Alkyd emulsions with improved water resistance and improved hardness development

Abstract

The present invention relates to an alkyd emulsion comprising a conjugated fatty acid-based alkyd resin and a reactive surfactant. The invention also encompasses methods for preparing alkyd emulsions and their use in decorative coatings. The coatings obtained using the alkyd emulsion have improved properties in terms of water resistance and hardness development.

Description

Technical Field

[0001] The present invention relates to an alkyd emulsion comprising an alkyd resin based on conjugated fatty acids and a reactive surfactant. The invention also covers a process for preparing the alkyd emulsion and its use in decorative coatings. The coatings obtained using the alkyd emulsion show improved performance qualities in terms of water resistance and hardness development. Background Art

[0002] Polyester resins are obtained by reacting polyacids and polyols. Polyester resins can be modified by adding fatty components, especially oils or fatty acids, to form a specific type of polyester resin: alkyd resins. Alkyd resins have been used to form coatings, especially decorative coatings and industrial coatings, for more than 50 years.

[0003] The presence of the fatty component in the alkyd resin provides flexibility and gloss to the resulting coating. When the fatty component comprises unsaturated groups, the alkyd resin can be dried by auto-oxidation (addition of a drying agent).

[0004] Alkyd resins in organic solvent media, also called solvent-based alkyd resins, have long been known to those skilled in the art and are commonly used in decorative and industrial paint formulations and coatings. In order to address the issues of comfort of use, odor and toxicity related to the use of volatile organic compounds (VOCs), alkyd emulsions have been developed and marketed for about twenty years with favorable performance levels in terms of gloss, drying, appearance / color, stability and odor.

[0005] Alkyd emulsions, also called post-emulsified alkyds, are obtainable by emulsifying alkyd resins by addition of surfactants and water. For example, patent application WO 2018 / 029407 A1 describes alkyd emulsions based on conjugate acids. Application WO 2018 / 092158 describes alkyd emulsions with reactive surfactants. However, the performance qualities of these alkyd emulsions, in particular with regard to water resistance and hardness development, are still inferior to solvent-based alkyds.

[0006] There is a need for alkyd emulsions having excellent water resistance and good hardness development while maintaining good application properties, particularly in terms of gloss, adhesion to substrate, flexibility, abrasion resistance, resistance to self-tack (blocking), mechanical strength, drying, appearance / color, stability and odor.

[0007] Surprisingly, the Applicant Company has found that the combined use of alkyd resins based on conjugated acids and reactive surfactants makes it possible to simultaneously improve the water resistance and hardness development of coatings obtained from alkyd emulsions. The Applicant Company does not wish to be bound by any one theory but assumes that the formation of a ring between the conjugated acid and the reactive surfactant by a Diels-Alder reaction may be the cause of the observed synergistic effect. Summary of the invention

[0008] The subject matter of the present invention relates to an alkyd emulsion comprising:

[0009] a) an alkyd resin having an oil content of 20% to 50%, the alkyd resin being based on an acid component A and an alcohol component B, the acid component A comprising a conjugated fatty acid component A1, the component A1 accounting for at least 5% of the total weight of the components A and B, preferably from 5% to 40%, more preferably from 10% to 35%;

[0010] b) a surfactant comprising a reactive surfactant, preferably an ethylenically unsaturated surfactant;

[0011] c) Water.

[0012] The present invention also relates to a process for preparing the emulsion according to the invention, said process comprising the following steps:

[0013] i) preparing component a) comprising an alkyd resin in a molten state;

[0014] ii) adding water and component b) comprising a reactive surfactant,

[0015] iii) neutralization of the acidity of components a) and b) by adding a base,

[0016] iv) emulsification by phase transition,

[0017] v) Optionally adjusting the solids content of the alkyd emulsion.

[0018] The invention also relates to a composition comprising the alkyd emulsion according to the invention.

[0019] The invention also relates to the use of the alkyd emulsion according to the invention as a binder for obtaining coatings, adhesives or mastics, in particular for obtaining coatings, more particularly for obtaining films, paints, varnishes, lacquers, stains, adhesive primers or inks.

[0020] The invention also relates to a coating, adhesive or mastic obtained by applying and drying the composition according to the invention. DETAILED DESCRIPTION

[0021] definition

[0022] In this patent application, the terms "comprising (including) a" and "including (comprising) an" mean "comprising (including) one or more (one or more)".

[0023] Unless otherwise indicated, weight percentages in a compound or composition are expressed relative to the weight of the compound or composition.

[0024] Within the meaning of the present invention, ethylenically unsaturated groups are groups which contain polymerizable carbon-carbon double bonds.

[0025] Within the meaning of the present invention, a polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. Polymerizable carbon-carbon double bonds generally include acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleates, fumarates, itaconates, allyls, propenyls, vinyls and corresponding combinations, preferably acrylates, methacrylates, allyls and vinyls. Carbon-carbon double bonds of aromatic rings are not considered polymerizable carbon-carbon double bonds.

[0026] Within the meaning of the present invention, an alkyl group is of the formula -C n H 2n+1 The alkyl group may be linear or branched. 1 -C 6 Alkyl refers to an alkyl group containing from 1 to 6 carbon atoms.

[0027] Within the meaning of the present invention, an alkenyl group is a monovalent acyclic group having one or more C═C double bonds. An alkenyl group may be linear or branched.

[0028] Within the meaning of the present invention, an alkoxy group is a group of the formula -O-alkyl.

[0029] Within the meaning of the present invention, an aryl group is a group containing at least one aromatic ring. The aryl group may contain a single aromatic ring or multiple rings, at least one of which is an aromatic ring. The aromatic ring corresponds to a ring that follows the Huckel rule. Examples of aryl groups are phenyl, biphenyl, naphthyl and anthracenyl. The aryl group of the present invention preferably contains from 6 to 12 carbon atoms. Still more preferably, the aryl group of the present invention is a phenyl group.

[0030] Within the meaning of the present invention, an alkylaryl group is a group of the formula -A-aryl, wherein A is alkylene. Preferably, an alkylaryl group is of the formula -CR 2 R 3 -Ph group and R 2 and R 3 are independently H or Me, more preferably of the formula -CH(CH 3 )-Ph group.

[0031] Within the meaning of the present invention, an alkylene group is a group derived from the formula C by removing a hydrogen atom at each point of attachment of the group. m H 2m+2 A divalent aliphatic radical of an alkane of the type C, wherein m = 2 to 50. The alkylene group may be linear or branched. 2 -C 4 Alkylene refers to an alkylene group containing from 2 to 4 carbon atoms.

[0032] Within the meaning of the present invention, an oxyalkylene group is a group of the formula -OA-, wherein A is alkylene.

[0033] Within the meaning of the present invention, a polyoxyalkylene group is of the formula -O-[AO] n -, wherein each A is independently C 2 -C 4 Alkylene, preferably ethylene or propylene, and n ranges from 1 to 100, from 2 to 60, from 3 to 50, from 4 to 40 or from 5 to 30.

[0034] Within the meaning of the present invention, an aliphatic group or compound is a non-aromatic non-cyclic group or compound. It may be linear or branched, saturated or unsaturated, and substituted or unsubstituted. It may contain one or more bonds / functional groups, for example selected from ethers, esters, amides, carbamates, ureas and mixtures thereof.

[0035] Within the meaning of the present invention, a cycloaliphatic group or compound is a non-aromatic group or compound comprising a ring. It may be substituted or unsubstituted. It may contain one or more bonds / functional groups as defined for the term "aliphatic".

[0036] Within the meaning of the present invention, an aromatic group or compound is a group or compound containing an aromatic ring, that is to say a ring which complies with the Huckel rule for aromaticity, in particular a group or compound containing a phenyl group. It may be substituted or unsubstituted. It may contain one or more bonds / functional groups as defined for the term "aliphatic".

[0037] Within the meaning of the present invention, a saturated group or compound is a group or compound which contains no carbon-carbon double or triple bonds.

[0038] Within the meaning of the present invention, an unsaturated group or compound is a group or compound which contains a carbon-carbon double bond or triple bond, in particular a carbon-carbon double bond.

[0039] Within the meaning of the present invention, a substituted group or compound is a group or compound in which one or more hydrogen atoms are replaced by a group or functional group independently selected from the group consisting of alkyl, hydroxyl (-OH), alkoxy, halogen (Br, Cl, I), cyano (-CN), isocyanate (-NCO), oxo (=O), amine (-NR 2 ), carboxylic acid (-COOH), ester (-COOR'), anhydride (-CO-O-COR'), sulfonyl (-S(=O) 2 OR''), phosphono (-P(=O)(OR'') 2 )、sulfate (-OS(=O) 2 OR'') and phosphate (-OP(=O)(OR'') 2 ), each R is independently H or an alkyl group, each R' is independently an alkyl group, and each R'' is independently a hydrogen atom, a metal salt, or a hydrocarbon chain.

[0040] Alkyd emulsion

[0041] The present invention firstly relates to an alkyd emulsion comprising an alkyd resin, a surfactant and water.

[0042] Within the meaning of the present invention, an emulsion corresponds to a liquid organic phase (discontinuous phase) dispersed in the form of droplets in an aqueous phase (continuous phase), the droplets being stabilized by surfactants. According to a particular embodiment, the alkyd emulsion is not in the form of a dispersion of a solid or semisolid organic phase in an aqueous phase; in other words, it is not in the form of a colloidal suspension or a latex.

[0043] The aqueous phase is a liquid comprising water. The liquid may additionally comprise a solvent other than water, such as, for example, butanediol.

[0044] According to one embodiment, the alkyd emulsion contains less than 10% by weight, in particular less than 5% by weight, more particularly less than 1% by weight, still more particularly less than 0.1% by weight of solvents other than water, relative to the weight of the emulsion. Thus, the alkyd emulsion exhibits a low content of volatile organic compounds (VOC), that is to say less than 10% by weight, in particular less than 5% by weight, more particularly less than 1% by weight, still more particularly less than 0.1% by weight of VOC, relative to the weight of the emulsion.

[0045] The liquid organic phase comprises an alkyd resin as described below. According to a particular embodiment, the alkyd resin is not self-emulsifiable, that is, it does not contain a sufficient amount of ionizable functional groups to spontaneously form an emulsion after the addition of water under stirring. In other words, the presence of a surfactant is necessary to stabilize the alkyd emulsion according to the invention.

[0046] The surfactant may in particular be as described below.

[0047] According to one embodiment, the alkyd emulsion exhibits a solid content (also referred to as solid content) of 35% to 65% by weight, particularly 40% to 60% by weight, more particularly 45% to 55% by weight. The solid content can be measured by ISO 3251:2008 method.

[0048] The alkyd emulsion may in particular exhibit a pH of from 7 to 9, in particular from 7.5 to 8.5.

[0049] The viscosity of the alkyd emulsion may specifically range from 1 to 1000 mPa·s, specifically range from 2 to 500 mPa·s, more specifically range from 5 to 100 mPa·s. The viscosity may be measured at 23° C. according to the measurement method described below.

[0050] The alkyd emulsion may in particular exhibit an average size of particles ranging from 50 to 1000 nm, in particular from 75 to 500 nm, more particularly from 100 to 300 nm. The average size of the particles may correspond to the volume average size measured by laser particle size analysis.

[0051] Alkyd resin

[0052] The alkyd emulsions according to the invention comprise an alkyd resin, also referred to as component a).

[0053] Alkyd resins are based on an acid component A and on an alcohol component B. In other words, alkyd resins are obtained by polycondensation of the acid component A and the alcohol component B.

[0054] The acid component A comprises at least one acid. The acid component A may comprise a mixture of acids. Preferably, the acid component A consists of all acids used for preparing the alkyd resin.

[0055] Alcohol component B comprises at least one alcohol. Alcohol component B may comprise a mixture of alcohols. Preferably, alcohol component B comprises all alcohols used for the preparation of the alkyd resin.

[0056] Within the meaning of the present invention, the term "acid" refers to a compound containing at least one carboxylic acid (-COOH) functional group or a functional group that can generate a carboxylic acid functional group in situ (especially by hydrolysis). The term "acid" therefore includes acid derivatives, such as anhydrides and esters. When an acid contains a single carboxylic acid functional group (or a single functional group that can generate a carboxylic acid functional group in situ), it is a monoacid. When an acid contains more than one carboxylic acid functional group (or more than one functional group that can generate a carboxylic acid functional group in situ), it is a polyacid.

[0057] Within the meaning of the present invention, the term "alcohol" refers to a compound containing at least one hydroxyl (-OH) functional group. When an alcohol contains a single hydroxyl functional group, it is a monohydric alcohol. When an alcohol contains more than one hydroxyl functional group, it is a polyhydric alcohol.

[0058] Component A may in particular represent from 50% to 95%, in particular from 60% to 90%, more particularly from 70% to 80% of the total weight of components A and B. In other words, the alkyd resin comprises from 50% to 95% by weight, in particular from 60% to 90% by weight, more particularly from 70% to 80% by weight, of units derived from an acid, relative to the total weight of the alkyd resin.

[0059] Component B may in particular represent from 5% to 50%, in particular from 10% to 40%, more particularly from 20% to 30%, of the total weight of components A and B. In other words, the alkyd resin comprises from 5% to 50% by weight, in particular from 10% to 40% by weight, more particularly from 20% to 30% by weight, of units derived from alcohol, relative to the total weight of the alkyd resin.

[0060] In particular, the combined weight of components A and B represents the total weight of the alkyd resin.

[0061] Alkyd resins exhibit an oil length of 20% to 50%.

[0062] The oiliness of the alkyd resin may correspond in particular to the % by weight of the fatty component used to obtain the alkyd resin (or the % by weight of units derived from the fatty component), relative to the total weight of the alkyd resin. The fatty component comprises in particular all the fatty acids used to prepare the alkyd resin.

[0063] Within the meaning of the present invention, the term "fatty acid" refers to an acid with a fatty chain, that is to say a (non-cyclic) hydrocarbon chain containing from 10 to 60, in particular from 12 to 55, more particularly from 14 to 50 consecutive carbon atoms. Fatty acids may be saturated or unsaturated. Saturated fatty acids are fatty acids that do not contain a C=C double bond. Unsaturated fatty acids contain at least one C=C double bond. Monounsaturated fatty acids contain a single C=C double bond. Polyunsaturated fatty acids contain more than one C=C double bond. The hydrocarbon chain of the fatty acid may be substituted, in particular by one or more hydroxyl or carbonyl functional groups. The term "fatty acid" includes fatty acid derivatives, that is to say compounds that can generate fatty acids in situ, in particular by hydrolysis, and by reactions between several fatty acids, in particular dimerization, trimerization, polymerization (standardization, standolization), estolidation (estolidation)) compounds. Fatty acid derivatives include, in particular, fatty acid esters (especially fatty acid alkyl esters and triglycerides or oils), stand oils, estolides and fatty acid dimers and trimers.

[0064] The acid component A comprises a conjugated fatty acid component A1.

[0065] Component A1 comprises at least one conjugated fatty acid. Component A1 may comprise a mixture of conjugated fatty acids. In particular, component A1 consists of all conjugated fatty acids used for preparing alkyd resins.

[0066] Within the meaning of the present invention, the term "conjugated fatty acid" refers to a polyunsaturated fatty acid comprising two C=C double bonds separated by a single C-C bond. The conjugated fatty acid may in particular be obtained from the isomerization of polyunsaturated fatty acids (in particular of natural origin, more particularly of plant or animal origin), such as linoleic acid, α-linolenic acid, γ-linolenic acid, octadecatetraenoic acid, eicosapentaenoic acid or docosahexaenoic acid. The conjugated fatty acid may also be obtained from the dehydration of hydroxylated unsaturated fatty acids (in particular of natural origin, more particularly of plant origin), such as ricinoleic acid.

[0067] Examples of conjugated fatty acids are 9,11-octadecadienoic acid, 10,12-octadecadienoic acid, 8,10,12-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, 9,11,15-octadecatrienoic acid, 9,13,15-octadecatrienoic acid, 6,9,11-octadecatrienoic acid, 10,12,14-octadecatrienoic acid, 9,11,13,15-octadecatetraenoic acid, 10,12-nonadecadienoic acid, 5,7,9,14,17-eicosapentaenoic acid and 5,8,10,12,14-eicosapentaenoic acid. Preferably, the conjugated fatty acid is 9,11-octadecadienoic acid.

[0068] Component A1 represents at least 5%, preferably from 5% to 40%, more preferentially from 10% to 35% of the total weight of components A and B. In other words, the alkyd resin comprises at least 5% by weight, preferably from 5% to 40% by weight, more preferentially from 10% to 35% by weight of units derived from conjugated fatty acids, relative to the total weight of the alkyd resin.

[0069] Conjugated fatty acids can be introduced in the form of a mixture of fatty acids, which mixture comprises one or more conjugated fatty acids and one or more selected from the following fatty acids: saturated fatty acids, monounsaturated fatty acids, non-conjugated polyunsaturated fatty acids, and derivatives thereof. Such mixtures can be particularly derived from oils or fats of natural origin, particularly vegetable oils or animal oils, such as castor oil, sunflower oil, linseed oil, soybean oil, tall oil, Chinese wood oil (tung oil), chia seed oil, perilla oil, poppy seed oil, cottonseed oil, lesquerella oil, safflower oil, oiticica oil, rapeseed oil, corn oil, marigold oil, hemp oil or fish oil. Oil can be particularly modified by dehydration and / or isomerization reaction to generate a vegetable oil of conjugated double bonds.

[0070] In particular, the conjugated fatty acids can be obtained from modified vegetable oils, preferably selected from dehydrated castor oil, isomerized sunflower oil, isomerized linseed oil or isomerized soybean oil, more preferably dehydrated castor oil.

[0071] Examples of mixtures comprising conjugated fatty acids are Nouracid® DE 656, DE 655, DE 554, DE 503, DE 402 or DZ 453 (dehydrated castor fatty acids - available from Oléon); Nouracid® HE 456, HE 306, HE 305, HE 304, HE 303 or HE 301 (isomerized sunflower fatty acids - available from Oléon); Nouracid® LE 805 (isomerized linseed fatty acids - available from Oléon); Nouracid® SE 305 (isomerized soya fatty acids - available from Oléon); Dedico® 5981 (dehydrated castor fatty acids - available from Croda); Isomerized acids SK, SY or SF (isomerized vegetable fatty acids - available from Hobum Oleochemicals GmbH), Pamolyn® 300, (isomerized tall oil fatty acid - available from Eastman).

[0072] The acid component A may comprise a polyacid component A2. Component A2 comprises at least one polyacid. Component A2 may comprise a mixture of polyacids. In particular, component A2 consists of all polyacids used to prepare alkyd resins.

[0073] The polyacid may be in particular unsaturated or saturated, in particular saturated. The polyacid may in particular be selected from dicarboxylic acids, tricarboxylic acids, monocarboxylic acid dimers, monocarboxylic acid trimers, derivatives of these, and mixtures of these. The polyacid may in particular contain from 3 to 54, in particular from 4 to 20, more particularly from 5 to 15 carbon atoms. According to one embodiment, the polyacid is a saturated or unsaturated polyacid. According to one embodiment, the polyacid is an aliphatic, alicyclic or aromatic, preferably an aromatic polyacid.

[0074] The polyacid may in particular have a functionality (number of carboxylic acid functions or carboxylic acid derivative functions) ranging from 2 to 4, in particular from 2 to 3 and more particularly equal to 2.

[0075] Examples of saturated aliphatic polybasic acids are malonic acid, succinic acid, 2-methylsuccinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, propane-1,2,3-tricarboxylic acid, saturated C 32 To C 36 Fatty acid dimers, saturated C 54 Fatty acid trimers, and mixtures thereof.

[0076] Examples of unsaturated aliphatic polyacids are itaconic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid and mixtures of these.

[0077] An example of a saturated cycloaliphatic polyacid is cyclohexanedicarboxylic acid.

[0078] An example of an unsaturated cycloaliphatic polyacid is tetrahydrophthalic acid.

[0079] Examples of the aromatic polyacid are phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, trimellitic acid, 2,5-furan dicarboxylic acid and mixtures of these.

[0080] The polyacid may be a polyacid derivative. Such a derivative may be converted into a polyacid by hydrolysis. The polyacid derivative includes partially or fully esterified forms of the polyacids defined above, in particular C 1 -C 6 Alkyl monoesters, diesters and triesters, and cyclic anhydrides. The polyacid derivatives may contain in particular from 5 to 60, in particular from 6 to 25, more particularly from 7 to 20 carbon atoms.

[0081] Examples of suitable polyacid derivatives of the ester type are dimethyl malonate, diethyl malonate, dimethyl adipate, dimethyl glutarate and dimethyl succinate.

[0082] The polyacid derivative may in particular be a cyclic anhydride. The cyclic anhydride may be saturated or unsaturated, in particular unsaturated. The cyclic anhydride may be alicyclic or aromatic, in particular aromatic.

[0083] Examples of saturated cyclic anhydrides are succinic anhydride and hexahydrophthalic anhydride. Examples of unsaturated alicyclic anhydrides are maleic anhydride, fumaric anhydride and tetrahydrophthalic anhydride. An example of aromatic anhydrides is phthalic anhydride.

[0084] According to a preferred embodiment, the polyacid component A2 comprises a cyclic anhydride, more particularly an unsaturated cyclic anhydride, still more particularly an aromatic anhydride, in particular phthalic anhydride.

[0085] Component A2 accounts for from 0% to 50%, in particular from 10% to 45%, more particularly from 20% to 40%, of the total weight of components A and B. In other words, the alkyd resin comprises from 0% to 50% by weight, in particular from 10% to 45% by weight, more particularly from 20% to 40% by weight, of units derived from polyacids, relative to the total weight of the alkyd resin.

[0086] Acid component A may comprise a non-fatty monoacid component A3. Component A3 comprises at least one non-fatty monoacid. Component A3 may comprise a mixture of non-fatty monoacids. In particular, component A3 consists of all non-fatty monoacids used to prepare alkyd resins.

[0087] Within the meaning of the present invention, the term "non-fatty monobasic acid" refers to C 2 -C 9 Monoacids, that is to say monoacids having from 2 to 9 carbon atoms.

[0088] The non-fatty monoacid may be an aliphatic, cycloaliphatic or aromatic monoacid, especially an aromatic monoacid.

[0089] Examples of suitable non-fatty monobasic acids are benzoic acid, tert-butylbenzoic acid, hexahydrobenzoic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, and mixtures of these.

[0090] According to a particular embodiment, component A3 comprises an aromatic non-fatty monoacid, more particularly benzoic acid.

[0091] Component A3 accounts for from 0% to 50%, in particular from 5% to 30%, more particularly from 10% to 20% of the total weight of components A and B. In other words, the alkyd resin comprises from 0% to 50% by weight, in particular from 5% to 30% by weight, more particularly from 10% to 20% by weight of units derived from non-fatty monobasic acids, relative to the total weight of the alkyd resin.

[0092] The acid component A may comprise a saturated fatty acid component A4. Component A4 comprises at least one saturated fatty acid. Component A4 may comprise a mixture of saturated fatty acids. In particular, component A4 consists of all saturated fatty acids used to prepare alkyd resins.

[0093] Examples of saturated fatty acids are capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, eicosanoic acid, 14-hydroxyeicosanoic acid, and mixtures of these. Saturated fatty acids can be obtained in particular from palm oil, coconut oil, hydrogenated castor oil, animal fats and mixtures thereof.

[0094] Component A4 represents from 0% to 20%, in particular from 0% to 10%, more particularly from 0% to 5%, of the total weight of components A and B. In other words, the alkyd resin comprises from 0% to 20% by weight, in particular from 0% to 10% by weight, more particularly from 0% to 5% by weight, of units derived from saturated fatty acids, relative to the total weight of the alkyd resin.

[0095] The acid component A may comprise a monounsaturated fatty acid component A5. Component A5 comprises at least one monounsaturated fatty acid. Component A5 may comprise a mixture of monounsaturated fatty acids. In particular, component A5 consists of all monounsaturated fatty acids used to prepare the alkyd resin.

[0096] Examples of monounsaturated fatty acids are myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, gadoleic acid, ricinoleic acid (12-hydroxy-9-octadecenoic acid), elaidic acid, trans-vaccenic acid, erucic acid, nervonic acid, brassidic acid, lesquerolic acid (14-hydroxy-11-eicosenoic acid), and mixtures of these.

[0097] The monounsaturated fatty monoacids can be obtained in particular from vegetable oils as described above.

[0098] Component A5 comprises from 0% to 20%, in particular from 1% to 10%, more particularly from 2% to 8% of the total weight of components A and B. In other words, the alkyd resin comprises from 0% to 20% by weight, in particular from 1% to 10% by weight, more particularly from 2% to 8% by weight of units derived from monounsaturated fatty acids, relative to the total weight of the alkyd resin.

[0099] Acid component A may comprise a non-conjugated polyunsaturated fatty acid component A6. Component A6 comprises at least one non-conjugated polyunsaturated fatty acid. Component A6 may comprise a mixture of non-conjugated polyunsaturated fatty acids. In particular, component A6 consists of all non-conjugated polyunsaturated fatty acids used to prepare alkyd resins.

[0100] Examples of non-conjugated polyunsaturated fatty acids are fatty acids of the omega-3 and omega-6 type, such as, in particular, 7,10,13-hexadecatrienoic acid, 9,12,15-octadecatrienoic acid, 6,9,12,15-octadecatrienoic acid, 11,14,17-eicosatrienoic acid, 8,11,14,17-eicosatetraenoic acid, 5,8,11,14,17-eicosapentaenoic acid, 6,9,12,15,18-heneicosapentaenoic acid, acid), 7,10,13,16,19-docosapentaenoic acid, 4,7,10,13,16,19-docosahexaenoic acid, 9,12,15,18,21-tetracosapentaenoic acid, 6,9,12,15,18,21-tetracosahexaenoic acid, 9,12-octadecadienoic acid, 6,9,12-octadecatrienoic acid, 11,14-eicosadienoic acid Acid, 8,11,14-eicosatrienoic acid, 5,8,11,14-eicosatrienoic acid, 13,16-docosadienoic acid, 7,10,13,16-docosatetraenoic acid, 4,7,10,13,16-docosapentaenoic acid, 9,12,15,18-tetracosatetraenoic acid, 6,9,12,15,18-tetracospentaenoic acid, and mixtures thereof.

[0101] The polyunsaturated fatty acids may in particular be obtained from vegetable oils as described for the conjugated fatty acids (preferably without modification, such as isomerization). Preferably, the non-conjugated polyunsaturated fatty acids are obtained from a vegetable oil selected from soybean oil, sunflower oil or tall oil.

[0102] Component A6 accounts for from 0% to 50%, in particular from 1% to 30%, more particularly from 5% to 20% of the total weight of components A and B. In other words, the alkyd resin comprises from 0% to 50% by weight, in particular from 1% to 30% by weight, more particularly from 5% to 20% by weight of units derived from non-conjugated polyunsaturated fatty acids, relative to the total weight of the alkyd resin.

[0103] The alcohol component B may comprise a polyol component B1. Component B1 comprises at least one polyol. Component B1 may comprise a mixture of polyols. In particular, component B1 consists of all polyols used for preparing the alkyd resin.

[0104] The polyol may in particular have a functionality (number of hydroxyl functions) ranging from 2 to 6, in particular from 3 to 6 and more particularly equal to 4.

[0105] The polyol may in particular be an aliphatic, alicyclic or aromatic polyol, especially an aliphatic or alicyclic polyol. The polyol may in particular be a saturated polyol. Preferably, the polyol is a saturated aliphatic polyol.

[0106] According to one embodiment, the polyol has a molar mass of less than 400 g / mol, less than 350 g / mol, less than 300 g / mol, less than 250 g / mol, less than 200 g / mol or less than 150 g / mol.

[0107] Examples of suitable polyols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyalkylene glycols such as polyethylene glycol or polypropylene glycol (preferably having an OH value in the range of from 250 to 3000, calculated as a function of the OH value). g / mol number average molecular weight Mn), 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, glycerol, diglycerol, tricyclodecane dimethanol, trimethylolpropane, di(trimethylolpropane), trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, erythritol, pentaerythritol, di(pentaerythritol), neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-methyl-1,2-propanediol, sorbitol alcohol, mannitol, xylitol, isosorbide, isoidol, isomannide, methyl glucoside, polyester polyols (especially polycaprolactone polyols), polycarbonate polyols, polyorganosiloxane polyols (especially polydimethylsiloxane polyols), polyglycerols such as glycerol oligomers, for example polyglyceryl-3 (glycerol trimer) and decaglycerol, hydroxyl-terminated polybutadiene, diols derived from hydrogenated or non-hydrogenated fatty acid dimers or trimers, alkoxylated (especially ethoxylated and / or propoxylated) derivatives of the above-mentioned polyols, and mixtures of these.

[0108] According to a particular embodiment, component B1 comprises a saturated aliphatic polyol selected from trimethylolethane, trimethylolpropane, glycerol, di(trimethylolpropane), pentaerythritol, dipentaerythritol, polyglycerol, sorbitol, diols derived from hydrogenated or non-hydrogenated fatty acid dimers or trimers, alkoxylated (in particular ethoxylated and / or propoxylated) derivatives of the above-mentioned polyols, and mixtures of these.

[0109] Component B1 represents from 0% to 50%, in particular from 10% to 40%, more particularly from 20% to 30%, of the total weight of components A and B. In other words, the alkyd resin comprises from 0% to 50% by weight, in particular from 10% to 40% by weight, more particularly from 20% to 30% by weight, of units derived from polyols, relative to the total weight of the alkyd resin.

[0110] The alcohol component B may comprise a monohydric alcohol component B2. Component B2 comprises at least one monohydric alcohol. Component B2 may comprise a mixture of monohydric alcohols. In particular, component B2 consists of all monohydric alcohols used to prepare the alkyd resin.

[0111] The monoalcohol may in particular be an aliphatic, alicyclic or aromatic monoalcohol, especially an aliphatic or alicyclic monoalcohol. The monoalcohol may in particular be a saturated monoalcohol. Preferably, the monoalcohol is a saturated aliphatic monoalcohol.

[0112] Monohydric alcohols may be particularly C 6 -C 60 , especially C 8 -C 55 , more specifically C 10 -C 50 Monohydric alcohol.

[0113] Examples of suitable monohydric alcohols are octan-1-ol, octan-2-ol, 2-ethyl-1-hexanol, nonan-1-ol, decan-1-ol, undecan-1-ol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, alkoxylated (in particular ethoxylated and / or propoxylated) derivatives of the abovementioned monohydric alcohols, and mixtures of these.

[0114] Component B2 represents from 0% to 20%, in particular from 0% to 10%, more particularly from 0% to 5%, of the total weight of components A and B. In other words, the alkyd resin comprises from 0% to 20% by weight, in particular from 0% to 10% by weight, more particularly from 0% to 5% by weight, of units derived from monohydric alcohols, relative to the total weight of the alkyd resin.

[0115] The alkyd resin may in particular have a number average molecular weight Mn ranging from 2500 to 6000 g / mol, in particular from 3500 to 5000 g / mol. The number average molecular weight may in particular be measured by GPC in THF as polystyrene equivalent.

[0116] The acid number of the alkyd resin may in particular be less than 25 KOH / g, preferably from 5 to 20 mg KOH / g, more preferentially from 8 to 13 mg KOH / g.

[0117] The hydroxyl number of the alkyd resin may in particular be from 20 to 150 mg KOH / g, preferably from 30 to 100 mg KOH / g.

[0118] The alkyd resin may in particular have an average functionality f ranging from 1.9 to 2.1. The average functionality is defined according to the following relationship:

[0119] f = 2 Σ i n i f i / Σ i n i

[0120] Where n i and f i are the number of moles and functionality (average of all reactive acid and alcohol components) of the acid or alcohol component i, respectively.

[0121] The alkyd resin may in particular have a Noury ​​viscosity at 110° C. according to the AFNOR XPT51213 method ranging from 7000 to 13000 mPa.s, preferably from 9000 to 12000 mPa.s.

[0122] The weight content of component a) may range from 35% to 65%, in particular from 40% to 60%, more particularly from 45% to 55%, relative to the weight of the alkyd emulsion.

[0123] Surfactants

[0124] The alkyd emulsions according to the invention comprise a surfactant component, also referred to as component b).

[0125] Component b) comprises a reactive surfactant. Component b) may comprise a mixture of reactive surfactants. Component b) may additionally comprise a non-reactive surfactant.

[0126] Within the meaning of the present invention, surfactants are amphiphilic compounds (that is to say, have both a hydrophilic part and a hydrophobic part). The surfactant must in particular be able to stabilize the alkyd resin in the form of droplets dispersed in water. In particular, surfactants suitable for forming oil-in-water emulsions may have a hydrophilic-lipophilic balance (HLB) value greater than 8, in particular greater than 10, more particularly greater than 12.

[0127] Within the meaning of the present invention, a reactive surfactant corresponds to a surfactant comprising functional groups capable of reacting with functional groups of the alkyd resin. Thus, the reactive surfactant can be incorporated directly into the backbone formed by the alkyd resin (in particular via a covalent bond). Preferably, the reactive surfactant is an ethylenically unsaturated surfactant.

[0128] Within the meaning of the present invention, "ethylenically unsaturated surfactant" refers to a surfactant comprising a polymerizable carbon-carbon double bond.

[0129] According to a specific embodiment, component b) comprises an anionic reactive surfactant. In particular, the anionic reactive surfactant may be a phosphate-based, phosphonate-based, sulfate-based, sulfonate-based, sulfosuccinate-based or carboxylate-based reactive surfactant, more particularly a sulfate-based reactive surfactant.

[0130] The anionic reactive surfactant may contain an aromatic ring. In particular, the anionic reactive surfactant may contain a carbon-carbon double bond in the α or β position of the aromatic ring, more particularly in the α position of the aromatic ring.

[0131] The anionic reactive surfactant may in particular correspond to the following formula (Ia):

[0132]

[0133] in:

[0134] Z is an ethylenically unsaturated group, preferably of the formula -CH=CH 2 、-CH=CHCH 3 or -CH 2 -CH=CH 2 ;

[0135] Each R 1 independently selected from H, alkyl, alkenyl, alkoxy, aryl and alkylaryl;

[0136] L is a bond, an alkylene group, an oxyalkylene group or a polyoxyalkylene group;

[0137] X comprises a hydrophilic group, preferably selected from -SO 3 M, -CO 2 M, -P(Y)O 2 M、-C(=O)-CH(SO 3 M)-CH 2 -C(=O)-Y or -C(=O)-CH 2 -CH(SO 3 M)-C(=O)-Y, more preferably -SO 3 M;

[0138] M is H, a metal cation (especially sodium or potassium) or ammonium;

[0139] Y is OM or the residue of the following formula (Ib):

[0140] .

[0141] The anionic reactive surfactant may in particular correspond to the following formula (Ic):

[0142]

[0143] Where R 1 and M are as defined above;

[0144] Each A is independently C 2 -C 4 Alkylene, preferably ethylene or propylene;

[0145] n ranges from 1 to 100, from 2 to 60, from 3 to 50, from 4 to 40 or from 5 to 30.

[0146] The anionic reactive surfactant may in particular correspond to the following formula (Id):

[0147]

[0148] wherein A, M and n are as defined above;

[0149] m is 1 or 2.

[0150] Examples of suitable anionic reactive surfactants are available from Dai-Ichi Kogyo Seiyaku under the following reference numbers: Hitenol® BC-3025, Hitenol® AR-1025, Hitenol® AR-10, Hitenol® KH-1025, Hitenol® KH-10, Hitenol® KH-05, Hitenol® BC-20, Hitenol® BC-1025, and Hitenol® BC-20.

[0151] The weight content of the anionic reactive surfactant may range from 0% to 5%, preferably from 1% to 4%, and more preferentially from 2% to 3%, relative to the weight of the alkyd emulsion.

[0152] According to a specific embodiment, component b) may comprise a nonionic reactive surfactant. In particular, the nonionic reactive surfactant may be a polyether-based reactive surfactant.

[0153] The nonionic reactive surfactant may contain an aromatic ring. In particular, the nonionic reactive surfactant may contain a carbon-carbon double bond in the α or β position of the aromatic ring, more particularly in the α position of the aromatic ring.

[0154] The nonionic reactive surfactant may in particular correspond to the following formula (IIa):

[0155]

[0156] in:

[0157] Z' is an ethylenically unsaturated group, preferably of the formula -CH=CH 2 、-CH=CHCH 3 or -CH 2 -CH=CH 2 ;

[0158] Each R 3 independently selected from H, alkyl, alkenyl, alkoxy, aryl and alkylaryl;

[0159] Each A is independently C 2 -C 4 Alkylene, preferably ethylene or propylene;

[0160] n ranges from 1 to 100, from 2 to 60, from 3 to 50, from 4 to 40 or from 5 to 30.

[0161] The nonionic reactive surfactant may in particular correspond to the following formula (IIb):

[0162]

[0163] Where R 3 , A and n are as defined above.

[0164] The nonionic reactive surfactant may in particular correspond to the following formula (IIc):

[0165]

[0166] wherein A and n are as defined above;

[0167] Alk is an alkyl group, preferably C 6 -C 30 alkyl.

[0168] The nonionic reactive surfactant may be an aliphatic surfactant.

[0169] The nonionic reactive surfactant may in particular correspond to the following formula (IIIa):

[0170]

[0171] in:

[0172] L' is C 6 -C 30 an alkylene group, which is preferably branched;

[0173] Z'' is an ethylenically unsaturated group, preferably of the formula -C(=O)-CR 4 =CH 2 or -CH 2 -CR 5 =CH 2 ;

[0174] R 4 and R 5 are independently selected from H and methyl;

[0175] Each A is independently C 2 -C 4 Alkylene, preferably ethylene or propylene;

[0176] n ranges from 1 to 100, from 2 to 60, from 3 to 50, from 4 to 40 or from 5 to 30.

[0177] Examples of suitable nonionic reactive surfactants are available from Dai-Ichi Kogyo Seiyaku under the following reference numbers: Noigen® RN-10, Noigen® RN-20, Noigen® RN-30, Noigen® RN-40, Noigen® RN-5065, Noigen® KN-10, Noigen® AN5065, Noigen® AN-30, Noigen® AN-20, and Noigen® AN-10.

[0178] The weight content of the nonionic reactive surfactant may range from 0% to 5%, preferably from 1% to 4%, and more preferentially from 2% to 3%, relative to the weight of the alkyd emulsion.

[0179] According to a specific embodiment, component b) may comprise anionic reactive surfactants and nonionic reactive surfactants. For example, the weight ratio of anionic reactive surfactants to nonionic reactive surfactants may be from 0.5 to 4, preferably from 1 to 3, more preferably from 1.5 to 2.5.

[0180] In addition to the reactive surfactants, component b) may comprise non-reactive surfactants. Component b) may comprise a mixture of non-reactive surfactants.

[0181] Within the meaning of the present invention, non-reactive surfactants are surfactants which comprise no functional groups capable of reacting with the functional groups of the alkyd resin, in particular no polymerizable carbon-carbon double bonds.

[0182] Non-reactive surfactant can be selected from anionic non-reactive surfactant, nonionic non-reactive surfactant and mixture thereof, such as mixture of anionic non-reactive surfactant and nonionic non-reactive surfactant. Without limiting it, the example of preferred anionic non-reactive surfactant includes alkyl sulfate, alkyl ether sulfate, alkyl sulfonate, alkyl benzene sulfonate, optionally substituted diphenyl oxide disulfonate, optionally alkoxylated sulfosuccinic acid monoester or diester, phosphonic acid monoester or diester, phosphoric acid monoester or diester, and mixture thereof. Without limiting it, the example of preferred non-ionic non-reactive surfactant includes optionally alkoxylated fatty alcohol, optionally alkoxylated fatty acid, optionally alkoxylated sorbitol ester, optionally alkoxylated fatty ester, ethoxy-propoxy block copolymer (EO-PO copolymer), and mixture thereof. The list of suitable surfactants can be obtained from the book "Surfactantsand Polymers in Aqueous Solutions" (Holmberg et al., 2002, John Wiley & Sons).

[0183] Examples of suitable alkyl sulfates and alkyl ether sulfates are optionally ethoxylated C 6 -C 22 Fatty alcohol sulfates, such as decyl sulfate, lauryl sulfate (such as Disponil® SLS), stearyl sulfate or C 12 -C 14 Fatty alcohol ether sulfates (such as Disponil® FES 77, Disponil® FES 27, Disponil® FES 993, Disponil® FES 32 or Rhodapex LA 120s).

[0184] Examples of suitable alkyl sulfonates are C 6 -C 22 Fatty alcohol sulfonates, such as decyl sulfonate, lauryl sulfonate and stearyl sulfonate.

[0185] Examples of suitable alkylbenzene sulfonates are linear or branched C 6 -C 22 Alkyl group-substituted benzene sulfonates, such as sodium dodecylbenzene sulfonate (such as Polystep® A-16-22 or Rhodacal® DS-4).

[0186] An example of a suitable diphenyl oxide disulfonate is sodium dodecyl diphenyl oxide disulfonate (such as Dowfax® 2A1 or Calfax® DB45).

[0187] Examples of suitable sulfonated succinic acid monoesters or diesters are optionally alkoxylated sulfonated succinic acid (C 6 -C 22 ) alkyl mono- or diesters (such as Aerosol® A-102, Aerosol® MA-80 or Aerosol® GPG).

[0188] Examples of suitable phosphoric acid monoesters or phosphoric acid diesters are compounds of formula (I) or (II) (such as Rhodafac® RS 410, Rhodafac® RS 610, Rhodafac® RS 710, Rhodafac® RS 960 or Rhodafac® Re 610):

[0189] Monoester RO(R'O) n -P(=O)[-O - M + ] 2 (I)

[0190] Diester [RO(R'O) n ] 2 -P(=O)-O - M + (II)

[0191] in:

[0192] Each R is independently C 6 To C 50 , preferably C 8 To C 30 , more priority C 10 To C 20 alkyl;

[0193] Each R' is independently ethylene or propylene;

[0194] n ranges from 2 to 50, preferably from 4 to 40, more preferably from 8 to 30;

[0195] M is selected from hydrogen, a metal cation (especially a sodium or potassium cation) or ammonium.

[0196] The phosphoric acid monoester and the phosphoric acid diester may be in particular in the form of a mixture, and the weight ratio of the phosphoric acid monoester to the phosphoric acid diester may be from 0.8 to 12.

[0197] Examples of suitable fatty alcohols are alkoxylated C 6 -C 22 Fatty alcohols, such as C 12 -C 14 Alcohol ethoxylates (such as Tergitol® 15-S-20), C 13Alcohol ethoxylates (such as Emulan® TO4070 or Emulan® TO 2080), C 16 -C 18 Alcohol ethoxylates (such as Empilan® KM80), propoxylated / ethoxylated C 4 -C 8 alcohols (wherein the weight ratio of propoxyl / ethoxyl is about 1), ethoxylated (2-40 EO) isocyanuric acid 10 Fatty alcohols and ethoxylated (2-40 EO)C 10 -C 18 Monobranched fatty alcohol.

[0198] Examples of suitable sorbitol esters are C 18 Sorbitol esters and ethoxylated (5-20 EO units) sorbitol esters.

[0199] Examples of suitable fatty acids are ethoxylated (7-100 EO)C 12 -C 18 Fatty acids, ethoxylated (30-40 EO) castor oil, and ethoxylated (7-60 EO) hydrogenated castor oil.

[0200] Examples of suitable fatty esters are glyceryl palmitate, glyceryl stearate, ethylene glycol stearate, diethylene glycol stearate, propylene glycol stearate, polyethylene glycol 200 stearate (Mn of PEG=200) or ethoxylated (2-15 EO)C 18 Fatty esters.

[0201] An example of an ethoxy-propoxy block copolymer is an EO-PO butoxy copolymer (such as Maxemul® 7101).

[0202] According to a particular embodiment, component b) comprises a non-reactive surfactant selected from optionally ethoxylated C 6 -C 22 Fatty alcohol sulfates, EO-PO butoxy, and mixtures of these.

[0203] Preferably, when the reactive surfactant is an anionic surfactant, component b) may additionally comprise a nonionic non-reactive surfactant. Alternatively, when the reactive surfactant is a nonionic surfactant, component b) may additionally comprise an anionic non-reactive surfactant.

[0204] According to a specific embodiment, component b) may comprise anionic reactive surfactants and nonionic non-reactive surfactants. For example, the weight ratio of anionic reactive surfactants to nonionic non-reactive surfactants may be from 1 to 4, from 2 to 3, preferably from 1.5 to 2.5.

[0205] According to an alternative embodiment, component b) may comprise a nonionic reactive surfactant and an anionic non-reactive surfactant. For example, the weight ratio of the nonionic reactive surfactant to the anionic non-reactive surfactant may be from 1 to 4, from 2 to 3, preferably from 1.5 to 2.5.

[0206] The weight content of the non-reactive surfactant varies from 0% to 5%, preferably from 0.5% to 3%, and more preferentially from 1% to 2%, relative to the weight of the alkyd emulsion.

[0207] The weight content of component b) varies from 1% to 15%, preferably from 2% to 12% and more preferentially from 3% to 10%, relative to the weight of the alkyd emulsion.

[0208] The alkyd emulsions according to the invention can be prepared in particular according to the process described below.

[0209] Process for the preparation of alkyd emulsions

[0210] The present invention also relates to a process for the preparation of an alkyd emulsion, the process comprising the following steps:

[0211] i) preparation of component a) comprising an alkyd resin in the molten state;

[0212] ii) addition of component b) comprising a reactive surfactant and water,

[0213] iii) neutralization of the acidity of components a) and b) by addition of a base,

[0214] iv) emulsification by phase inversion,

[0215] v) Optionally adjusting the solids content of the alkyd emulsion.

[0216] The alkyd resin of component a) can be prepared in particular by polycondensation of an acid component A and an alcohol component B. Components A and B can in particular be as described above. Components A and B can be heated to a temperature ranging from 80° C. to 250° C. The water formed during the polycondensation can be gradually removed by distillation. The course of the polycondensation can be monitored by the acid number of the reaction mixture. When the desired acid number is reached, the alkyd resin can be cooled to ambient temperature (20-30° C.) for storage for subsequent emulsification. Alternatively, the alkyd resin can be introduced directly in a molten state (e.g. at a temperature of 80° C. to 110° C.) in step ii) of the process according to the invention.

[0217] Step ii) may be carried out by adding component b) and water to the reaction medium. Component b) may in particular be as described above. Step ii) may be carried out at a temperature ranging from 80°C to 100°C.

[0218] Step iii) can be carried out in particular by adding a base to the reaction medium. The base can be selected from LiOH, KOH, NaOH, NH 4 OH or a tertiary amine. Step iii) may be performed at a temperature ranging from 60°C to 85°C.

[0219] Step iv) can be carried out in particular by gradually adding water to the reaction mixture under stirring. The temperature of the reaction mixture can be maintained at a temperature ranging from 60° C. to 85° C. Upon completion of the emulsification, the temperature of the reaction mixture can be returned to ambient temperature (20° C. to 25° C.).

[0220] Optional step v) can be carried out by adding water to obtain the desired solid content. In particular, the solid content can be adjusted to reach from 35% to 65%, preferably from 40% to 60%, more preferably from 45% to 55%.

[0221] Compositions, coatings and uses

[0222] Another subject matter according to the invention relates to a coating composition comprising an alkyd emulsion as defined above.

[0223] The composition may contain a drier. The drier may increase the rate of polymerization of the alkyd resin. The drier is typically a metal salt, particularly a cadmium, tin, cobalt, manganese, zirconium, lead, iron or calcium salt, or an organic compound such as a fatty acid.

[0224] According to another embodiment, the composition does not contain a desiccant and is dried simply by atmospheric oxygen. It is sufficient for the aqueous phase to be removed naturally by drying.

[0225] The composition according to the invention can be applied to a wide variety of substrates, including wood, metal, stone, plaster, concrete, glass, fabric, leather, paper, plastic and composites. Application can be carried out in a conventional manner, in particular using a brush or roller, by spraying, dipping or covering.

[0226] After application of the composition, the water may be removed naturally by drying in air, especially at ambient temperature, or by heating.

[0227] The composition may in particular be a coating, mastic or adhesive composition.

[0228] In particular, the composition may be a coating composition, more particularly a decorative coating composition, in particular a film, a paint, a varnish, a lacquer, a stain, an adhesive primer or an ink composition.

[0229] According to a particular embodiment, the composition is a paint, varnish or stain composition, in particular a finishing paint, varnish or stain composition. Such a composition can be particularly applied indoors or outdoors, for example on wood, metal, wall or plastic.

[0230] The composition can be used in particular for obtaining a coating (in particular a film, a paint, a varnish, a lacquer, a stain, an adhesive primer or an ink), an adhesive or a mastic.

[0231] A further subject matter of the present invention is the use of the alkyd emulsions according to the invention as binders for obtaining coatings (in particular films, paints, varnishes, lacquers, stains, adhesive primers or inks), mastics or putties.

[0232] The invention also relates to a coating (in particular a film, paint, varnish, lacquer, stain, adhesive primer or ink), a mastic or a putty obtained by applying and drying the composition according to the invention.

[0233] The following examples illustrate the invention and its performance qualities without limiting its scope in any way.

[0234] Experimental Section

[0235] Starting Materials

[0236] The starting materials used in the examples are described in Table 1 below.

[0237] [Table 1]

[0238]

[0239] Test and measurement methods

[0240] These tests and methods are generally valid for the properties mentioned in the description and particularly in the examples presented.

[0241] Solid content

[0242] The evaluation was carried out in compliance with ISO 3251:2008 according to the following conditions: 1 g of the dispersion was subjected to 125° C. for 1 hour and the result was expressed in %.

[0243] Noury ​​Viscosity

[0244] The Noury ​​viscosity of the alkyd resin is measured at 110° C. according to standard AFNOR XP T51-213 (1995) and is expressed in mPa.s.

[0245] Brookfield viscosity

[0246] The Brookfield viscosity of the alkyd resins is measured at 23°C, 10 rpm on a Brookfield RVDVE-230 viscometer using 2 and 3 spindles according to standard ISO 2555:2018.

[0247] Particle size

[0248] The size of the particles of the alkyd emulsion is measured using an item of equipment of the Zetasizer-Malvern Instruments Ltd type. The dispersion sample is diluted in a transparent container with filtered deionized water. The volume average size (Dv50) of the particles is measured by 90° laser light scattering.

[0249] Acid value and hydroxyl value

[0250] The acid value of alkyd resins is evaluated according to standard ISO 3682:1996.

[0251] The hydroxyl number of alkyd resins is evaluated according to standard ISO 4326:2019.

[0252] Storage stability

[0253] The storage stability corresponds to the change in the solids content of the alkyd emulsion at 50° C. for 1 month. The storage stability consists in measuring the solids content at the surface of the sample and in comparing it with the solids content measured at the bottom of the sample. The stability is considered good if, after storage for one month at 50° C., the difference in the measured solids content is not greater than 2%.

[0254] Water resistance

[0255] The water resistance of the coating is measured on such a film, which has a thickness of 150 μm. The formulation is applied using a film coater on a Leneta P121-10N panel and dried at 23°C (+ / -2°C) for 24 hours at 50% humidity. After drying, drops of water are deposited on the surface of the painted film. The more contact time (e.g., 5 min, 15 min, 30 min, 1 h, 2 h, 4 h, 8 h, 16 h, or even 24 h) is selected, the more drops of water will be deposited. These drops can be covered (by a watch glass, a bottle cap, etc.) and / or deposited on a small piece of filter paper to slow down evaporation (it is recommended to continue a long contact time). After the selected contact time has passed, the drops are gently removed using absorbent paper and the condition of the test surface is evaluated. The grading is performed immediately after the drops of water are removed. The second grading is performed after the test specimen is reconditioned in a climate-controlled chamber at 23°C and 50%RH for 24 h to evaluate the ability of the coating to regain its initial appearance. Water resistance is qualitatively evaluated according to the following scale:

[0256] 4: No visible change

[0257] 3: Slight gloss change / paint swelling / color change (fading) / paint softening is visible when light source is reflected onto the test surface

[0258] 2: Changes in the coating structure occur (slight bubbling, wrinkling)

[0259] 1: The coating structure changes significantly (strong foaming)

[0260] hardness

[0261] The hardness of the coating is measured on a film having a thickness of 100 µm, obtained according to the method described in the measurement of water resistance. The pendulum is cleaned with acetone. The film is placed under the pendulum. The pendulum is gently brought to the surface of the film. The pendulum is turned without lateral movement of the pivot until the appropriate angle (i.e. 12° for the Persoz pendulum) and temporarily locked using a rod. The counter is reset to zero and the pendulum is released. The measurement is completed when the pendulum is stationary and the counter is no longer increasing. The value is recorded. Three measurements are performed on each film and the average of the three values ​​is taken.

[0262] Example 1 (according to the present invention)

[0263] 1.1) Synthesis of alkyd resin

[0264] In a 1.5-liter reactor containing

[0265] - a dip tube for the introduction of nitrogen,

[0266] - Temperature probe,

[0267] - a reflux condenser supplied with water at 12°C, and

[0268] - a round-bottom flask for collecting the water obtained from the polycondensation,

[0269] The following starting materials were introduced:

[0270] - 345.5 g of Nouracid® DE554,

[0271] -241.2 g of pentaerythritol,

[0272] -263.1 g of phthalic anhydride and

[0273] -150.2 g of benzoic acid.

[0274] While bubbling nitrogen through it, the combined mixture was brought to 240° C. using an electric heating mantle and the water formed was distilled as it formed, until an acid value of less than 11 mg KOH / g was obtained. At the end of the synthesis, a viscous alkyd resin exhibiting the following characteristics was obtained:

[0275] -Acid value 10.9 mg KOH / g

[0276] -Solid content 100%

[0277] -Noury ​​viscosity: 10 900 mPa.s

[0278] 1.2) Emulsification of alkyd resin to obtain alkyd emulsion

[0279] 477.1 g of alkyd resin obtained according to the operating conditions of 1.1) described above, melted in advance at 80-100° C., was introduced into a 1 liter reactor. When the temperature of the reactor was stabilized at 85° C., 94.4 g of Hitenol® AR1025 (25% by weight aqueous solution) was introduced. The mixture was stirred for 30 minutes. Subsequently, 35.66 g of LiOH (10% by weight aqueous solution) was introduced over a period of 30 minutes to neutralize the alkyd resin. The mixture was stirred at 85° C. for 30 minutes. Finally, 375.22 g of water was introduced over a period of 2 hours while the temperature was maintained at 80° C. The reactor was then cooled to ambient temperature and the solid content was adjusted to 50%. At the end, an alkyd emulsion exhibiting the following characteristics was obtained:

[0280] -50% solid content

[0281] - pH: 7.5

[0282] -Brookfield viscosity at 23°C: < 100 mPa.s

[0283] -Particle size: < 200 nm

[0284] -Storage stability: Good

[0285] Example 2 (according to the present invention)

[0286] Example 1 was repeated, using an equal weight of Emulsogen® CPA 100 instead of Hitenol® AR 1025. At a comparable solids content, an alkyd emulsion was obtained having qualities similar to those of the emulsion obtained during Example 1 (particle size, pH, viscosity, stability on storage).

[0287] Example 3 (according to the present invention)

[0288] Example 1 was repeated, using equal weights of a mixture of Hitenol® AR 1025 and Noigen® KN 20 (weight ratio 2 / 1) instead of Hitenol® AR 1025. At a comparable solids content, an alkyd emulsion was obtained having qualities similar to those of the emulsion obtained during Example 1 (particle size, pH, viscosity, storage stability).

[0289] Example 4 (Comparative)

[0290] Example 1 was repeated, using an equal weight of Disponil® FES 77 instead of Hitenol® AR 1025. At a comparable solids content, an alkyd emulsion was obtained having qualities (particle size, pH, viscosity, stability on storage) similar to those of the emulsion obtained during Example 1.

[0291] Preparation

[0292] 150 g of the alkyd emulsion from Examples 1 to 4 were introduced into a 250 ml beaker. 0.5% by weight of Borchi® OXY-Coat 1101 (based on the weight of the solids content of the emulsion) was subsequently added over a period of 5 minutes with vigorous stirring (600 rpm).

[0293] The water resistance and hardness of the varnishes obtained using the formulations are detailed in Table 2.

[0294] [Table 2]

[0295]

[0296] The varnish containing the reactive surfactant exhibited better water resistance and better hardness than the varnish containing the non-reactive surfactant.

Claims

1. Alkyd emulsion, characterized in that, It contains: a) an alkyd resin having an oil content of 20% to 50%, the alkyd resin being based on an acid component A and on an alcohol component B, the acid component A comprising a conjugated fatty acid component A1, the component A1 accounting for at least 5%, preferably from 5% to 40%, more preferably from 10% to 35% of the total weight of components A and B; b) a surfactant comprising a reactive surfactant, preferably an ethylenically unsaturated surfactant; c) Water.

2. The alkyd emulsion according to claim 1, characterized in that The conjugated fatty acids are obtained from modified vegetable oils, preferably selected from dehydrated castor oil, isomerized sunflower oil, isomerized linseed oil or isomerized soybean oil, more preferably dehydrated castor oil.

3. The alkyd emulsion according to claim 1 or 2, characterized in that The acid component A comprises a polyacid component A2, in particular an aromatic anhydride, more particularly phthalic anhydride.

4. Alkyd emulsion according to one of claims 1 to 3, characterized in that The acid component A comprises a non-fatty monoacid component A3, in particular an aromatic non-fatty monoacid, more particularly benzoic acid.

5. Alkyd emulsion according to one of claims 1 to 4, characterized in that The alcohol component B comprises polyols, in particular polyols having a functionality ranging from 2 to 6, more particularly saturated aliphatic polyols selected from the group consisting of trimethylolethane, trimethylolpropane, glycerol, di(trimethylolpropane), pentaerythritol, dipentaerythritol, polyglycerol, sorbitol, diols derived from hydrogenated or non-hydrogenated fatty acid dimers or trimers, alkoxylated derivatives of the abovementioned polyols, and mixtures of these.

6. Alkyd emulsion according to one of claims 1 to 5, characterized in that The weight content of component a) varies from 35% to 65%, preferably from 40% to 60%, more preferentially from 45% to 55%, relative to the weight of the alkyd emulsion.

7. Alkyd emulsion according to one of claims 1 to 6, characterized in that The acid value of the alkyd resin is less than 25 mg KOH / g, preferably from 5 to 20 mg KOH / g, more preferentially from 8 to 13 mg KOH / g.

8. The alkyd emulsion according to any one of claims 1 to 7, characterized in that The component b) comprises anionic reactive surfactants, in particular phosphate-based, phosphonate-based, sulfate-based, sulfonate-based, sulfosuccinate-based or carboxylate-based reactive surfactants, more particularly sulfate-based reactive surfactants.

9. The alkyd emulsion according to claim 8, characterized in that The anionic reactive surfactant comprises an aromatic ring; in particular, the anionic reactive surfactant comprises a carbon-carbon double bond in the α or β position of the aromatic ring, more particularly in the α position of the aromatic ring.

10. Alkyd emulsion according to one of claims 8 or 9, characterized in that The anionic reactive surfactant corresponds to the following formula (Ia): ,in: Z is an ethylenically unsaturated group, preferably a group of the formula -CH=CH2, -CH=CHCH3 or -CH2-CH=CH2; Each R1 is independently selected from H, alkyl, alkenyl, alkoxy, aryl and alkylaryl; L is a bond, an alkylene group, an oxyalkylene group or a polyoxyalkylene group; X comprises a hydrophilic group, preferably selected from -SO3M, -CO2M, -P(Y)O2M, -C(=O)-CH(SO3M)-CH2-C(=O)-Y or -C(=O)-CH2-CH(SO3M)-C(=O)-Y, more preferably -SO3M; M is H, a metal cation or ammonium; Y is OM or the residue of the following formula (Ib): 。 11. The alkyd emulsion according to any one of claims 8 to 10, characterized in that The anionic reactive surfactant corresponds to the following formula (Ic): , where R 1 and M is as defined in claim 10; Each A is independently C2-C4 alkylene, preferably ethylene or propylene; n ranges from 1 to 100, from 2 to 60, from 3 to 50, from 4 to 40 or from 5 to 30.

12. The alkyd emulsion according to any one of claims 8 to 10, characterized in that The anionic reactive surfactant corresponds to the following formula (Id): , wherein M is as defined in claim 10; A and n are as defined in claim 11; m is 1 or 2.

13. Alkyd emulsion according to one of claims 8 to 12, characterized in that The weight content of the anionic reactive surfactant varies from 0% to 5%, preferably from 1% to 4%, and more preferentially from 2% to 3%, relative to the weight of the alkyd emulsion.

14. Alkyd emulsion according to one of claims 1 to 13, characterized in that The component b) comprises a nonionic reactive surfactant, preferably a polyether-based nonionic reactive surfactant.

15. The alkyd emulsion according to claim 14, characterized in that The weight content of the nonionic reactive surfactant varies from 0% to 5%, preferably from 1% to 4%, and more preferentially from 2% to 3%, relative to the weight of the alkyd emulsion.

16. Alkyd emulsion according to claims 1 to 15, characterized in that The component b) comprises an anionic reactive surfactant and a nonionic reactive surfactant, and the weight ratio of the anionic reactive surfactant to the nonionic reactive surfactant preferably ranges from 0.5 to 4, more preferably from 1 to 3, and still more preferably from 1.5 to 2.

5.

17. Alkyd emulsion according to one of claims 1 to 16, characterized in that The component b) comprises a non-reactive surfactant.

18. The alkyd emulsion according to claim 17, characterized in that The weight content of the non-reactive surfactant varies from 0% to 5%, preferably from 0.5% to 3%, and more preferentially from 1% to 2%, relative to the weight of the alkyd emulsion.

19. Alkyd emulsion according to one of claims 1 to 18, characterized in that The weight content of said component b) varies from 1% to 15%, preferably from 2% to 12% and more preferentially from 3% to 10%, relative to the weight of the alkyd emulsion.

20. Process for preparing an alkyd emulsion as defined in one of claims 1 to 19, characterized in that The process comprises the following steps: i) preparing component a) comprising an alkyd resin in a molten state; ii) adding water and component b) comprising a reactive surfactant, iii) neutralization of the acidity of components a) and b) by adding a base, iv) emulsification by phase transition, v) Optionally adjusting the solids content of the alkyd emulsion.

21. A composition, characterized in that It comprises an alkyd emulsion as defined according to one of claims 1 to 19 or obtained by a process as defined according to claim 20.

22. The composition according to claim 21, characterized in that It is a coating, mastic or adhesive composition, in particular a coating composition, more particularly a film, paint, varnish, lacquer, stain, adhesive primer or ink composition.

23. Use of an alkyd emulsion as defined in one of claims 1 to 19 or obtained by a process as defined in claim 20 as a binder for obtaining a coating, an adhesive or a mastic, in particular for obtaining a coating, more particularly for obtaining a film, a paint, a varnish, a lacquer, a stain, an adhesive primer or an ink.

24. A coating, adhesive or mastic obtainable by application and drying of a composition as claimed in claim 21 or 22.

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