New use of diacid compounds in the field of surface coatings

Abstract

Novel use of diacid compounds in surface coatings. The present invention relates to the use of diacid compounds as a precursor to a binder in a coating composition. The diacid compounds are derived from a plant source, cashew nut shell oil, thus making use of a natural resource that has been little utilized until now. (no figures)

Description

Title of the invention: New use of diacid compounds in the field of surface coatings

[0001] The present invention relates to a novel use of compounds in the field of surface coatings, in particular paints. The invention also relates to novel coating compositions, as well as methods for coating surfaces.

[0002] Conventionally used paint compositions contain a large proportion, often predominantly, of petroleum-based products. On the other hand, in most cases, paints are made up of harmful products, such as organic solvents, drying agents, or even toxic monomers, such as, for example, acrylate-based monomers.

[0003] However, today, consumers are increasingly concerned about ecological and health issues, and are therefore waiting for paint compositions that are environmentally friendly and safe for health.

[0004] In this context, we now find on the market paints containing components of plant origin, but these paints nevertheless contain a significant proportion of components derived from petroleum and / or posing ecological problems. In addition, these are vegetable oils from intensive cultivation and therefore the manufacture of these paints often competes with human food.

[0005] There is therefore a need to provide consumers with alternative paints that are sustainably bio-sourced and can be used in the absence of organic solvents and drying agents. CONTEXT OF THE INVENTION

[0006] One of the aims of the invention is the use of compounds inspired by natural products in a coating composition.

[0007] Another object of the invention is the use of compounds derived from plant sources in a coating composition.

[0008] Another object of the invention is the use of compounds obtained from natural compounds contained in waste from agricultural production.

[0009] Yet another aim of the present invention is to provide new coating compositions, in particular comprising bio-sourced materials.

[0010] Yet another object of the invention is to be able to use the compounds in processes for coating a surface.

[0011] The inventors surprisingly found that compounds derived from shells of Cashew nuts, currently little or not valued, as well as products inspired by these compounds, with similar structures, can be transformed into derivatives with interesting properties in the field of paint.

[0012] Indeed, the phenolic compounds present in cashew nut oil (CNSL) can be alkylated to lead to diacid compounds. The inventors surprisingly found that these diacid derivatives can serve as a binder precursor, unlike the phenolic compounds naturally present in CNSL.

[0013] A first object of the present invention is the use of at least one compound of Formula 1, as a precursor of a binder in a coating composition

[0014] [Chem.l]

[0015] Formula 1 in which:

[0016] • n= 1, 2, 3 or 4, • the substituents R1, R2, R3, R4 and R5 are independently chosen from:

[0017] • a hydrogen atom, • an alkyl group of 1 to 18 carbons, • an alkenyl group of 2 to 18 carbons, • a group chosen from a carboxylic acid or

[0018] [Chem.2] O

[0019] n having the same meaning as in Formula 1,

[0020] and in which:

[0021] • at least one of the substituents R1, R2, R3, R4 or R5 is an alkenyl group of 2 to 18 carbons, and • at least one of the substituents R1, R2, R3, R4 or R5 is a group chosen from a carboxylic acid or

[0022] [Chem.3]

[0023] n having the same meaning as in Formula 1,

[0024] wherein the coating composition is a paint, varnish, lacquer or stain.

[0025] By "coating composition" is meant a composition which can be used in the technical field of painting, and includes varnishes, paints, lacquers and stains.

[0026] For the purposes of the present invention, paints include any composition that can be used in the field of painting, such as, for example, colored paints or lacquered paints.

[0027] By “coating composition” we therefore mean the composition before its use, undried.

[0028] The compounds used in the composition of the present invention have the function of "precursor of a binder" in a coating composition.

[0029] The binder makes it possible to bind the different components of a paint, such as pigment particles or fillers, into a film that can adhere to a surface.

[0030] The binders generally used in coating compositions are most often polymers, formed after application of the coating composition, e.g. paint, to a surface. In the context of a binder in polymer form, said binder is formed on the surface by polymerization, and optionally crosslinking, of monomers.

[0031] For example, in an acrylic paint, the binder is formed by polymerization of acrylate monomers.

[0032] In the context of the present invention, the compounds of Formula 1, present in the coating composition, are precursors of the binder.

[0033] Without being bound by theory, the drying of the coating composition, e.g. paint, varnish, lacquer or stain, is carried out by a mechanism of polymerization of the unsaturated alkenyl chains represented by at least one of the substituents R1 to R5 in the compound of Formula 1.

[0034] This polymerization is facilitated by the presence of two carboxylic acid functions in these molecules. The presence of these two carboxylic functions probably allows the compounds to self-organize, in order to facilitate polymerization.

[0035] The following diagram 1 illustrates a possible self-organization mechanism of compounds, allowing the positioning of the alkenyl chains and thus facilitating the formation of the binder, exemplified for anacardic acid:

[0036] [Chem.4]

[0037] Scheme 1 - Self-organization of anacardic oxyacetic acid derivatives.

[0038] It is postulated that the formation of the binder involves a polymerization of the alkenyl chains.

[0039] Thus, the presence of two acid functions allows an increase in the drying kinetics, compared to compounds not comprising said acid functions.

[0040] Thus, it was found that anacardic acid dries much less quickly, or not at all (not dry even after several days in daylight and at room temperature) than the oxyacetic anacardic acid of scheme 1 (dry after only 1 day in daylight and at room temperature).

[0041] The efficiency with which the compounds used in the invention form a binder makes it possible to do without a drying agent in the coating composition.

[0042] By "alkyl group of 1 to 18 carbons" is meant a linear alkyl group chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and preferably a linear alkyl chain of 15 carbon atoms.

[0043] The alkyl group may also be branched. By branched alkyl group is meant an alkyl group as defined above comprising substituents chosen from the list of linear alkyl groups defined above. Among the branched alkyl groups, mention may in particular be made of a tert-butyl, sec-butyl and isopropyl group.

[0044] By “alkenyl group of 2 to 18 carbons” is meant: a linear alkyl chain of 2 to 18 carbon atoms, comprising one or more double bond(s) carbon-carbon, in particular a linear alkyl chain of 10 to 18 carbon atoms, comprising in particular 1, 2, or 3 double bonds, and preferably a linear alkyl chain of 15 carbon atoms, comprising 1, 2, or 3 double bonds.

[0045] The alkenyl group may also be branched. By branched alkenyl group is meant an alkenyl group as defined above comprising substituents chosen from linear alkyl groups as defined above.

[0046] The coating composition in which the at least one compound of Formula 1 is used may further comprise other ingredients usually present in such a composition, such as for example pigments, oils, fillers or solvents.

[0047] The coating composition in which the at least one compound of Formula 1 is used is in particular a paint, comprising a pigment as defined below.

[0048] According to a particular embodiment, the present invention relates to the use as defined above, in which the at least one compound of Formula 1 is such that:

[0049] • n= 1, 2, 3 or 4, • the substituent R2 is an alkenyl group of 2 to 18 carbons, • one of the substituents R1, R3, R4 or R5 is a group chosen from an acid carboxylic or

[0050] [Chem.5] o

[0051] n having the same meaning as in Formula 1,

[0052] • three of the substituents R1, R3, R4 and R5 are a hydrogen atom.

[0053] According to another particular embodiment, the present invention relates to the use as defined above, in which the composition comprises at least one compound of Formula 2, or at least one compound of Formula 3, or a mixture of these compounds.

[0054] [Chem.6] 2 3

[0055] in which:

[0056] • n= 1, 2, 3 or 4, • the substituent R2 is an alkenyl group of 2 to 18 carbons.

[0057] According to another particular embodiment, the present invention relates to the use as defined above, in which the at least one compound of Formula 1, 2 or 3 is such that n = 1.

[0058] According to another particular embodiment, the present invention relates to the use as defined above, in which the composition comprises at least one compound of Formula 4, or at least one compound of Formula 5, or a mixture of these compounds:

[0059] [Chem.7]

[0060] in which:

[0061] • the substituent R2 is an alkenyl group of 2 to 18 carbons.

[0062] According to another particular embodiment, the present invention relates to the use as defined above, in which Formulae 1, 2, 3, 4 and 5 are such that the substituent R2 is chosen from a pentadeca-8,11,14-trienyl group, a pentadeca-8,11-dienyl group, a pentadec-8-enyl group and a pentadecyl group, or a mixture of these groups.

[0063] According to another particular embodiment, the present invention relates to the use as defined above, in which the composition comprises at least one compound of Formula 4, or at least one compound of Formula 5, or a mixture of these compounds.

[0064] [Chem. 8]

[0065] in which:

[0066] • the substituent R2 is an alkenyl group of 2 to 18 carbons,

[0067] in particular in which:

[0068] • the substituent R2 is chosen from a pentadeca-8,11,14-trienyl group, a pentadeca-8,11-dienyl group, a pentadec-8-enyl group and a group pentadecyl, or a mixture of these groups.

[0069] According to a particularly advantageous embodiment, the coating composition used comprises compounds of Formulas 4 and 5, in a mixture, in which the substituent R2 is itself a mixture of at least the following 3 alkenyl groups: pentadeca-8,11,14-trienyl, pentadeca-8,11-dienyl, and pentadec-8-enyl.

[0070] According to another particular embodiment, the present invention relates to the use as defined above, in which the at least one compound of Formula 1, 2, 3, 4 or 5, is derived from CNSL, in particular from crude non-decarboxylated CNSL.

[0071] CNSL is a natural oil derived from cashew nut shells.

[0072] The main components of crude CNSL are phenolic compounds: anacardic acid, cardol and cardanol.

[0073] Methyl cardol is also present, but in trace amounts.

[0074] Each of these compounds is itself a mixture of products, substituted by an alkyl or alkenyl chain, said alkenyl chain having 1, 2 or 3 double bonds (Scheme 2):

[0075] [Chem.9] OH O OH OH OH anacardic acid cardol 65% 15 to 20% methyl cardol cardanol trace 10%

[0076] Scheme 2 - chemical structures of the main constituents of CNSL.

[0077] CNSL can be classified into 2 types, depending on the extraction method used:

[0078] • CNSL extract, obtained by extraction using a solvent, • Technical CNSL, obtained by hot processes, in particular by a tor high temperature reduction, eg >250°C.

[0079] Technical CNSL comprises a reduced amount of anacardic acid, due to partial decarboxylation during roasting. In some cases, the decarboxylation is even complete, and the CNSL no longer contains anacardic acid.

[0080] By "crude, non-decarboxylated CNSL" is meant a CNSL which has not undergone, or has only partially undergone, decarboxylation of anacardic acid. Crude, non-decarboxylated CNSL is therefore characterized by the presence of anacardic acid within the mixture.

[0081] The CNSL used in the present invention is preferably a "crude CNSL", which has not undergone decarboxylation, or a CNSL which has undergone only partial decarboxylation of anacardic acid.

[0082] In other words, the CNSL used in the present invention is preferably a "CNSL" comprising at least 5% by mass of anacardic acid, or in which the sum of the percentage of anacardic acid, cardol, and methyl cardol is at least 15% by mass.

[0083] By "at least 5% by mass of anacardic acid" is also meant: at least 10% by mass, at least 20% by mass, at least 30% by mass, at least 40% by mass, at least 50% by mass, preferably at least 60% by mass.

[0084] By "the sum of the percentage of anacardic acid, cardol, and methyl cardol is at least 15% by mass" is also meant: at least 25% by mass, at least 35% by mass, at least 45% by mass, at least 55% by mass, at least 65% by mass, preferably at least 75% by mass.

[0085] By "CNSL derivative" is meant a compound, or compounds, obtained from CNSL. In this context, the CNSL mixture can be converted as exemplified by Scheme 3 above:

[0086] [Chem. 10] oV CNSL-access

[0087] Scheme 3 - General scheme of the conversion of the main constituents into diacids.

[0088] In this context, some of the compounds present in the mixture, such as cardanol, do not form diacids, but monoacids. The presence of these monoacids does not hinder the possibility of using the mixture as a binder precursor.

[0089] Furthermore, CNSL can be used in a mixture, but it is also possible to isolate Anacardic acid or cardol, or methyl cardol, in order to provide "pure" diacids.

[0090] In this embodiment, the pure diacids are however made up of a mixture of compounds in which the substituent R (or R2) is a mixture of chains as defined in diagram 3 above.

[0091] According to another particular embodiment, the present invention relates to the use as defined above, of a mixture of compounds of Formula 1, 2, 3, 4 or 5.

[0092] By mixture is meant that the coating composition comprises at least two compounds of Formula 1, at least two compounds of Formula 2, at least two compounds of Formula 3, at least two compounds of Formula 4 or at least two compounds of Formula 5.

[0093] According to another particular embodiment, the present invention relates to the use as defined above, in which the mixture is a mixture obtained from CNSL, in particular from crude non-decarboxylated CNSL.

[0094] According to a particularly advantageous embodiment, the coating composition used is derived from crude, non-decarboxylated CNSL and comprises compounds of Formulas 4 and 5, as a mixture. Formulas 4 and 5, in which the substituent R2 is a mixture of at least the following 3 alkenyl groups:

[0095] pentadeca-8,11,14-trienyl, pentadeca-8,11-dienyl, and pentadec-8-enyl.

[0096] It is understood that this mixture can also comprise other compounds such as, for example, oxyacetic cardanol, or dioxyacetic methyl cardol and also, in small proportion, saturated alkyl chains on the R2 position.

[0097] According to another preferred embodiment, the present invention relates to the use as defined above, in which the mixture of compounds is obtained by treatment of said CNSL with an alkylating agent, in particular sodium chloroacetate.

[0098] The alkylating agent makes it possible to alkylate the phenolic groups present in the molecules making up CNSL.

[0099] The compounds used in the invention can in fact be obtained by alkylation of a phenolic derivative with an alkylating agent, as generally exemplified

[0100] in Scheme 4, where x is a leaving group. [Chem. 11]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109] Scheme 4 - General scheme for the preparation of compounds of Formula 1 from phenolic derivatives. The scheme below exemplifies a specific preparation in which anacardic acid and cardol are reacted with sodium chloroacetate, in the presence of a base such as sodium hydroxide or potassium hydroxide, to produce the corresponding diacids (Scheme 5): [Chem. 12] C( O 1) , KOH 0^3 anacardic acid cardol Scheme 5 -Preparation of oxyacetic derivatives from a mixture of anacardic acid and cardol. For the particular case where the CNSL mixture is used, the synthesis is illustrated by diagram 3 above. According to another preferred embodiment, the present invention relates to the use as defined above, wherein the at least one compound of Formula 1, 4 or 5, is derived from CNSL, in particular from crude non-decarboxylated CNSL, in particular from a mixture of compounds of Formula 1, 4 or 5, obtained from CNSL, in particular from crude non-decarboxylated CNSL, said compound of Formula 4 being derived from anacardic acid, said compound of Formula 5 being derived from cardol. According to another particular embodiment, the present invention relates to the use as defined above, in which the coating composition is a paint. Unless otherwise indicated, the definitions of the objects relating to the compounds of Formulae 1 to 5 above are also valid for the compounds of Formulae 1-B to 5-B and 1-C to 5-C below. A second subject of the present invention is a coating composition chosen from a paint, a varnish, a lacquer and a stain, said composition comprising:

[0110] • at least one compound of Formula 1-B [YES] [Chem. 13]

[0112] in which:

[0113] • n= 1, 2, 3 or 4, • the substituents R1, R2, R3, R4 and R5 are independently chosen from:

[0114] • a hydrogen atom, • an alkyl group of 1 to 18 carbons, • an alkenyl group of 2 to 18 carbons, • a group chosen from a carboxylic acid or

[0115] [Chem. 14]

[0116] n having the same meaning as in Formula 1-B,

[0117] and in which:

[0118] * at least one of the substituents R1, R2, R3, R4 or R5 is an alkenyl group of 2 to 18 carbons, and • at least one of the substituents R1, R2, R3, R4 or R5 is a group chosen from a carboxylic acid or

[0119] [Chem. 15]

[0120] n having the same meaning as in Formula 1-B,

[0121] • a pigment and / or an oil and / or a filler, and • optionally a solvent.

[0122] It is understood that the presence of a pigment makes it possible to provide a color, which may be white, to the coating composition according to the invention. In this case, the com coating position is in particular a colored paint, a varnish or a stain. Any pigment usually used in coating compositions can be used in the composition according to the present invention.

[0123] The presence of an oil gives a glossy appearance to the paint, varnish, lacquer, or stain. Consequently, an oil is notably included in the coating composition, in the context of a lacquer. Any oil usually used in coating compositions can be used in the composition according to the present invention.

[0124] Considering the compounds of Formula 1-B to be oils, the presence of an oil refers to the presence of an oil other than the compounds of Formula 1-B.

[0125] The filler, added to a binder, makes it possible to seal irregular surfaces in order to make them flat. The filler also makes the paints solid but also makes them aesthetic. Any filler usually used in coating compositions can be used in the composition according to the present invention.

[0126] The solvent may be present in the coating composition according to the invention. The solvent makes it possible to fluidify the composition in order to facilitate its use, that is to say, its application to a surface.

[0127] The presence of a solvent is not essential in the coating composition of the invention, but if a solvent is used, it is preferable to use a water-based solvent, and to omit harmful or ecotoxic solvents such as volatile organic compounds.

[0128] The coating composition according to the invention comprises in particular:

[0129] • either a pigment, • or a charge, • or an oil other than an oil comprising the compounds of Formula 1-B, • or a pigment and an oil, • or a pigment and a filler, • or an oil and a charge, • or a pigment, an oil and a filler.

[0130] Although not essential, the coating composition may further comprise a drying agent, serving to catalyze the drying of the coating.

[0131] According to a particular embodiment, the present invention relates to a coating composition as defined above, in which the at least one compound of Formula 1-B is such that:

[0132] • n= 1, 2, 3 or 4, • the substituent R2 is an alkenyl group of 2 to 18 carbons, • one of the substituents R1, R3, R4 or R5 is a group chosen from an acid carboxylic or

[0133] [Chem. 16]

[0134] n having the same meaning as in Formula 1-B,

[0135] • three of the substituents R1, R3, R4 and R5 are a hydrogen atom.

[0136] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the composition comprises at least one compound of Formula 2-B, or at least one compound of Formula 3-B, or a mixture of these compounds:

[0137] [Chem. 17] O 2-B 3-B

[0138] in which:

[0139] • n= 1, 2, 3 or 4, • the substituent R2 is an alkenyl group of 2 to 18 carbons.

[0140] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the at least one compound of Formula 1-B, 2-B or 3-B is such that n = 1.

[0141] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the composition comprises at least one compound of Formula 4-B, or at least one compound of Formula 5-B, or a mixture of these compounds

[0142] [Chem. 18] 4-B 5-B

[0143] in which:

[0144] • the substituent R2 is an alkenyl group of 2 to 18 carbons.

[0145] According to another particular embodiment, the present invention relates to a coating composition as defined above, wherein Formulas 1-B, 2-B, 3-B, 4-B and 5-B are such that the substituent R2 is selected from a pentadeca-8,11,14-trienyl group, a pentadeca-8,11-dienyl group, a pentadec-8-enyl group and a pentadecyl group, or a mixture of these groups.

[0146] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the composition comprises at least one compound of Formula 4-B, or at least one compound of Formula 5-B, or a mixture of these compounds

[0147] [Chem. 19] o 4-B 5-B

[0148] in which:

[0149] • the substituent R2 is an alkenyl group of 2 to 18 carbons.

[0150] in particular in which:

[0151] • the substituent R2 is chosen from a pentadeca-8,11,14-trienyl group, a pentadeca-8,11-dienyl group, a pentadec-8-enyl group and a pentadecyl group, or a mixture of these groups.

[0152] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the at least one compound of Formula 1-B, 2-B, 3-B, 4-B or 5-B, is derived from CNSL, in particular from crude non-decarboxylated CNSL.

[0153] According to another particular embodiment, the present invention relates to a coating composition as defined above, comprising a mixture of compounds of Formula 1-B, 2-B, 3-B, 4-B or 5-B.

[0154] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the mixture of compounds is a mixture obtained from CNSL, in particular from crude non-decarboxylated CNSL.

[0155] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the mixture of compounds is obtained by treatment of said CNSL with an alkylating agent, in particular sodium chloroacetate.

[0156] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the at least one compound of Formula 1-B, 4-B or 5-B, is derived from CNSL, in particular from crude undecarboxylated CNSL, in particular from a mixture of compounds of Formula 1-B, 4-B or 5-B, obtained from CNSL, in particular from crude undecarboxylated CNSL, said compound of Formula 4-B being derived from anacardic acid, said compound of Formula 5-B being derived from cardol.

[0157] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the at least one compound of Formula 1-B, 2-B, 3-B, 4-B or 5-B is present in an amount of 5 to 50% by weight relative to the total weight of the composition.

[0158] Below 20% binder, there is a risk of poor coverage when the coating composition is applied to a surface. Above 50% binder, the coating composition may be too thick for easy use in painting.

[0159] By "from 5 to 50%" we also mean the following ranges: from 5 to 40%, from 5 to 30%, from 5 to 20%, from 5 to 10%, from 10 to 50%, from 20 to 50%, from 30 to 50%, from 40 to 50%, and in particular from 30 to 40%.

[0160] It is understood that these percentages refer to the sum of all the compounds of Formulas 1-B, 2-B, 3-B, 4-B and 5-B present in the coating composition. In the case of the use of a composition derived from crude CNSL, these percentages refer to the sum of the -diacids present in the mixture, and therefore do not include the weight of the non-diacid compounds such as, for example, cardanol oxyacetic acid. Thus, in the context of a mixture derived from CNSL, the total weight of the diacid compounds of Formula 1-B, 2-B, 3-B, 4-B or 5-B corresponds to the sum of the quantities of cardol dioxyacetic acid, methyl cardol dioxyacetic acid and anacardic acid oxyacetic acid.

[0161] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the pigment is present in an amount of 0 to 20% by weight relative to the total weight of the composition.

[0162] By “from 0 to 20%” we also mean the following ranges: from 0 to 5%, from 0 to 10%, from 0 to 15%, from 5 to 20%, from 10 to 20%, from 15 to 20%, and from 5 to 15%.

[0163] It is understood that the value 0% means the absence of the pigment.

[0164] The pigment is notably absent from the composition if this composition is a lacquer. In this case, an oil is present.

[0165] In the context of a colored paint, or a varnish, a person skilled in the art is able to choose the proportion of pigments to be included in the coating composition.

[0166] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the oil is present in an amount of 0 to 20% by weight relative to the total weight of the composition.

[0167] By "from 0 to 20%" we also mean the following ranges: from 0 to 5%, from 0 to 10%, 0 to 15%, 5 to 20%, 10 to 20%, 15 to 20%, and 5 to 15%.

[0168] It is understood that the value 0% means the absence of an oil.

[0169] An oil is notably included in the coating composition if this composition is a lacquer. In this case, a pigment may also, but not necessarily, be present.

[0170] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the filler is present in an amount of 0 to 50% by weight relative to the total weight of the composition.

[0171] By “from 0 to 50%” we also mean the following ranges: from 0 to 40%, from 0 to 30%, from 0 to 20%, from 0 to 10%, from 10 to 50%, from 20 to 50%, from 30 to 50%, from 40 to 50%, from 10 to 40%, and from 20 to 30%.

[0172] It is understood that the value 0% means the absence of the load.

[0173] A filler is notably absent when the coating composition is a lacquer.

[0174] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the solvent is present in an amount of 0 to 80% by weight relative to the total weight of the composition.

[0175] In the event that more than 80% solvent is used, the coating composition may be too diluted for use in a paint.

[0176] By “from 0 to 80%” we also mean the following ranges: from 0 to 60%, from 0 to 40%, from 0 to 20%, from 20 to 80%, from 40 to 80%, from 60 to 80%, and from 20 to 60%.

[0177] It is understood that if several solvents are present in the composition, for example a water / ethanol mixture, these percentages refer to the sum of the solvents present in said composition.

[0178] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which:

[0179] • the at least one compound of Formula 1-B, 2-B, 3-B, 4-B or 5-B is present in an amount of 5 to 50% by weight relative to the total weight of the composition, and / or • the pigment is present in an amount of 0 to 20% by weight relative to the total weight of the composition, and / or • the oil is present at a rate of 0 to 20% by weight relative to the total weight of the composition, and / or • the filler is present at a rate of 0 to 50% by weight relative to the total weight of the composition, and / or • the solvent is present at a rate of 0 to 80% by weight relative to the total weight of the composition.

[0180] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the pigment is chosen from red iron oxide, blue iron oxide and yellow iron oxide.

[0181] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the oil is a vegetable oil, in particular linseed oil.

[0182] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the filler is chosen from calcium carbonate, talc, dolomite, titanium dioxide, kaolin or other fillers.

[0183] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which the solvent is chosen from an alcohol, a water / co-solvent mixture, or water comprising a surfactant and / or a base.

[0184] The coating composition according to the invention is in certain cases in liquid form. It is therefore not always necessary to use a diluting solvent. However, in cases where it is preferable to dilute, water, or a water-based solvent is preferred. Since the compounds of the invention are not soluble in water, it is necessary, if the water solvent is used, to add a co-solvent to the aqueous phase, for example an alcohol, to obtain a homogeneous appearance of the composition. It is also possible to use an emulsifier to achieve this objective.

[0185] In this context, it is possible to add a base to the composition to effect deprotonation of the acid groups of the compounds of Formula 1-B, 2-B, 3-B, 4-B and 5-B.

[0186] The anions thus formed have emulsifying properties. Thus, sodium hydroxide at a rate of 0.01 molar equivalent relative to the compounds of Formula 1-B, 2-B, 3-B, 4-B and 5-B can, for example, be added to a composition in which the solvent is water.

[0187] Among the alcohols that can be used as solvents, mention may be made of ethanol and isopropanol.

[0188] Among the co-solvents, mention may be made of an alcohol as defined above. The co-solvent is notably present at a rate of 20% to less than 100% by weight relative to the total weight of the solvent.

[0189] The surfactant is in particular a deprotonated compound of Formula 1-B, 2-B, 3-B, 4-B or 5-B.

[0190] A surfactant is notably present at a rate of 0.5 to 2 mol% relative to the compounds of Formula 1-B, 2-B, 3-B, 4-B or 5-B.

[0191] Among the bases, we can cite sodium hydroxide, potassium hydroxide, sodium carbonate, or any other base capable of deprotonating a carboxylic acid function.

[0192] According to another particular embodiment, the present invention relates to a coating composition as defined above, in which:

[0193] • the pigment is chosen from red iron oxide, blue iron oxide and yellow iron oxide, and / or • the oil is linseed oil, and / or • the filler is chosen from calcium carbonate, talc, dolomite, titanium dioxide and kaolin, and / or • the solvent is chosen from an alcohol, or a water / co-solvent mixture, or water comprising a surfactant and / or a base.

[0194] According to another particular embodiment, the present invention relates to a coating composition as defined above, said composition being a paint.

[0195] A third object of the present invention is a method for coating a surface, the method comprising the following steps:

[0196] • a step A of applying a coating composition to a surface, to obtain a surface coated with a non-dry coating composition, • a step B of drying polymerization of the non-dry coating composition. to obtain a surface coated with a dry coating composition, in which the coating composition comprises:

[0197] • at least one compound of Formula 1-C,

[0198] [Chem.20] 1-C

[0199] in which:

[0200] • n= 1, 2, 3 or 4, • the substituents R1, R2, R3, R4 and R5 are independently chosen from:

[0201] • a hydrogen atom, • an alkyl group of 1 to 18 carbons, • an alkenyl group of 2 to 18 carbons, • a group chosen from a carboxylic acid or

[0202] [Chem.21]

[0203] n having the same meaning as in Formula 1-C,

[0204] and in which:

[0205] • at least one of the substituents R1, R2, R3, R4 or R5 is an alkenyl group of 2 to 18 carbons, and • at least one of the substituents R1, R2, R3, R4 or R5 is a group chosen from a carboxylic acid or

[0206] [Chem.22]

[0207] n having the same meaning as in Formula 1-C,

[0208] said coating composition being a paint, a varnish, a lacquer or a stain.

[0209] The method of the invention can be implemented to coat any type of surface usually subject to the application of paint, varnish, lacquer or stain.

[0210] The expression "application of a coating composition to a surface" means "the action of painting" the surface with a coating composition in liquid form. Said application can be done for example with a roller, a brush, a paint gun, or any other tool available to the painter.

[0211] Before drying step B, the coating, or layer of paint, varnish, of the lacquer or stain is said to be "non-dry". To the touch, the paint, varnish or stain still looks wet and sticks to the finger.

[0212] Drying step B allows the paint, varnish, lacquer or stain to dry.

[0213] Without being bound by theory, this drying is the result of both an evaporation of the solvents, if present, and the formation of the binder from the compounds of Formula 1, present in the composition.

[0214] Although not essential, the coating composition may further comprise a drying agent, serving to catalyze the drying of the coating.

[0215] According to a particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the at least one compound of Formula 1-C is such that:

[0216] • n= 1, 2, 3 or 4, • the substituent R2 is an alkenyl group of 2 to 18 carbons, • one of the substituents R1, R3, R4 or R5 is a group chosen from an acid carboxylic or

[0217] [Chem.23]

[0218] n having the same meaning as in Formula 1-C,

[0219] • three of the substituents R1, R3, R4 and R5 are a hydrogen atom.

[0220] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the at least one compound of Formula 1-C is such that n = 1.

[0221] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the composition comprises at least one compound of Formula 2-C, or at least one compound of Formula 3-C, or a mixture of these compounds

[0222] [Chem.24] 2-C 3-C

[0223] in which

[0224] • n= 1, 2, 3 or 4, • the substituent R2 is an alkenyl group of 2 to 18 carbons.

[0225] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the coating composition comprises at least one compound of Formula 4-C, or at least one compound of Formula 5-C or a mixture of these compounds

[0226] [Chem.25] 4-C 5-C

[0227] in which:

[0228] • the substituent R2 is an alkenyl group of 2 to 18 carbons.

[0229] According to another particular embodiment, the present invention relates to a A process for coating a surface as defined above, wherein Formulae 1-C, 2-C, 3-C, 4-C and 5-are such that the substituent R2 is selected from a pentadeca-8,11,14-trienyl group, a pentadeca-8,11-dienyl group, a pentadec-8-enyl group and a pentadecyl group, or a mixture of these groups.

[0230] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the coating composition comprises at least one compound of Formula 4-C, or at least one compound of Formula 5-C or a mixture of these compounds

[0231] [Chem.26] o 4-C 5-C

[0232] in which:

[0233] • the substituent R2 is an alkenyl group of 2 to 18 carbons,

[0234] in particular in which:

[0235] • the substituent R2 is chosen from a pentadeca-8,11,14-trienyl group, a pentadeca-8,11-dienyl group, a pentadec-8-enyl group and a pentadecyl group, or a mixture of these groups.

[0236] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the at least one compound of Formula 1-C, 2-C, 3-C, 4-C or 5-C, is derived from CNSL, in particular from crude non-decarboxylated CNSL.

[0237] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the coating composition comprises a mixture of compounds of Formula 1-C, 2-C, 3-C, 4-C or 5-C.

[0238] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the mixture of compounds is a mixture obtained from CNSL, in particular from crude non-decarboxylated CNSL.

[0239] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the mixture of compounds is obtained by treating said CNSL with an alkylating agent, in particular sodium chloroacetate.

[0240] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the at least one compound of Formula 1-C, 4-C or 5-C, is derived from CNSL, in particular from crude undecarboxylated CNSL, in particular from a mixture of compounds of Formula 1-C, 4-C or 5-C, obtained from CNSL, in particular from crude undecarboxylated CNSL, said compound of Formula 4-C being derived from anacardic acid, said compound of Formula 5-C being derived from cardol.

[0241] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the coating composition further comprises an oil, in particular a vegetable oil, in particular linseed oil.

[0242] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the coating composition further comprises a pigment, in particular a pigment chosen from red iron oxide, blue iron oxide and yellow iron oxide.

[0243] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the coating composition further comprises a filler, in particular a filler chosen from calcium carbonate, talc, dolomite, titanium dioxide and kaolin.

[0244] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the coating composition further comprises a solvent, in particular a solvent chosen from an alcohol, water / co-solvent, or water comprising a surfactant and / or a base.

[0245] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the coating composition further comprises:

[0246] • an oil, in particular linseed oil, and / or • a pigment, in particular a pigment chosen from red iron oxide, blue iron oxide and yellow iron oxide, and / or, • a filler, in particular a filler chosen from calcium carbonate, talc, dolomite, titanium dioxide and kaolin, and / or • a solvent, in particular a solvent chosen from an alcohol, or a water / co-solvent mixture, or water comprising a surfactant and / or a base.

[0247] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the at least one compound of Formula 1-C, 2-C, 3-C, 4-C or 5-C is present, in the coating composition, in an amount of 5 to 50% by weight relative to the total weight of the composition.

[0248] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the pigment is present, in the coating composition, in an amount of 0 to 20% by weight relative to to the total weight of the composition.

[0249] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the oil is present, in the coating composition, in an amount of 0 to 20% by weight relative to the total weight of the composition.

[0250] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the filler is present, in the coating composition, in an amount of 0 to 50% by weight relative to the total weight of the composition.

[0251] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the solvent is present, in the coating composition, in an amount of 0 to 80% by weight relative to the total weight of the composition.

[0252] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which:

[0253] • at least one compound of Formula 1-C, 2-C, 3-C, 4-C or 5-C is present, in the coating composition, in an amount of 5 to 50% by weight relative to the total weight of the composition, and / or • the pigment is present, in the coating composition, at a rate of 0 to 20% by weight relative to the total weight of the composition, and / or • the oil is present, in the coating composition, at a rate of 0 to 20% by weight relative to the total weight of the composition, and / or • the filler is present, in the coating composition, at a rate of 0 to 50% by weight relative to the total weight of the composition, and / or • the solvent is present in the coating composition at a rate of 0 to 80% by weight relative to the total weight of the composition.

[0254] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the surface is a surface made of wood, metal, stone, plaster, paper, glass, textile or plastic.

[0255] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the drying step B is carried out in the presence of light, and / or in the presence of a polymerization initiator, and optionally in the open air.

[0256] The inventors have found that the drying of the coating composition can be carried out in the presence of light. UV and visible light are usable. It has been found that the presence of oxygen is beneficial for drying, but not essential.

[0257] Therefore, drying can be done in the open air, in the presence of oxygen, which is useful in the painting profession.

[0258] Furthermore, the inventors have also found that drying takes place in the presence of a polymerization initiator, which can initiate radical polymerization, the postulated mechanism for the formation of the binder.

[0259] For the purposes of the present invention, the polymerization initiators are radical type initiators, including for example 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO), razobisisobutyronitrile (AIBN), or peroxides such as for example benzoyl peroxide (BPO), di-tert-butyl peroxide (TBP), tert-butyl peroxide (TBHP).

[0260] [Chem.27] .... i £ । y SPO ABH CASE [84---36--3] CASE [7S--À7--Ï] TE8PO IBP TBHP CASE

[0261] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the light, used in drying step B, comes from exposure to the sun.

[0262] In the field of "painting", the action of painting is often done in daylight.

[0263] The coating compositions used in the process of the invention dry upon exposure to direct or indirect sunlight or daylight.

[0264] According to another particular embodiment, the present invention relates to a process for coating a surface as defined above, in which the polymerization initiator, used in drying step B, is chosen from: AIBN, TEMPO a peroxide.

[0265] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the drying step B is carried out for a time of 1 to 24 hours.

[0266] In a coating process according to the invention, drying time of one day is typically respected.

[0267] According to another particular embodiment, the present invention relates to a process for coating a surface as defined above, in which drying step B is carried out:

[0268] • in the presence of light, in particular light from exposure to the sun and / or • in the presence of a polymerization initiator, notably chosen from AIBN, TEMPO and a peroxide, and

[0269] optionally in the open air,

[0270] said drying step B being carried out in particular for a time of 1 to 24 hours.

[0271] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the drying step B is carried out at room temperature.

[0272] “Room temperature” means a temperature between 10 and 30°C, in particular between 15 and 25°C.

[0273] According to another particular embodiment, the present invention relates to a method for coating a surface as defined above, in which the coating composition is a paint.

[0274] A fourth subject of the present invention is a coated surface obtainable by the method for coating a surface as defined above.

[0275] The inventors have surprisingly found that cashew nut shell oil (CNSL), or certain of its components or analogues, can be transformed into components usable as a binder in a paint, varnish, lacquer or stain.

[0276] The paints of the invention can be used in the absence of solvent or drying agents, which makes their use interesting in a health and ecological approach, especially since cashew nut shell is currently a waste product that is not recovered.

[0277] The following examples and Figures illustrate the invention, without limiting its scope.

[0278] [Fig. 1] represents a photograph of a thin layer chromatography (TLC) plate of the product (mixture of oxyacetic acids from CNSL) obtained according to Example 10.

[0279] [Fig.2] represents the proton NMR spectrum of the product (mixture of oxyacetic acids from CNSL) obtained according to example 10.

[0280] [Fig.3] represents the carbon NMR spectrum of the product (mixture of oxyacetic acids from CNSL) obtained according to example 10.

[0281] [Fig.4] represents photographs of the glass plates on which paints have been dried according to Example 11.

[0282] Figure 1A shows the result of room temperature drying of the di- derivatives oxyacetics of cardol.

[0283] Figure 1B shows the result of drying the CNSL oxyacetic acid mixture at 60°C.

[0284] [Fig.5] represents photographs of the glass plates on which paints, including Kaolin, were dried according to Example 12.

[0285] Figure 5A shows the result of room temperature drying of a mixture Kaolin - oxyacetic acids from CNSL.

[0286] Figure 5B shows the result of drying at room temperature of a kaolin - cardol oxyacetic acid mixture.

[0287] Figure 5C shows the result of drying at room temperature a kaolin - oxyacetic acid mixture of anacardic acid.

[0288] [Fig.6] represents photographs of a painting comprising dolomite, according to example 13.

[0289] Figure 6A shows the paint after its preparation in the mixer.

[0290] Figure 6B shows the paint in a pot.

[0291] Figure 6C shows the wall of the laboratory in Antananarivo, coated with paint.

[0292] Figure 6D shows a brick, coated with paint.

[0293] Figure 6E shows a wood and glass surface coated with paint.

[0294] Figure 6F shows the wall of the laboratory in Antananarivo, coated with paint, after 8 months. EXAMPLES

[0295] Example 1 extraction of CNSL

[0296] CNSL was obtained by extraction from cashew nut shells.

[0297] 500 g of crushed shells were introduced into a 1 L soxhlet, then 1 L of hexane was added. was added to a 2 L two-necked flask and 500 mL in the Soxhlet. The assembly was completed with a condenser and a heating mantle to bring the solvent in the flask to a boil (approximately 68 °C). The extraction lasted 10 h after the last siphon, then the hexane extract was filtered and evaporated. 185 g or 37% of CNSL was obtained.

[0298] Example 2 separation of CNSL components

[0299] Anacardic acid and cardol were isolated from the CNSL mixture obtained in Example 1 according to the procedure described in Phani Kumar P, Paramashivappa R, Vi-thayathilPJ, Subba Rao PV, Srinivasa Rao A. J Agric Food Chem. 2002;50:4705-4708.

[0300] Example 3 synthesis of oxyacetic ester of anacardic acid

[0301] [Chem.28] 80°C

[0302]

[0303]

[0304]

[0305]

[0306] 8.6 g (25 mmol) of anacardic acid were added to 25 mL of ethyl chloroacetate (10 mol / mol), in the presence of 7 g (2.2 mol / mol) of potassium carbonate and 875 mg (10 mol%) of tetrabutylammonium acid sulfate. The reaction medium was heated at 80°C for 24 h. Salts (potassium chloroacetate) were formed with the desired products. After cooling, the reaction medium was filtered and the filtrate was evaporated to recover the products and excess ethyl chloroacetate. Then the residue (salt) from the filtration was washed with 100 mL of ethyl acetate to recover the remaining products. After evaporation of the ethyl acetate extract, 92% of anacardic acid oxyacetic ester was obtained in the form of a brown oil. 1H NMR (300 MHz, CDC13, TMS): 5 (ppm) 7.4-6.7 (m, 3H, aromatic CH); 5.8-5 (m, 5H, -CH2CH=CHCH2-;-CH2CH=CH2); 4.7 (s, 2H,-O-CH2-C=O); 4.3 (m, 2H,0-CH2-CH3); 2.7 (m, 2H, Ar-CH2CH2CH2-); 2.5-1.1 (m,12H, -CH2CH2CH2-); 0.9 (m, 3H, -CH3). TLC: eluent Hexane / AcOEt (8 / 2, V / V), developer: Sulfuric vanillin Example 4 synthesis of di-oxyacid esters of cardol [Chem.29] .o

[0307]

[0308] 7.9 g (25 mmol) of cardol were added to 25 mL of ethyl chloroacetate (10 mol / mol) in the presence of 7 g (2.2 mol / mol) of potassium carbonate and 875 mg (10 mol%) of tetrabutylammonium acid sulfate. The reaction medium was heated at 80°C for 24 h. Salts (potassium chloroacetate) were formed with the desired products. After cooling, the suspension was filtered and the filtrate evaporated to recover the products and excess ethyl chloroacetate. Then the residue (salt) from the filtration was washed with 100 mL of ethyl acetate to recover the remaining products. After evaporation of the ethyl acetate extract, 95% of cardol oxyacetic ester was obtained in the form of a brown oil. 1H NMR (300 MHz, CDC13, TMS): 5 (ppm) 6.3 (s, 3H, aromatic CH); 5.8-5 (m, 5H, -CH2CH=CHCH2-;-CH2CH=CH2); 4.7 and 4.55 (s, 4H,-O-CH2-C=O); 4.3 (m, 4H,O-CH2-CH3); 2.8 (m, 2H, Ar-CH2CH2CH2-); 2.5-1.1 (m,12H, -CH2CH2CH2-); 0.9 (m, 3H, -CH3).

[0309] TLC: eluent Hexane / AcOEt (8 / 2, V / V), developer: Sulfuric vanillin

[0310] Example 5 synthesis of oxyacetic esters of CNSL

[0311] [Chem.30]

[0312] 34.2 g (-100 mmol) of CNSL was added to 100 mL of ethyl chloroacetate (10 mol / mol) then: 28 g or 2.2 mol / mol of potassium carbonate and 4 g or 10 mol% of tetrabutylammonium acid sulfate were added. The mixture was heated at 80°C for 24 h. After cooling, the solution was filtered to remove the salts formed. The filtrate was evaporated to recover the products and excess ethyl chloroacetate. Then, the residue (salt) was washed with 200 mL of ethyl acetate to recover the remaining products. After evaporation of the ethyl acetate extract, 93% of the oxyacetic esters of CNSL were obtained in the form of a brown oil.

[0313] 'H NMR (300 MHz, CDCl3, TMS): 5 (ppm) 6.7-7.4 (m, 3H, aromatic CH for the anacardic acid derivative); 6.5-6.3 (s, 3H, aromatic CH for the cardol derivative); however, those of the cardanol derivative appeared in low intensity. 5.8-4.8 (m, 15H, -CH2CH=CHCH2-; -CH2CH=CH2); 4.6-4.8 (s, 6H, -CH2-O-); 4.3 (m, 8H ,O-CH2-CH3 )2.7 (m, 6H, Ar-CH2CH2CH2-); L3-2.4(m,36H, -CH2CH2CH2-); 0.9 (m, 9H, -CH3).

[0314] TLC: eluent Hexane / AcOEt (8 / 2, V / V), developer: Sulfuric vanillin

[0315] Example of synthesis of oxyacetic acid from anacardic acid from oxyacetic ester of anacardic acid

[0316] [Chem.31]

[0317] 15.4 g or 36 mmol of oxyacetic ester of anacardic acid was mixed with 12.8 g (4.4 mol / mol) of sodium hydroxide in 180 mL of hydroalcoholic solution (1 / 1), and the mixture was stirred at a temperature of 80 °C for 12 h. After cooling, acidification with 2 N HCl solution (35 mL) was carried out to pH 3. 75% of oxyacetic acid of anacardic acid was recovered after evaporation of the ethyl acetate phase during the liquid-liquid separation AcOEt / H2O (100 / 100).

[0318] 'H NMR (300 MHz, CDC13, TMS): Ô(ppm) 7.25-6.7 (m, 3H, aromatic CH); 5,.6-5 (m, 5H, -CH2CH=CHCH2-;-CH2CH=CH2); 4.7 (s, 2H,-CH2-O-); 2.6 (m, 2H, Ar-CH2 CH2CH2-); 2.4-1.1(m.12H, -CH2CH2CH2-); 0.9 (m, 3H, -CH3).

[0319] TLC: eluent AcOEt / AcOH (9 / 1, V / V), developer: Sulfuric vanillin

[0320] Example 7 synthesis of oxyacetic acid from anacardic acid with sodium chloroacetate

[0321] [Chem.32] 33%

[0322] 3.42 g or 10 mmol of anacardic acid were mixed with 1.8 mol / mol of chlo- sodium roacetate in the presence of 2 mol / mol potassium hydroxide in 10 mL ethanol, then the mixture was stirred at a temperature of 70 °C for 24 h. After cooling, acidification with 2 N HCl solution (7.8 mL) was carried out to pH 3. Liquid-liquid separation AcOEt / H2O (100 / 100) was carried out, then the organic phase was washed 3 times with water (100 mL) to remove salts. The ethyl acetate phase was dried and evaporated to obtain 93% oxyacetic acid of anacardic acid in the form of a brown pasty product.

[0323] 'H NMR (300 MHz, CDC13, TMS): <5 (ppm) 7.25-6.7 (m, 3H, aromatic CH); 5,.6-5 (m, 5H, -CH2CH=CHCH2-;-CH2CH=CH2); 4.7 (s, 2H,-CH2-O-); 2.6 (m, 2H, Ar-CH2 CH2CH2-); 2.4-1.1(m.12H, -CH2CH2CH2-); 0.9 (m, 3H, -CH3).

[0324] TLC: eluent AcOEt, developer: Sulfuric vanillin

[0325] Example of the synthesis of di-oxyacetic acids of cardol from the oxyacetic ester of cardol

[0326] [Chem.33]

[0327] 17.5 g or 36 mmol of cardol oxyacetic ester was mixed with 12.8 g or 4.4 mol / mol of sodium hydroxide in 180 mL of hydroalcoholic solution (1 / 1), then the mixture was stirred at a temperature of 80 °C for 12 h. After cooling, acidification with 2 N HCl solution (34 mL) was carried out until

[0328]

[0329]

[0330]

[0331] pH 3. 78% of dioxyacetic acids from cardol were recovered after evaporation of the ethyl acetate phase during the liquid-liquid separation AcOEt / H2 O (100 / 100). It is a brown-colored pasty product. 'H NMR (300 MHz, CDC13, TMS): <5 (ppm) 6.45-6.29 (s, 3H, aromatic CH); 5.7-5 (m, 5H, -CH2CH=CHCH2-; -CH2CH=CH2); 4.66 (s, 2H,-CH2-O-); 2.8 (m, 2H, Ar-CH2CH2CH2-); 1.3-2.6(m.12H, -CH2CH2CH2-); 0.9 (m, 3H, -CH3). TLC: eluent AcOEt / AcOH (9 / 1, V / V), developer: Sulfuric vanillin Example 9 synthesis of cardol di-oxyacetic acids with sodium chloroacetate [Chem. 34] 92%

[0332]

[0333]

[0334]

[0335] 4 g or 10 mmol of cardol were mixed with 2.4 mol / mol of sodium chloroacetate in the presence of 2 mol / mol of potassium hydroxide in 10 mL of ethanol at a temperature of 70 °C for 24 h. After cooling, acidification with 2N HCl solution (8.2 mL) was carried out to pH 3. Liquid-liquid separation AcOEt / H2O (100 / 100) was carried out, then successive washings 3 times with water (100 mL) were made to remove the salts. Then the ethyl acetate phase was evaporated and 92% of dioxyacetic acids of cardol (11) were recovered. It is a brown pasty product. TLC: eluent AcOEt, developer: Sulfuric vanillin Example of the synthesis of oxyacetic acids from CNSL [Chem. 35] cry su 98% (76%)

[0336] 34.2 g or 100 mmol of CNSL were mixed with 1.8 mol / mol of chloroacetate of sodium in the presence of 2 mol / mol of potassium hydroxide in 100 mL of ethanol, then the mixture was stirred at a temperature of 70 °C for 24 h. After cooling, acidification with 80 mL 2 N HCl solution was carried out to pH 3. A liquid-liquid separation AcOEt / H2O (200 / 200) was carried out, then the organic phase was washed 3 times with water (200 mL) to remove the salts. The ethyl acetate phase was evaporated and 98% of oxyacetic acids of the crude CNSL were recovered. The product obtained is very colored (black brown) and decolorization with activated carbon was carried out. The oxyacetic acids of CNSL were mixed with 50% by mass of activated carbon in 100 mL of ethyl acetate. The suspension was stirred at room temperature for 5 h. After successive filtration and washing with ethyl acetate, 76% of oxyacetic acids from CNSL were recovered after evaporation, in the form of a light brown pasty product.

[0337] 'H NMR (300 MHz, MeOD, TMS): 5 (ppm) 6.7-7.4 (m, 3H, aromatic CH for the anacardic acid derivative); 6.5-6.3 (s, 3H, aromatic CH for the cardol derivative); however, those of the cardanol derivative appeared in low intensity. 5.8-4.8 (m, 15H, -CH2CH=CHCH2-; -CH2CH=CH2); 4.6-4.8 (s, 6H, -CH2-O-); 2.7 (m, 6H, Ar-CH2CH2 CH2-); 1.3-2.4 (m, 36H, -CH2CH2CH2-); 0.9 (m, 9H, -CH3).

[0338] TLC: eluent AcOEt, developer: Sulfuric vanillin

[0339] [Fig.l] shows the TLC analysis of the raw materials and the products obtained.

[0340] Figures 2 and 3 show the proton and ion NMR spectra, respectively. carbon of the product obtained.

[0341] Example: Drying test of oxyacetic acid derivatives

[0342] The drying tests were carried out on a glass plate. Each of the products was solubilized in AcOEt (100 mg / mL) and then poured onto the glass plate. The products were air-dried at room temperature and then in an oven at 60°C if there was no drying at room temperature. A sticky finger test was carried out every 2 hours to assess the drying of the products.

[0343] The dioxyacetic acids of cardol, obtained according to example 8 or 9, dried after one day in air at room temperature (Figure 4A).

[0344] The mixture of oxyacetic acids of CNSL, obtained according to Example 10, was dried at 60°C in an oven (Figure 4B).

[0345] The dried products are insensitive to water and hexane but peel off on contact with acetone and ethyl acetate.

[0346] Example 12 drying test of oxyacetic acid derivatives with 10% by mass of kaolin

[0347] Tests with kaolin-oxyacetic acid mixtures were also carried out. The kaolin-oxyacetic acid mixture of CNSL, obtained according to Example 10, were dried in air at room temperature after 3 d (Figure 5A), the kaolin-oxyacetic acid mixture of cardol was dry after 1 d (Figure 5B) and the kaolin-oxyacetic acid mixture of anacardic acid was dry after 3 d (Figure 5C).

[0348] It is therefore possible to formulate paints from these oxyacetic acid derivatives, because the fillers (kaolin) have effects on the drying speed of these monomers.

[0349] Example 13 formulations of paints from oxyacetic acids of CNSL

[0350] 3g or 7.5 mmol (30% by mass) of oxyacetic acids of CNSL (binder) were mixed with 1.2 g of dolomite (filler) (12% by mass) and 8% or 0.8 g of red iron oxide (pigment) in a metal cup. The whole is mixed with 50% or 5 mL of diluent (Water) containing 1% NaOH by mol of the binder. The mixture was stirred with a mechanical stirrer (700 rpm) at room temperature for 20 to 30 min until a stable emulsion was obtained. A paint with good texture and good viscosity was obtained.

[0351] Different plates (glass plate, metal plate, wooden plate, piece of cement) were painted with brush and even the outside wall of our laboratory to test the effectiveness of the paint. The paints on the plates dried after 1d to 4d. And after each drying, water sensitivity tests were carried out. Images of obtained paints are shown in [Fig.6].

[0352] Thus, a photo of the paint as obtained in the mixer is shown in Figure 6A, and Figure 6B shows the paint after potting. Figures 6C to 6F show surfaces coated with the paint of Figure 6B, namely: the wall of the laboratory in Antananarivo (6C), a brick (3D), wooden and glass surfaces (6E), and the wall of the laboratory in Antananarivo (6F) after 8 months.

[0353] The coatings remained stable, including outdoors (painting of a small surface of the exterior wall of the laboratory in Antananarivo) for 8 months (duration of observation).

[0354] The following Table 1 shows different coating formulations that were made and tested in the formation of paints according to the above procedure. All of the tested products dry on various surfaces, and are therefore usable as coating compositions. The last column provides the “Water sensitivity after drying”.

[0355] It has been demonstrated that the compositions "RMM 249, RMM 250, RMN 251 and RMN 252 are sensitive to water. In other words, even if these paints are dry, they do not remain on the surface in question when exposed to water. These paints may nevertheless be of practical interest, for example in the context of a temporary display. Table 1: Paint formulation tests

[0356] Ref Binder Filler Pigment Solvent Water sensitivity after drying RMM 249 5g (25%) + 500mg NaHCO3 Carbonate grade 2Q prochimad (CaCO3) 5g or 25% Blue iron oxide 10% or 2g Water 15ml On glass: yes On metal: yes On wood: yes RMM 250 5g (25%) + 500mg NaHCO3 TALC (Mg3Si4Oio (OH)2) 5g or 25% Yellow iron oxide py 42 10% or 2g Water 10ml On glass: yes On metal: yes On wood: yes RMM 251 5g (25%) + 500mg NaHCO3 Dolomite 20 (CaMg(CO3)2) 5g or 25% Yellow iron oxide py 42 10% or 2g Water 10ml On glass: yes On metal: yes On wood: no RMM 252 5g (25%) + 500mg NaHCO3 Kaolin (Al2Si2O5 (OH)45g or 25% Green iron oxide 10% or 2g Water 10ml On glass: yes On metal: yes On wood: no RMM 265 3.5g (35%) Fine dolomite (CaMg(CO3)2) 1,5g or 15% Red iron oxide 10% or 1g Water / EtOH 3g / 1g On glass: no On metal: no On wood: no On cement: no RMM 266 4g (40%) Fine dolomite (CaMg(CO3)2) 1g or 10% Red iron oxide 10% or 1g Water / EtOH 3g / 1g On glass: no On metal: no On wood: no On cement: no RMM 274 3g (30%) Fine dolomite (CaMg(CO3)2) 1.2g or 12% Red iron oxide 8% or 0.8g Water / EtOH 4.5g / 0.5g On glass: no On metal: no On wood: no On cement: no RMM 269 3.5g (35%) Fine dolomite (CaMg(CO3)2) 1.5g or 15% Red iron oxide 10% or 1g Water / NaOH IN 3 ml / 1ml On glass: no On metal: no On wood: no On cement: , No RMM 271 3g (30%) Fine dolomite (CaMg(CO3)2) 1.2g or 12% Red iron oxide 8% or 0.8g Water / NaOH IN 4ml / 1ml On glass: no On metal: no On wood: no On wall: no On cement: no RMM 270 3g (30%) Fine dolomite (CaMg(CO3)2) 1.2g or 12% Red iron oxide 8% or 0.8g Water / NaOH 5ml / 10% in mol of the binder On glass: no On metal: no On wood: no On wall: no On cement: no RMM 272 3g (30%) Fine dolomite (CaMg(CO3)2) 1.2g or 12% Red iron oxide 8% or 0.8g Water / NaOH 5ml / 5% in mol of the binder On glass: no On metal: no On wood: no On the wall: no On the cement: no RMM 273 3g (30%) Fine dolomite (CaMg(CO3)2) 1.2g or 12% Red iron oxide 8% or 0.8g Water / NaOH 5ml / 2% in mol of the binder On glass: no On metal: no On wood: no On the wall: no On the cement: no RMM 275 3g (30%) Fine dolomite (CaMg(CO3)2) 1.2g or 12% Red iron oxide 8% or 0.8g8 g Water / NaOH 5 ml / 1% in mol of the binder On glass: no On metal: no On wood: no On the wall: no On cement: no,

[0357] Thus, without separation of the CNSL constituents, in one synthesis step, paint binders, compatible with numerous fillers and numerous pigments, were obtained. The preparation of these paints is particularly simple since it does not require the introduction of organic solvent or surfactant, antifoam or thickening compounds.

[0358] Example 14 synthesis of oxyethanol from anacardic acid

[0359] [Chem.36] Under nitrogen

[0360] 10 mmol or 3.42 g of anacardic acid was mixed with 2.1 g (24 mmol) of ethylene carbonate in the presence of potassium carbonate (2.5 mol%). The mixture was stirred at 150 °C under nitrogen atmosphere for 2 h. A crude yield of 95% was obtained. The product was purified by chromatographic column with an eluent system (Hexane 500 mL) and silica of mass equal to 10 times the mass of the product. The expected product was isolated in the form of a brown oil, with a yield of 25%.

[0361] H NMR (300 MHz, CD3OD, TMS): δ (ppm) 7.25-6.7 (m, 3H, aromatic CH); 5.6-5 (m, 5H, -CH2CH=CHCH2-;-CH2CH=CH2); 4 and 3.8 (m, 4H,OH-CH2-CH2-O-); 2.6 (m, 2H, Ar-CH2CH2CH2-); 2,4-l,l(m,12H, -CH2CH2CH2-); 0.9 (m, 3H, -CH3).

[0362] TLC: Hexane / AcOEt (8 / 2, V / V)

[0363] Example 15 synthesis of oxyethanol from Cardol

[0364] [Chem.37] Under nitrogen

[0365] 10 mmol or 4 g of cardol was mixed with 2.1 g (24 mmol) of ethylene carbonate in the presence of potassium carbonate (2.5 mol%). The mixture was stirred at 150 °C under nitrogen atmosphere for 2 h. A crude yield of 95% was obtained. To purify the product, a chromatographic column was made with an eluent system (Hexane / AcOEt, 80 / 20; V / V) and silica of mass equal to 10 times the mass of the product and an isolated yield of 52% was obtained.

[0366] The oxyethanol of purified cardol has an oily, brown appearance. It was analyzed by 'H NMR in CH2Cl2-d2, with a frequency of 300 MHz.

[0367] 'H NMR (300 MHz, CH2Cl2-d2, TMS): δ (ppm) 6.45-6.29 (s, 3H, aromatic CH); 5.7-5 (m, 5H, -CH2CH=CHCH2-; -CH2CH=CH2); 4 and 3.8 (m, 8H,OH-CH2-CH2-O-); 2.8 (m, 2H, Ar-CH2CH2CH2-); 1,3-2,6(m,12H,-CH2CH2CH2-); 0.9 (m, 3H, -CH3).

[0368] Example 16 drying test of oxyethanol derivatives

[0369] The oxyethanol derivatives obtained according to Examples 14 and 15 were tested in drying tests.

[0370] The tests were carried out on a glass plate. Each of the products was solubilized in AcOEt (100 mg / mL) on the glass plate, then air-dried. A sticky finger test was carried out every day to assess the drying of the products.

[0371] Even after 10 days, no drying was observed, the products remained very sticky as on the first day, including at 60°C.

[0372] Thus, it has been demonstrated that compounds not comprising 2 carboxylic acids in their structure do not dry.

[0373] Example 17 drying test of oxyacetic ester derivatives

[0374] The oxyacetic ester derivatives obtained according to example 5 were tested in drying tests.

[0375] Two types of tests were carried out: one with a wooden board and the other on a glass plate. Each of the products was solubilized in AcOEt (100 mg / mL) and then poured onto the wooden board and the glass plate. Then the products were air-dried at room temperature or at 60°C in an oven. A sticky finger test was carried out every day to assess the drying of the products. Even after 10 days, no drying was observed; the products remained very sticky.

[0376] Thus, it has been demonstrated that compounds not comprising 2 carboxylic acids in their structure do not dry.

Claims

Claims

1. Use of at least one compound of Formula 1, as a precursor of a binder in a coating composition [Chem. 3 8] HCk R R' Formula 1 in which: • n = 1, 2, 3 or 4, • the substituents R1, R2, R3, R4 and R5 are independently chosen from: • a hydrogen atom, • an alkyl group of 1 to 18 carbons, • an alkenyl group of 2 to 18 carbons, • a group chosen from a carboxylic acid or [Chem. 39] O n having the same meaning as in Formula 1, and in which: • at least one of the substituents R1, R2, R3, R4 or R5 is an alkenyl group of 2 to 18 carbons, and • at least one of the substituents R1, R2, R3, R4 or R5 is a group chosen from a carboxylic acid or [Chem. 40] n having the same meaning as in Formula 1, in which the coating composition is a paint, varnish, lacquer or stain.

2. Use according to claim 1, wherein the composition comprises at least one compound of Formula 4, or at least one compound of Formula 5, or a mixture of these compounds [Chem.41] 1 JL JL ° Cv 4 5 in which: • the substituent R2 is an alkenyl group of 2 to 18 carbons, in particular in which: • the substituent R2 is chosen from a pentadeca-8,11,14-trienyl group, a pentadeca-8,11-dienyl group, a pentadec-8-enyl group and a pentadecyl group, or a mixture of these groups.

3. Use according to one of claims 1 or 2, wherein the at least one compound of Formula 1, 4 or 5 is derived from CNSL, in particular from crude undecarboxylated CNSL, in particular from a mixture of compounds of Formula 1, 4 or 5, obtained from CNSL, in particular from crude undecarboxylated CNSL, said compound of Formula 4 being derived from anacardic acid, said compound of Formula 5 being derived from cardol.

4. A coating composition selected from a paint, a varnish, a lacquer and a stain, said composition comprising: at least one compound of Formula 1-B [Chem. 42] 1-B in which: n = 1, 2, 3 or 4, the substituents R1, R2, R3, R4 and R5 are independently chosen from: a hydrogen atom, an alkyl group of 1 to 18 carbons, an alkenyl group of 2 to 18 carbons, a group chosen from a carboxylic acid or [Chem. 43] n having the same meaning as in Formula 1-B, and in which: at least one of the substituents R1, R2, R3, R4 or R5 is an alkenyl group of 2 to 18 carbons, and at least one of the substituents R1, R2, R3, R4 or R5 is a group chosen from a carboxylic acid or [Chem. 44] n having the same meaning as in Formula 1-B, said composition comprising: • a pigment and / or an oil and / or a filler, and • optionally a solvent.

5. A coating composition according to claim 4, wherein the composition comprises at least one compound of Formula 4-B, or at least one compound of Formula 5-B, or a mixture of these compounds [Chem. 45] 5-B in which: • the substituent R2 is an alkenyl group of 2 to 18 carbons.

6.

7. in particular in which: • the substituent R2 is chosen from a pentadeca-8,11,14-trienyl group, a pentadeca-8,11-dienyl group, a pentadec-8-enyl group and a pentadecyl group, or a mixture of these groups. Coating composition according to one of claims 4 or 5, wherein the at least one compound of Formula 1-B, 4-B or 5-B, is derived from CNSL, in particular from crude undecarboxylated CNSL, in particular from a mixture of compounds of Formula 1-B, 4-B or 5-B, obtained from CNSL, in particular from crude undecarboxylated CNSL, said compound of Formula 4-B being derived from anacardic acid, said compound of Formula 5-B being derived from cardol. Coating composition according to one of claims 4 to 6, in which: • the at least one compound of Formula 1-B, 2-B, 3-B, 4-B or 5-B is present in an amount of 5 to 50% by weight relative to the total weight of the composition, and / or • the pigment is present in an amount of 0 to 20% by weight relative to the total weight of the composition, and / or • the oil is present in an amount of 0 to 20% by weight relative to the total weight of the composition, and / or • the filler is present in an amount of 0 to 50% by weight relative to the total weight of the composition, and / or • the solvent is present in an amount of 0 to 80% by weight relative to the total weight of the composition.

8. Coating composition according to one of claims 4 to 7, in which: • the pigment is chosen from red iron oxide, blue iron oxide and yellow iron oxide, and / or • the oil is linseed oil, and / or • the filler is chosen from calcium carbonate, talc, dolomite, titanium dioxide and kaolin, and / or • the solvent is chosen from an alcohol, or a water / co-solvent mixture, or water comprising a surfactant and / or a base.

9. A method for coating a surface, the method comprising the following steps: • a step A of applying a coating composition to a surface, to obtain a surface coated with a non-dry coating composition, • a step B of drying the non-dry coating composition, to obtain a surface coated with a dry coating composition, the surface being in particular a surface made of wood, metal, stone, plaster, paper, glass, textile or plastic, wherein the coating composition comprises: at least one compound of Formula 1-C [Chem.46] 1-C in which: • n = 1, 2, 3 or 4, • the substituents R1, R2, R3, R4 and R5 are independently chosen from: a hydrogen atom, an alkyl group of 1 to 18 carbons, an alkenyl group of 2 to 18 carbons, a group chosen from a carboxylic acid or [Chem. 47] o n having the same meaning as in Formula 1-C, and in which: • at least one of the substituents R1, R2, R3, R4 or R5 is an alkenyl group of 2 to 18 carbons, and • at least one of the substituents R1, R2, R3, R4 or R5 is a group chosen from a carboxylic acid or [Chem.48] n having the same meaning as in Formula 1-C, said coating composition being a paint, varnish, lacquer or stain.

10. A method for coating a surface according to claim 9, wherein the coating composition comprises at least one compound of Formula 4-C, or at least one compound of Formula 5-C or a mixture of these compounds [Chem.49] S 0 A, 4-C 5-C in which: • the substituent R2 is an alkenyl group of 2 to 18 carbons, in particular in which: • the substituent R2 is chosen from a pentadeca-8,11,14-trienyl group, a pentadeca-8,11-dienyl group, a pentadec-8-enyl group and a pentadecyl group, or a mixture of these groups.

11. A method for coating a surface according to one of claims 9 or 10, wherein the at least one compound of Formula 1-C, 4-C or 5-C is derived from CNSL, in particular from crude undecarboxylated CNSL, in particular from a mixture of compounds of Formula 1-C, 4-C or 5-C, obtained from CNSL, in particular from crude undecarboxylated CNSL, said compound of Formula 4-C being derived from anacardic acid, said compound of Formula 5-C being derived from cardol.

12. A method for coating a surface according to one of claims 9 to 11, wherein the coating composition further comprises: • an oil, in particular linseed oil, and / or • a pigment, in particular a pigment chosen from oxide of red iron, blue iron oxide and yellow iron oxide, and / or • a filler, in particular a filler chosen from calcium carbonate, talc, dolomite, titanium dioxide and kaolin, and / or • a solvent, in particular a solvent chosen from an alcohol, or a water / co-solvent mixture, or water comprising a surfactant and / or a base.

13. A method for coating a surface according to one of claims 9 to 12, wherein: • at least one compound of Formula 1-C, 2-C, 3-C, 4-C or 5-C is present, in the coating composition, at a rate of 5 to 50% by weight relative to the total weight of the composition, and / or • the pigment is present, in the coating composition, at a rate of 0 to 20% by weight relative to the total weight of the composition, and / or • the oil is present, in the coating composition, at a rate of 0 to 20% by weight relative to the total weight of the composition, and / or • the filler is present, in the coating composition, at a rate of 0 to 50% by weight relative to the total weight of the composition, and / or • the solvent is present in the coating composition at a rate of 0 to 80% by weight relative to the total weight of the composition.

14. A method for coating a surface according to one of claims 9 to 13, wherein drying step B is carried out: • in the presence of light, particularly light from exposure to the sun and / or • in the presence of a polymerization initiator, notably chosen from AIBN, TEMPO and a peroxide, and optionally in the open air, said drying step B being carried out in particular for a time included from 1 to 24 hours.

15. Coated surface obtainable by the method for coating a surface according to one of claims 9 to 14.

Images