Alkyd emulsion based on modified rosin

Abstract

The present invention relates to an alkyd emulsion comprising an alkyd resin based on modified rosin. The invention also relates to a method for preparing the alkyd emulsion and to the use thereof for obtaining a coating, in particular a decorative or industrial coating.

Description

[0001] DESCRIPTION

[0002] Title: Modified Rosin-Based Alkyd Emulsion

[0003] TECHNICAL FIELD

[0004] The present invention relates to an alkyd emulsion comprising a modified rosin-based alkyd resin. The invention also covers a method for preparing the alkyd emulsion and its use for obtaining a coating, particularly a decorative or industrial one.

[0005] PREVIOUS TECHNIQUE

[0006] Polyester resins are obtained by reacting polyacids and polyols. Polyester resins can be modified by adding a fatty component, such as an oil or fatty acid, to form a specific type of polyester resin: alkyd resins. Alkyd resins have been used for over 50 years to create coatings, including decorative and industrial paints.

[0007] The presence of an oily component in alkyd resins gives flexibility and gloss to the resulting coating. When the oily component contains unsaturates, the alkyds can dry out through auto-oxidation (siccation).

[0008] Alkyd resins in an organic solvent medium, also known as solvent-based alkyd resins, have long been known to those skilled in the art and are generally used in coatings and decorative and industrial paint formulations. To address issues of ease of use, odor, and toxicity related to the use of volatile organic compounds (VOCs), alkyd emulsions have been developed. Alkyd emulsions, also called post-emulsified alkyd resins, can be obtained by emulsifying an alkyd resin with the addition of a surfactant and water. Alkyd emulsions can advantageously have a high bio-based renewable carbon (BRC) content due to the use of bio-based acids and / or alcohols such as rosin, vegetable oil fatty acids, plant-derived diacids, glycerol, and polyglycerols.

[0009] Rosin-based alkyd emulsions are described in WO 2012 / 042153. The introduction of rosin into an alkyd resin allows, in particular, for an increase in the bio-based content of the resin. However, rosin-based alkyd resins have a long cycle time (the duration of the polycondensation reaction). Surprisingly, the Applicant discovered that using modified rosin to manufacture the alkyd resin reduces the cycle time for forming the alkyd resin while maintaining acceptable properties in terms of hardness development, gloss, adhesion to the substrate, flexibility, abrasion resistance, resistance to self-adhesion (blocking), mechanical strength, water resistance, and resistance to yellowing.This leads to a solution that is friendly to both humans and the environment due to the absence of organic solvents and drying agents, as well as the choice of essential raw materials, a high proportion of which can be from renewable and sustainable sources. Thus, the alkyd emulsion according to the invention can contain a proportion of renewable raw materials exceeding 80% by weight of the overall resin composition, while maintaining a competitive cost.

[0010] SUMMARY OF THE INVENTION

[0011] The object of the present invention relates to an alkyd emulsion comprising an alkyd resin based on an acid component A and an alcohol component B, in which component A comprises a modified rosin component A1 obtained by reaction between a rosin and a dienophile, the molar ratio between the dienophile and the rosin ranging from 0.25 to 0.40.

[0012] The invention also relates to a method for preparing an emulsion according to the invention, the method comprising the following steps: i) preparation of a molten alkyd resin, the alkyd resin being based on an acid component A and an alcohol component B, component A comprising a modified rosin component A1 obtained by reaction between a rosin and a dienophile, the molar ratio between the dienophile and the rosin ranging from 0.25 to 0.40; ii) addition of a surfactant component T and water; iii) neutralization of the acidity of the reaction mixture by adding a base; iv) emulsification by phase inversion; v) optionally adjustment of the dry extract of the alkyd emulsion.

[0013] The invention also relates to a composition comprising an alkyd emulsion according to the invention.

[0014] The invention also relates to the use of the alkyd emulsion according to the invention as a binder for obtaining a coating, adhesive, or sealant, particularly for obtaining a coating, more specifically for obtaining a film, paint, varnish, lacquer, stain, adhesion primer, or ink. The invention also relates to a coating, adhesive, or sealant obtained by applying and drying the composition according to the invention.

[0015] DETAILED DESCRIPTION

[0016] Definitions

[0017] In this application, the terms "includes one" and "includes an" mean respectively "includes one or more" and "includes one or more".

[0018] Unless otherwise stated, percentages by weight in a compound or composition are expressed relative to the weight of the compound or composition.

[0019] For the purposes of the present invention, an ethylenically unsaturated group or compound is a group or compound containing a polymerizable carbon-carbon double bond.

[0020] For the purposes of this 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. A polymerizable carbon-carbon double bond is generally comprised of a group selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl, and corresponding combinations thereof, preferably selected from acrylate, methacrylate, allyl, and vinyl. The carbon-carbon double bonds of an aromatic ring are not considered polymerizable carbon-carbon double bonds.

[0021] For the purposes of the present invention, an alkyl group is a monovalent saturated acyclic group of formula -C n H 2n +i. An alkyl can be linear or branched. A C1-C6 alkyl means an alkyl comprising 1 to 6 carbon atoms.

[0022] For the purposes of the present invention, an alkenyl group is a monovalent acyclic group having one or more C=C double bonds. An alkenyl can be linear or branched.

[0023] For the purposes of the present invention, an alkoxy group is a group of formula -O-alkyl.

[0024] For the purposes of the present invention, an aryl group is a group containing at least one aromatic ring. An aryl may contain a single aromatic ring or several rings, at least one of which is aromatic. An aromatic ring is a ring that obeys Hückel's rule. Examples of aryl groups are phenyl, biphenyl, naphthyl, and anthracenyl. The aryl groups of the invention preferably comprise from 6 to 12 carbon atoms. Even more preferably, the aryl group of the invention is a phenyl group. For the purposes of the present invention, an alkylaryl group is a group of formula -A-aryl, in which A is an alkylene. Preferably, an alkylaryl group is a group of formula -CR2R3-Ph, where R2 and R3 are independently H or Me, and more preferably a group of formula -CH(CH3)-Ph.

[0025] For the purposes of the present invention, an alkylene group is a divalent aliphatic radical derived from an alkane of formula C mH2m+2, where m = 2 to 50, is formed by removing a hydrogen atom from each attachment point of the radical. An alkylene can be linear or branched. A C2-C4 alkylene means an alkylene containing 2 to 4 carbon atoms.

[0026] For the purposes of the present invention, an oxyalkylene group is a group of formula -OA- in which A is an alkylene.

[0027] For the purposes of the present invention, a polyoxyalkylene group is a group of formula -O-[AO] n - in which each A is independently a C2-C4 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.

[0028] For the purposes of this invention, an aliphatic group or compound is a non-aromatic acyclic group or compound. It may be linear or branched, saturated or unsaturated, substituted or unsubstituted. It may comprise one or more bonds / functional groups, for example selected from ether, ester, amide, urethane, urea, and mixtures thereof.

[0029] For the purposes of this invention, a cycloaliphatic group or compound is a non-aromatic group or compound comprising a ring. It may be substituted or unsubstituted. It may comprise one or more bonds / functional groups as defined for the term "aliphatic".

[0030] For the purposes of this invention, an aromatic group or compound is a group or compound comprising an aromatic ring, i.e., complying with Hückel's rule of aromaticity, in particular a group or compound comprising a phenyl group. It may be substituted or unsubstituted. It may comprise one or more bonds / functional groups as defined for the term "aliphatic".

[0031] For the purposes of the present invention, a saturated group or compound means a group or compound that does not include a carbon-carbon double or triple bond.

[0032] For the purposes of the present invention, an unsaturated group or compound means a group or compound which includes a carbon-carbon double or triple bond, in particular a carbon-carbon double bond. For the purposes of the present invention, a substituted group or compound is a group or compound in which one or more hydrogen atoms have been replaced by a group or function independently selected from alkyl, hydroxyl (-OH), alkoxy, halogen (Br, Cl, I), cyano (-CN), isocyanate (-NCO), oxo (=O), amine (-NR2), carboxylic acid (-COOH), ester (-COOR'), anhydride (-CO-O-COR'), a sulfonylated group (-S(=O)2OR), a phosphonylated group (-P(=O)(OR”)2), a sulfated group (-OS(=O)2OR”) and a phosphated group (-OP(=O)(OR”)2), each R being independently H or alkyl, each R' being independently alkyl and each R” being independently a hydrogen atom, a metal salt or a hydrocarbyl chain.

[0033] alkvde emulsion

[0034] The invention relates firstly to an alkyd emulsion comprising an alkyd resin. The alkyd emulsion may further comprise at least one surfactant component T and water.

[0035] An emulsion can, in particular, consist of a liquid organic phase (discontinuous phase) dispersed as droplets in an aqueous phase (continuous phase), the droplets possibly being stabilized by a surfactant. According to a specific embodiment, the alkyd emulsion is not in the form of a dispersion of a solid or semi-solid organic phase in an aqueous phase; in other words, it is not in the form of a colloidal suspension or a latex.

[0036] The aqueous phase can include a liquid containing water. This liquid may also include a solvent other than water, such as butyl glycol.

[0037] According to one embodiment, the alkyd emulsion comprises less than 10%, in particular less than 5%, more particularly less than 1%, and even more particularly less than 0.1%, by weight of solvent other than water relative to the weight of the emulsion. Thus, the alkyd emulsion has a low volatile organic compound (VOC) content, that is, less than 10%, in particular less than 5%, more particularly less than 1%, and even more particularly less than 0.1%, by weight of VOCs relative to the weight of the emulsion.

[0038] The liquid organic phase may include an alkyd resin as described below. In one particular embodiment, the alkyd resin is not self-emulsifying, meaning it does not contain a sufficient quantity of ionizable functional groups to spontaneously form an emulsion after the addition of water while stirring. In other words, a surfactant is preferably added to stabilize the alkyd emulsion according to the invention. The surfactant may be, in particular, as described below.

[0039] According to one embodiment, the alkyd emulsion has a solids content (also called dry extract) of 35 to 65%, particularly 40 to 60%, and more particularly 45 to 55% by weight. The dry extract can be measured by the ISO 3251:2008 method.

[0040] Alkyd emulsion can have a pH of 7 to 9, particularly 7.5 to 8.5.

[0041] The viscosity of the alkyd emulsion can range from 1 to 1000 mPa s, in particular from 2 to 500 mPa s, and more specifically from 5 to 100 mPa.s. The viscosity can be measured at 23°C according to the measurement method described below.

[0042] Alkyd emulsions can have an average particle size of 50 to 1000 nm, particularly 75 to 500 nm, and more specifically 100 to 300 nm. The average particle size can correspond to the average volume size measured by laser granulometry.

[0043] Alkyd resin

[0044] The alkyd emulsion according to the invention comprises an alkyd resin.

[0045] Alkyd resin is based on an acid component A and an alcohol component B. In other words, alkyd resin is obtained by polycondensation of an acid component A and an alcohol component B.

[0046] Acid component A comprises at least one acid. Acid component A may comprise a mixture of acids. Preferably, acid component A consists of all the acids used to prepare the alkyd resin.

[0047] Alcohol component B comprises at least one alcohol. Alcohol component B may comprise a mixture of alcohols. Preferably, alcohol component B consists of all the alcohols used to prepare the alkyd resin.

[0048] For the purposes of this invention, the term "acid" means a compound comprising at least one carboxylic acid functional group (-COOH) or a functional group capable of generating a carboxylic acid functional group in situ (in particular by hydrolysis). The term "acid" therefore includes acid derivatives such as anhydrides and esters. When the acid contains only one carboxylic acid functional group (or only one functional group capable of generating a carboxylic acid functional group in situ), it is a monoprotic acid. When the acid contains more than one carboxylic acid functional group (or more than one functional group capable of generating a carboxylic acid functional group in situ), it is a polyprotic acid. For the purposes of this invention, the term "alcohol" means a compound comprising at least one hydroxyl functional group (-OH). When the alcohol contains only one hydroxyl functional group, it is a monoprotic alcohol. When the alcohol contains more than one hydroxyl functional group, it is a polyol.

[0049] Component A may represent from 50 to 95%, in particular from 60 to 90%, more particularly from 70 to 85% of the total weight of components A and B. In other words, the alkyd resin comprises from 50 to 95%, in particular from 60 to 90%, more particularly from 70 to 85%, by weight of units derived from an acid relative to the total weight of the alkyd resin.

[0050] Component B may represent from 5 to 50%, in particular from 10 to 40%, more particularly from 15 to 30% of the total weight of components A and B. In other words, the alkyd resin comprises from 5 to 50%, in particular from 10 to 40%, more particularly from 15 to 30%, by weight of alcohol-derived units relative to the total weight of the alkyd resin.

[0051] In particular, the total weight of components A and B represents the total weight of the alkyd resin.

[0052] Alkyd resin can notably have an oil content of 0 to 60%, in particular 5 to 50%, more particularly 10 to 40%.

[0053] The oil length of an alkyd resin can be defined as the percentage by weight of the fatty component used to obtain the alkyd resin (or the percentage by weight of units derived from a fatty component) relative to the total weight of the alkyd resin. The fatty component includes, in particular, all the fatty acids used to prepare the alkyd resin.

[0054] For the purposes of this invention, the term "fatty acid" means an acid having a fatty chain, that is, a hydrocarbyl (non-cyclic) chain comprising 10 to 60, in particular 12 to 55, and more particularly 14 to 50, consecutive carbon atoms. A fatty acid may be saturated or unsaturated. A saturated fatty acid is a fatty acid that does not contain any C=C double bonds. An unsaturated fatty acid contains at least one C=C double bond. A monounsaturated fatty acid contains a single C=C double bond. A polyunsaturated fatty acid contains more than one C=C double bond. The hydrocarbyl chain of the fatty acid may be substituted, in particular by one or more hydroxyl or carbonyl groups.The term "fatty acid" includes fatty acid derivatives, that is, compounds capable of generating a fatty acid in situ, notably by hydrolysis, as well as compounds obtained by reactions between several fatty acids (including dimerization, trimerization, standolization, and estolidation). Fatty acid derivatives include, in particular, fatty acid esters (especially alkyl esters of fatty acids and triglycerides or oils), standolies, estolides, and fatty acid dimers and trimers.

[0055] Component A1 and component A4 as described below are not considered fatty components and therefore do not enter into the calculation of oil length.

[0056] Acid component A includes a modified rosin component, also called component A1. Preferably, acid component A does not include any rosin other than component A1.

[0057] Component A1 is a modified rosin obtained by reaction between a rosin and a dienophile.

[0058] For the purposes of this invention, the term "rosin" refers to a resin obtained from resinous trees, particularly conifers, such as pines, cedars, firs, hemlocks, larches, or spruces. Rosin can be produced by heating conifer oleoresin (i.e., gum taken from living conifers) to remove water and volatile liquid terpene components, also known as turpentine. Rosin produced by this process may be called gum rosin. Gum rosin generally comprises resin acids and is substantially free of fatty acids. Alternatively, rosin can be produced from the distillation of crude tallol (tall oil). Rosin produced by this process may be called tallol rosin or tallol pitch and is referenced under CAS number [number missing in original text]. [8016-81-7], Crude tallol is a by-product resulting from the manufacture of paper pulp by the Kraft process.When softwood chips are treated with a mixture of sodium hydroxide and sodium sulfide in warm weather, the lignin and hemicellulose degrade and dissolve into the liquor, while the cellulose can be recovered as pulp and then washed. The liquor, which also contains resin acids and fatty acids in the form of sodium carboxylates, can be collected and concentrated. The foam that forms on the surface of the concentrated liquor, also called kraft soap or resin soap, can be collected and acidified under warm conditions with sulfuric acid to yield crude tallol. The crude tallol can then be distilled at reduced pressure to provide tallol rosin as a residual non-volatile fraction. Tallol rosin typically comprises tallol resin acids and fatty acids (primarily palmitic acid, oleic acid, and linoleic acid).When rosin comprises resin acids and tallol fatty acids, the latter are counted in components A2 and A5 to A7 described below. The term "rosin" therefore encompasses gum rosin, tallol rosin, a resin acid, and a mixture of resin acids. The composition of rosin varies depending on the resinous tree used and its origin. For the purposes of this invention, a "resin acid," also called "resin acid" or "rosin acid," refers to a polycyclic compound, in particular a terpenoid, bearing a carboxylic acid group that is derived from resinous trees, particularly conifers. A resin acid may, in particular, be represented by one of the following formulas (A) and (B):

[0059] [Chem 1] in which the dotted bonds can be independently chosen from single carbon-carbon bonds and double carbon-carbon bonds.

[0060] Examples of resin acids include abietic acid, pimaric acid, levopimaric acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, palustric acid, neoabietic acid, isopimaric acid, sandaracopimaric acid, and mixtures thereof.

[0061] For the purposes of this invention, the term "modified rosin" refers to the reaction product between rosin and a dienophile, with a molar ratio of dienophile to rosin ranging from 0.25 to 0.40. Modified rosin may, in particular, comprise rosin that has reacted with the dienophile (hereinafter referred to as cycloadducted rosin) mixed with rosin that has not reacted with the dienophile (hereinafter referred to as initial rosin), and optionally, reaction byproducts. The cycloadducted rosin may, in particular, be a Diels-Alder cycloadduct. Such a cycloadduct is formed by a Diels-Alder reaction between two conjugated carbon-carbon double bonds of the rosin, which acts as a diene, and a carbon-carbon double bond of the dienophile.

[0062] For the purposes of this invention, the term "dienophile" refers to a compound having a carbon-carbon double bond capable of reacting with a diene in a Diels-Alder reaction. The dienophile may be selected, in particular, from maleic anhydride, fumaric acid, and mixtures thereof. Preferably, the dienophile is maleic anhydride. The modified rosin may be obtained, in particular, by heating rosin and the dienophile, for example, at a temperature of 150 to 200°C.

[0063] According to a preferred embodiment, the molar ratio between dienophile and rosin ranges from 0.28 to 0.38, preferably from 0.30 to 0.37, more preferably from 0.32 to 0.35.

[0064] Component A1 may represent from 30 to 85%, preferably from 40 to 80%, more preferably from 50 to 75%, of the total weight of components A and B. In other words, the alkyd resin may comprise from 30 to 85%, preferably from 40 to 80%, more preferably from 50 to 75%, by weight of units derived from a rosin relative to the total weight of the alkyd resin.

[0065] The acid component A may include a conjugated fatty acid component, also called component A2.

[0066] Component A2 comprises at least one conjugated fatty acid. Component A2 may comprise a mixture of conjugated fatty acids. In particular, component A2 consists of all the conjugated fatty acids used to prepare the alkyd resin.

[0067] For the purposes of this invention, the term "conjugated fatty acid" means a polyunsaturated fatty acid comprising two C=C double bonds separated by a single C-C bond. A conjugated fatty acid may, in particular, result from the isomerization of a polyunsaturated fatty acid (especially one of natural origin, more particularly of plant or animal origin) such as linoleic acid, alpha-linolenic acid, gamma-linolenic acid, stearidonic acid, icosapentaenoic acid, or docosahexaenoic acid. A conjugated fatty acid may also result from the dehydration of a hydroxylated unsaturated fatty acid (especially one of natural origin, more particularly of plant origin) such as ricinoleic acid.

[0068] 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-icosapentaenoic acid, 5,8, 10,12,14-icosapentaenoic acid. Preferably, the conjugated fatty acid is 9,11-octadecadienoic acid.

[0069] The conjugated fatty acid may be introduced in the form of a mixture of fatty acids comprising one or more conjugated fatty acids and one or more fatty acids selected from a saturated fatty acid, a monounsaturated fatty acid, a non-conjugated polyunsaturated fatty acid, and derivatives thereof. Such mixtures may be derived from a naturally occurring oil or fat, including vegetable or animal oils such as castor oil, sunflower oil, linseed oil, soybean oil, tall oil (tallol or "tall oil"), tung oil, chia seed oil, perilla oil, poppy seed oil, cottonseed oil, lesquerella oil, safflower oil, oiticica oil, rapeseed oil, corn oil, calendula oil, hemp oil, and fish oil. The oil can notably be a vegetable oil modified by a dehydration and / or isomerization reaction to generate conjugated double bonds.

[0070] In particular, the conjugated fatty acid may be derived from a modified vegetable oil, preferably chosen from dehydrated castor oil, isomerized sunflower oil, isomerized linseed oil, isomerized soybean oil, more preferably dehydrated castor oil.

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

[0072] Component A2 may represent from 0 to 20%, preferably from 0 to 15%, more preferably from 0 to 10% of the total weight of components A and B. In other words, the alkyd resin may comprise from 0 to 20%, preferably from 0 to 15%, more preferably from 0 to 10%, by weight of units derived from a conjugated fatty acid relative to the total weight of the alkyd resin.

[0073] Acid component A may include a polyacid component, also called component A3. Component A3 comprises at least one polyacid. Component A3 may comprise a mixture of polyacids. In particular, component A3 consists of all the polyacids used to prepare the alkyd resin.

[0074] The polyacid may be unsaturated or saturated, particularly saturated. The polyacid may be selected from a dicarboxylic acid, a tricarboxylic acid, a monocarboxylic acid dimer, a monocarboxylic acid trimer, a derivative thereof, or a mixture thereof. The polyacid may comprise 3 to 54 carbon atoms, particularly 4 to 45, and more particularly 5 to 40. In one embodiment, the polyacid is saturated or unsaturated. In another embodiment, the polyacid is aliphatic, cycloaliphatic, or aromatic, preferably aliphatic or cycloaliphatic.

[0075] The polyacid can in particular have a functionality (number of carboxylic acid or carboxylic acid derivative functions) ranging from 2 to 4, in particular from 2 to 3, more particularly equal to 2.

[0076] Examples of saturated aliphatic polyacids include 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, a C32-C36 saturated fatty acid dimer, a C54 saturated fatty acid trimer, and mixtures thereof.

[0077] Examples of unsaturated aliphatic polyacids include itaconic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid, a C32-C36 unsaturated fatty acid dimer, a C54 unsaturated fatty acid trimer, and mixtures thereof.

[0078] Examples of saturated cycloaliphatic polyacids include 1,2-, 1,3- or 1,4-cyclohexane dicarboxylic acid, a C32-C36 cycloaliphatic fatty acid dimer, a C54 cycloaliphatic fatty acid trimer, and mixtures thereof.

[0079] An example of an unsaturated cycloaliphatic polyacid is tetrahydrophthalic acid.

[0080] Examples of aromatic polyacids include phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, trimellitic acid, 2,5-furan dicarboxylic acid and mixtures thereof.

[0081] A polyacid can be a polyacid derivative. Such a derivative can be transformed into a polyacid by hydrolysis. Polyacid derivatives include partially or fully esterified forms of the polyacids defined above, notably the C1-C6 alkyl mono-, di-, and triesters of the polyacids defined above, as well as cyclic anhydrides. Polyacid derivatives may include, in particular, 5 to 60, especially 6 to 25, and more particularly 7 to 20, carbon atoms.

[0082] Examples of suitable ester-type polyacid derivatives include dimethyl malonate, diethyl malonate, dimethyl adipate, dimethyl glutarate, and dimethyl succinate. The polyacid derivative may be a cyclic anhydride. The cyclic anhydride may be saturated or unsaturated, particularly unsaturated. It may also be cycloaliphatic or aromatic, particularly aromatic.

[0083] Examples of saturated cyclic anhydrides include succinic anhydride and hexahydrophthalic anhydride. Examples of unsaturated cycloaliphatic anhydrides include maleic anhydride, fumaric anhydride, and tetrahydrophthalic anhydride. Phenyl anhydride is an example of an aromatic anhydride.

[0084] According to a preferred embodiment, the polyacid component A3 comprises at least one fatty acid dimer in C32 to C36.

[0085] Component A3 can represent from 0 to 50%, in particular 1 to 40%, more particularly 3 to 30% of the total weight of components A and B. In other words, the alkyd resin can comprise from 0 to 50%, in particular 1 to 40%, more particularly 3 to 30% by weight of units derived from a polyacid relative to the total weight of the alkyd resin.

[0086] Acid component A may include a non-fatty monoacid component, also called component A4. Component A4 comprises at least one non-fatty monoacid. Component A4 may comprise a mixture of non-fatty monoacids. In particular, component A4 consists of all the non-fatty monoacids required to prepare the alkyd resin.

[0087] For the purposes of the present invention, the term "non-fatty monoacid" means a C2-C9 monoacid, that is to say, a monoacid having 2 to 9 carbon atoms.

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

[0089] Examples of suitable non-fatty monoacids include benzoic acid, tert-butylbenzoic acid, hexahydrobenzoic acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, pentenoic acid, pentadienoic acid, hexenoic acid, hexadienoic acid, heptenoic acid, heptadienoic acid, octenoic acid, octadienoic acid, nonenoic acid, nonadienoic acid, and mixtures thereof.

[0090] According to a particular embodiment, component A4 comprises an aromatic non-fatty monoacid, more particularly benzoic acid.

[0091] According to a particular embodiment, component A4 comprises an unsaturated non-fatty monoacid, more particularly a hexadienoic acid, in particular sorbic acid. Component A4 may represent 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 may comprise from 0 to 20%, in particular from 0 to 10%, more particularly from 0 to 5% by weight of units derived from a non-fatty monoacid relative to the total weight of the alkyd resin.

[0092] The acid component A may include a saturated fatty acid component, also called component A5. Component A5 comprises at least one saturated fatty acid. Component A5 may comprise a mixture of saturated fatty acids. In particular, component A5 consists of all the saturated fatty acids used to prepare the alkyd resin.

[0093] Examples of saturated fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, icosanoic acid, 14-hydroxyicosanoic acid, and mixtures thereof. Saturated fatty acids can be derived from sources such as palm oil, coconut oil, hydrogenated castor oil, animal fats, and mixtures thereof.

[0094] Component A5 may represent from 0 to 20%, in particular from 0.05 to 10%, more particularly from 0.1 to 5% of the total weight of components A and B. In other words, the alkyd resin may comprise from 0 to 20%, in particular from 0.05 to 10%, more particularly from 0.1 to 5%, by weight of units derived from a saturated fatty acid relative to the total weight of the alkyd resin.

[0095] The acid component A may include a monounsaturated fatty acid component, also called component A6. Component A6 comprises at least one monounsaturated fatty acid. Component A6 may comprise a mixture of monounsaturated fatty acids. In particular, component A6 consists of all the monounsaturated fatty acids used to prepare the alkyd resin.

[0096] Examples of monounsaturated fatty acids include 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-icosenoic acid) and mixtures thereof.

[0097] Monounsaturated fatty acids can notably be derived from a vegetable oil such as the one described above.

[0098] Preferably, component A6 comprises oleic acid. Component A6 may represent from 0 to 20%, in particular from 0.5 to 15%, more particularly from 1 to 10% of the total weight of components A and B. In other words, the alkyd resin may comprise from 0 to 20%, in particular from 0.5 to 15%, more particularly from 1 to 10%, by weight of units derived from a monounsaturated fatty acid relative to the total weight of the alkyd resin.

[0099] The acid component A may include an unconjugated polyunsaturated fatty acid component, also called component A7. Component A7 comprises at least one unconjugated polyunsaturated fatty acid. Component A7 may comprise a mixture of unconjugated polyunsaturated fatty acids. In particular, component A7 consists of all the unconjugated polyunsaturated fatty acids used to prepare the alkyd resin.

[0100] Examples of unconjugated polyunsaturated fatty acids include omega-3 and omega-6 fatty acids, such as 7,10,13-hexadecatrienoic acid, 9,12,15-octadecatrienoic acid, 6,9,12,15-octadecatretraenoic acid, 11,14,17-icosatrienoic acid, 8,11,14,17-icosatetraenoic acid, 5,8,11,14,17-icosapentaenoic acid, 6,9,12,15,18-heneicosapentaenoic acid, 7,10,13,16,19-docosapentaenoic acid, and 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, linoleic acid (9,12-octadecadienoic acid), 6,9,12-octadecatrienoic acid, 11,14-icosadienoic acid, 8,11,14-icosatrienoic acid, 5,8,11,14-icosatetraenoic 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-tetracosapentaenoic acid, and mixtures thereof.

[0101] The polyunsaturated fatty acid can be derived from a vegetable oil as described for the conjugated fatty acid (preferably without modification such as isomerization). Preferably, the unconjugated polyunsaturated fatty acid is derived from a vegetable oil selected from soybean oil, sunflower oil, or tall oil (tallol).

[0102] Preferably, component A7 comprises linoleic acid.

[0103] Component A7 may represent from 0 to 20%, in particular from 0.5 to 15%, and more particularly from 1 to 10%, of the total weight of components A and B. In other words, the alkyd resin may comprise from 0 to 20%, in particular from 0.5 to 15%, and more particularly from 1 to 10%, by weight of units derived from an unconjugated polyunsaturated fatty acid relative to the total weight of the alkyd resin. Components A1, A2, A3, A4, A5, A6, and A7 are distinct from one another. Preferably, component A does not comprise any component other than components A1, A2, A3, A4, A5, A6, and A7.

[0104] Alkyd resin is based on a component alcohol B.

[0105] The alcohol component B may include 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 the polyols used to prepare the alkyd resin.

[0106] Component B1 can have a functionality (number of hydroxyl groups) ranging from 2 to 6, particularly from 2.5 to 5.5, and more specifically from 3 to 5. When component B1 comprises a mixture of polyols, the functionality of component B1 corresponds to the average functionality of the polyol component, also called f B i.

[0107] The average functionality f Bi The composition of a polyol component comprising a mixture of n polyols can notably be determined using the following equation:

[0108] [Math 1] in which

[0109] X is the mole fraction of polyol i (corresponding to the number of moles of polyol i divided by the total number of moles of polyols in component B1); f is the functionality of polyol i (corresponding to the number of hydroxyl functions of polyol i).

[0110] Component B1 may include an aliphatic, cycloaliphatic, or aromatic polyol, particularly an aliphatic or cycloaliphatic polyol. Component B1 may include a saturated polyol. Preferably, component B1 includes a saturated aliphatic polyol.

[0111] According to one embodiment, the polyol(s) contained in component B1 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.

[0112] 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 with a number-average molecular weight (Mn), calculated from the OH index, ranging from 250 to 3000 g / mol), 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, a polyglycerol (i.e.a mixture of glycerol oligomers such as Polyglycerol-3 (which is a mixture of glycerol oligomers containing a major proportion of triglycerol), 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, mannitol, xylitol, isosorbide, isoidide, isomannide, methyl glucoside, polyester polyols (including polycaprolactone polyol), polycarbonate polyols, polyorganosiloxane polyols (including polydimethylsiloxane polyol), a hydroxy-terminated polybutadiene, a diol derived from a dimer or trimer of hydrogenated or non-hydrogenated fatty acid, alkoxylated derivatives (in particular ethoxylated and / or propoxylated) of the polyols mentioned above, and mixtures thereof.

[0113] According to a particular embodiment, component B1 comprises a saturated aliphatic polyol selected from trimethylolethane, trimethylolpropane, glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, a polyglycerol, di(trimethylolpropane), pentaerythritol, dipentaerythritol, sorbitol, a diol derived from a dimer or trimer of hydrogenated or non-hydrogenated fatty acid, alkoxylated derivatives (in particular ethoxylated and / or propoxylated) of the polyols mentioned above, and mixtures thereof.

[0114] Preferably, component B1 includes glycerol.

[0115] Component B1 can represent from 0 to 50%, in particular from 10 to 40%, more particularly from 15 to 30% of the total weight of components A and B. In other words, the alkyd resin can comprise from 0 to 50%, in particular from 10 to 40%, more particularly from 15 to 30%, by weight of units derived from a polyol relative to the total weight of the alkyd resin.

[0116] Component alcohol B may include a monoalcohol component B2. Component B2 includes at least one monoalcohol. Component B2 may include a mixture of monoalcohols. In particular, component B2 consists of all the monoalcohols used to prepare the alkyd resin.

[0117] The monoalcohol may be, in particular, an aliphatic, cycloaliphatic, or aromatic monoalcohol, especially aliphatic or cycloaliphatic. The monoalcohol may also be a saturated monoalcohol. Preferably, the monoalcohol is a saturated aliphatic monoalcohol.

[0118] The monoalcohol can notably be a monoalcohol in C6-C60, in particular C8-C55, more particularly C10-C50.

[0119] Examples of suitable monoalcohols 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, docosanol, alkoxylated derivatives (especially ethoxylated and / or propoxylated) of the monoalcohols mentioned above, and mixtures thereof.

[0120] 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%, in particular from 0 to 10%, more particularly from 0 to 5%, by weight of units derived from a monoalcohol relative to the total weight of the alkyd resin.

[0121] Alkyd resin can have a number-average molecular weight (Mn) ranging from 2500 to 9000 g / mol, particularly from 3500 to 6000 g / mol. The number-average molecular weight can be measured by GPC in THF as polystyrene equivalents.

[0122] The acid value of the alkyd resin may in particular be less than 25 mg KOH / g, preferably from 5 to 20 mg KOH / g, more preferably from 6 to 15 mg KOH / g.

[0123] The hydroxyl value of the alkyd resin can be from 20 to 150 mg KOH / g, preferably from 30 to 100 mg KOH / g.

[0124] Alkyd resin can notably have an average functionality f ranging from 1.8 to 2.1. This average functionality is defined according to the following relationship: f = 2 Zi ni / i ni with ni and f being respectively the number of moles and functionality of the acid or alcohol component i (average over all the reactive acid and alcohol components).

[0125] Alkyd resin can in particular have a cone-plate viscosity at 125°C according to the ISO 2884-1:1999 method ranging from 1,500 to 4,000 mPa.s, preferably from 2,000 to 3,000 mPa.s.

[0126] The weight ratio of alkyd resin to alkyd emulsion can range from 35 to 65%, particularly from 40 to 60%, and more specifically from 45 to 55%.

[0127] Surfactant

[0128] The alkyd emulsion according to the invention may include a surfactant component, also called component T. Component T comprises a surfactant. Component T may comprise a mixture of surfactants.

[0129] For the purposes of this invention, a surfactant is an amphiphilic compound (i.e., having both a hydrophilic and a hydrophobic part). The surfactant must, in particular, be capable of stabilizing the alkyd resin in the form of droplets dispersed in water. Specifically, a surfactant suitable for forming an oil-in-water emulsion may have a hydrophilic-lipophilic balance (HLB) value greater than 8, particularly greater than 10, and more particularly greater than 12.

[0130] Component T may comprise a surfactant selected from an anionic surfactant, a cationic surfactant, and mixtures thereof. Preferably, component T comprises a mixture of an anionic surfactant and a nonionic surfactant. For example, the weight ratio of the anionic surfactant to the nonionic surfactant may be 1 to 4, preferably 1 to 3, and more preferably 1.5 to 2.5.

[0131] Component T may include, among other things, an anionic surfactant selected from an alkyl sulfate, an alkyl ether sulfate, an alkylsulfonate, an alkylbenzenesulfonate, a diphenyl oxide disulfonate (optionally substituted), a sulfosuccinate mono- or diester (optionally alkoxylated), a phosphonate mono- or diester, a phosphate mono- or diester, a polymerizable anionic surfactant, and mixtures thereof. A list of suitable surfactants is available in the book "Surfactants and Polymers in Aqueous Solutions" (Holmberg et al., 2002, John Wiley & Sons).

[0132] Examples of suitable alkylsulfates and alkylethersulfates are possibly ethoxylated C6-C22 fatty alcohol sulfates, such as decyl sulfate, lauryl sulfate (like Disponil® SLS), stearyl sulfate, C12-C14 fatty alcohol ether sulfate with 2 to 50 OE units (like Disponil® FES 77, Disponil® FES 27, Disponil® FES 993, Disponil® FES 32, Rhodapex® LA 120s, Rhodapex® AB / 20).

[0133] Examples of suitable alkylsulfonates are C6-C22 fatty alcohol sulfonates such as decyl sulfonate, lauryl sulfonate, and stearyl sulfonate.

[0134] Examples of suitable alkylbenzenesulfonates are benzenesulfonates substituted with a linear or branched C6-C22 alkyl group, such as sodium dodecylbenzenesulfonate (like POLYSTEP® A-16-22, Rhodacal® DS-4), dodecylbenzenesulfonate as an ammonium salt derived from isopropylamine (Maxemul® 7201).

[0135] An example of a suitable diphenyl oxide disulfonate is sodium diphenyl oxide dodecyl disulfonate (such as Dowfax® 2A1, Calfax® DB45). Examples of suitable sulfosuccinate mono- or diesters are C6-C22 alkyl monoesters or diesters of sulfosuccinic acid, possibly alkoxylated (such as Aerosol® A-102, Aerosol® MA-80, Aerosol® GPG).

[0136] Examples of suitable phosphate mono- or diesters are compounds of formula (I) or (II) (such as Rhodafac® Rs 410, Rhodafac® Rs 610, Rhodafac® Rs 710, Rhodafac® Rs 960, Rhodafac® Re 610, Hostaphat® 1306): monoester RO(R'O) n - P(=O) [-O' M + ]2(I) diester [RO(R'O) n ]2- P(=O)-Q- M + (II) in which each R is independently an alkyl in C6 to C50, preferably in C8 to C30, more preferably in C to C20; each R' is independently ethylene or propylene; n ranges from 2 to 50, preferably from 4 to 40 more preferably from 8 to 30;

[0137] M is chosen from hydrogen, a metallic cation (in particular sodium or potassium) or an ammonium.

[0138] Phosphate mono- and diesters can notably be in the form of a mixture, the weight ratio of phosphate monoester to phosphate diester being from 0.8 to 1.2.

[0139] The anionic surfactant can be a polymerizable anionic surfactant (i.e., an ethylenically unsaturated surfactant), in particular a polymerizable surfactant based on phosphate, phosphonate, sulfate, sulfonate, sulfosuccinate or carboxylate, more particularly a sulfate-based polymerizable surfactant.

[0140] The polymerizable anionic surfactant may include an aromatic ring. In particular, the polymerizable anionic surfactant may include a carbon-carbon double bond in the alpha or beta position of the aromatic ring, more particularly in the alpha position of the aromatic ring.

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

[0142] [Chem 2] in which

[0143] Z is an ethylenically unsaturated group, preferably a group of the formula -CH=CH2, -CH=CHCH3 OR -CH2-CH=CH2 each R 1 is independently chosen from H, alkyl, alkenyl, alkoxy, aryl and alkylaryl;

[0144] L is a bond, an alkylene, an oxyalkylene or a polyoxyalkylene;

[0145] X comprises a hydrophilic group, preferably chosen 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;

[0146] M is H, a metallic cation (especially sodium or potassium) or an ammonium;

[0147] Y is OM or a residue of the following formula (Ib):

[0148] [Chem 3]

[0149] The polymerizable anionic surfactant may correspond in particular to the following formula:

[0150] [Chem 4] in which R 1 and M are as defined above; each A is independently a 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.

[0151] The polymerizable anionic surfactant may correspond in particular to the following formula (Id): in which A, M and n are as defined above; m is 1 or 2.

[0152] Examples of suitable polymerizable anionic surfactants are available under the references Hitenol® BC-3025, Hitenol® AR-1025, Hitenol® AR-10, Hitenol® KH-1025, Hitenol® KH-10, Hitenol® KH-05, Hitenol® BC-20, Hitenol® BC-1025, Hitenol® BC-20 from Dai-lchi Kogyo Seiyaku.

[0153] According to a particular embodiment, component T comprises an anionic surfactant selected from a phosphate monoester, a phosphate diester and mixtures thereof.

[0154] Component T may include, among other things, a nonionic surfactant selected from a fatty alcohol (possibly alkoxylated), a fatty acid (possibly alkoxylated), a sorbitol ester (possibly alkoxylated), a fatty ester (possibly alkoxylated), an ethoxy-propoxy block copolymer (EO-PO copolymer), a polymerizable nonionic surfactant, and mixtures thereof. A list of suitable surfactants is available in the book "Surfactants and Polymers in Aqueous Solutions" (Holmberg et al., 2002, John Wiley & Sons).

[0155] Examples of suitable fatty alcohols include C6-C22 alkoxylated fatty alcohols with 2 to 50 alkoxy units, such as C12-C14 alcohol ethoxylates (like Tergitol® 15-S-20, Disponil® A 1080, Disponil® A 1580, or Disponil® A 3065), C13 alcohol ethoxylates (like Emulan® TO 4070, Emulan® TO 2080), C16-C18 alcohol ethoxylates (like Empilan® KM80 or Disponil® A 4065), propoxylated / ethoxylated C4-C8 alcohols with a propoxy / ethoxy weight ratio of approximately 1, and ethoxylated iso-Cio fatty alcohol (2-40 EO), monobranched fatty alcohols ethoxylated at C10-C18 (2-40 EO).

[0156] Examples of suitable sorbitol esters are Ci8 sorbitol esters and ethoxylated sorbitol esters (5-20 EO motifs).

[0157] Examples of suitable fatty acids are ethoxylated C12-C18 fatty acids (7-100 EO), ethoxylated castor oil (30-40 EO), and ethoxylated hydrogenated castor oil (7-60 EO). Examples of suitable fatty esters are glyceryl palmitate, glyceryl stearate, ethylene glycol stearate, diethylene glycol stearate, propylene glycol stearate, polyethylene glycol 200 stearate (Mn=200 PEG), or ethoxylated fatty esters (2-15 EO) in Ois.

[0158] Examples of ethoxy-propoxy block copolymers are Butoxy EO-PO copolymers (such as Maxemul® 7101).

[0159] The non-ionic surfactant can be a polymerizable non-ionic surfactant (i.e., an ethylenically unsaturated surfactant), in particular a polymerizable surfactant based on a polyether.

[0160] A polymerizable non-ionic surfactant may include an aromatic ring. In particular, a polymerizable non-ionic surfactant may include a carbon-carbon double bond in the alpha or beta position of the aromatic ring, more specifically in the alpha position of the aromatic ring.

[0161] The polymerizable non-ionic surfactant may correspond in particular to the following formula (lia):

[0162] [Chem 6] in which

[0163] Z' is an ethylenically unsaturated group, preferably a group of the formula -CH=CH2, -CH=CHCH3 OR -CH2-CH=CH2 each R 3 is independently chosen from H, alkyl, alkenyl, alkoxy, aryl and alkylaryl; each A is independently a 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.

[0164] The polymerizable non-ionic surfactant may correspond in particular to the following formula (llb): in which R 3 , A and n are such as defined above.

[0165] The polymerizable non-ionic surfactant may correspond in particular to the following formula (Ile):

[0166] [Chem 8]

[0167] Alk in which A and n are such as defined above;

[0168] Alk is an alkyl, preferably in C6-C30.

[0169] The non-ionic polymerizable surfactant can be an aliphatic surfactant.

[0170] The polymerizable non-ionic surfactant may correspond in particular to the following formula (Ilia):

[0171] [Chem 9] in which

[0172] L' is a C6-C30 alkylene, preferably branched;

[0173] Z” is an ethylenically unsaturated group, preferably a group of the formula -C(=O)-CR 4 =CH2, -CH2-CR 5 =CH2

[0174] R 4 and R 5are independently chosen from H and methyl; each A is independently a 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.

[0175] Examples of suitable polymerizable nonionic surfactants are available under the references Noigen® RN-10, Noigen® RN-20, Noigen® RN-30, Noigen® RN-40, Noigen® RN-5065, Noigen® KN-10, Noigen® AN 5065, Noigen® AN-30, Noigen® AN-20, and Noigen® AN-10 from Dai-lchi Kogyo Seiyaku. In one particular embodiment, component T comprises a nonionic surfactant selected from an ethoxy-propoxy block copolymer.

[0176] The weight percentage of component T relative to the weight of the alkyd emulsion varies from 1 to 15%, preferably from 2 to 12% and more preferably from 3 to 10%.

[0177] The alkyd emulsion according to the invention can in particular be prepared according to the process described below.

[0178] Method for preparing an alkvde emulsion

[0179] The invention also relates to a method for preparing an alkyd emulsion, the method comprising the following steps: i) preparation of an alkyd resin in the molten state, the alkyd resin being as defined above; ii) addition of a surfactant component T and water; iii) neutralization of the acidity of the reaction mixture by adding a base; iv) emulsification by phase inversion; v) optionally adjustment of the dry extract of the alkyd emulsion.

[0180] The alkyd resin of step i) can be prepared, in particular, by polycondensation of an acid component A and an alcohol component B. Components A and B can be as described previously. Components A and B can be heated to a temperature ranging from 80 to 250°C. The water formed during the polycondensation can be gradually removed by distillation. The progress of the polycondensation can be controlled by the acid value of the reaction mixture. Once the desired acid value is reached, the alkyd resin can be cooled to room temperature (20-30°C) for storage for subsequent emulsification.

[0181] Alternatively, the alkyd resin can be directly introduced in a molten state (for example at a temperature of 80 to 110°C) in step ii) of the process according to the invention.

[0182] Step ii) can be carried out by adding component T and water to the reaction medium. Component T can be, in particular, as described previously. Step ii) can be carried out at a temperature ranging from 80 to 100°C.

[0183] Step iii) can be carried out by adding a base to the reaction medium. The base can be chosen from LiOH, KOH, NaOH, NH4OH, a tertiary amine, or a mixture thereof. Step iii) can be carried out at a temperature ranging from 60 to 85°C. The neutralization achieved in step iii) is not necessarily complete; that is, the alkyd resin may have carboxylic acid groups in free form (-COOH) at the end of step iii).

[0184] Step iv) can be carried out by gradually adding water to the reaction mixture while stirring. The temperature of the reaction mixture can be maintained between 60 and 85°C. Once emulsification is complete, the reaction mixture can be allowed to return to room temperature (20 to 25°C).

[0185] Optional step v) can be carried out by adding water to obtain the desired dry extract. In particular, the dry extract can be adjusted to reach 35 to 65%, preferably 40 to 60%, and more preferably 45 to 55%.

[0186] Composition, coating and use

[0187] Another object, according to the invention, relates to a coating composition comprising an alkyd emulsion as defined above.

[0188] The composition may include a drying agent. The drying agent increases the polymerization rate of the alkyd resin. Drying agents are typically metallic salts, including salts of cadmium, tin, cobalt, manganese, zirconium, lead, iron, or calcium; or organic compounds such as fatty acids.

[0189] In another embodiment, the composition does not include a drying agent and simply dries with atmospheric oxygen. The aqueous phase then simply evaporates naturally through drying.

[0190] 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 composite materials. Application can be carried out conventionally, in particular with a brush or roller, by spraying, immersion, or coating.

[0191] After application of the composition, the water can be eliminated naturally by air drying, particularly at room temperature or by heating.

[0192] The composition may include a coating, sealant, or adhesive composition.

[0193] In particular, the composition may be a coating composition, more specifically a decorative coating composition, including a film, paint, varnish, lacquer, stain, adhesion primer, or ink composition. According to a particular embodiment, the composition is a paint, varnish, or stain composition, including a finishing paint, varnish, or stain composition. Such a composition may be applied indoors or outdoors, for example, on wood, metal, walls, or plastic.

[0194] The composition can notably be used to obtain a coating (in particular a film, paint, varnish, lacquer, stain, adhesion primer or ink), an adhesive or a sealant.

[0195] Another object of the invention relates to the use of the alkyd emulsion according to the invention, as a binder to obtain a coating (in particular a film, a paint, a varnish, a lacquer, a stain, an adhesion primer or an ink), an adhesive or a sealant.

[0196] The invention also relates to a coating (in particular a film, a paint, a varnish, a lacquer, a stain, an adhesion primer or an ink), an adhesive or a sealant obtained by application and drying of the composition according to the invention.

[0197] The following examples illustrate the invention and its performance and in no way limit its scope.

[0198] EXPERIMENTAL SECTION

[0199] Raw materials

[0200] The raw materials used in the examples are described in Table 1 below.

[0201] [Table 1]

[0202] Tests and measurement methods

[0203] These tests and methods are generally valid for the characteristics mentioned in the description and particularly in the examples presented. Dry extract

[0204] Evaluation according to ISO 3251:2008 under the following conditions: 1 g of dispersion during

[0205] 1 hour at 125°C and the result is expressed as a percentage.

[0206] Cone-plane viscosity

[0207] The cone-plane viscosity of the alkyd resin is measured at 125°C according to ISO 2884-1:1999 and expressed in mPa.s.

[0208] Brookfield Viscosity

[0209] The Brookfield viscosity of the alkyd emulsion is measured at 23°C, with a Brookfield DVII apparatus (mobile S34) according to ISO 3219:1993.

[0210] The particle size of the alkyd emulsion is measured using a Zetasizer-Malvern Instruments Ltd. instrument. The dispersion sample is diluted in a transparent cuvette with filtered deionized water. The volume-average particle size (Dv50) is measured by 90° laser scattering.

[0211] The acid value of the alkyd resin is evaluated according to ISO 3682:1996.

[0212] The hydroxyl value of the alkyd resin is evaluated according to ISO 4326:2019.

[0213] 1.1) Synthesis of alkyd resin

[0214] In a 2-liter reactor containing:

[0215] - a submersible rod for introducing nitrogen,

[0216] - a temperature probe,

[0217] - a refrigerant supplied with water at 12°C, and

[0218] - a tank to collect the water from the polycondensation; the following raw materials were used:

[0219] - 882.4 g of FOR 85 (comprising 767.7 g of rosin and 44.1 g of fatty acid)

[0220] - 83.3 g of maleic anhydride

[0221] - 48.1 g of Radiacid® 951

[0222] - 96 g of tall fatty acid

[0223] - 248.8 g of glycerol

[0224] Under nitrogen bubbling, FOR 85 and maleic anhydride were introduced. The mixture was heated to 180°C for 2 hours. Radiacid® 951, tall fatty acid, and glycerol were then added. The mixture was heated to 265°C using an electric heating mantle, and the water formed was distilled continuously until an acid value of 13.7 mg KOH / g was reached. This step lasted 14 hours. At the end of the synthesis, a viscous alkyd resin with the following characteristics was obtained:

[0225] - Acid value 13.7 mg KOH / g

[0226] - Dry extract: 100%

[0227] - Cone-plate viscosity: 2900 mPa.s

[0228] 1.2) Emulsification of the alkyd resin to obtain an alkyd emulsion

[0229] In a 1-liter reactor, 373.4 g of alkyd resin, prepared according to the operating conditions of section 1.1 described above and previously melted at 110°C, were introduced. Once the reactor temperature had stabilized at 105°C, 88.9 g of Rhodapex® AB / 20 were added. When the temperature reached 85°C, 11.51 g of LiOH (10% by weight aqueous solution) were added. The mixture was stirred at 85°C for 30 minutes. Finally, 317.02 g of water were added over a period of 2 hours, while maintaining the temperature at 85°C. 7.47 g of Disponil® A3065 were then added, and the mixture was stirred at 65°C for 30 minutes. The reactor was then cooled to room temperature and the dry extract adjusted to 49.7%. The final product was an alkyd emulsion with the following characteristics:

[0230] Dry extract: 49.7% - pH: 7.9

[0231] Brookfield viscosity at 23°C: 168 mPa.s

[0232] Particle size: 140 nm Storage stability: good

[0233] Example 2 (comparative) Example 1 was reproduced using 56.24 of maleic anhydride.

[0234] The time required to achieve an acid value of 13.7 mg KOH / g at the end of step 1.1) was 30 hours.

Claims

DEMANDS

1. Alkyd emulsion comprising an alkyd resin based on an acid component A and an alcohol component B, characterized in that component A comprises a modified rosin component A1 obtained by reaction between a rosin and a dienophile, the molar ratio between the dienophile and the rosin ranging from 0.25 to 0.

40.

2. Alkyd emulsion according to claim 1, characterized in that the alkyd resin has an oil length of 0 to 60%, in particular 5 to 50%, more particularly 10 to 40%.

3. Alkyd emulsion according to claim 1 or 2, characterized in that the molar ratio between dienophile and rosin ranges from 0.28 to 0.38, preferably from 0.30 to 0.37, more preferably from 0.32 to 0.

35.

4. Alkyd emulsion according to any one of claims 1 to 3, characterized in that component A1 represents from 30 to 85%, preferably from 40 to 80%, more preferably from 50 to 75%, of the total weight of components A and B.

5. Alkyd emulsion according to any one of claims 1 to 4, characterized in that the acid component A comprises a polyacid component A3, in particular component A3 comprises at least one fatty acid dimer in C32 to C36.

6. Alkyd emulsion according to any one of claims 1 to 5, characterized in that the acid component A comprises a monounsaturated fatty acid component A6, in particular component A6 comprises oleic acid.

7. Alkyd emulsion according to any one of claims 1 to 6, characterized in that the acid component A comprises a polyunsaturated fatty acid component A7, in particular component A7 comprises linoleic acid.

8. Alkyd emulsion according to any one of claims 1 to 7, characterized in that the alcohol component B comprises a polyol component B1, in particular a polyol component B1 having a functionality from 2 to 6, in particular from 2.5 to 5.5, more particularly from 3 to 5.

9. Alkyd emulsion according to claim 8, characterized in that component B1 comprises at least one saturated aliphatic polyol selected from trimethylolethane, trimethylolpropane, glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, a polyglycerol, di(trimethylolpropane), pentaerythritol, dipentaerythritol, sorbitol, a diol derived from a dimer or trimer of hydrogenated or non-hydrogenated fatty acid, alkoxylated derivatives of the polyols mentioned above, and mixtures thereof.

10. Alkyd emulsion according to any one of claims 1 to 9, characterized in that the weight ratio of the alkyd resin to the weight of the alkyd emulsion varies from 35 to 65%, preferably from 40 to 60%, more preferably from 45 to 55%.

11. Alkyd emulsion according to any one of claims 1 to 10, 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 preferably from 6 to 15 mg KOH / g.

12. Alkyd emulsion according to any one of claims 1 to 11, characterized in that the emulsion comprises a surfactant component T, in particular a component T comprising a surfactant selected from an anionic surfactant, a non-ionic surfactant and mixtures thereof.

13. Alkyd emulsion according to claim 12, characterized in that the weight ratio of component T relative to the weight of the alkyd emulsion varies from 1 to 15%, preferably from 2 to 12% and more preferably from 3 to 10%.

14. A process for preparing an alkyd emulsion as defined according to any one of claims 1 to 13, characterized in that the process comprises the following steps: i) preparation of a molten alkyd resin, the alkyd resin being based on an acid component A and an alcohol component B, component A comprising a modified rosin component A1 obtained by reaction between a rosin and a dienophile, the molar ratio between the dienophile and the rosin ranging from 0.25 to 0.40; ii) addition of a surfactant component T and water; iii) neutralization of the acidity of the reaction mixture by adding a base; iv) emulsification by phase inversion; v) optionally adjustment of the dry extract of the alkyd emulsion.

15. Composition characterized in that it comprises an alkyd emulsion as defined according to any one of claims 1 to 13 or obtained by the process as defined according to claim 14.

16. Composition according to claim 15, characterized in that it is a coating, sealant or adhesive composition, in particular a composition coating, more specifically a composition of film, paint, varnish, lacquer, stain, adhesion primer or ink.

17. Use of the alkyd emulsion as defined according to any one of claims 1 to 13 or obtained by the process as defined according to claim 14, as a binder for obtaining a coating, adhesive or sealant, in particular for obtaining a coating, more particularly for obtaining a film, paint, varnish, lacquer, stain, adhesion primer or ink.

18. A coating, adhesive or sealant obtained by applying and drying the composition according to claim 15 or 16.

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