Waterproofing compositions with non-stick properties for cellulosic supports or compounds with hydroxyl functions

Abstract

Oil-in-water (O / W) type emulsion comprising in water, a zirconium carbonate salt, at least one fatty acid, an alkaline agent, an emulsifying agent having an HLB number greater than or equal to 10, and optionally an emulsifying agent having an HLB number less than 10; its use as a waterproofing composition with non-stick properties for cellulosic supports and method for treating cellulosic supports using said emulsion.

Description

Title of the invention: Waterproofing compositions with non-stick properties for cellulosic supports or compounds with hydroxyl functions

[0001] The invention belongs to the fields of the paper and textile industries. Its subject is new waterproofing and non-stick compositions for any type of cellulosic support.

[0002] Compositions comprising complexes of metals and fatty acids are commonly used to give cellulosic supports such as paper, cardboard and certain textiles, whether woven or non-woven, so-called "barrier" properties, in particular with respect to water, polar solvents or greases of any kind. Indeed, the coating of the metal-fatty acid complex on the surface of the cellulosic support makes it possible, thanks to the presence of hydroxyl functions on the cellulose fibers, to form ionic bonds with the metal complex, inducing a sort of crosslinking of the system which gives the support surface properties different from those of the untreated support. These compositions thus make it possible to make it water-repellent and / or oil-repellent and therefore to limit or even prevent the absorption of these aforementioned liquids or greases.

[0003] The cellulosic supports thus treated can be used to make waterproof and / or stain-resistant clothing, textile articles and wooden articles. In the case of fibrous cellulosic supports such as paper, they give the supports non-stick properties, sought after in the case of adhesive and / or food release papers. They can be applied alone or coupled with other non-stick agents such as silicone and / or fluorinated compounds and / or waxes and / or polymers, to obtain textile printing support papers, laminate separator papers, interleaves for sliced ​​foods, erasable papers or separators for the manufacture of batteries.

[0004] British patent published under number GB 652,186 describes aqueous compositions comprising a double salt of zirconium carbonate and fatty acid soaps, such as soaps of oleic, stearic and palmitic acids, and their use for imparting water-resistant properties to textiles and other fibrous materials. Such compositions are impregnated onto the support to be treated, which must then be placed at a temperature above 60°C.

[0005] British patent published under number GB 684,686 describes a method for making the water-resistant treatment of textiles, paper and other fibrous materials more effective. Such a method involves a step of impregnating the material to be treated with an aqueous composition of zirconium carbonate salts, fatty acid soaps and optionally an emulsified wax, followed by a step of immersing the treated material in a solution comprising a salt of a metal from groups II, IV or VIII of the periodic table of chemical elements.

[0006] British patent published under number GB 1,002,103 describes aqueous compositions containing zirconium derivatives, such as for example zirconium ammonium carbonate, as well as at least one carboxylic acid having from 1 to 4 carbon atoms and at least one carboxylic acid having more than 4 carbon atoms; such compositions are used to confer water-resistant properties to the support on which they are applied, such as paper. However, they require the use of a third solvent, such as isopropyl alcohol, to obtain a homogeneous composition.

[0007] US patent published under number 4,612,255 discloses water-dispersible compositions conferring water-resistant properties to the support on which they are applied; said compositions contain a saturated hydrocarbon wax, at least one surfactant, at least one liposoluble metal salt of an organic carboxylic acid and at least one hydrocarbon solvent.

[0008] British patent published under number GB 1,078,648 discloses compositions having a pH between 7 and 8, in the form of oil-in-water emulsions in which the oily phase comprises a wax, a zirconium or titanium derivative, said emulsion being stabilized by casein or a metal salt of rosin. This patent also discloses the use of such compositions for providing water-resistant properties to the surfaces of paper and other cellulosic materials to which they have been applied.

[0009] Chinese patent application published under number CN 102816484 A describes aqueous compositions comprising water, an aqueous solution of zirconium salts, such as sodium zirconium carbonate salt, fatty acids, such as stearic or lauric acids, and polyvinyl alcohols. These aqueous compositions are applied to the surface of papers to give them transfer properties.

[0010] However, none of the aforementioned documents describes compositions in the form of oil-in-water emulsions which comprise both a zirconium carbonate salt and salified fatty acids, stabilized by emulsifying agents.

[0011] None of the compositions disclosed in the documents cited above makes it possible to maintain the fatty acids or fatty substances on the surface of the support to be treated, to be physically and chemically stable, to show rheofluidifying rheological behavior and to confer non-wetting properties to the supports. on which it is applied, with respect to water, polar solvents and fatty substances, making it impermeable to them.

[0012] According to a first aspect, the invention relates to an oil-in-water type emulsion (emulsion (O / W)) comprising for 100% by mass: - a) a zirconium carbonate salt with one or more cations chosen from the group consisting of alkali metal cations and the ammonium cation, in a mass proportion greater than or equal to 2% and less than or equal to 20% of the mass proportion of fat present in said oil-in-water type emulsion; - b) from 5% to 35% by mass of a fatty acid or a mixture of fatty acids, chosen from the group consisting of saturated or unsaturated, linear or branched carboxylic acids containing from eight to twenty carbon atoms and mixtures of several of these acids; - c) at least one alkaline agent chosen from the group consisting of ammonia, aqueous potash solutions or aqueous sodium hydroxide solutions, in the mass proportion necessary to maintain within said emulsion (O / W), a pH value greater than 8 and less than or equal to 9.5, said pH being measured at room temperature, that is to say at a temperature between approximately 20°C and approximately 30°C; - d) from 1% to 10% by mass of an oil-in-water type emulsifying agent or a mixture of emulsifying agents, said mixture being of the oil-in-water type, chosen from the group consisting of alkyl ether sulfates with an alkyl chain comprising from eight to eighteen carbon atoms salified with a metal cation or the ammonium cation, alkyl ether sulfates with an alkyl chain comprising from eight to eighteen carbon atoms salified with a metal cation or the ammonium cation, (poly)glycerol esters with an acyl chain comprising from eight to eighteen carbon atoms, N-acylated derivatives of amino acids with an acyl chain comprising from eight to eighteen carbon atoms and alkyl polyglycosides with an alkyl chain comprising from eight to eighteen carbon atoms; and mixtures of several of these compounds; and - e) water, said water having a hardness expressed in French hydrotimetric degrees (°f), greater than or equal to 0°f and less than or equal to 20°f.

[0013] By alkyl chain comprising from eight to eighteen carbon atoms, is meant in particular, in the definition of said oil-in-water type emulsifying agent or of said mixture of emulsifying agents, said mixture being of the oil-in-water type, the elements of the group consisting of the octyl, decyl, lauryl, myristyl, stearyl, oleyl, linoleyl and linolenyl radicals, more particularly chosen from the decyl, lauryl, myristyl or stearyl radicals and very particularly the lauryl radical.

[0014] By acyl chain comprising from eight to eighteen carbon atoms, is meant in particular, in the definition of said emulsifying agent of oil-in-water type or of said mixture of emulsifying agents, said mixture agent being of the oil-in-water type, the elements of the group consisting of the octanoyl, decanoyl, lauroyl, myristoyl, stearoyl, oleoyl, linoleoyl and linolenoyl radicals, more particularly chosen from the decanoyl, lauroyl, myristoyl or stearoyl radicals and very particularly the lauroyl radical.

[0015] The emulsion (O / W) as defined above, makes it possible to maintain the fatty acids or fatty substances on the surface of the support to be treated, to be physically and chemically stable, to show a rheofluidifying rheological behavior and to make this support impermeable to water, polar solvents, and fatty substances.

[0016] In the context of the present invention the above-mentioned properties are evaluated as follows: - The evaluation of the waterproofing property is carried out by measuring the contact angle associated with the liquid whose wetting character of the support is to be evaluated when the latter is treated with the emulsion (O / W) according to the invention. The more a liquid is wetting with respect to a support thus treated, the more it negatively affects the waterproofing properties of the emulsion (O / W) according to the invention. A liquid does not wet a surface on which it is applied if the contact angle formed by a drop of this liquid is equal to or greater than 90°. Wetting is partial if the contact angle is greater than 0° but less than 90°. The more the contact angle tends towards 90°, the weaker the wetting of the support by the liquid. Wetting is said to be perfect when the contact angle is equal to 0°. - The physical stability of the emulsion (O / W) according to the invention is evaluated by observing over time its appearance and the absence of phase separation, after a storage period of at least 3 months, at a temperature of - 4°C to 40°C; - The chemical stability of the emulsion (O / W) according to the invention is evaluated by measuring the following parameters over time: - i) The acid index expressed in mg of potash per gram of emulsion; it is determined over time by the standardized analysis NFT 60-204 (2020); - ii) The pH of the emulsion; it is determined over time by the standardized analysis NFT 73-206 (2004); - The level of glycerol present in the emulsion expressed as a mass percentage is determined over time by chromatography; - The rate of fatty acids present in the emulsion expressed as a mass percentage is determined over time by chromatography; - The evaluation of the rheological behavior of the shear-thinning type is carried out by determining the percentage drop in the dynamic viscosity of the emulsion (O / W) according to the invention under shear by facilitating their implementation. By shear-thinning behavior is meant a reduction in the value of the dynamic viscosity under shear indicated by a percentage drop in viscosity (Aq) under shear which starts at 80 s 1 to reach a plateau at 1,200 s1. Aq = (q80s i - T|i20s i) / (hsos i) * 100. If (Aq) is greater than or equal to 50% with a viscosity value at rest not exceeding approximately 50 Pa.s corresponding to the value of the viscosity at the origin (q0 ), determined from the flow curve with imposed gradient, from 0 to 1200 s1, the emulsion has a rheofluidifying character which allows it to be conveyed by a mechanical pump, knowing that the shear rate produced by such a pump is generally between 100 and 1000 s1. - The evaluation of the non-stick character of the emulsion (O / W) according to the invention is carried out by determining the peel force (F) expressed in Newton (N) over time by the so-called Finat analysis using standardized adhesive tapes TES A 7475. - The evaluation of the gloss of the support after coating the emulsion (O / W) according to the invention on the support is carried out with an angle of incidence of the light equal to 60°.

[0017] Zirconium, sodium, potassium or ammonium carbonates are commercially available in dry form or in aqueous solutions sometimes comprising salts of acetic acid or tartaric acid which act as stabilizers.

[0018] The mass proportions of zirconium, sodium, potassium or ammonium carbonate indicated in the definition of the emulsion (O / W) which is the subject of the present invention relate to the dry matter.

[0019] The invention more particularly relates to the (O / W) emulsion as defined above, further comprising, for 100% by mass: - f) up to 10% by mass of a water-in-oil type emulsifying agent or a mixture of emulsifying agents, said mixture being of the water-in-oil type, chosen from the group consisting of mineral or vegetable oils, mineral or natural waxes, casein, glycerol mono-, di- or triesters having a melting point above 50°C, sorbitan mono-, di- or triesters having a melting point above 50°C, water-in-oil type surfactants and mixtures of several of these compounds.

[0020] By fatty matter present within said emulsion (O / W) as defined above, is meant, in the context of the present invention, the set of compounds consisting of said at least one fatty acid defined under b), of said at least one emulsifier defined under d), and if present, of said at least one emulsifier defined under f).

[0021] The invention more particularly relates to the (O / W) emulsion as defined above, in which said zirconium carbonate salt defined under a) is zirconium and ammonium carbonate, said alkaline agent defined under c) is ammonia and said oil-in-water type emulsifying agent defined under d) is an alkyl chain ammonium alkyl sulfate containing from eight to eighteen carbon atoms or an alkyl ether ammonium sulfate containing from eight to eighteen carbon atoms.

[0022] The invention more particularly relates to the (O / W) emulsion as defined above, in which the mass proportion of said zirconium carbonate salt is greater than or equal to 4% and less than or equal to 15% of the mass proportion of fat present in said emulsion.

[0023] By a fatty acid chosen from the group consisting of saturated or unsaturated, linear or branched carboxylic acids containing from eight to twenty carbon atoms, is meant in particular, in the definition of the O / W emulsion which is the subject of the present invention, lauric, myristic, palmitic, stearic, 12-hydroxy stearic, oleic, linoleic, linolenic, arachidic acids. According to a particular aspect of the present invention, said fatty acid or said mixture of fatty acids defined under b) is chosen from the group consisting of lauric, myristic, palmitic and stearic acids and mixtures of several of these acids.

[0024] By oil-in-water (O / W) type emulsifying agent or mixture of emulsifying agents, said mixture being of (O / W) type, is meant more particularly, in the definition of the O / W emulsion which is the subject of the present invention, the emulsifying agents or said mixtures having an HLB number greater than or equal to 10 and more particularly the alkyl sulfates with an alkyl chain comprising from eight to eighteen salified carbon atoms, the alkyl polyglucosides with an alkyl chain comprising from twelve to sixteen carbon atoms, for example Simulsol™ SL26.

[0025] By water-in-oil (W / O) type emulsifying agent or mixture of emulsifying agents, said mixture being of (W / O) type, is meant more particularly, in the definition of the (O / W) emulsion which is the subject of the present invention, the emulsifying agents or said mixtures having an HLB number of less than 10 and more particularly paraffin oil, linseed oil, paraffin wax, beeswax, casein, glycerol monostearate, sorbitan monostearate, sorbitan palmitate or sorbitan isostearate and mixtures of several of these compounds.

[0026] The W / O emulsion which is the subject of the present invention may also comprise, for 100% by mass: - g) up to 15% by mass of one or more auxiliary compounds selected from the group consisting of hydroxy acids, for example tartaric, glycolic, citric or lactic acids in salified form, water-soluble solvents, for example alcohols such as ethanol, propanol, isopropanol, butanol or isobutanol, DMSO, Rhodiasolve™ or Augeo™, film-forming agents, for example modified celluloses such as HPC, HMPC, starches, modified starches, alginates, gums or polyvinyl alcohols.

[0027] The invention particularly relates to an emulsion (O / W) as defined above and comprising for 100% by mass: - a) zirconium and ammonium carbonate, in a mass proportion greater than or equal to 4% and less than or equal to 15% of the mass proportion of fat present in said emulsion; - b) from 10% to 25% by mass of a fatty acid or a mixture of fatty acids, said fatty acid and said mixture of fatty acids being chosen from the group consisting of stearic acid, myristic acid, palmitic acid and mixtures of several of these acids; - c) ammonia, in a mass proportion necessary to maintain within said emulsion a pH greater than 8 and less than or equal to 9; - d) from 1% to 5% by mass of an oil-in-water type emulsifying agent chosen from the group consisting of ammonium lauryl sulfate and alkyl polyglucosides with an alkyl chain containing from twelve to sixteen carbon atoms; and - e) water, said water having a hardness expressed in French hydrotimetric degrees (°f), greater than or equal to 0°f and less than or equal to 15°f.

[0028] According to this very particular aspect, the oil-in-water (O / W) type emulsion as defined above may further comprise, for 100% by mass: - f) from 1% by mass to 10% by mass of a water-in-oil type emulsifying agent or a mixture of emulsifying agents, said mixture of emulsifying agents being of the water-in-oil type, chosen from the group consisting of glycerol monostearate, sorbitan monostearate, paraffin wax, beeswax, linseed oil, paraffin oil and mixtures of several of these compounds.

[0029] The various embodiments of the oil-in-water (O / W) emulsion according to the invention described above may comprise one or more additional ingredients not listed, but compatible with the emulsion, the listed ingredients and the intended use of the emulsion. In other cases, the amount of water present in any of the different embodiments of the oil-in-water (O / W) emulsion according to the invention described above in an amount qs 100% by mass of the emulsion.

[0030] The invention also relates to the use of the O / W emulsion as defined above, as a waterproofing composition and conferring non-stick properties to the cellulose support to which it is applied, as well as a method for treating a cellulose support to make it impermeable to water or to polar or apolar solvents and to confer non-stick properties on it, comprising the following steps: - a step a) during which the oil-in-water type emulsion as defined previously is dissolved in water to form an emulsion (O / W) comprising between 1% and 2% of fat, and - a step b) of coating said cellulose support with said emulsion (O / W) prepared in step a), at a dry matter deposit rate of between 20 and 30 grams per square meter.

[0031] In the context of the present invention, the term “cellulosic support” refers in particular to fibrous supports, such as paper or cardboard, and woven or non-woven textile articles.

[0032] In the process as defined above, 1-octanol and hexadecane are representative of said polar or apolar solvents mentioned.

[0033] By waterproofing property of a support, is meant in the sense of the present application to make a material (fabric, paper, leather, etc.) waterproof by means of said compositions to prevent it from being crossed or soaked by a polar liquid for example water or any other "fatty" liquid such as melted waxes or oils.

[0034] The analysis methods used in the experiments set out in the following paragraphs are explained below: - The evaluation of the waterproofing property is carried out by measuring the contact angle associated with the liquid whose wetting character of the support is to be evaluated when the latter is treated with the emulsion (O / W) according to the invention. The more a liquid is wetting with respect to a support thus treated, the more it negatively affects the waterproofing properties of the emulsion (O / W) according to the invention. A liquid does not wet a surface on which it is applied if the contact angle formed by a drop of this liquid is equal to or greater than 90°. Wetting is partial if the contact angle is greater than 0° but less than 90°. The more the contact angle tends towards 90°, the weaker the wetting of the support by the liquid. Wetting is said to be perfect when the angle contact angle is equal to 0°. The measurement of contact angles is carried out using a DS A 305 goniometer marketed by the company Kruss Scientific; The physical stability of the emulsion (O / W) according to the invention is evaluated by observing over time its appearance and the absence of phase separation, after a storage period of at least 3 months, at a temperature of -4°C to 40°C; The chemical stability of the emulsion (O / W) according to the invention is evaluated by determining the following parameters over time: - i) The acid index expressed in mg of potash per gram of emulsion; it is determined over time by the standardized analysis NFT 60-204 mentioned above; - ii) The pH of the emulsion; it is determined over time by the aforementioned standardized analysis NFT 73-206; The level of glycerol present in the emulsion expressed as a mass percentage is determined over time by gas chromatography; The rate of fatty acids present in the emulsion expressed as a mass percentage is determined over time by gas chromatography; The evaluation of the rheological behavior of the shear-thinning type is carried out by determining the percentage drop in the dynamic viscosity of the emulsion (O / W) according to the invention under shear by facilitating their implementation. By shear-thinning behavior is meant a reduction in the value of the dynamic viscosity under shear indicated by a percentage drop in viscosity (Aq) under shear which starts at 80 s 1 to reach a plateau at 1,200 s1. Ap = (p80s-l - P120S-1) / 0180S-1) • 100. If (Aq) is greater than or equal to 50% with a viscosity value at rest not exceeding approximately 50 Pa.s corresponding to the value of the viscosity at the origin (p0), determined from the imposed gradient flow curve, from 0 to 1200 s1, the emulsion has a shear-thinning character which allows it to be conveyed by a mechanical pump, knowing that the shear rate produced by such a pump is generally between 100 and 1000 s1. The analysis is carried out using a Brookfield DV II™ viscometer; The evaluation of the non-stick character of the emulsion (O / W) according to the invention is carried out by determining the peeling force (F) expressed in Newton (N) over time by the aforementioned so-called Finat analysis using TESA 7475 standard adhesive tapes; - The evaluation of the gloss of the support after coating the emulsion (O / W) according to the invention on the support is carried out with an angle of incidence of the light equal to 60° using a gloss meter.

[0035] A first series of experiments aims to evaluate the influence of the components of the emulsion on the properties mentioned in the previous paragraph. Influence of the surfactant: the results recorded in the following table illustrate the influence of the constituents on different parameters.

[0036] Shear-thinning behavior of compositions according to the invention. [Tables 1] Formulation No. J, 1 2 3 4 5 6 Components of formulation J, Proportions (in mass percentages) Stearic acid 12.50 12.50 12.50 12.50 12.50 12.50 Ammonium zirconium carbonate (A ZC) - 1.25 1.25 1.25 1.25 1.25 NH4OH or NaOH - - qsp 8 < pH < 9.5 Ammonium lauryl sulfate - - - 2.00 - - Sodium lauryl sulfate - - - - 2.00 - Alkyl glucoside Ci2-Ci6 - - - - - 2.00 Water qsp 100% Formulation appearance At = 0 After one day Formulation 1 Phase separation - Formulation 2 Phase separation - Formulation 3 Gel with grains Homogeneous Formulation 4 Homogeneous Homogeneous Formulation 5 Homogeneous Homogeneous Formulation 6 Homogeneous Homogeneous Formulation No. J, 1 2 3 4 5 6 Viscosity after 1 day at room temperature (Ta) (in Pa.s) speed (v) = 100 revolutions / minute (rpm) - - 4.80 1.86 >6.00 3.12 Flow curve at 20°C; Viscosity (in Pa.s), Shear rate (in s ') Rise: q8os i - - 1.7 2.1 3.2 1.6 Level: T|i.2oos-i - - 0.060 0.075 0.090 0.040 Aq - - 96% 96% 97% 97% q0 (in Pa.s) - - 750 2.53 100 2.5-3

[0037] The results recorded in Table 1 above show the following: - Formulation 2, an aqueous solution composed solely of stearic acid and the complexing agent, is not stable; - Formulations 4, 5 and 6 which contain a hydrophilic emulsifying surfactant are homogeneous milks, whereas without this compound formulation 3 is not; - Formulations 4, 5 and 6 are stable and shear-thinning but only formulations 4 and 6 have a viscosity at rest that meets our selection criterion, i.e. less than 50 Pa.s; and - The behavior of lauryl sulfates depends on the nature of the counterion with which it is associated. Ammonium is preferred to obtain better fluidity of the formulation.

[0038] Influence of alkanes: Table 2 below lists the physical aspects and rheological behaviors of formulations of different compositions (formulations 8 to 11) comprising alkanes in comparison with those of formulation 7 not comprising them. [Tables 2] Formulation No. J, 7 8 9 10 11 Components of formulation J, Proportions (in mass percentages) Stearic acid 22.50 12.50 12.50 12.50 12.50 AZC 2.25 2.25 2.25 2.25 2.25 NH4OH qsp 8 < pH < 9 Ammonium lauryl sulfate 2.00 2.00 2.00 2.00 2.00 Isohexadecane - 10.00 - - - Hexadecane - - - 10.00 - Paraffin oil - - 10.00 - - Paraffin wax - - - - 10.00 Water qsp 100% pH Formulation appearance J, At=0 After one day Formulation 7 8.6 Homogeneous Homogeneous e Formulation 8 8.5 Homogeneous Homogeneous Formulation 9 9.0 Homogeneous Homogeneous Formulation 10 8.5 Homogeneous Homogeneous Formulation 11 8.9 Homogeneous blue Homogeneous Formulation No. J, 7 8 9 10 11 Viscosity after 1 day at Ta (in Pa.s); v = 100 rpm >6.00 5.00 3.87 5.80 4.00 Flow curve at 20°C Rise: q8os i 2.7 1.25 1.7 1.8 2.1 Level: T|i.2oos-i 0.09 0.05 0.07 0.09 0.09 Aq 97% 96% 96% 95% 96% q0 (in Pa.s) 45 30 20 20 30

[0039] The results recorded in Table 2 above show the following: - Formulations containing alkanes (formulations 8 to 11) have a lower dynamic viscosity than the reference formulation not containing them (formulation 7); - Isohexadecane is more shear-thinning than n-hexadecane (formulation 8 vs. formulation 10); - Paraffin wax is more shear-thinning than paraffin oil (formulation 9 vs. formulation 11); - All these formulations meet our resting viscosity criterion.

[0040] Influence of beeswax and linseed oil: Table 3 below lists the physical aspects and rheological behaviors of formulations of different compositions (formulations 12 and 13) comprising beeswax or linseed oil in comparison with those of formulation 7 not comprising them. [Tables 3] Formulation No. J, 7 12 13 Components of formulation J, Proportions (in mass percentages) Stearic acid 22.50 12.50 12.50 AZC 2.25 2.25 2.25 NH4OH qsp 8 < pH < 9 Ammonium lauryl sulfate 2.00% 2.00% 2.00% Linseed oil - 10.00% - Beeswax - - 10.00% Water qsp 100% pH Appearance At=0 After one day Formulation 7 8.6 Homogeneous Homogeneous Formulation 12 8.4 Homogeneous Homogeneous Formulation 13 8.2 Homogeneous Homogeneous Formulation No. J, 7 12 13 Viscosity after 1 day at Ta (in Pa.s); v = 100 rp m >6.00 5.98 4.80 Flow curve at 20°C: Rise: p8os 1 2.70 2.59 2.01 Level: T|i.2oos-i 0.09 0.07 0.05 Aq 97% 97% 97% q0 (in Pa.s) 45 75 75

[0041] The results recorded in Table 3 above show that the presence of natural oil or wax in the formulations (formulations 12 and 13) leads to an increase in viscosity compared to that of the reference formulation (formulation 7), which does not make them conform to our selection criterion, i.e. a viscosity at rest of less than 50 Pa.s.

[0042] Influence of polyol esters: Table 4 below lists the physical aspects and rheological behaviors of formulations of different compositions (formulations 14 to 17) comprising polyol esters, in comparison with those of formulation 7 not comprising them. [Tables 4] Formulation No. J, 7 14 15 16 17 Components of the formulation]. Proportions (in mass percentages) Stearic acid 22.50 12.50 12.50 12.50 12.50 AZC 2.25 2.25 2.25 2.25 2.25 NH4OH qsp 8 < pH < 9 Ammonium lauryl sulfate 2.00 2.00 2.00 2.00 2.00 Sorbitan monostearate - - - 10.00 - Sorbitan monoisostearate - 10.00 - - - Sorbitan monooleate - - 10.00 - - Glycerol monostearate - - - - 10.00 Water qsp 100% PH Formulation appearance At=0 After one day Formulation 7 8.6 Homogeneous Homogeneous Formulation 14 8.5 Homogeneous Homogeneous Formulation 15 8.3 Homogeneous Homogeneous Formulation 16 8.6 Homogeneous Homogeneous Formulation 17 8.3 Homogeneous Homogeneous Formulation No. J, 7 14 15 16 17 Viscosity after 1 day at Ta (in Pa.s); speed: 100 rpm >6.00 5.85 >6.00 4.11 3.24 Flow curve at 20°C Rise: p8os 1 2.70 2.00 3.00 2.30 2.30 Level: T|i.2oos-i 0.09 0.12 0.17 0.12 0.12 Aq 97% 94% 94% 95% 95% q0 (in Pa.s) 45 100 100 150-200 45

[0043] The results recorded in Table 4 above show that all these formulations have a viscosity equivalent to or greater than that of the reference formulation (formulation 7). Only formulation 17 has a viscosity at rest qO conforming to our selection criterion, i.e. less than 50 Pa.s.

[0044] Influence of water / oil type emulsifiers: Table 5 below lists the physical aspects and rheological behaviors of formulations of different compositions (formulations 18 to 20) comprising pairs of water-in-oil type emulsifiers, in comparison with those of formulation 17 comprising only one water-in-oil type emulsifier. [Tables 5] Formulation No. J, 17 18 19 20 Components of formulation J, Proportions (in mass percentages) Stearic acid 12.50% 12.50% 12.50% 12.50% AZC 2.25% 2.25% 2.25% 2.25% NH4OH qsp 8 < pH < 9 Ammonium lauryl sulfate 2.00 2.00 2.00 2.00 Glycerol monostearate 10.00 5.00 5.00 5.00 Sorbitan monostearate - 5.00 - - Paraffin wax - - 5.00 - Paraffin oil - - - 5.00 Water qsp 100% pH Formulation appearance At=0 After one day Formulation 17 8.3 Homogeneous Homogeneous Formulation 18 8.3 Homogeneous Homogeneous Formulation 19 8.4 Homogeneous Homogeneous Formulation 20 8.4 Homogeneous Homogeneous Viscosity after 1 day at Ta (in Pa.s); v = 100 rp m Formulation No. J, 17 18 19 20 3.24 2.00 2.34 1.66 Flow curve at 20°C Formulation No. J, 17 18 19 20 Rise: p8os i 2.30 1.90 1.90 1.20 Level: T|i.2oos-i 0.12 0.12 0.11 0.08 Aq 95% 94% 94% 93% q0 (in Pa.s) 45 35 35 20

[0045] The results recorded in Table 5 above show that the use of pairs of emulsifiers leads to a reduction in viscosity.

[0046] Influence of fatty acids: The two tables, 6 and 7, below list the physical aspects and rheological behaviors of formulations (formulations 21 to 25) comprising different fatty acids other than stearic acid, in comparison with those of formulation 7 comprising the latter acid. [Tableauxô] Formulation N% 7 21 22 23 Formulation components J, Proportions (in mass percentages) Lauric acid - 12.50 - - Copra acid C8-C[8 - - 12.50 - Myristic acid - - - 12.50 Stearic acid 25.00 - - - Behenic acid - - - - AZC 2.25 2.25 2.25 2.25 NH4OH qsp 8 < pH < 9 Ammonium lauryl sulfate 2.00 2.00 2.00 2.00 Glycerol monostearate - 10.00% 10.00 10.00 Water qsp 100% PH Formulation appearance At=0 After one day Formulation 7 8.6 Homogeneous Homogeneous Formulation 21 8.3 Homogeneous Homogeneous Formulation 22 8.5 Homogeneous Homogeneous Formulation 23 8.3 Homogeneous Homogeneous Formulation No. J, 7 21 22 23 Viscosity after 1 day at Ta (in Pa.s); v = 100 rpm >6.00 0.99 0.24 1.38 Flow curve at 20°C Rise: i^os i 2.70 1.20 1.30 1.30 Level: T|i.2oos-i 0.10 0.10 0.20 0.15 Ar| 97% 93% 87% 90% r|o (in Pa.s) 45 30 40 35-40 [Paintings?] Formulation No. J, 7 24 25 Components of formulation J, Proportions (in mass percentages) Lauric acid - - Coconut acid C8-C[8 - - - Myristic acid - - - Stearic acid 25.00 12.50 - Behenic acid - - 12.50 AZC 2.25 2.25 2.25 NH4OH qsp 8 < pH < 9 Ammonium lauryl sulfate 2.00 2.00 2.00 Glycerol monostearate - 10.00 10.00 Water qsp 100% PH Formulation appearance At=0 After one day Formulation 7 8.6 Homogeneous Homogeneous Formulation 24 8.3 Homogeneous Homogeneous Formulation 25 8.7 Homogeneous Homogeneous Formulation N°J, 7 24 25 Viscosity after 1 day at Ta (in Pa.s); speed: 100 rpm >6.00 3.24 1.45 Flow curve at 20°C Rise: p8os i 2.70 2.60 1.40 Level: T|i.2oos-i 0.10 0.10 0.2 Aq 97% 95% 85% q0 (in Pa.s) 45 45 70

[0047] The results recorded in Tables 6 and 7 above show that behenic acid, which has the highest melting temperature, thickens the composition compared to other shorter fatty acids or those which are liquid at room temperature.

[0048] Influence of other compounds: Table 8 below lists the physical aspects and rheological behaviors of formulations of different compositions (formulations 27 to 33) comprising different dispersants and emulsifiers. [Tables 8] Formulation No. J, Components of formulation J, 27 28 29 30 32 Proportions (in mass percentages) Stearic acid 6.6 5.0 10.0 6.6 5.0 Glycerol monostearate 8.2 6.3 - 8.2 6.3 Beeswax 6.5 5.0 - - 5.0 Sorbitan isostearate - - 2.5 - - Acacia gum - - 0.5 - - Ammonium lauryl sulfate 5.0 2.5 1.5 - - Casein - - - - 1.0 Water (TH = 9°f) 67.1 76.6 81.25 78.2 77.6 NH4OH at 10% qsp 8 < pH <9 AZC 2.1 1.6 1.25 2.1 1.6 PH 8.6 8.2 7.5 8.6 8.5 Appearance Homogenous Homogenous Homogenous Homogenous Homogenous eeeee

[0049] The results recorded in Table 8 above show that acacia gum and casein alone or coupled with other emulsifiers lead to fluid, easy-to-handle formulations.

[0050] Influence of the emulsifier and / or complexing agent level: Table 9 below lists the physical aspects and rheological behaviors of formulations of different compositions (formulations 34 to 37) having different emulsifier and / or KZC levels in comparison with those of formulation 21. [Tables 9] Formulation No. J, 21 34 35 36 37 Components of formulation J, Proportions (in mass percentages) Stearic acid 12.50 12.50 12.50 12.50 12.50 AZC 2.25 2.25 2.25 4.50 9.00 NH4OH qsp 8 < pH < 9.5 Ammonium lauryl sulfate 2.00 4.00 6.00 2.00 2.00 Glycerol monostearate 10.00 10.00 10.00 10.00 10.00 Water qsp 100% PH Appearance At=0 After one day Formulation 21 8.3 Homogeneous Homogeneous Formulation 34 8.3 Homogeneous Homogeneous Formulation 35 8.3 Homogeneous Homogeneous Formulation 36 8.4 Homogeneous Homogeneous Formulation 37 8.5 Homogeneous Homogeneous Formulation No. J, 21 34 35 36 37 Viscosity after 1 day at Ta (in Pa.s); v = 100 rpm 3.24 0.75 0.72 2.47 5.65 Flow curve at 20°C Rise: p8os i 2.6 0.7 0.8 2.6 2.3 Level: T|i.2oos-i 0.12 0.08 0.08 0.09 0.10 Aq 95% 88% 89% 96% 96% q0 (in Pa.s) 45 6.5 8.5 40 30

[0051] The results recorded in Table 9 above show that the emulsifying agent level influences the viscosity of this composition. Its optimal level is around 4%. On the other hand, an increase in the complexing agent level thickens it. All these formulations meet the rheological criteria.

[0052] The development of the process for preparing an emulsion (O / W) according to the invention is carried out on the following formulation: [Tables 10] Components of formulation J, Mass percentages AZC 2 Stearic acid 10 5% ammonia solution qsp 8 < pH < 9 Ammonium lauryl sulfate 2 Water qsp 100 Glycerol monostearate 5 Sorbitan monostearate 5

[0053] The process for preparing the formulation according to the invention comprises three stages: - Stage a): Introduction into the reactor of the fatty acid, the emulsifiers and the emulsifier previously brought to a temperature of at least 70°C; - Step b): addition of water, previously brought to 70°C, with mechanical stirring in the mixture obtained in step a) and maintaining the mixture at 70°C with stirring for five minutes; - Step c): Cooling the mixture obtained in step b) with stirring to a temperature of 40°C; then adding ammonium zirconium carbonate with stirring; completing the cooling phase with stirring to a temperature between 25-30°C, with the addition of water and, if necessary, adjusting the pH within the stability range of the complexing agent. The emulsion obtained is a perfectly pourable homogeneous product.

[0054] The aim of this new series of experiments is to establish operating conditions appropriate for the use of the emulsion (O / W) according to the invention, as a waterproofing and / or anti-adhesive composition for a cellulose support. - Paper coating techniques: The emulsion (O / W) according to the invention is diluted in water at room temperature and with stirring, at a dry extract rate adapted to the wet coating process used and to the dry deposition rate targeted after coating. This solution, called "coating and / or coating sauce", can be applied at room temperature, by different methods known to those skilled in the art in size presses, blade or curtain coaters, by spraying or by coating bar. In the case of textiles, the treatment can be carried out by dipping then padding at room temperature or by a coating technique. The support thus treated is then dried according to the methods and conditions known to those skilled in the art. - Coating operating conditions: The experimental conditions were defined from the following formulation: [Table 11] [Tableauxll] Components of formulation J, Mass percentages) Stearic acid 12.50% Glycerol monostearate 5.00% Sorbitan monostearate 5.00% Ammonium lauryl sulfate 2.00% Water 70.85% NH4OH 20% Qsp 8 <pH < 9,5 AZC 2,25%

[0055] The parameters evaluated for the preparation of the coating sauce are as follows: - The quality of the water (Permuted water and Hard water according to WHO); - The concentration of the “coating sauce”: 6% (1.35% MG) and 18% (4.05% MG) (MG = fat); pH (pH = 8.5) - The parameters evaluated for the coating are as follows: - i) the coating rate (mass of dry matter deposited (in grams per coated surface (in m2): from 0.34 to 1.52 g / m2; - ii) the drying temperature: from 110 to 140°C; - iii) the drying time: t = from 1 to 3 minutes; - iv) reconditioning time: from 1 hour to 24 hours (recovery %H at ambient temperature ~21°C - 45-50%H); - v) adhesive aging on paper: from 0.5 hours to 24 hours.

[0056] The aim of this series of experiments is to determine which constituents and in what proportions can they be used so that emulsions are suitable for acceptable use as a waterproofing and / or anti-adhesive composition for a cellulosic support. Eighteen formulations were prepared for this purpose (emulsions M1 to M18).

[0057] Preparation of formulations M1 to M18. - Step a): introduction into the reactor of the fatty acids, the emulsifier and possibly the emulsifiers previously brought to a temperature of at least 70°C; - Step b): introduction of water (e) previously brought to 70°C into the mixture formed in a), under mechanical stirring, deflocculating pale at a speed of 500 rpm initially increased to 900 rpm. Maintain the temperature and stirring for 5 minutes. - Step c) cooling to 40°C then introducing the ammonia solution then the ammonium zirconium carbonate with stirring. These compounds fluidify the medium. Complete the cooling phase with stirring to a temperature between 25-30°C. Top up the water if necessary and adjust the pH according to the stability range of the complexing agent.

[0058] Preparation of coating sauces: Formulations Ml to Ml8 are diluted in water with a water hardness (TH) equal to 9° French (°f) at a rate of 7% by mass at room temperature with stirring for 10 minutes with a stirring speed of 1000 revolutions per minute.

[0059] Coating conditions: the coating sauces are coated on the support with a Meyer bar at a rate of 25g / m2, i.e. a coating rate of 0.4 grams of fat per m2 of support;

[0060] The results of the experiments are listed in the following tables 12 to 14; the parameter F30mn 30 min expresses the peel force at 30 minutes of reconditioning then 30 minutes after bonding, the parameter F3omn 24h the peel force at 30 minutes of reconditioning then 24 hours after bonding and the parameter F24H the peel force at 24 hours of reconditioning then 30 minutes after bonding. [Tables 12] Formulation J, Ml M2 M3 M4 M5 M6 Components of formulation J, Proportions (in mass percentages) Stearic acid 11.50 - - - 11.50 - Myristic acid - - 11.50 - - 11.50 Behenic acid - 11.50 - 11.50 - - Glycerol monostearate 11.50 1.50 - 11.50 - - Sorbitan monostearate - - 150 11.50 - - Sorbitan palmitate - - - - 11.50 11.50 Ammonium lauryl sulfate 3.00 - 3.00 - - 3.00 Alkyl polyglucoside Ci2-Ci6 - 3.00 - 3.00 3.00 AZC 2.25 2.25 2.25 2.25 2.25 2.25 NH4OH qsp 8< pH < 9 Water TH = 9°f qsp 100% Viscosity - v = 100 rpm (in mPa .s) 252 468 520 312 240 480 Characteristics of the coating sauce Contact angle on untreated paper 51.2 23.9 47.5 26.0 35.5 50.5 Characteristics of the treated supports Ultra-exchanged water0 100.9 98.8 90.2 91.3 99.9 86.5 n Octanol0 43.1 39.3 34.2 36.4 37.6 35.7 n Hexadecane0 42.9 39.2 37.0 39.8 43.4 40.1 Gloss at 60° 6.0 6.1 5.1 5.7 5.7 5.3 F 30mn 30 mn (CU N) 5.9 6.6 8.6 6.3 5.6 8.4 F 30mn 24H (in N) 6.2 7.4 8.4 8.3 7.3 11.6 F 24H(in N) 10.0 9.5 13.7 7.2 11.0 13.2 [Tables 13] Formulation J, M7 M8 M9 M10 Mil M12 [Formulation components]. Proportions (in mass percentages) Stearic acid 11.50 - - - 11.50 - Myristic acid - - 11.50 - - 11.50 Behenic acid - 11.50 - 11.50 - - Paraffin wax 11.50 11.50 - - - - Paraffin oil - - 11.50 11.50 - - Linseed oil - - - - 11.50 11.50 Ammonium lauryl sulfate 3.00 - 3.00 3.00 - 3.00 Alkyl polyglucoside Ci2-Ci6 - 3.00 - - 3.00 - AZC 2.25 2.25 2.25 2.25 2.25 2.25 NH4OH qsp 8< pH < 9 Water hardness TH = 9° qsp 100% Viscosity ; V = 100 rpm 30” (in mPa.s) 216 210 240 120 430 300 Characteristics of the coating sauce Contact angle vs. paper 53.4 19.4 50.7 58.8 41.9 46.4 Characteristics of the treated supports Ultra-exchanged water0 96.6 69.9 81.3 78.5 104.6 101.9 n Octanol0 34.5 28.2 29.6 23.7 44.8 37.7 n Hexadecane0 36.2 28.6 25.2 19.6 42.1 32.5 Gloss at 60° 5.3 5.0 4.7 5.0 5.1 5.0 F 30mn 30 min (in N) 6.3 13.4 10.8 12.0 5.3 11.4 F 30 min 24 h (in N) 7.0 10.6 11.8 11.5 4.4 12.3 F 24 h (in N) 8.7 11.8 15.1 13.3 7.8 15.2 [Tables 14] Formulation J, M13 M14 M15 M16 M17 M18 Components of formulation J, Proportions (in mass percentages) J, Stearic acid 11.50 - - 11.50 11.50 11.50 Myristic acid - 11.50 - - - - Behenic acid - - 11.50 - - - Sorbitan monostearate - - - 11.50 - - Beeswax 11.50 11.50 11.50 - - 11.50 Paraffin wax - - - - 11.50 - Ammonium lauryl sulfate - - 3.00 - - - Alkyl polyglucoside Ci2-Ci6 3 3 - 3.00 3.00 3.00 AZC 2.25 2.25 2.25 2.25 2.25 2.25 NH40H qsp 8 < pH < 8.5 Water hardness TH = 9° qsp 100% Viscosity; v = 100 rpm 30” (in mPa.s) 350 200 350 300 270 1020 Characteristics of the coating sauce Contact angle vs. paper 40.4 45.8 50.4 36.7 40.5 44.9 Characteristics of the treated supports Ultra-exchanged water0 99.3 89.5 68.4 95.3 87.0 71.4 n Octanol0 40.5 38.7 17.3 41.3 38.4 36.0 n Hexadecane0 40.1 42.1 12.9 38.6 39.2 35.7 Gloss at 60° 5.4 5.5 5.4 5.6 5.3 5.5 F30mn30mn* (in N) 4.7 6.3 11.7 6.4 8.6 8.7 F30mn24H* (in N) 7.8 10.1 12.4 6.8 9.6 7.5 F24h* (in N) 8.3 9.5 12.7 8.5 8.7 9.1

[0061] In Tables 15 and 16 below, examples of O / W emulsions according to the invention are listed which have the desired advantages: they make it possible to maintain the fatty acids or fatty substances on the surface of the support to be treated, to be physically and chemically stable, to show a rheofluidifying rheological behavior and to make this support impermeable to water, polar solvents, and fatty substances. [Tables 15] Formulation No. J, 34 35 36 37 Components of formulation J, Proportions (in mass percentages) Stearic acid 11.5 20.0 20.0 12.5 Paraffin wax 11.5 5.0 5.0 12.5 apgc12-c16 3.0 1.5 3.0 1.5 AZC 2.3 2.5 2.5 2.5 NH4OH 4% qs 8 < pH 5:9.5 Water qs 100% Appearance of the formulation at t= 0 Fluid Viscosity Brookfield DV II; v = lOOrpm, t: 3 0sec 0.27 2.60 2.40 2.39 Gloss at 60° 5.3 + 0.1 5.0 5.4 + 0.3 5.3 FsOmn 30 min (CU N) 8.6 + 0.3 7.4 3.5 + 0.2 5.3 F30mn24h(in N) 8.7 + 0.2 - 5.4+1.7 - F24h(in N) 9.6 + 0.3 - 7.0 + 0.5 - [Tables 16] Formulation No. J, 38 39 40 41 Components of formulation J, Proportions (in mass percentages) Stearic acid 12.5 5.0 5.0 20.0 Paraffin wax 12.5 20.0 20.0 5.0 apgc12-c16 3.0 1.5 3.0 1.5 Ammonium lauryl sulfate - - - 1.5 AZC 2.5 2.5 2.5 2.5 NH4OH 4% qsp 8 < pH < 9.5 Water qsp 100% Appearance of the formulation at t= 0 J, Formulation 38 Homogeneous Formulation 39 Homogeneous Formulation 40 Homogeneous Formulation 41 Homogeneous 38 39 40 41 Brookfield Viscosity DV II; v = 100rpm, t : 30sec 0.10 0.17 0.16 0.30 Brightness at 60° 5.0 + 0.3 4.9 + 0.1 5.3 + 0.2 5.4 + 0.2 FsOmn 30 min 9.2 ± 0.2 13.9 ±0.5 12.3 ±0.3 6.2 ± 0.5 FsOmn 24 h - - - 5.1 ± 1.8 F 24 h - - - 3.4 ± 0.2

[0062] The results shown in Tables 15 and 16 above show that formulations 36 and 41 based on the same stearic acid / paraffin wax pair in the 80 / 20 ratio lead to peel forces comparable to the reference. Formulation 41 has a lower viscosity, linked to its emulsifying system which combines ammonium lauryl sulfate and C12-C16 APG.

[0063] The aim of this new series of experiments is to study the stability of emulsions according to the invention, and at different temperatures. The compositions of the emulsions chosen for this study are listed in the following table 17. [Tables 17] Formulation No. J, 42 43 Components of formulation J, Proportions (in mass percentage) Stearic acid 6.50 6.50 Glycerol monostearate 9.50 9.50 Beeswax 6.50 6.50 Ammonium lauryl sulfate 4.00 4.00 AZC (10%vs MG) 2.25 2.25 NH4OH 5% qsp 8 < pH< 9 Water qsp 100.00% Appearance at t=0 Homogeneous

[0064] In the following table 18, the viscosities of the formulations at room temperature (25°C) over time are listed (Brookfield viscosity, spindle 4, speed 100 rpm, in mPa.s). [Tables 18] Viscosities t -> 1 day 3 days 7 days 15 days 1 month 3 months Formulation 42 465 2.300 3.090 3.370 4.300 4.980 Formulation 43 510 960 1.640 3.400 3.600 3.060

[0065] In the following table 19, the physical aspects of the formulations are listed at different ambient temperatures (25°C) over time (Brookfield viscosity, spindle 4, speed 100 rpm, in mPa.s). [Tables 19] Appearance of formulations at Ta over time (t) t -> 3 days 7 days 15 days 1 month 6 months Formulation 42 Homogeneous Homogeneous Homogeneous Homogeneous Homogeneous Formulation 43 Flowable Flowable Flowable Flowable Flowable Appearance of formulations at 40°C over time t-> 3 days 7 days 15 days 1 month 6 months Formulation 42 Homogeneous Homogeneous Homogeneous Homogeneous Homogeneous Formulation 43 Homogeneous Homogeneous Homogeneous Homogeneous Appearance of formulations at 5°C over time (t) t -> 3 days 7 days 15 days 1 month 6 months Formulation 42 Homogeneous Formulation 43 Homogeneous Appearance of formulations after a temperature cycle (5°C, Ta, then 40°C) over time (t) 3 days 7 days 15 days 1 month 6 months Formulation 42 Homogeneous Homogeneous Homogeneous Homogeneous Homogeneous Formulation 43 Homogeneous Homogeneous Homogeneous Homogeneous Homogeneous

[0066] These results show that these emulsions are stable over time but sensitive to temperature; room temperature will be preferred for their use.

[0067] The aim of this new series of experiments is to study the chemical stability of emulsions according to the invention (formulations 44 and 45), and at different temperatures. The compositions of the emulsions chosen for this study are listed in the following table 20. [Tables20] Formulation No. J, 44 45 Components of formulation J, Proportions (in mass percentages) Palmitic acid 1.98% 3.75% Stearic acid 4.62% 8.75% Glycerol ester (Ci6-Ci8) 8.2% 5.0% Sorbitan monostearate - 5.0% AZC (10% vs MG) 0.7% 2.25% NH40H 10% qs 8< pH < 9.5 Water qs 100%

[0068] The results of chemical stability analyses of formulation 44 over time at room temperature are listed in the following table 21 (the contents are expressed in mass percentages). [Tables21] t -> t = 0 t = 1 month t = 6 months Acid index 13.9 15.7 17.0 PH 9.1 8.9 8.8 Dry extract content - 14.7% 14.7% Glycerol content 0.17% 0.39% 0.53% Acid content in C16 2.20% 2.6% 2.5% Acid content in C[8 4.7% 5.6% 5.7%

[0069] The results of chemical stability analyses of formulation 45 over time at room temperature and at 40°C are listed in the following table 22 (the contents are expressed in mass percentages). [Tables22] t -> t = 0 t = 1 month t = 3 months Temperature —> 25°C 25 °C 40°C 25°C 40°C Acid index 28.2 29.4 34.7 30.1 40.7 PH 8.8 8.7 8.2 8.7 8.0 Dry extract 23.3% 23.0% 23.1% 23.1% 23.8% Glycerol content 0.10% 0.18% 0.45% 0.22% 0.77% Ci6 acid content 4.0% 4.4% 5.3% 4.4% 5.9% Ci8 acid content 8.4% 9.2% 11.2% 9.5% 12.1%

[0070] These results show that the fatty acid content increases slightly over time, which is consistent with the increase in the acid index, a probable cause of the decrease in pH. In addition, increasing glycerol content for a constant dry extract tends to show a slight hydrolysis of the glycerol ester.

Claims

1. Claims Oil-in-water emulsion having a pH value greater than 8 and less than or equal to 9.5, measured at a temperature between 20°C and 30°C, comprising per 100% by mass: - a) a zirconium carbonate salt with one or more cations chosen from the group consisting of alkali metal cations and the ammonium cation, in a mass proportion greater than or equal to 2% and less than or equal to 20% of the mass proportion of fat present in said oil-in-water type emulsion; - b) from 5% to 35% by mass of a fatty acid or a mixture of fatty acids, chosen from the group consisting of saturated or unsaturated, linear or branched carboxylic acids containing from eight to twenty carbon atoms and mixtures of several of these acids; - c) at least one alkaline agent chosen from the group consisting of ammonia, aqueous potash solutions or aqueous sodium hydroxide solutions, in the mass proportion necessary to maintain within said emulsion (O / W), a pH value greater than 8 and less than or equal to 9.5, measured at a temperature between 20°C and 30°C; - d) from 1% to 10% by mass of an oil-in-water type emulsifying agent or a mixture of emulsifying agents, said mixture being of the oil-in-water type, chosen from the group consisting of alkyl ether sulfates with an alkyl chain containing from eight to eighteen carbon atoms salified with a metal cation or the ammonium cation, alkyl ether sulfates with an alkyl chain containing from eight to eighteen carbon atoms salified with an alkali metal cation or the ammonium cation, (poly)glycerol esters with an acyl chain containing from eight to eighteen carbon atoms, N-acylated derivatives of amino acids with an acyl chain containing from eight to eighteen carbon atoms, alkylpolyglycosides with an alkyl chain containing from eight to eighteen carbon atoms and mixtures of several of these compounds; and - e) water, said water having a hardness expressed in French hydrotimetric degrees (°f), greater than or equal to 0°f and less than or equal to 20°f.

2. An oil-in-water emulsion according to claim 1, further comprising, per 100% by mass: - f) up to 10% by mass of a water-in-oil emulsifying agent or a mixture of emulsifying agents, said mixture being of the water-in-oil type, selected from the group consisting of mineral or vegetable oils, mineral or natural waxes, casein, glycerol mono-, di- or triesters having a melting point above 50°C, sorbitan mono-, di- or triesters having a melting point above 50°C, water-in-oil surfactants and mixtures of several of these compounds.

3. An oil-in-water emulsion according to any one of claims 1 or 2, wherein said zirconium carbonate salt defined under a) is ammonium zirconium carbonate, said alkaline agent defined under c) is ammonia and said oil-in-water emulsifying agent defined under d) is an alkyl chain ammonium alkyl sulfate having from eight to eighteen carbon atoms or an alkyl chain ammonium alkyl ether sulfate having from eight to eighteen carbon atoms.

4. Oil-in-water type emulsion according to any one of claims 1 to 3, in which the mass proportion of said zirconium carbonate salt defined under a), is greater than or equal to 4% and less than or equal to 15% of the mass proportion of fat present in said emulsion.

5. An oil-in-water emulsion according to any one of claims 1 to 4, wherein said fatty acid or said mixture of fatty acids defined under b), is selected from the group consisting of lauric, myristic, palmitic and stearic acids and mixtures of several of these acids.

6. An oil-in-water emulsion according to any one of claims 1 to 5, wherein said emulsifying agent or said mixture of emulsifying agents defined under d), is selected from the group consisting of chain salified alkyl sulfates alkyl containing from eight to eighteen carbon atoms and alkyl polyglucosides with an alkyl chain containing from twelve to sixteen carbon atoms.

7. An oil-in-water emulsion according to any one of claims 2 to 6, wherein said water-in-oil emulsifying agent or mixture of emulsifying agents is selected from the group consisting of paraffin oil, linseed oil, paraffin wax, beeswax, casein, glycerol monostearate, sorbitan monostearate, sorbitan palmitate or sorbitan isostearate and mixtures of several of these compounds.

8. Oil-in-water emulsion according to one of claims 1 to 7 further comprising for 100% by mass: - g) up to 15% by mass of one or more auxiliary compounds chosen from the group consisting of hydroxy acids, for example tartaric, glycolic, citric or lactic acids in salified form, water-soluble solvents, for example alcohols such as ethanol, propanol, isopropanol, butanol or isobutanol, DMSO, Rhodiasolve™ or Augeo™, film-forming agents, for example modified celluloses such as HPC, HMPC, starches, modified starches, alginates, gums or polyvinyl alcohols.

9. Oil-in-water emulsion according to any one of claims 1 to 8, comprising for 100% by mass: - a) zirconium and ammonium carbonate, in a mass proportion greater than or equal to 4% and less than or equal to 15% of the mass proportion of fat present in said emulsion; - b) from 10% to 25% by mass of a fatty acid or a mixture of fatty acids chosen from the group consisting of stearic acid, myristic acid, palmitic acid and mixtures of several of these acids; - c) ammonia, in a mass proportion necessary to maintain within said emulsion a pH greater than 8 and less than or equal to 9; - d) from 1% to 5% by mass of an oil-in-water emulsifying agent chosen from the group consisting of lauryl ammonium sulfate and alkyl polyglucosides with an alkyl chain containing from twelve to sixteen carbon atoms; and - e) water, said water having a hardness expressed in French hydrotimetric degrees (°f), greater than or equal to 0°f and less than or equal to 15°f.

10. An oil-in-water emulsion according to claim 9, further comprising, per 100% by mass: - f) from 1% by mass to 10% by mass of a water-in-oil emulsifying agent or a mixture of emulsifying agents, said mixture of emulsifying agents being of the water-in-oil type, selected from the group consisting of glycerol monostearate, sorbitan monostearate, paraffin wax, beeswax, linseed oil, paraffin oil and mixtures of several of these compounds.

11. Use of the oil-in-water type emulsion according to any one of claims 1 to 10, as a waterproofing composition and conferring non-stick properties to the cellulose support on which it is applied.

12. Process for treating a cellulosic support to make it impermeable to water or to polar or apolar solvents and to give it non-stick properties, comprising the following steps: - a step a) during which the oil-in-water type emulsion according to any one of claims 1 to 10 is dissolved in water to form an (O / W) emulsion comprising between 1% and 2% of fat, and - a step b) of coating said cellulosic support with said (O / W) emulsion prepared in step a), at a dry matter deposit rate of between 20 and 30 grams per square meter.