a polyisocyanate.
• a polyurethane, polyether or polyethylene prepolymer carrying two OH (or amine) functions with a polyisocyanate.
• an organosilane carrying an isocyanate group is then added. The process is therefore carried out in several stages.
• Patent EP2785801 discloses a process for obtaining a curable film-forming composition applied to the substrate to attenuate the accumulation of ice on the substrate. This composition consists of two layers that are applied one after the other.
• Patent EP3209739 discloses a composition for obtaining a two-component coating.
• the coating as a product, does not contain isocyanate which has not reacted during the production process, which is an essential characteristic of this document. Unreacted isocyanates are removed from the mixture in an additional step. The crosslinking is done via epoxy or acrylate functions. Thus, the processes of the prior art are carried out in two stages, each being well controlled.
• Quaternary ammoniums coupled to an aliphatic chain have been used as a bactericidal or even virucidal agent for the development of antibacterial or antiviral coatings, in particular those in the form of an organosilane, such as 3- (trihydroxysilyl) propyldimethyloctadecyl-ammonium chloride. Indeed, several scientific studies show that quaternary ammoniums prevent the growth of bacteria and certain viruses on solid supports.
• Document EPI 863865 discloses a process for the preparation of a quaternary ammonium antibacterial agent containing silica combined with other polymers.
• Document EP2285857 presents an antibacterial coating in the form of an interconnected polyurethane-silica network with quaternary ammoniums used as an antibacterial agent.
• the process is carried out in two stages, the first stage consists in preparing a polyurethane functionalized by a siloxane function and a second stage where the siloxane functions carried by the polyurethane react with the siloxanes carrying quaternary ammoniums at temperatures between room temperature and 100°C.
• the advantage of a two-step process is that there is good control of the different reactions, that any excess reagents can be neutralized. Also, catalysts or other compounds that are not desired in the coating are easily removed.
• Patent application KR 10-2020-0103424 describes a process for obtaining a coating in which dimethyl octadecyl (3- (trimethoxysilyl) propyl) ammonium (TPDA) is mixed with a polysilsequioxane derivative (TEOS), and then , a second and then a third quantity of TPDA are added, the mixture then being applied to its substrate.
• TPDA dimethyl octadecyl (3- (trimethoxysilyl) propyl) ammonium
• TEOS polysilsequioxane derivative
• the present invention aims to solve the drawbacks of the state of the art, in particular to provide a process for obtaining a coating which is easy, rapid and economical, the coating being biocidal and virucidal and having reinforced mechanical resistance.
• a first object of the present invention consists of a process for obtaining a transparent and biocidal coating in which: a cyclic organic molecule is mixed comprising at least two silane functions which can be hydrolyzed into two silanol groups and dimethyloctadecyl(3- (trimethoxysilyl) propyl) ammonium (or any other molecule having a biocidal function and an equivalent structure, but whose hydrocarbon chain comprises a carbon number other than 18, for example 8, 9, 10, 11, 12, 13, 14 , 15, 16, 17) in an aqueous solution or a water/water-soluble organic solvent mixture, this mixture is acidified and left to gel, this gelled mixture is applied to a substrate under conditions allowing the crosslinking of the groups silanol formed.
• a cyclic organic molecule is mixed comprising at least two silane functions which can be hydrolyzed into two silanol groups and dimethyloctadecyl(3- (trimethoxysilyl) propyl)
• the substrate is glass, a metallic surface (non-ferrous or ferrous, including steel), plastic.
• a related aspect of the present invention relates to the coating obtainable by the above process.
• this related aspect of the present invention relates to a coating of a surface which is transparent, bactericidal and virucidal comprising at least 20% by mass of dimethyloctadecyl (3- (trimethoxysilyl) propyl) ammonium (or any other molecule having a biocidal function and an equivalent structure, but whose hydrocarbon chain comprises a carbon number other than 18, for example 8, 9, 10, 11, 12, 13, 14 , 15, 16, 17) and at least 25% by mass of a crosslinking agent being a cyclic organic molecule comprising at least two silane functions hydrolysable into two silanol groups, said silanol groups having formed a siloxane network with the silyl functions of said dimethyloctadecyl(3-(trimethoxysilyl)propyl)ammonium molecule.
• Another aspect of the present invention relates to the virucidal use of this coating.
• Another aspect of the present invention relates to a glass or a plastic covered by this coating.
• adding this molecule in large quantities is difficult because the physical properties of the coating (transparency, adhesion, scratch resistance, mechanical strength) must be preserved, in particular for a coating to be applied to glass: the high concentrations may cause clumping or precipitation, resulting in an unacceptable coating.
• a first object of the present invention consists of a process for obtaining a coating in which: a cyclic organic molecule is mixed comprising at least two silane functions which can be hydrolyzed into two silanol groups ('crosslinking agent') and dimethyloctadecyl ( 3-(trimethoxysilyl) propyl) ammonium ('quaternary amine' and/or biocidal molecule; or any other molecule having a biocidal function and an equivalent structure, but whose hydrocarbon chain comprises a carbon number other than 18, for example 8, 9, 10, 11, 12, 13, 14, 15, 16, 17) in an aqueous solution or a water/water-soluble organic solvent mixture, this mixture is acidified and left to gel, this mixture is applied gelled on a substrate under conditions allowing the crosslinking of the silanol groups formed.
• this multifunctional (di- or trifunctional) cyclic organic crosslinking agent provides rigidity to the final product and allows correct crosslinking.
• hydrolyzable silane functions in silanol group preferably means that an Si atom is derivatized by 1, 2, or, preferably 3, hydrolyzable groups, such as alkoxy groups . Methoxy or ethoxy groups are preferred. During the steps of the process, at least one of these groups will be hydrolyzed (in an acid medium), so as to release an alcohol and to generate Si-OH (silanol) functions, which can then be crosslinked together, so as to create a siloxane network. In the part of the invention relating to the coating, this terminology is sometimes retained and signifies the origin of the product, but also includes any alkoxy functions which would not have not been hydrolyzed.
• sil is also used to designate the molecule, regardless of whether it is original (alkoxy-silane) or hydrolyzed to silanol.
• Controlled acidification and the choice of water concentration allow crosslinking kinetics that are neither too fast nor too slow. Too rapid cross-linking resulting in inhomogeneities in the gel and/or precipitation, which is detrimental. A properly formed gel can be easily applied and will be transformed into a coating with the required qualities.
• the quaternary ammonium (biocidal molecule) is added via a composition and this quaternary ammonium is substantially pure, for example at a concentration of at least 40% (weight of the quaternary ammonium: total weight of the composition including the solvent ), at least 50% (by weight), at least 60% (by weight), or even at least 70% (by weight); alternatively, without counting the solvent, the quaternary ammonium is at least 80% pure (quaternary ammonium weight dry weight of the composition), at least 83%, ideally even purer. This means that there are few 'dry' contaminants in the composition comprising the quaternary ammonium.
• viral activity in the context of the present invention, is preferably meant the ability of the coating or one of its constituents to significantly reduce the quantity of virus which would be placed therein, in particular of viruses enveloped in a membrane.
• the reduction is at least 80%, preferably at least 85%, at least 90%, at least 95%, even 99% or more, this preferably for a measurement time of between 30 minutes and 5 hours , advantageously after approximately 3 hours of measurement.
• viruses enveloped in a membrane placed on the coating according to the invention are thus neutralized due to the interaction of the coating or of one of its constituents with its membrane, which makes them non-infectious (even if they can still be recognized by the immune system, which is, in practice, advantageous: in addition to passive immunization of populations, such deactivated viruses could be harvested from the surfaces according to the invention and administered to patients, in particular in countries where it is difficult to administer vaccines that must be stored at very low temperatures).
• the mixture further comprises an (adhesion) molecule comprising a function that can be hydrolyzed into a silanol group and a function allowing adhesion to the substrate, the method further comprising the step of fixing the gelled mixture (further comprising this adhesion molecule) on the substrate by a physical means, such as a baking step (eg at 100° C.-170° C., for example around 150° C.) or UV treatment, or else by reaction chemical with the substrate or with any primer coat that may have been deposited on the substrate.
• a physical means such as a baking step (eg at 100° C.-170° C., for example around 150° C.) or UV treatment, or else by reaction chemical with the substrate or with any primer coat that may have been deposited on the substrate.
• this adhesion molecule dilutes the concentration of crosslinking agent and of quaternary amine, so that its concentration must be well adapted. Ideally no more than about 20% by weight (weight of this adhesion molecule weight of constituents of the composition), thus a preferred value range is from 5% to about 20% by weight.
• the group (ii) can advantageously react with the thiol or with the amine of the primary layer if it is present, or directly with the substrate, for example if the group (ii) is an acrylate derivatized by a (tetra hydro)furan and the substrate is the plastic (by means of UV radiation).
• dry constituents preferably includes all of the molecules inserted into the mixture, with the exception of solvents such as water and alcohols (eg isopropanol, but also ethanol, methanol, or even other organic solvents used).
• the dry constituents therefore include at least the crosslinking agent and dimethyloctadecyl (3- (trimethoxysilyl) propyl) ammonium (and/or any other molecule having a biocidal function and an equivalent structure, but whose hydrocarbon chain comprises another number of carbon than 18, for example 8, 9, 10, 11, 12, 13, 14, 15, 16, 17).
• dry constituents will also include any dry contaminants of dimethyloctadecyl(3-(trimethoxysilyl)propyl)ammonium such as (3-chloropropyl)trimethoxysilane, any adhesion molecules, or even the polymer (adjuvant) derivatized at both ends, each by a silane group which can be hydrolyzed to silanol (see below).
• dry constituents essentially consist of all the molecules inserted into the mixture (described above in this paragraph), with the exception of the solvents.
• the crosslinking agent the crosslinking agent
• the cyclic organic molecule comprising at least two hydrolyzable silane functions in two silanol groups
• the percentage is by weight: weight of this cyclic organic molecule comprising at least two silane functions which can be hydrolyzed into two silanol groups, relative to the weight of the sum of the dry constituents as described above.
• Such a percentage ensures the rigidity of the coating, its scratch resistance, and good cross-linking. This percentage may be reduced somewhat (eg 20 or 25%) when the polymer (adjuvant) derivatized at both ends is added (see below).
• more than 20%, preferably more than 25%, 30%, 35% such as about 40%, in (quaternary ammonium biocide) dimethyloctadecyl (3- (trimethoxysilyl) propyl) ammonium is added to the composition. It is a percentage wt:wt of dimethyloctadecyl(3-(trimethoxysilyl)propyl)ammonium, based on the weight of the sum of the dry constituents, as described above.
• this method comprises the step of adding to the mixture a polymer (polymer adjuvant) comprising at each of its two ends a terminal silane function hydrolyzable in silanol group (therefore in all two terminal silane/silanol functions).
• this polymer is a copolymer having segments of different stiffness.
• this (co-)polymer is chosen from polyester, polyether, polyurethane, polycarbonate and polyacrylate, or even a mixture of two (two polyesters, or a polyester and one of the other polymers, a polyether and one of the other polymers, a polyurethane and one of the other polymers, a polycarbonate and one of the other polymers).
• this (co-)polymer has a mass of between 500 and 2200 Da (i.e. 300 to 2000 Da of polymer without counting the silane-alkoxy functions), preferably between 700 and 1700 Da (i.e. 500 to 1500 Da of polymer without counting the silane-alkoxy functions) or between 700 and 1200 Da (i.e. 500 to 1000 Da of polymer without counting the silane-alkoxy functions).
• this (co-) polymer (adjuvant) is added at a content of between 5 and 25% by weight: weight of the (co-) polymer, weight of all the dry constituents of the mixture, preferably between 7 and 20 % by weight, more preferably between 10 and 15% by weight.
• the content of crosslinking agent can be reduced, for example to a content of 25% by weight, or 30% by weight (weight of crosslinking agent: weight of the sum of the dry constituents). This maintains the high biocidal quaternary amine content. Alternatively, it may even be somewhat reduced, given the excellent results obtained by the inventors.
• this particular (co-)polymer allowed more quaternary ammonium functions (biocide) to be exposed to the surface of the coating, which retained its mechanical properties.
• the coating retains its advantageous physical properties and the final biocidal effect, in particular virucidal effect, is advantageously increased.
• the inventors have noted a more advantageous effect when the polymer is, in practice, a copolymer (eg composed of two different polyesters) and/or a structure having a more rigid segment and a less rigid. According to the expertise of the inventors, the more rigid segments provide mechanical strength, while the less rigid segments (certain polyesters, or oligoethers) provide better impact resistance.
• the mixture is acidified to a pH between 2.5 and 5.0, advantageously between 3 and 4 (3.0 and 4.0).
• This pH is advantageously fixed by adding a medium-strength acid (see below).
• the mixture resulting from this process is applied to the substrate by centrifugation (spin coating): application in one or more places on the substrate, then centrifugation in such a way to evenly cover the substrate.
• centrifugation spin coating
• Other methods that can be applied on a larger scale are spraying, dip coating, flow coating or the roll to roll procedure.
• the substrate is glass, a metallic surface (non-ferrous or ferrous, including steel), ceramic or plastic.
• the substrate is glass, which represents a particular difficulty since the transparency of the coating must be ensured everywhere.
• the method comprises the preliminary step of applying a primer layer to the glass, the primer layer consisting (essentially) of a siloxane network comprising primary amines or thiol functions; in addition the (adhesion) molecule comprising a function that can be hydrolyzed into a silanol group and a function allowing adhesion to the substrate is present: this function allowing adhesion to the substrate (to the primer layer) is preferably an epoxide, of preferably the 3- Glycidyloxypropyl)trimethoxysilane; CAS 2530-83-8), this method preferably comprising a final stage of baking on the substrate at a temperature above 100° C. (eg at around 150° C.).
• the (adhesion) molecule comprising a function that can be hydrolyzed into a silanol group comprises, as function allowing adhesion to the substrate (to the primer layer), an acrylate or a methacrylate.
• the adhesion molecule is incorporated at a content of between 10 and 30% by weight: weight of the adhesion molecule: dry weight of the mixture, preferably between 15 and 20% by weight. Since this adhesion molecule is added to the detriment of the crosslinking agent and of the bifunctional polymer (adjuvant) (if present), or even of the biocidal quaternary ammonium, its presence somehow dilutes the active principles, so that the lowest content which ensures good attachment to the substrate is preferred.
• the epoxide or acrylate groups will react with the amines or thiols of the primer layer, which ensures good attachment of the coating to its substrate (the glass). This also works when the substrate is the metal (same primer layer comprising a primary amine or a thiol, adhesion molecule comprising a (meth)acrylate).
• a catalyst of the phosphine type is added during the baking step.
• Another advantageous substrate is plastic, preferably plastics which resist temperatures of 100° C. or even higher. Indeed, many surfaces potentially contaminated by pathogens are made of plastic (door handles, everyday objects, shopping carts, support systems in public transport, public seats, kitchen utensils, surfaces in communities, etc. .): the inventors have understood that the covering of these surfaces with the biocidal coating of the present invention would solve a major problem, which goes beyond the management of Covid-19.
• the method comprises the step of adding to the reaction mixture an adhesion molecule being an acrylate (and/or a methacrylate), for example an a (meth)acrylate comprising one or more hydrolysable functions into a silanol and (a (meth)acrylate) group comprising one or more (tetrahydro)furan function(s) (ideally the same molecule carries both functions); the method further comprising the step of fixing the mixture to the substrate by baking (at a temperature compatible with plastics), or by applying ultraviolet radiation, preferably before applying the conditions allowing the crosslinking of the silanol groups formed ( curing at a temperature compatible with the plastic, such as at a temperature of approximately 100°C), or during conditions allowing the crosslinking of the silanol groups formed (eg slower crosslinking at a temperature below 100°C) .
• an adhesion molecule being an acrylate (and/or a methacrylate), for example an a (meth)acrylate comprising one or more hydroly
• the adhesion molecule (acrylate) is incorporated at a content of between 10 and 40% by weight: weight of the adhesion molecule: dry weight of the mixture, preferably between 15 and 20% by weight. Since this molecule is added to the detriment of the crosslinking agent, or even of the biocidal quaternary ammonium, its presence dilutes the active ingredients in a way, so that the lowest content which ensures good attachment to the substrate is preferred. . However, in case the acrylate and/or methacrylate (adhesion molecule) is the adjuvant polymer (e.g.
• this acrylate copolymer can be incorporated in larger quantities, since its dilutive effect is nuanced, since it replaces the adhesion copolymer, the adjuvant polymer and the adhesion molecule being the same entity.
• the cyclic organic molecule (crosslinking agent) comprising at least two silane functions which can be hydrolyzed into two silanol groups consists (is) of a planar organic ring, preferably the ring consists solely of carbon and nitrogen atoms, these (at least 2) carbon and/or nitrogen atoms being derivatized by an alkoxysilyl group, preferably said molecule is Tris[3-(trimethoxysilyl)propyl]isocyanurate; CAS 261 15-70-8, or 1,4-Bis(trimethylsilyl)benzene; CAS 13183-70-5.
• the silane group is not part of the cycle and is grafted onto one of the atoms (C or N) constituting the cycle.
• the solvent is a water:alcohol mixture (a water-soluble alcohol), preferably water:isopropanol, preferably in a mass ratio of between 1:1 and 1:5, such as around:2.
• a water:alcohol mixture a water-soluble alcohol
• water:isopropanol preferably in a mass ratio of between 1:1 and 1:5, such as around:2.
• the inventors have noticed that the addition of an alcohol slows down the hydrolysis of the silane groups into silanol.
• Alcohols are preferred over other organic solvents that do not have a hydroxyl function.
• Preferred alcohols are short chain, and/or water soluble. Methanol, ethanol, propanol isomers, and mixtures thereof are preferred.
• the acid is of medium strength (l ⁇ pKa ⁇ 4; preferably l ⁇ pKa ⁇ 2) and is added at a maximum content of 5% by weight of the acid (weight of the acid: weight dry constituents), so as to obtain the acid pH (pH from 2.5 to 5 or from 3 to 4).
• this acid has a boiling point close to the cooking temperature (between 100°C and 170°C; for example either approximately 100°C, or approximately 150°C, or between 100°C and 150°C ), which preferably means a boiling temperature lower than or equal to the cooking temperature expressed in degrees Celsius plus or minus 15% (preferably plus or minus 10%).
• a preferred acid is an ester of phosphoric acid, such as phosphoric acid dibutyl ester.
• a related aspect of the present invention relates to the coating obtainable by the above process.
• this coating has a thickness of between 1 and 40 ⁇ m, preferably between 2 and 20 ⁇ m, more particularly between 3 and 10 ⁇ m, or even between 3 and 5 ⁇ m.
• this related aspect of the present invention relates to a coating of a surface which is transparent, bactericidal and virucidal comprising at least 20% by mass of dimethyloctadecyl (3- (trimethoxysilyl) propyl) ammonium and at least 30% by mass of a crosslinking agent being a cyclic organic molecule comprising at least two silane functions which can be hydrolyzed into two silanol groups, said silanol groups having formed a siloxane network with the silyl functions of said molecule being dimethyloctadecyl(3-(trimethoxysilyl)propyl)ammonium.
• this coating comprises at least 35% (preferably about 40% by mass) by mass of the biocidal quaternary ammonium having been incorporated: weight of dimethyloctadecyl(3- (trimethoxysilyl) propyl) ammonium: sum of the weights of the dry constituents of the composition and at least 25% (preferably at least 30 or 35%) by weight of a crosslinking agent (weight of the crosslinking agent: weight of all of the dry constituents of the composition).
• this coating also comprises a polymer (adjuvant) comprising two silane functions which can be hydrolyzed into silanol groups, one at each of the two ends of the polymer, which is inserted into the siloxane network.
• this polymer is a copolymer having segments of different stiffness.
• this polymer has a size of between 500 and 2200 Da (i.e. 300 to 2000 Da of polymer without counting the silane-alkoxy functions), preferably between 700 and 1700 Da (i.e. 500 to 1500 Da of polymer without counting silane-alkoxy functions) or between 700 and 1200 Da (i.e. 500 to 1000 Da of polymer without counting the silane-alkoxy functions).
• this polymer is chosen from polyester, polyether, polyurethane, polycarbonate and polyacrylate; polyester being preferred.
• this coating allows the reduction of at least 85% of the viral load, calculated according to the ISO21702:HCoV-229E standard, preferably at least 90%, at least 95%, or even 99% reduction in the viral load.
• Another aspect of the present invention relates to the virucidal use of this coating.
• Another aspect of the present invention relates to a glass, a metal surface or a plastic covered by this coating.
• Another aspect of the present invention relates to a method for the neutralization of (membrane) viruses, comprising the step of coating a surface with the virucidal coating of the present invention.
• this method further comprises the step of harvesting the neutralized viruses.
• composition comprising these neutralized viruses.
• Another related aspect of the invention relates to a primary composition for the coating of the present invention, this primary composition comprising (or consisting essentially of) (i) a molecule comprising a function hydrolyzable into a silanol group and a primary amine function or secondary, or a thiol group, and (ii) a tetravalent molecule, chosen from tetraalkoxy silicate, tetraalkoxy titanate and tetraalkoxy zirconate.
• the terminology “consisting essentially of (i) a molecule comprising a function hydrolysable into a silanol group and a primary or secondary amine function, or a thiol group, and (ii) a tetravalent molecule, chosen from tetraalkoxy silicate, tetraalkoxy titanate and tetraalkoxy zirconate” preferably means that the sum of the weights of molecules (i) and (ii) is greater than 50% of the dry weight (excluding solvents such as water or alcohols) of the primary composition, preferably greater than 60%, preferably greater than 70%, preferably greater than 80%, 90% or even greater than 95%.
• a related aspect is a kit comprising in a container the molecule comprising a function hydrolysable into a silanol group and a primary or secondary amine function, or a thiol group and, in a second container, a tetravalent molecule, chosen from among tetraalkoxy silicates , tetraalkoxy titanate and tetraalkoxy zirconate.
• the tetravalent molecule is a tetraalkoxy silicate, preferably (i) said tetraalkoxy silicate, and (ii) the molecule comprising a function hydrolysable into a silanol group and a primary or secondary amine function, or a thiol group being in a ratio mass between 90:10 and 50:50, preferably 75:25 and 55:45, such as about 60:40.
• the molecular mass of the molecule comprising a function hydrolysable into a silanol group and a primary or secondary amine function, or a thiol group is that of 3 -aminopropyltriethoxysilane, which is the preferred molecule.
• the tetravalent molecule is a tetraalkoxy silicate
• the latter can be formulated directly with the molecule comprising a function which can be hydrolyzed into a silanol group and a primary or secondary amine function, or a thiol group.
• this formulation is under anhydrous conditions and without the addition of a hydrolysis catalyst such as a weak acid.
• the tetravalent molecule is a tetraalkoxy titanate, preferably said tetraalkoxy titanate and the molecule comprising a function hydrolyzable into a silanol group and a primary or secondary amine function, or a group Thiol are therefore in a mass ratio between 1:99 and 20:90, preferably 2:98 and 10:90, such as about 5:95.
• the tetraalkoxy titanate and the molecule comprising a function which can be hydrolyzed into a silanol group and a primary or secondary amine function, or a thiol group are preferably packaged in two containers.
• the mixture will preferably be placed in the presence of the solvent being a water:alcohol mixture, for example at least 50% (v:v) of alcohol, at least 60, 70, 80, 90, 95% alcohol, or even without water added to the alcohol.
• the alcohol preferably being methanol, ethanol or an isomer of propanol.
• the tetravalent molecule is a tetraalkoxy zirconate, preferably said tetraalkoxy zirconate and the molecule comprising a function hydrolysable into a silanol group and a primary or secondary amine function, or a thiol group being in a mass ratio of between 1 :99 and 20:90, preferably 2:98 and 10:90, such as about 5:95.
• the inventors have noticed that these last two molecules, based on Ti or Zr, react much more quickly, which explains the reduced contents.
• the tetraalkoxy zirconate and the molecule comprising a function which can be hydrolyzed into a silanol group and a primary or secondary amine function, or a thiol group are preferably packaged in two containers.
• the mixture will preferably be placed in the presence of the solvent being a water:alcohol mixture, for example at least 50% (v:v) of alcohol, at least 60, 70, 80, 90, 95% alcohol, or even without water added to the alcohol.
• the alcohol preferably being methanol, ethanol or an isomer of propanol.
• Another related aspect is a process for applying the primer to its substrate, the substrate preferably being chosen from among glass, metal and ceramic, comprising the steps of mixing a molecule comprising a hydrolysable function into a silanol group and a primary or secondary amine, or a thiol group, with a tetravalent molecule, chosen from among tetraalkoxy silicates, tetraalkoxy titanates and tetraalkoxy zirconates, or to obtain such an anhydrous mixture of these two molecules, to dissolve this mixture in water, alcohol or a water:alcohol mixture in the presence of a catalyst, and applying it to the substrate.
• this method then comprises the step of applying the coating of the invention described above and finally, preferably, when the substrate is glass, metal or a ceramic, a physical treatment, such as firing at a temperature above 100°C.
• the preferred alcohol is selected from methanol, ethanol and propanol isomers.
• a preferred catalyst is a weak acid, such as acetic acid.
• Figure 2 effect of the adjuvant polymer.
• a mixture containing 10 g of isopropanol + 3.36 g of Tris[3- (trimethoxysilyl) propyl] isocyanurate + 2 g of 3-Glycidyloxypropyl- trimethoxysilane + 3.64 g of dimethyloctadecyl (3- (trimethoxysilyl) propyl) ammonium (same composition used only in Example 1) is stirred. 5g of H2O + 0.2 g of dibutyl ester phosphoric acid are added to the mixture to initiate the reactions between the silane functions (siloxane). The mixture is left stirring for 2 to 4 hours at room temperature. The mass % of dimethyloctadecyl(3-(trimethoxysilyl)propyl)ammonium)) relative to the dry matter is 40.4%.
• the 2 mixtures are deposited on glass substrates by “spin-coating” followed by firing at 150°C/2h.
• the scratch resistance, the antibacterial effectiveness and the antiviral effectiveness of the two types of coating are evaluated.
• the staining test with bromothymol confirms the presence of quaternary ammonium on the surface. A few drops of bromothymol are deposited on each of the coatings for 15 minutes. At the end, the coatings are rinsed several times with water.
• the inventors have attempted to further increase the quaternary amine content (44% by mass; 38% of the crosslinking agent): the antiviral activity is retained, but the mechanical properties of the coating are less good, with some visible scratches .
• Example 2 The inventors then compared the composition of Example 2 with a composition in which the content of the crosslinking agent is reduced to 25.2% (by weight), and 12.1% (by weight) of a polymer adjuvant (polyester-silane) is added. As shown in Figure 2, the intensity of the blue color is greatly increased, and the antibacterial and antiviral activities are still excellent, as are the mechanical properties and scratch resistance.
• a polymer adjuvant polymer-silane
• the inventors have produced various primary layers from 3-aminopropyltriethoxysilane, as an example of a molecule comprising an amine residue and a group that can be hydrolyzed into silanol.
• 3-aminopropyltriethoxysilane is dissolved in 60 g of a water/ethanol mixture, then 0.01 g of acetic acid is added to the mixture and stirred at room temperature for 1 hour.
• This primer is applied to its substrate, here on glass, by spin coating, and the coating of example 2 is then applied before heating at 150° C. for 2 hours, for complete crosslinking.
• Example 5 The composition of example 5 was adapted by the inventors, in which 0.6 g of a tetra-alkoxysilane were added, replacing 0.6 g of 3-aminopropyltriethoxysilane. Then the same procedure as for Example 5 is followed. In this case, the inventors have noticed that the adhesion remains excellent, and that the resistance of the coating to humidity is further increased.

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• 2021
  • 2021-11-24 BE BE20215916A patent/BE1029958B1/fr not_active IP Right Cessation
• 2022
  • 2022-11-24 EP EP22822374.9A patent/EP4437055A2/de not_active Withdrawn
  • 2022-11-24 WO PCT/EP2022/083182 patent/WO2023094547A2/fr not_active Ceased

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