Nanoemulsion, its production method and related uses and products

Abstract

The present invention relates to nanoemulsions of alkyd in aqueous liquids, for example nanoemulsions prepared by emulsifying an alkyd mixture in an aqueous liquid, the alkyd mixture comprising an alkyd and an unsaturated hydroxy fatty acid. The present invention also relates to methods for producing the nanoemulsions and uses of the nanoemulsions and / or alkyd nanodroplets contained therein.

Description

Technical Field

[0001] The present invention relates to nanoemulsions of alkyd in aqueous liquids, for example nanoemulsions prepared by emulsifying an alkyd mixture in an aqueous liquid, the alkyd mixture comprising an alkyd and an unsaturated hydroxy fatty acid. The present invention also relates to methods for producing the nanoemulsions and uses of the nanoemulsions and / or alkyd nanodroplets contained therein. Background Art

[0002] Emulsions of alkyds are frequently used as coating bases in the coatings industry and benefit from the ability of alkyd droplets to remain dispersed, uncured when dispersed in an aqueous liquid and to form a cured film when applied to a surface and the water is allowed to evaporate.

[0003] Alkyd emulsions can be prepared, for example, by mechanical shearing of alkyd in water or by phase inversion of an emulsion of water in alkyd. Under some conditions, the phase inversion can result in the formation of nanoemulsions of alkyds, which are particularly interesting and provide improved stability of the coating product during storage. Summary of the invention

[0004] The present inventors have discovered that the emulsifiers conventionally used for the emulsification of alkyds can be replaced with a new class of renewable and environmentally friendly emulsifiers that were not previously considered useful for alkyd emulsification. Such new classes include:

[0005] i) Free unsaturated hydroxy fatty acid (fuhfa),

[0006] ii) oligoesters of such unsaturated hydroxy fatty acids (ouhfa), and

[0007] iii) Esters of small hydroxycarboxylic acids with i) or ii) (hcuhfa).

[0008] The present inventors have found that these compounds are particularly advantageous since they are easily derivable from renewable, biosustainable materials such as vegetable oils by purifying fatty acids from, for example, castor oil which contains a high content of the fatty acid ricinoleic acid, or by simple modification of polyunsaturated fatty acids, many of which are found in vegetable oils.

[0009] The present invention thus allows the preparation of coating products with improved biosustainability.

[0010] One aspect of the present invention relates to a method for producing a nanoemulsion comprising nanodroplets containing an alkyd acid, the nanodroplets being dispersed in an aqueous liquid, the method comprising the steps of:

[0011] a) providing an alkyd mixture comprising a source of unsaturated hydroxy fatty acid (suhfa) and an alkyd, the source comprising:

[0012] i) free unsaturated hydroxy fatty acids,

[0013] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0014] iii) esters of hydroxycarboxylates according to i) or ii) wherein the molecular weight of the hydroxycarboxylic acid is at most 250 g / mol,

[0015] b) optionally, adding an alkalizing agent to deprotonate at least some of the carboxylic acids of the alkyd mixture,

[0016] c) forming a nanoemulsion of the alkyd mixture in an aqueous liquid.

[0017] Another aspect of the present invention is directed to an alkyd mixture comprising a source of unsaturated hydroxy fatty acids and an alkyd, the source comprising:

[0018] i) free unsaturated hydroxy fatty acids,

[0019] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0020] iii) the hydroxycarboxylic acid esters of i) or ii) wherein the hydroxycarboxylic acid has a molecular weight of up to 250 g / mol.

[0021] Yet another aspect of the present invention relates to a nanoemulsion comprising nanodroplets of an alcoholic acid, the nanodroplets further comprising a source of unsaturated hydroxy fatty acids, the source comprising:

[0022] i) free unsaturated hydroxy fatty acids,

[0023] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0024] iii) the hydroxycarboxylic acid esters of i) or ii) wherein the hydroxycarboxylic acid has a molecular weight of up to 250 g / mol.

[0025] Another aspect of the present invention relates to a method of producing a coating product comprising nanodroplets containing an alkyd acid dispersed in an aqueous solvent, the method comprising the steps of:

[0026] 1) providing a nanoemulsion as defined herein or nanodroplets containing an alkyd as defined herein,

[0027] 2) contacting the nanoemulsion or nanodroplet with one or more additional ingredients, such as water, pigment, thickener, defoamer, desiccant, dispersant, silicone, thixotropic agent, anti-settling agent, bactericide, fungicide, algaecide, and any combination thereof, to obtain a coating mixture,

[0028] 3) Optionally, subject the coating mixture to one or more further processing steps, e.g.

[0029] -mix

[0030] - Degassing

[0031] -filter

[0032] 4) Optionally, package the final product in a suitable container.

[0033] Another aspect of the present invention relates to a coating product, for example obtainable by the above method, comprising nanodroplets as defined herein and a drying agent.

[0034] Another aspect of the present invention relates to an emulsifier composition, the emulsifier composition comprising:

[0035] a) One or more of the following:

[0036] i) free unsaturated hydroxy fatty acids,

[0037] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0038] iii) esters of the hydroxycarboxylates of i) or ii) wherein the molecular weight of the hydroxycarboxylic acid is at most 250 g / mol, and

[0039] b) Alkalizing agents containing basic nitrogen atoms.

[0040] Yet another aspect of the present invention relates to a method for producing an emulsifier composition, the method comprising the steps of:

[0041] -combination:

[0042] a) One or more of the following:

[0043] i) free unsaturated hydroxy fatty acids,

[0044] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0045] iii) esters of hydroxycarboxylates according to i) or ii) wherein the molecular weight of the hydroxycarboxylic acid is at most 250 g / mol,

[0046] b) an alkalizing agent containing a basic nitrogen atom, and

[0047] c) optionally, one or more further ingredients, for example further emulsifiers,

[0048] - combining a), b) and optionally c) in amounts sufficient to obtain an emulsifier composition, and

[0049] - Optionally, packaging the emulsifier composition.

[0050] Further aspects of the invention relate to the use of the products defined herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 Micrographs of two reference emulsions are shown.

[0052] Figure 2 Shown in Figure 1 Micrograph of a nanoemulsion according to the invention in a comparable setting. The alkyd droplets of this nanoemulsion are barely visible.

[0053] Figure 3 Shown are the droplet size distributions of the nanoemulsions according to the invention (C to E and H to K) compared to reference emulsions (A, B, F and G).

[0054] Figure 4 It is shown how the alkyd droplet size depends on the dosage of neutralized ricinoleic acid.

[0055] Figure 5 Shown is how the molar ratio between ethanolamine (base) and ricinoleic acid (RA) affects the average droplet size of an alkyd emulsion.

[0056] Figure 6 Shown is how the molar ratio between 1-amino-2-propanol (base) and ricinoleic acid (RA) affects the average droplet size of an alkyd emulsion. DETAILED DESCRIPTION

[0057] One aspect of the present invention relates to a method for producing a nanoemulsion comprising nanodroplets containing an alkyd acid, the nanodroplets being dispersed in an aqueous liquid, the method comprising the steps of:

[0058] a) providing an alkyd mixture comprising a source of unsaturated hydroxy fatty acids and an alkyd, the source comprising:

[0059] i) free unsaturated hydroxy fatty acids,

[0060] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0061] iii) esters of hydroxycarboxylates according to i) or ii) wherein the molecular weight of the hydroxycarboxylic acid is at most 250 g / mol,

[0062] b) optionally, adding an alkalizing agent to deprotonate at least some of the carboxylic acids of the alkyd mixture,

[0063] c) forming a nanoemulsion of the alkyd mixture in an aqueous liquid.

[0064] In the context of the present invention, the term "alkyd" refers to a polyester of a polyol and a dicarboxylic acid or tricarboxylic acid, which is modified by the addition of fatty acids and other components. Polyesters of alkyds are typically produced by reacting a polyol with a dicarboxylic acid or tricarboxylic acid or a carboxylic anhydride. The fatty acid is esterified to the polyester backbone of the alkyd and imparts a tendency to form a flexible coating. Alkyds are therefore frequently used in coatings and in molds for casting. Alkyds are the main resin or "binder" in most commercial "oil-based" coatings. The terms "alkyd" and "alkyd resin" are used interchangeably herein.

[0065] In the context of the present invention, the term "alkyd mixture" relates to a mixture comprising alkyd, suhfa and optionally further emulsifiers. However, in some preferred embodiments of the present invention, suhfa is predominant, e.g. the only emulsifier present in the alkyd mixture.

[0066] In the context of the present invention, the term "unsaturated hydroxy fatty acid", abbreviated to "uhfa (unsaturated hydroxy fatty acid)", relates to a fatty acid comprising one or more double bonds and also comprising one or more hydroxyl groups. An example of an unsaturated hydroxy fatty acid is ricinoleic acid. As used herein, the term uhfa means both free uhfa and bound uhfa, and includes both uhfa in protonated form and uhfa in deprotonated form.

[0067] In the context of the present invention, the term "source of unsaturated hydroxy fatty acids", abbreviated to "suhfa", relates to a source or a combination of sources which provide the alkyd mixture with:

[0068] i) free unsaturated hydroxy fatty acids,

[0069] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0070] iii) the hydroxycarboxylic acid esters of i) or ii) wherein the hydroxycarboxylic acid has a molecular weight of up to 250 g / mol.

[0071] In the context of the present invention, the term "free unsaturated hydroxy fatty acid", abbreviated to "fuhfa", relates to an unsaturated hydroxy fatty acid in protonated or deprotonated form which does not form a covalent bond with any other molecule. Thus, the term fuhfa encompasses both the free acid form of fuhfa as well as neutralized forms (e.g. in the form of one or more salts).

[0072] In the context of the present invention, the term "oligoester of unsaturated hydroxyfatty acid", abbreviated to "ouhfa (oligoester of unsaturated hydroxyfatty acid)", relates to free esters of 2 to 6 uhfa, preferably uhfa of the same type. Examples are diricinoleic acid, triricinoleic acid, tetraricinoleic acid, pentaricinoleic acid and hexaricinoleic acid. The term ouhfa encompasses both the free acid form of ouhfa and its salts.

[0073] In the context of the present invention, the term "hydroxycarboxylic acid ester of fuhfa or ouhfa", abbreviated to "hcuhfa", relates to the free ester of fuhfa or ouhfa with a hydroxycarboxylic acid having a molecular weight of up to 250 g / mol. An example of hcuhfa is the ester of lactic acid with ricinoleic acid. The term hcuhfa encompasses both the free acid form of hcuhfa and its salts.

[0074] Step a) requires providing an alkyd mixture comprising a source of unsaturated hydroxy fatty acid and an alkyd, wherein the suhfa comprises:

[0075] i) free unsaturated hydroxy fatty acids,

[0076] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0077] iii) the hydroxycarboxylic acid esters of i) or ii) wherein the hydroxycarboxylic acid has a molecular weight of up to 250 g / mol.

[0078] In some preferred embodiments of the present invention, the alkyd mixture comprises an alkyd and a suhfa, the suhfa comprising or even consisting essentially of a fuhfa.

[0079] In further preferred embodiments of the present invention, the alkyd mixture comprises an alkyd and a suhfa, the suhfa comprising an ouhfa or even consisting essentially of an ouhfa.

[0080] In further preferred embodiments of the present invention, the alkyd mixture comprises an alkyd and a suhfa, the suhfa comprising or even consisting essentially of hcuhfa.

[0081] In some preferred embodiments of the present invention, the alkyd comprises or even consists of:

[0082] -Long oil alkyd,

[0083] -Medium oil alkyd, and / or

[0084] -Short oil alkyd.

[0085] Long oil alkyds contain greater than 60 wt% fatty acids, medium oil alkyds contain 40 to 60 wt% fatty acids, and short oil alkyds contain less than 40 wt% fatty acids.

[0086] In some preferred embodiments of the present invention, the alkyd is a long oil alkyd. In other preferred embodiments of the present invention, the alkyd is a short oil alkyd. In particularly preferred embodiments of the present invention, the alkyd is a medium oil alkyd.

[0087] In some preferred embodiments of the present invention, the acid value of the alkyd is at most 20 mg KOH / g, preferably at most 15 mg KOH / g, even more preferably at most 10 mg KOH / g.

[0088] The acid value of the alkyd is typically in the range of 1 to 20 mg KOH / g, preferably 2 to 16 mg KOH / g, more preferably 4 to 14 mg KOH / g, most preferably 5 to 10 mg KOH / g.

[0089] Low acid values ​​of alkyds provide a high degree of hydrophobicity, while higher acid values ​​provide increased hydrophilicity and increased water permeability of alkyd-based dried coatings.

[0090] The term "acid value" is well known to the skilled person and denotes the amount of KOH in mg required to neutralize 1 g of material. The acid value is determined according to Example 1.4.

[0091] In some preferred embodiments of the present invention, the water content of the alkyd is at most 5% w / w, preferably at most 2% w / w, more preferably at most 1% w / w, even more preferably at most 0.5% w / w, most preferably at most 0.1% w / w.

[0092] The water content of the alkyd was measured according to Example 1.5.

[0093] In some preferred embodiments of the present invention, the volatile organic compound (VOC) content of the alkyd is at most 50 g / L, preferably at most 20 g / L, more preferably at most 5 g / L, even more preferably at most 1 g / L, and most preferably at most 0.1 g / L.

[0094] In some preferred embodiments of the present invention, the fuhfa content of the alkyd is at most 4% w / w, preferably at most 2% w / w, more preferably at most 1% w / w, even more preferably at most 0.5% w / w, most preferably at most 0.1% w / w.

[0095] In some preferred embodiments of the invention, the suhfa comprises one or more of the following:

[0096] i) at least 10% w / w of free unsaturated hydroxy fatty acids,

[0097] ii) at least 1% w / w of di(unsaturated hydroxy fatty acid) (duhfa), and

[0098] iii) at least 1% w / w of tri(unsaturated hydroxy fatty acid) (tuhfa).

[0099] In other preferred embodiments of the present invention, suhfa comprises

[0100] i) 10% w / w to 99% w / w of free unsaturated hydroxy fatty acids,

[0101] ii) 1% w / w to 50% w / w of di(unsaturated hydroxy fatty acids), and

[0102] iii) 0% w / w to 30% w / w of tri(unsaturated hydroxy fatty acid).

[0103] More preferably, suhfa comprises

[0104] i) 60% w / w to 95% w / w of free unsaturated hydroxy fatty acids,

[0105] ii) 5% w / w to 40% w / w of di(unsaturated hydroxy fatty acids), and

[0106] iii) 0% w / w to 30% w / w of tri(unsaturated hydroxy fatty acid).

[0107] In other preferred embodiments of the present invention, suhfa comprises

[0108] i) 1% w / w to 50% w / w of free unsaturated hydroxy fatty acids,

[0109] ii) 10% w / w to 98% w / w of di(unsaturated hydroxy fatty acids), and

[0110] iii) 1% w / w to 30% w / w of tri(unsaturated hydroxy fatty acid).

[0111] In other preferred embodiments of the present invention, suhfa comprises

[0112] i) 0% w / w to 30% w / w of free unsaturated hydroxy fatty acids,

[0113] ii) 1% w / w to 40% w / w of di(unsaturated hydroxy fatty acid) a, and

[0114] iii) 10% w / w to 98% w / w of tri(unsaturated hydroxy fatty acid).

[0115] In some preferred embodiments of the present invention, the suhfa comprises at least 50% w / w fuhfa, preferably at least 60% w / w fuhfa, more preferably at least 80% w / w fuhfa, even more preferably at least 90% w / w fuhfa, most preferably at least 95% w / w fuhfa. It is particularly preferred that the suhfa comprises about 100% w / w fuhfa.

[0116] In other preferred embodiments of the present invention, the sum of fuhfa, duhfa and tuhfa accounts for at least 10% w / w, preferably at least 20% w / w, more preferably at least 50% w / w, even more preferably at least 70% w / w, most preferably at least 90% w / w of the total weight of suhfa.

[0117] In some preferred embodiments of the present invention, the water content of suhfa is at most 5% w / w, preferably at most 2% w / w, more preferably at most 1% w / w, even more preferably at most 0.5% w / w, most preferably at most 0.1% w / w.

[0118] The present inventors have discovered that suhfa having a low water content can be mixed into alkyd more effectively than suhfa having a higher water content.

[0119] The inventors have observed that effective mixing of suhfa and alkyd can be achieved if fuhfa, ouhfa and / or hcuhfa are in their protonated form when mixed with the alkyd. The degree of protonation can be measured by the acid value.

[0120] Thus, in some preferred embodiments of the present invention, the acid value of the suhfa is at least 140 mg KOH / g sample, preferably at least 150 mg KOH / g sample, even more preferably at least 160 mg KOH / g sample. These acid values ​​are particularly preferred for suhfa with a high content of fuhfa, such as suhfa comprising fuhfa in an amount of at least 60% w / w. The acid value of the suhfa may, for example, be in the range of 140 mg KOH / g sample to 250 mg KOH / g sample, preferably in the range of 150 mg KOH / g sample to 220 mg KOH / g sample, even more preferably in the range of 160 mg KOH / g sample to 200 mg KOH / g sample.

[0121] In other preferred embodiments of the present invention, the acid value of suhfa is at least 130 mg KOH / g sample, more preferably at least 135 mg KOH / g sample. The acid value of suhfa may, for example, be in the range of 130 mg KOH / g sample to 250 mg KOH / g sample, more preferably in the range of 135 mg KOH / g sample to 220 mg KOH / g sample.

[0122] The inventors have also seen that effective mixing of suhfa and alkyd can also be achieved if the fuhfa, ouhfa and / or hcuhfa of suhfa are in their deprotonated form. This mixing is particularly effective if fuhfa, ouhfa and / or hcuhfa are in a form that is soft enough to be mixed into the alkyd. It is particularly preferred to use fuhfa, ouhfa and / or hcuhfa in combination with an alkalizer containing a basic nitrogen atom. Alkalizers containing basic nitrogen atoms are preferably used to deprotonate fuhfa, ouhfa and / or hcuhfa. Alkalizers containing basic nitrogen atoms can be added to the suhfa before being added to the alkyd or can be added to the alkyd before, during and / or after the addition of the suhfa.

[0123] The inventors have found that it is advantageous to combine suhfa with an alkalizing agent containing a basic nitrogen atom before it is added to the alkyd mixture. Preferably, suhfa and the alkalizing agent containing a basic nitrogen atom are in the form of an emulsifier composition as defined herein when added to the alkyd.

[0124] In the context of the present invention, the term "basic nitrogen atom-containing alkalizing agent" relates to an amine compound, ammonia or a combination thereof. The amine compound may, for example, comprise a primary amine, a secondary amine, a tertiary amine or a combination thereof. The molecular weight of the alkalizing agent containing a basic nitrogen atom is preferably at most 300 g / mol, more preferably at most 150 g / mol.

[0125] In some preferred embodiments of the present invention, the alkalizing agent containing a basic nitrogen atom has a molecular weight of at most 300 g / mol.

[0126] In an even more preferred embodiment of the present invention, the alkalizing agent containing a basic nitrogen atom has a molecular weight of at most 150 g / mol.

[0127] In some preferred embodiments of the present invention, the alkalizing agent containing a basic nitrogen atom contains one or two hydroxyl groups.

[0128] In further preferred embodiments of the present invention, the alkalizing agent containing a basic nitrogen atom comprises or even consists of one or more amino alcohols, more preferably one or more alkanolamines.

[0129] The present inventors have found that amino alcohols are advantageous over, for example, hydroxyl-free amines, since the latter tend to release an unpleasant fishy odor, whereas amino alcohols are more sensorially neutral.

[0130] In some preferred embodiments of the present invention, the alkalizing agent containing a basic nitrogen atom comprises one or more of 1-amino-2-propanol, 1-amino-3-propanol and / or ethanolamine, or even consists of one or more of 1-amino-2-propanol, 1-amino-3-propanol and / or ethanolamine.

[0131] The preferred alkalizing agent containing a basic nitrogen atom of the present invention is 1-amino-2-propanol.

[0132] The suhfa, alkyd mixture, nanoemulsion, nanodroplets of alkyd and / or coating product preferably comprises a molar ratio between the alkalizing agent containing a basic nitrogen atom and the sum of fuhfa and ouhfa in the range of 1:3 to 5:1, more preferably in the range of 1:2 to 4:1, even more preferably in the range of 1:1 to 3:1.

[0133] When mixed with the suhfa or alkyd mixture, at least some of the alkalizing agent containing basic nitrogen atoms will be protonated when neutralizing the carboxylic acid.

[0134] Particularly preferred are:

[0135] - the molecular weight of the alkalizing agent containing a basic nitrogen atom is at most 150 g / mol and the alkalizing agent containing a basic nitrogen atom further comprises one or two hydroxyl groups, and

[0136] -suhfa, alkyd mixture, nanoemulsion and / or nanodroplets of alkyd comprise a molar ratio between the alkalizing agent containing a basic nitrogen atom and the sum of fuhfa and ouhfa in the range of 1:3 to 5:1, more preferably in the range of 1:2 to 4:1, even more preferably in the range of 1:1 to 3:1.

[0137] In some preferred embodiments of the present invention, the hydroxyl value of suhfa is at least 140 mg KOH / g sample, preferably at least 145 mg KOH / g, more preferably at least 150 mg KOH / g, and even more preferably at least 155 mg KOH / g. The hydroxyl value of suhfa may, for example, be in the range of 140 mg KOH / g sample to 250 mg KOH / g sample, preferably in the range of 145 mg KOH / g to 220 mg KOH / g, more preferably in the range of 150 mg KOH / g to 220 mg KOH / g, and even more preferably in the range of 155 mg KOH / g to 200 mg KOH / g.

[0138] In other preferred embodiments of the present invention, the hydroxyl value of suhfa is in the range of 140 mg KOH / g sample to 500 mg KOH / g sample, more preferably in the range of 145 mg KOH / g to 400 mg KOH / g, even more preferably in the range of 150 mg KOH / g to 350 mg KOH / g, and most preferably in the range of 155 mg KOH / g to 300 mg KOH / g.

[0139] The hydroxyl value of the composition is measured according to Example 1.3.

[0140] In some preferred embodiments of the present invention, the iodine value of suhfa is at least 60g I2 / 100g, preferably at least 70g I2 / 100g, more preferably at least 80g I2 / 100g, and most preferably at least 85g I2 / 100g. The iodine value of suhfa may, for example, be in the range of 60g I2 / 100g to 200g I2 / 100g, preferably in the range of 65g I2 / 100g to 150g I2 / 100g, more preferably in the range of 70g I2 / 100g to 100g I2 / 100g, and most preferably at least 75g I2 / 100g to 95g I2 / 100g.

[0141] In other preferred embodiments of the present invention, the iodine value of suhfa is in the range of 60 g I2 / 100 g to 100 g I2 / 100 g, preferably in the range of 62 g I2 / 100 g to 90 g I2 / 100 g, more preferably in the range of 64 g I2 / 100 g to 80 g I2 / 100 g, and most preferably at least 65 g I2 / 100 g to 75 g I2 / 100 g.

[0142] The iodine value of the composition was measured according to Example 1.2.

[0143] The uhfa is preferably a C14-C24 fatty acid, more preferably a C16 to C20 fatty acid, and most preferably a C18 fatty acid.

[0144] In some preferred embodiments of the invention, the uhfa comprises or even consists of omega-9 fatty acids.

[0145] Useful examples of UHFAs are ricinoleic acid, lesquerolic acid, densipolic acid and auricolic acid.

[0146] In some particularly preferred embodiments of the present invention, the uhfa comprises ricinoleic acid or even consists of ricinoleic acid. Thus, a particularly preferred example of uhfa is ricinoleic acid.

[0147] Suhfa may be derived from natural sources or prepared synthetically. In some preferred embodiments of the invention, suhfa is a fatty acid moiety prepared by hydrolyzing castor oil and removing non-fatty acid components. Such suhfa has a very high content of ricinoleic acid.

[0148] Alternatively but also preferably, suhfa can be prepared by partially adding water to the double bonds of the polyunsaturated fatty acids. The addition is partial in the sense that only some of the double bonds should have water added to avoid the fatty acids becoming too saturated.

[0149] The alkyd mixture typically comprises a total amount of alkyd of at least 60% w / w, preferably at least 70% w / w, more preferably at least 80% w / w, even more preferably at least 90% w / w.

[0150] In some preferred embodiments of the present invention, the alkyd mixture comprises a total amount of alkyd in the range of 60% w / w to 97% w / w, preferably in the range of 70% w / w to 96% w / w, more preferably in the range of 80% w / w to 95% w / w, even more preferably in the range of 85% w / w to 94% w / w.

[0151] In some preferred embodiments of the present invention, the weight ratio between the total amount of suhfa and the total amount of alkyd of the alkyd mixture of step a) is 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0152] In the context of the present invention, the "weight ratio between component A and component B" is calculated as weight 组分A / weight 组分B , where both weights are expressed in the same weight unit. For example, the weight ratio between the total amount of suhfa and the total amount of alkyd should be calculated as the weight suhfa的总量 / weight 醇酸的总量 .

[0153] In some preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa+duhfa+tuhfa of the alkyd mixture of step a) and the total amount of alkyd is 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0154] In some particularly preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa+duhfa of the alkyd mixture of step a) and the total amount of alkyd is 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, and most preferably 0.06 to 0.12.

[0155] In other particularly preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa and the total amount of alkyd in the alkyd mixture of step a) is from 0.01 to 0.30, preferably from 0.02 to 0.25, more preferably from 0.03 to 0.20, even more preferably from 0.05 to 0.18, most preferably from 0.06 to 0.12.

[0156] In the context of the present invention, the term "the total amount of fuhfa+duhfa+tuhfa" means the sum of the total amount of fuhfa, the total amount of duhfa and the total amount of tuhfa.

[0157] In the context of the present invention, the term "total amount of fuhfa+duhfa" means the sum of the total amount of fuhfa and the total amount of duhfa.

[0158] Although it is envisioned that alkyd mixtures will be commercially available in the future, they are preferably prepared by mixing an alkyd with a suhfa, preferably in the weight ratios described herein or in amounts sufficient to provide the amounts of fuhha, ouhfa, and / or hcuhfa described herein. The mixing can be performed, for example, by combining the alkyd with the suhfa and optional other ingredients and stirring the composition sufficiently to obtain an alkyd mixture.

[0159] The temperature during such mixing is typically in the range of 0°C to 200°C, preferably in the range of 10°C to 150°C, more preferably 20°C to 100°C.

[0160] The alkyd mixture may also comprise other ingredients. The alkyd mixture may, for example, comprise one or more co-surfactants and / or one or more additional emulsifiers.

[0161] In some preferred embodiments of the present invention, the alkyd mixture contains one or more additional emulsifiers, such as those conventionally used to emulsify alkyds to produce alkyd dispersions. Additional examples may include: emulsifiers of the nonionic ethylene oxide propylene oxide block copolymer type, alkylbenzene sulfonates, fatty alcohol ethoxylates, fatty alcohol ether sulfates, polyglycerol esters of fatty acids, polyglycerol polyricinoleate, and surfactants based on styrenated phenol. Additional examples include: polypropylene glycol esters of fatty acids; poly-(1,3-propylene glycol) esters of fatty acids; copolymers of any monomer selected from glycerol, propylene glycol, 1,3-propylene glycol esterified with fatty acids.

[0162] In some preferred embodiments of the invention, the alkyd mixture comprises one or more co-surfactants. Such co-surfactants interact with the uhfa, preferably improving its functionality, but need not be surfactants themselves. Preferred co-surfactants can be found, for example, in amine compounds, amino alcohols, ammonia, normal alcohols, glycol ethers, polyethylene glycols, and alkyl carboxylic acids and carboxylates.

[0163] The co-surfactant is preferably present in the suhfa, alkyd mixture, nanoemulsion and / or nanodroplets of alkyd in an amount sufficient to bind to a majority of the carboxylic acid groups of fuhfa or ouhfa. The suhfa, alkyd mixture, nanoemulsion, nanodroplets of alkyd and / or coating product preferably comprises a molar ratio between the co-surfactant and the sum of fuhfa and ouhfa in the range of 1:10 to 10:1, more preferably in the range of 1:5 to 5:1, even more preferably in the range of 1:1 to 3:1.

[0164] In some preferred embodiments of the invention, the process does not comprise step b) and therefore comprises step a) directly followed by step c). For example, if fuhfa, ouhfa and / or hcuhfa are already present in the alkyd mixture in deprotonated form, for example in combination with an alkalizing agent containing a basic nitrogen atom as described above, step b) is not required.

[0165] However, in other preferred embodiments, the method of the invention comprises a step b) of adding an alkalizing agent to deprotonate at least some of the carboxylic acids of the alkyd mixture. The alkalizing agent is preferably mixed into the alkyd mixture. In some preferred embodiments of the invention, the amount of alkalizing agent added is sufficient to deprotonate at least 75%, preferably at least 90%, even more preferably at least 100% of the fuhfa, ouhfa and / or hcuhfa of the alkyd mixture.

[0166] In some preferred embodiments of the present invention, the amount of alkalizing agent added is sufficient to deprotonate at least 10% of the alkyd acid, more preferably at least 20% of the alkyd acid, even more preferably at least 30% of the alkyd acid, and most preferably at least 40% of the alkyd acid.

[0167] In some preferred embodiments of the present invention, the alkalizing agent is added in solid, liquid or dissolved form. If the alkalizing agent is added in dissolved form, it is preferably added in the form of an aqueous solution.

[0168] In some preferred embodiments of the invention, the alkalizing agent comprises a hydroxide salt and / or an alkalizing agent containing a basic nitrogen atom as defined herein.

[0169] Step c) involves forming a nanoemulsion of the alkyd mixture in an aqueous liquid. Forming the nanoemulsion may, for example, involve mechanical shearing and / or phase inversion. Emulsification, for example by mechanical shearing and / or phase inversion, preferably provides a nanoemulsion comprising nanodroplets of the alkyd mixture dispersed in an aqueous liquid.

[0170] In the context of the present invention, the term "aqueous liquid" relates to a liquid used to emulsify the alkyd mixture. The aqueous liquid may comprise dispersed and / or dissolved substances in addition to water. The aqueous liquid preferably comprises water in an amount of at least 50% w / w, more preferably at least 70% w / w, even more preferably at least 90% w / w, most preferably at least 95% w / w.

[0171] In some preferred embodiments of the present invention, the aqueous liquid is water, such as demineralized water or tap water.

[0172] If the alkyd mixture is emulsified by mechanical shearing, the alkyd mixture is preferably mixed with the aqueous liquid by high shear mixing.Shear-based systems for emulsifying alkyd mixtures in aqueous liquids are well known to the skilled person.

[0173] It is particularly preferred to form the nanoemulsion by emulsifying an aqueous liquid into an alkyd mixture and causing a phase transition to occur. The phase transition provides a nanoemulsion comprising nanodroplets of the alkyd mixture. The nanodroplets of the alkyd mixture are dispersed in the aqueous liquid.

[0174] The term "alkyd-containing nanodroplets" means nanodroplets of an alkyd mixture as described herein.

[0175] A particularly preferred method for causing a phase transition to occur is to continue emulsifying the aqueous liquid into the alkyd mixture until a phase transition occurs and a nanoemulsion containing nanodroplets of the alkyd mixture is formed. The emulsification is preferably carried out by gradually adding and mixing water into the alkyd mixture. The initial emulsification results in the formation of a water-in-oil emulsion in which the aqueous liquid has been emulsified into the alkyd mixture. However, when enough aqueous liquid has been emulsified into the alkyd mixture, the water-in-oil emulsion becomes unstable and undergoes a phase transition to an oil-in-water emulsion of alkyd nanodroplets dispersed in the aqueous liquid. Without being bound by theory, it is believed that the phase transition is a so-called abrupt phase transition.

[0176] Alternatively, the phase transition may be induced in other ways, for example by changing physical and / or chemical parameters such as pH, temperature or pressure or by high shear treatment.

[0177] The present inventors have found that, in contrast to conventional emulsifiers used to prepare nanoemulsions of alkyds, fuhfa, ouhfa and hcuhfa do not appear to have a specific phase inversion temperature (PIT) at which emulsification and phase inversion must occur. This means that the emulsifiers of the present invention can be used to prepare nanoemulsions of alkyds over a wider temperature range and allow nanoemulsification of alkyds for which there were previously no compatible emulsifiers.

[0178] In some preferred embodiments of the present invention, the pH of the aqueous liquid of step c) is in the range of 5 to 13, preferably 6 to 9, more preferably pH is in the range of 7.0 to 8.5, most preferably pH is in the range of 7.0 to 8.0.

[0179] If the alkyd mixture contains ouhfa and / or hcuhfa, step c) may preferably be carried out at a pH above pH 7.5 and with moderate heating applied, for example to a temperature in the range of 30°C to 80°C, for a duration sufficient to hydrolyze the hcuhfa or ouhfa to fuhfa and optionally also to duhfa. Thus, in some preferred embodiments of the invention, the pH of the aqueous liquid of step c) is in the range of 8.0 to 13, preferably 8.5 to 12, more preferably the pH is in the range of 9.0 to 11.

[0180] The temperature during mixing in step c) is preferably chosen to be high enough to ensure good mixing conditions between the components in the alkyd mixture and the aqueous liquid during emulsification and at the same time low enough to provide the required shear for nanoemulsification to occur.

[0181] The temperature during mixing in step c) is preferably in the range of 0° C. to 200° C. and, if possible, preferably in the range of 10° C. to 50° C. If temperatures of 90° C. or higher are required, it is preferred that the addition and mixing of water is carried out in a closed system under pressure and / or under reflux to avoid uncontrolled evaporation of water during mixing.

[0182] The average hydrodynamic diameter of the alkyd-containing nanodroplets is preferably at most 350 nm, more preferably at most 300 nm, even more preferably at most 250 nm, most preferably at most 200 nm.

[0183] In some preferred aspects of the present invention, the average hydrodynamic diameter of the nanodroplets containing the alkyd is at most 300 nm, preferably at most 250 nm, more preferably at most 200 nm, and most preferably at most 180 nm.

[0184] The average hydrodynamic diameter of the particle population is measured according to Example 1.7.

[0185] Yet another aspect of the present invention relates to an alkyd mixture as described herein, comprising a mixture comprising a source of unsaturated hydroxy fatty acid and an alkyd, the suhfa comprising:

[0186] i) free unsaturated hydroxy fatty acids,

[0187] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0188] iii) the hydroxycarboxylic acid esters of i) or ii) wherein the hydroxycarboxylic acid has a molecular weight of up to 250 g / mol.

[0189] In some preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa+duhfa+tuhfa of the alkyd mixture and the total amount of alkyd is in the range of 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0190] In some particularly preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa+duhfa of the alkyd mixture and the total amount of alkyd is in the range of 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0191] In other particularly preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa of the alkyd mixture and the total amount of alkyd is in the range of 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0192] The alkyd mixture typically comprises a total amount of alkyd of at least 60% w / w, preferably at least 70% w / w, more preferably at least 80% w / w, even more preferably at least 90% w / w.

[0193] In some preferred embodiments of the present invention, the alkyd mixture comprises a total amount of alkyd in the range of 60% w / w to 97% w / w, preferably in the range of 70% w / w to 96% w / w, more preferably in the range of 80% w / w to 95% w / w, even more preferably in the range of 85% w / w to 94% w / w.

[0194] It is further preferred that the VOC content of the alkyd mixture, nanodroplets and / or coating product of the present invention is at most 50 g / L, preferably at most 20 g / L, more preferably at most 5 g / L, even more preferably at most 1 g / L, most preferably at most 0.1 g / L.

[0195] Another aspect of the invention relates to a nanoemulsion containing nanodroplets of an alcoholic acid, obtainable, for example, by the process described herein, said nanodroplets further comprising a source of unsaturated hydroxy fatty acids, said source comprising:

[0196] i) free unsaturated hydroxy fatty acids,

[0197] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0198] iii) the hydroxycarboxylic acid esters of i) or ii) wherein the hydroxycarboxylic acid has a molecular weight of up to 250 g / mol.

[0199] In some preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa+duhfa+tuhfa of the nanoemulsion of nanodroplets and the total amount of alkyd is in the range of 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0200] In some particularly preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa + duhfa of the nanoemulsion of nanodroplets and the total amount of alkyd is in the range of 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0201] In other particularly preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa and the total amount of alkyd of the nanoemulsion of nanodroplets is in the range of 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0202] The nanodroplets of the nanoemulsion typically comprise a total amount of at least 60% w / w, preferably at least 70% w / w, more preferably at least 80% w / w, even more preferably at least 90% w / w of alcoholic acid.

[0203] In some preferred embodiments of the present invention, the nanodroplets of the nanoemulsion comprise a total amount of alkyd in the range of 60% w / w to 97% w / w, preferably in the range of 70% w / w to 96% w / w, more preferably in the range of 80% w / w to 95% w / w, even more preferably in the range of 85% w / w to 94% w / w.

[0204] The nanoemulsion of the present invention is preferably an emulsion of a substance containing an alkyd acid in an aqueous medium.

[0205] In the context of the present invention, the term "aqueous medium" relates to the liquid in which the nanodroplets containing the alkyd are dispersed. In addition to water, the aqueous medium may also contain dispersed and / or dissolved substances. The aqueous medium preferably contains water in an amount of at least 50% w / w, more preferably at least 70% w / w, even more preferably at least 90% w / w, most preferably at least 95% w / w.

[0206] In some preferred embodiments of the present invention, the aqueous medium is water, such as demineralized water or tap water.

[0207] In some preferred embodiments of the present invention, the nanoemulsion does not contain a desiccant. This has the advantage that the nanoemulsion has a reduced sensitivity to oxygen and can therefore be processed in an oxygen-containing atmosphere without initiating polymerization of the alkyd.

[0208] Another aspect of the present invention relates to a population of nanodroplets containing an alkyd, such as can be obtained by the method described herein, the nanodroplets further comprising suhfa, the source comprising:

[0209] i) free unsaturated hydroxy fatty acids,

[0210] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0211] iii) the hydroxycarboxylic acid esters of i) or ii) wherein the hydroxycarboxylic acid has a molecular weight of up to 250 g / mol.

[0212] In some preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa+duhfa+tuhfa of the nanodroplets and the total amount of alkyd is in the range of 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0213] In some particularly preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa+duhfa of the nanodroplets and the total amount of alkyd is in the range of 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0214] In other preferred embodiments of the present invention, the weight ratio between the total amount of fuhfa and the total amount of alkyd of the nanodroplets is in the range of 0.01 to 0.30, preferably 0.02 to 0.25, more preferably 0.03 to 0.20, even more preferably 0.05 to 0.18, most preferably 0.06 to 0.12.

[0215] The nanodroplets typically comprise a total amount of at least 60% w / w, preferably at least 70% w / w, more preferably at least 80% w / w, even more preferably at least 90% w / w of alkyd.

[0216] In some preferred embodiments of the present invention, the nanodroplets comprise a total amount of alkyd in the range of 60% w / w to 97% w / w, preferably in the range of 70% w / w to 96% w / w, more preferably in the range of 80% w / w to 95% w / w, even more preferably in the range of 85% w / w to 94% w / w.

[0217] Another aspect of the present invention relates to a method of producing a coating product comprising nanodroplets containing an alkyd acid dispersed in an aqueous solvent, the method comprising the steps of:

[0218] 1) providing a nanoemulsion as described herein or nanodroplets containing an alcohol acid as described herein,

[0219] 2) contacting the nanoemulsion or nanodroplets with one or more additional ingredients (e.g. water, pigment, thickener, preservative, desiccant), preferably mixing, to obtain a coating mixture,

[0220] 3) optionally, subjecting the coating mixture to one or more further processing steps, such as hydration, further mixing and / or degassing,

[0221] 4) Optionally, package the final product in a suitable container.

[0222] In the context of the present invention, the term "aqueous solvent" relates to a liquid solution in which nanodroplets containing the alkyd are dispersed. In addition to water, the aqueous solvent may also contain dispersed and / or dissolved substances. The aqueous solvent preferably contains water in an amount of at least 50% w / w, more preferably at least 70% w / w, even more preferably at least 90% w / w, most preferably at least 95% w / w.

[0223] In some preferred embodiments of the present invention, the aqueous solvent is water, such as demineralized water or tap water.

[0224] The coating product is preferably an emulsion-type coating product having an aqueous continuous phase.

[0225] Yet another aspect of the present invention relates to a coating product, obtainable, for example, by the process described herein, comprising i) nanodroplets as described herein or ii) a nanoemulsion as described herein, and additionally comprising a drying agent and / or a pigment.

[0226] The coating product of the present invention is preferably a water-based coating product, meaning that it comprises, for example, alkyd-containing nanodroplets suspended in an aqueous continuous phase.

[0227] In some preferred embodiments of the present invention, the coating product comprises:

[0228] a total amount in the range of 10% w / w to 50% w / w, preferably in the range of 15% w / w to 45% w / w, more preferably in the range of 20% w / w to 40% w / w of nanodroplets as described herein,

[0229] - a total amount of water in the range of 10% w / w to 80% w / w, preferably in the range of 30% w / w to 75% w / w, more preferably in the range of 45% w / w to 70% w / w,

[0230] - a total amount of at least 0.05% w / w, preferably in the range of 0.1% w / w to 4% w / w, more preferably in the range of 0.2% w / w to 2% w / w of desiccants,

[0231] - a total amount of pigments in the range of 0% w / w to 40% w / w, preferably in the range of 1% w / w to 40% w / w, more preferably in the range of 5% w / w to 30% w / w,

[0232] - a total amount of an antifoaming agent in the range of 0% to 2%, preferably in the range of 0.01% w / w to 1.5% w / w, more preferably in the range of 0.05% w / w to 0.3% w / w,

[0233] - a total amount of thickeners in the range of 0% to 4%, preferably in the range of 0.1% w / w to 3% w / w, more preferably in the range of 0.3% w / w to 1% w / w,

[0234] - a total amount of preservatives in the range of 0% to 4%, preferably in the range of 0.1% w / w to 3% w / w, more preferably in the range of 0.3% w / w to 1% w / w.

[0235] The pH of the coating product is preferably in the range of 6-10, more preferably in the range of 7-9.

[0236] The inventors have found that the dried films of the coating products according to the invention exhibit high gloss and are very stable under all conditions studied. Some indications indicate a stabilizing effect under UV light. This is most likely due to the ability of suhfa to participate in autoxidation processes during coating formation. The high gloss of the films supports the view that the emulsifier becomes crosslinked within the coating, which is highly desirable to avoid migration to the surface of the surfactant, resulting in lower quality paints due to accumulation of hydrophilic components on the surface, and the possibility of color degradation when using pigments in coating formulations.

[0237] In some preferred embodiments of the present invention, the coating product, for example an alkyd emulsion-based clearcoat lacquer formulation, comprises:

[0238] Water 25% to 35%

[0239] Thickener 0% to 3%

[0240] Preservatives 0% to 1%

[0241] Desiccant 0% to 1%

[0242] Defoamer 0.1%

[0243] Alkyd emulsion 55% to 75%

[0244] In other preferred embodiments of the present invention, the coating product, such as a matte paint formulation, comprises:

[0245] Water 10% to 15%

[0246] Pigments, such as TiO2 10% to 15%

[0247] Filler, e.g. fine CaCO3 25% to 30%

[0248] Filler, e.g. medium CaCO3 25% to 30%

[0249] Dispersant 0% to 2%

[0250] Thickener 0% to 3%

[0251] Preservatives 0% to 1%

[0252] Defoamer 0.1%

[0253] Desiccant 0% to 1%

[0254] Alkyd emulsion 10% to 15%

[0255] In other preferred embodiments of the present invention, a coating product such as a water-based decorative / interior paint comprises

[0256] Water 0% to 2%

[0257] Pigment paste 30% to 40%

[0258] Desiccant 0.5%

[0259] Defoamer 0.3%

[0260] Alkyd emulsion 60% to 70%

[0261] Yet another aspect of the present invention relates to the dried film of the coating product.

[0262] Another aspect of the invention relates to the use of a suhfa or an emulsifier composition as defined herein as an emulsifier for forming a nanoemulsion of an alkyd in an aqueous liquid, e.g. as the sole emulsifier or in combination with one or more further emulsifiers and / or co-surfactants.

[0263] Another aspect of the invention relates to the use of an alkyd mixture as defined herein for producing a nanoemulsion.

[0264] Yet another aspect of the present invention relates to the use of i) the nanodroplets described herein or ii) the nanoemulsion described herein for producing a coating product.

[0265] Yet another aspect of the present invention relates to an emulsifier composition, the emulsifier composition comprising:

[0266] a) One or more of the following:

[0267] i) free unsaturated hydroxy fatty acids,

[0268] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0269] iii) esters of the hydroxycarboxylates of i) or ii) wherein the molecular weight of the hydroxycarboxylic acid is at most 250 g / mol, and

[0270] b) Alkalizing agents containing basic nitrogen atoms.

[0271] The present inventors have found that providing suhfa and an alkalizing agent containing a basic nitrogen atom as a mixture is advantageous because such a mixture is easier to blend into the alkyd than other neutralized forms of suhfa and also aids in the neutralization of the alkyd.

[0272] In some preferred embodiments of the present invention, the emulsifier composition comprises i) free unsaturated hydroxy fatty acids in a total amount ranging from 20% w / w to 99% w / w, more preferably from 50% w / w to 95% w / w, even more preferably from 70% w / w to 90% w / w, most preferably from 75% w / w to 85% w / w,

[0273] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0274] iii) the hydroxycarboxylic acid esters of i) or ii) wherein the hydroxycarboxylic acid has a molecular weight of up to 250 g / mol.

[0275] In other preferred embodiments of the present invention, the emulsifier composition comprises free unsaturated hydroxy fatty acids in a total amount ranging from 20% w / w to 99% w / w, more preferably from 50% w / w to 95% w / w, even more preferably from 70% w / w to 90% w / w, most preferably from 75% w / w to 85% w / w.

[0276] In some preferred embodiments of the present invention, the alkalizing agent containing a basic nitrogen atom has a molecular weight of at most 300 g / mol.

[0277] In other even more preferred embodiments of the present invention, the alkalizing agent containing a basic nitrogen atom has a molecular weight of at most 150 g / mol.

[0278] In some preferred embodiments of the present invention, the alkalizing agent containing a basic nitrogen atom contains one or two hydroxyl groups.

[0279] In further preferred embodiments of the present invention, the alkalizing agent containing a basic nitrogen atom comprises or even consists of one or more amino alcohols, more preferably one or more alkanolamines.

[0280] In some preferred embodiments of the present invention, the alkalizing agent containing a basic nitrogen atom comprises or even consists of one or more of 1-amino-2-propanol, 1-amino-3-propanol and / or ethanolamine.

[0281] In some preferred embodiments of the present invention, the emulsifier composition comprises an alkalizing agent containing a basic nitrogen atom in a total amount ranging from 1% w / w to 30% w / w, more preferably from 2% w / w to 25% w / w, even more preferably from 4% w / w to 20% w / w, most preferably from 5% w / w to 15% w / w.

[0282] In some preferred embodiments of the present invention, the molar ratio between the total amount of the alkalizer containing basic nitrogen atoms and the sum of fuhfa and ouhfa of the emulsifier composition is in the range of 1:3 to 5:1, more preferably in the range of 1:2 to 4:1, and even more preferably in the range of 1:1 to 3:1.

[0283] In other preferred embodiments of the present invention, the molar ratio between the total amount of the alkalizer containing basic nitrogen atoms and the amount of fuhfa of the emulsifier composition is in the range of 1:3 to 5:1, more preferably in the range of 1:2 to 4:1, even more preferably in the range of 1:1 to 3:1.

[0284] In some preferred embodiments of the present invention, the pH of the emulsifier composition is in the range of 4.8 to 11, more preferably in the range of 7.0 to 10.5, even more preferably in the range of pH 8.0 to 10.4, most preferably in the range of 8.5 to 10.3.

[0285] The pH values ​​mentioned herein are measured at 25° C. and are measured by finely dispersing 10 g of the composition in question in 90 g of distilled water and then measuring the pH.

[0286] In some preferred embodiments of the present invention, the emulsifier composition further comprises one or more additional emulsifiers. Useful examples of additional emulsifiers are, for example, emulsifiers of the nonionic ethylene oxide propylene oxide block copolymer type, alkylbenzene sulfonates, fatty alcohol ethoxylates, fatty alcohol ether sulfates, polyglycerol esters of fatty acids, polyglycerol polyricinoleate and / or surfactants based on styrenated phenol.

[0287] The additional emulsifier may for example be a co-surfactant which interacts with the uhfa preferably improving its functionality, but need not be a surfactant itself. Preferred co-surfactants may for example be found among glycol ethers, polyethylene glycols and alkyl carboxylic acids and carboxylates.

[0288] It is generally preferred to provide the emulsifier composition in packaged form, preferably packaged in drums, boxes, IBCs, pails, barrels and / or cans.

[0289] Yet another aspect of the present invention relates to a method for producing an emulsifier composition, the method comprising the steps of:

[0290] -combination:

[0291] a) One or more of the following:

[0292] i) free unsaturated hydroxy fatty acids,

[0293] ii) oligoesters of unsaturated hydroxy fatty acids, and / or

[0294] iii) esters of hydroxycarboxylates according to i) or ii) wherein the molecular weight of the hydroxycarboxylic acid is at most 250 g / mol,

[0295] b) an alkalizing agent containing a basic nitrogen atom, and

[0296] c) optionally, one or more further ingredients, for example further emulsifiers,

[0297] - combining a), b) and optionally c) in amounts sufficient to obtain an emulsifier composition, and

[0298] - Optionally, packaging the emulsifier composition.

[0299] The present invention has been described above with reference to specific embodiments. However, within the scope of the present invention, other embodiments other than those described above are equally possible. Unless otherwise indicated, the various embodiments of the present invention and the different features and steps of various aspects may be combined in other ways other than those described herein.

[0300] Example

[0301] Example 1: Analysis Method

[0302] Example 1.1: Fuhfa, ouhfa and hcuhfa in an alkyd mixture or a source of unsaturated hydroxy fatty acids Quantification

[0303] The amount of fuhfa, ouhfa and hcuhfa in the alkyd mixture or the source of unsaturated hydroxy fatty acids was quantified by HPLC using the following equipment and the following steps.

[0304] Equipment: Sonicator, various glassware and HPLC system.

[0305] Instrument Setup:

[0306] Pump: Agilent 1100 Quaternary LC Pump

[0307] Syringe: Agilent 1100 autosampler

[0308] Column: Luna 3u silica (2) 100A 100×4.60mm

[0309] Column oven at 40°C

[0310] Detector: Agilent 1200 series LT-ELSD. 3.5 bar. Temperature 40°C. Gain 4

[0311] Alternative detection: MS detection can be introduced to identify unknown peaks in the chromatogram. An example can be the Agilent 1100 series LC / MSD Trap.

[0312] Table 1: Gradient / Schedule:

[0313]

[0314]

[0315] Chemicals and reagents:

[0316] Solvent mixture: Chloroform:Methanol in a ratio of (2:1) + 10 mL / L 10% formic acid in isopropanol

[0317] Mobile Phase:

[0318] C. Hexane

[0319] D. 800 mL hexane + 100 mL isopropanol + 100 mL ethyl acetate + 10 mL 10% formic acid in isopropanol

[0320] Chemicals

[0321] Hexane pa, HPLC grade

[0322] Formic acid pa, (98% to 100%)

[0323] Isopropyl alcohol pa, HPLC grade

[0324] Ethyl acetate pa, HPLC grade

[0325] Chloroform pa, HPLC grade

[0326] step:

[0327] The samples to be analyzed (75 mg to 200 mg depending on the expected concentration) were each dissolved in 10 mL of the solvent mixture (complete dissolution was ensured by sonicating the sample + solvent mixture and visually inspecting it before further use of the material). Sonication was performed at 48°C for 30 minutes. If the sample was not completely dissolved, it had to be filtered before analysis. Filtration was performed through a 0.45 μm Millipore membrane filter.

[0328] HPLC analysis of samples: All samples were determined in duplicate. Samples had to be freshly prepared and analyzed on the same day.

[0329] Example 1.2: Determination of iodine value

[0330] The iodine value of the composition is determined according to "AOAC method 993.20 (41.1.15). First edition (Final action) 1993, final edition (Final Action) 1996". The results are shown in the following units: g I2 / 100 g sample.

[0331] Example 1.3: Determination of hydroxyl value

[0332] The hydroxyl value of the composition (defined as the amount of acetic anhydride consumed for the acetylation of 1 gram of sample) was determined according to "AOAC method 965.32 (41.1.12) 1969 final edition, DGF, CV 17a (98)". The results are shown in the following units: mg KOH / g sample.

[0333] Example 1.4: Determination of acid value

[0334] The acid value of the composition is determined according to "FCC 5. Editorial Appendix VII: Fats and Related Materials Page 934". The results are shown in the following units: mg KOH / g sample.

[0335] Example 1.5: Determination of water content

[0336] The water content of the composition is determined by gravimetric analysis according to FAO "Combined compendium of food additive specifications, volume 4, pages 216 to 217, 2006, ISBN 92-5-105569-6", and the result is reported as a weight percentage of water relative to the total weight of the composition. If the water content measured by gravimetric analysis is less than 2.0% w / w, a new water content determination is performed using the Karl Fisher method according to AOCS official method Ca 2e-84, and the result of the Karl Fisher method is used as the water content.

[0337] Example 1.6: Determination of VOC

[0338] The VOC content of anhydrous materials such as alkyds and anhydrous alkyd mixtures is determined according to ASTM D2369-10(2015)e1, Standard Test Method for Volatile Content of Coatings, (ASTM International, West Conshohocken, PA, 2015, www.astm.org ) to measure.

[0339] The VOC content of aqueous materials, such as aqueous alkyd emulsions, is measured according to STM D6886 (ASTM D6886-18, Standard Test Method for Determination of the Weight Percent Individual Volatile Organic Compounds in Waterborne Air-Dry Coatings by Gas Chromatography, ASTM International, West Conshohocken, PA, 2018, www.astm.org).

[0340] Example 1.7: Determination of the mean hydrodynamic diameter of particles in an emulsion

[0341] The particle size distribution of the nanoemulsion was measured using a NanoBrook Omni from Brookhaven Instruments Corporation operating on the principle of dynamic light scattering (DLS) (Thomas, S., Thomas, R., Zachariah, AK & Mishra, RK (eds.). (2017) Thermal and Rheological Measurement Techniques for Nanomaterials Characterization, Elsevier Inc. pp. 37-49).

[0342] DLS (also known as Photon Correlation Spectroscopy) is a method for measuring particle size and particle size distribution of dilute suspensions from 0.5 nm to 10 μm. Small particles move rapidly relative to larger particles as described by the following Stokes-Einstein equation:

[0343]

[0344] Where D is the diffusion coefficient, k B is the Boltzmann constant, T is the temperature, η is the viscosity of the solvent, and R0 is the hydrodynamic radius.

[0345] During the measurement, a dilute solution containing the particles is illuminated by a laser, and the intensity fluctuations of the detected scattered light are analyzed and correlated with the Brownian motion. The fluctuations of the scattered laser intensity are analyzed by a digital correlator, and the resulting correlation function is related to the Brownian motion of the particles and further fitted to the size distribution; a fast decaying correlation function represents very small particles, while a slowly decaying correlation function corresponds to particles of larger sizes. In order to avoid multiple scattering events of the laser, the emulsion should be highly diluted during sampling.

[0346] The average hydrodynamic diameter was measured using a high power diode laser (35 mW) at a wavelength of 640 nm at a scattering angle of 90° under the following conditions: particle refractive index 1.59, water refractive index 1.331, viscosity 0.933 Cp and at a temperature of 23° C. Five measurements of 300 seconds duration were performed, and the average value obtained based on the intensity distribution was used to report the size distribution of the particles.

[0347] Example 2: Production of alkyd emulsions based on different alkyds and emulsifiers

[0348] Starting Materials

[0349] A number of potential bio-based emulsifiers were tested in standard and experimental alkyd systems. In the following examples, the compounds in Table 2.1 were used.

[0350] Table 2.1 Tested bio-based emulsifiers

[0351]

[0352]

[0353] Commercially available, experimental or conventional alkyd resins can be used according to the invention. These are exemplified by resins having the compositions listed in Table 2.2. All resins used are solvent-free, ie, have a solids content of about 100%.

[0354] Table 2.2 Types and compositions of alkyds tested

[0355]

[0356]

[0357] Preparation of alkyd mixture

[0358] 30 g of alkyd was weighed into a 250 mL Pyrex beaker at room temperature. 2.4 g (8% w / w) or 3.0 g (10% w / w) of emulsifier was added and the mixture was stirred briefly at 200 rpm using an overhead Heidolph RZR 2041 stirrer equipped with a propeller impeller. Sufficient 27.7% NaOH solution was added to neutralize the emulsifier-alkyd mixture and ensure that the pH of the final emulsion was 8 to 9.

[0359] Preparation of emulsions by phase transition

[0360] 30 mL of demineralized water was slowly added at a rate of 30 mL / hour at room temperature or 50° C. The addition of water initially produced a water-in-oil emulsion that spontaneously transformed into an oil-in-water emulsion by a catastrophic phase transition (Bouchama, F., van Aken, GA, Autin, AJE, Koper, GJM (2003). On the mechanism of catastrophic phase inversion in emulsions. Colloids Surf. A 231 (1-3), 11-17.).

[0361] The emulsions in Table 2.3 were prepared using the general procedure outlined above.

[0362] Table 2.3 Prepared emulsion

[0363]

[0364]

[0365] in conclusion

[0366] All tested emulsifiers were able to produce emulsions. However, the texture, appearance and stability of the emulsions varied significantly.

[0367] Both emulsions A and B are viscous white emulsions. A comparison of the micrographs of the two emulsions can be seen at Figure 1 Immediately apparent is the greatly improved droplet size by the addition of PGPR to the emulsifier system.

[0368] Using SRL as suhfa, the resulting emulsion C was a fine light blue nanoemulsion ( Figure 2 ). It was found that the droplet size distribution correlated favorably with the pH of the emulsion. The nanoemulsion had a much lower viscosity than emulsions A and B and could be easily poured from a beaker into a storage container.

[0369] Emulsion D is directly based on 8% ricinoleic acid and has a similar light blue nanoemulsion appearance. The same conclusion can be drawn for emulsion E containing a slightly higher concentration (10%) of ricinoleic acid.

[0370] For comparison, emulsions F and G, based on oleic acid (unsaturated fatty acid but not hydroxy fatty acid) and 12-hydroxystearic acid (hydroxy fatty acid but not unsaturated fatty acid), respectively, did not produce nanoemulsions. Emulsion F produced a granular white emulsion that separated after a few days. Emulsion G was almost solid, colloidal and hydrophobic, indicating that phase transition may not have occurred during production.

[0371] Emulsions H to K all exhibited the properties of nanoemulsions. The average droplet size distribution of all emulsions H to K was below 300 nm and had very long shelf lives, ranging from months to years.

[0372] Emulsions L1 to L7 show the effect of systematically varying the concentration using a highly efficient uhfa RA neutralized with an amine (which can also function as a co-surfactant in the system). Droplet sizes as small as less than 120 nm were obtained using the highest concentration of emulsifier.

[0373] Emulsions M1 and M2 demonstrate that neutralized RA is very effective in linseed oil based alkyds. Furthermore, even without neutralizing the alkyd (which is a common practice during the production of traditional alkyd emulsions), the use of neutralized RA itself is effective, as is evident from the similar average droplet sizes. The inventors observed that similar results were obtained if the alkalizing agent used to neutralize the RA was ethanolamine.

[0374] Example 3: Preparation of a paint containing an alkyd emulsion

[0375] The emulsion of Example 2 is used to prepare a paint by employing standard techniques for waterborne alkyd paints. This requires starting with the appropriate amount of water, adding the desired thickener, in-can preservative, and optionally an additional biocide, then adding the appropriate drying agent typically used with conventional alkyd resins, adding a defoamer, and finally adding the desired amount of emulsion to obtain a final formulation of the appropriate binder content.

[0376] An example of a minimum formulation for a clearcoat based on an alkyd emulsion is given below:

[0377] Water 25% to 35%

[0378] Thickener 0% to 3%

[0379] Preservatives 0% to 1%

[0380] Desiccant 0% to 1%

[0381] Defoamer 0.1%

[0382] Alkyd emulsion 55% to 75%

[0383] Example of a standard matt paint formulation:

[0384] Water 10% to 15%

[0385] Pigments, such as TiO2 10% to 15%

[0386] Filler, e.g. fine CaCO3 25% to 30%

[0387] Filler, e.g. medium CaCO3 25% to 30%

[0388] Dispersant 0% to 2%

[0389] Thickener 0% to 3%

[0390] Preservatives 0% to 1%

[0391] Defoamer 0.1%

[0392] Desiccant 0% to 1%

[0393] Alkyd emulsion 10% to 15%

[0394] Examples of water-based decorative / interior paints:

[0395] Water 0% to 2%

[0396] Pigment paste 30% to 40%

[0397] Desiccant 0.5%

[0398] Defoamer 0.3%

[0399] Alkyd emulsion 60% to 70%

[0400] Example 4: Characterization and comparison of alkyd emulsions

[0401] Particle size

[0402] The particle size distribution of emulsions A to K is plotted on Figure 3 Very fine nanoemulsions were obtained for all experiments involving suhfa in the form of sodium ricinoleic lactylate (which can be further hydrolyzed under alkaline conditions to release free ricinoleate) as well as for direct use of ricinoleic acid. Figure 4 The effect of emulsifier concentration on droplet size for the L emulsion series is shown.

[0403] Emulsion stability

[0404] Emulsions C, D, E, H, I, J and K with average droplet size below 300 nm were stable for longer than 12 months. Emulsion A phase separated within 3 months, emulsion B within 1 month, and the same was true for emulsion F. Emulsion G failed from the beginning. All emulsions of the L series are expected to be stable for more than 12 months due to the very fine droplet size.

[0405] Visual inspection of coatings

[0406] Paints containing suhfa-based emulsions gave very good clear coatings when applied on wood and / or glass slides. Paints based on emulsion A became opaque over time, whereas paints based on emulsions C, D or E remained clear with high gloss values.

[0407] UV Curing

[0408] When exposed to outdoor light, paint samples based on emulsions C, D and E showed good drying characteristics. Under QUV testing conditions, the films showed good stability compared to standard alkyd paint formulations.

[0409] in conclusion

[0410] All results are summarized in Table 4.

[0411] Table 4. Properties of alkyd emulsions

[0412]

[0413] The inventors have found that alkyd emulsions stabilized by suhfa provide a stable, bio-based and environmentally friendly alternative to conventional emulsions based on standard emulsifiers commonly used for this purpose. The resulting films exhibit high gloss and are very stable under all conditions studied. Some evidence of a stabilizing effect under UV light is indicated. This is most likely due to the ability of suhfa to participate in autoxidation processes during coating formation. The high gloss of the films supports the view that the RA emulsifier becomes cross-linked within the coating, which is highly desirable to avoid migration of the emulsifier to the surface of the coating. Migration of the emulsifier typically results in lower quality paints due to accumulation of hydrophilic components on the surface and the possibility of color degradation when pigments are used in paint formulations.

[0414] Example 5: Neutralization effect of suhfa and its influence on the obtained alkyd nanoemulsion

[0415] Materials and experimental setup

[0416] Suhfa is a castor oil fatty acid rich in unsaturated hydroxy fatty acid ricinoleic acid RA. Two amino alcohols, 1-amino-2-propanol and ethanolamine, are used as alkalizing agents. Different molar ratios between alkali and RA are studied according to Tables 5 and 6.

[0417] Table 5. RA neutralized with ethanolamine

[0418]

[0419] Table 6. RA neutralized with 1-amino-2-propanol

[0420]

[0421] The pH of a 10% w / w solution of neutralized RA in demineralized water was measured and an alkyd emulsion using standard long oil alkyd was produced using 8% w / w neutralized RA relative to the alkyd. No additional alkalizing agent was added during emulsification. The average droplet size of each nanoemulsion was evaluated using dynamic light scattering according to Example 1.7.

[0422] Effects of different neutralization levels of suhfa

[0423] All results of the neutralization studies can be seen in Table 7.

[0424] Table 7. Effect on pH in 10% solution of neutralized RA and on average droplet size in alkyd nanoemulsions containing 8% w / w neutralized RA relative to alkyd.

[0425]

[0426] The results of different molar ratios between alkalizer and RA on the average droplet size of an emulsion of alkyd in water containing 8% w / w of the emulsifier mixture relative to the amount of alkyd are plotted in Table 1 for ethanolamine and 1-amino-2-propanol, respectively. Figure 5 and Figure 6 middle.

[0427] The inventors have found that a 1:1 molar ratio of base to RA produces almost the same alkyd droplet diameter, 207nm / 209nm, regardless of the nature of the amino alcohol. Ethanolamine neutralization appears slightly less sensitive to underdosing than 1-amino-2-propanol neutralization. Excess base gives slightly better results than the 1:1 ratio. This is due to the alkyd being neutralized by excess base, resulting in a more hydrophilic system that is easier to emulsify. Note that this effect can also be achieved by adding additional neutralizing agent to the alkyd mixture, which is a common practice in the industry. For molar ratios above 1:2, the effect of excess base appears to be more or less constant.

Claims

1. A method for producing a nanoemulsion comprising nanodroplets containing an alkyd, the nanodroplets being dispersed in an aqueous liquid, the method comprising the steps of: a) providing an alkyd mixture comprising a source of unsaturated hydroxy fatty acid and an alkyd, wherein the source of unsaturated hydroxy fatty acid is denoted as suhfa, and the source comprises: i) Free unsaturated hydroxy fatty acids, where free unsaturated hydroxy fatty acids are denoted as FUHFA, ii) oligoesters of unsaturated hydroxy fatty acids, wherein oligoesters of unsaturated hydroxy fatty acids are denoted as ouhfa, or iii) a free ester of said fuhfa or said ouhfa and a hydroxycarboxylic acid having a molecular weight of at most 250 g / mol, wherein the free ester of said fuhfa or said ouhfa and a hydroxycarboxylic acid having a molecular weight of at most 250 g / mol is denoted as hcuhfa, b) optionally, adding an alkalizing agent to deprotonate at least some of the carboxylic acids of the alkyd mixture, c) forming a nanoemulsion of the alkyd mixture in an aqueous liquid.

2. The method according to claim 1, wherein the alkyd comprises: -Long oil alkyd, -Medium oil alkyd, or -Short oil alkyd.

3. The process according to claim 1, wherein the alkyd has an acid value of at most 20 mg KOH / g.

4. The method according to claim 1, wherein the water content of the alkyd is at most 5% w / w.

5. The method according to claim 1, wherein the VOC content of the alkyd is at most 50 g / L.

6. The method according to claim 1, wherein the suhfa comprises one or more of the following, based on the total weight of the suhfa: i) at least 10% w / w of free unsaturated hydroxy fatty acids, ii) at least 1% w / w of di(unsaturated hydroxy fatty acids), denoted as DUHFAs, and iii) at least 1% w / w of tri(unsaturated hydroxy fatty acids), tri(unsaturated hydroxy fatty acids) being denoted as TUHFA.

7. The method according to the preceding claim 1, wherein the suhfa comprises at least 50% w / w fuhfa, based on the total weight of the suhfa.

8. The process according to claim 1, wherein the suhfa comprises 100% w / w fuhfa, based on the total weight of the suhfa.

9. The method according to claim 1, wherein the suhfa comprises, based on the total weight of the suhfa, i) 10% w / w to 99% w / w of free unsaturated hydroxy fatty acids, ii) 1% w / w to 50% w / w of di(unsaturated hydroxy fatty acids), and iii) 0% w / w to 30% w / w of tri(unsaturated hydroxy fatty acid).

10. The method according to claim 1, wherein the suhfa comprises, based on the total weight of the suhfa, i) 1% w / w to 50% w / w of free unsaturated hydroxy fatty acids, ii) 10% w / w to 98% w / w of di(unsaturated hydroxy fatty acids), and iii) 1% w / w to 30% w / w of a tri(unsaturated hydroxy fatty acid).

11. The method according to claim 1, wherein the suhfa comprises, based on the total weight of the suhfa, i) 0% w / w to 30% w / w of free unsaturated hydroxy fatty acids, ii) 1% w / w to 40% w / w of di(unsaturated hydroxy fatty acids), and iii) 10% w / w to 98% w / w of tri(unsaturated hydroxy fatty acid).

12. The process according to claim 6, wherein the sum of fuhfa, duhfa and tuhfa represents at least 10% w / w of the total weight of the suhfa.

13. The method according to claim 1, wherein the suhfa has an acid number of at least 140 mg KOH / g sample.

14. The method of claim 1, wherein the suhfa has a hydroxyl value of at least 140 mg KOH / g sample.

15. The method according to claim 1, wherein the suhfa has an iodine value of at least 60 g I2 / 100 g sample.

16. The method of claim 1, wherein the suhfa comprises omega-9 fatty acids.

17. The method of claim 1, wherein the suhfa comprises ricinoleic acid.

18. The method according to claim 1, wherein the weight ratio between the total amount of suhfa and the total amount of alkyd of the alkyd mixture of step a) is 0.01 to 0.

30.

19. The method according to the preceding claim 6, wherein the weight ratio between the total amount of fuhfa+duhfa+tuhfa and the total amount of alkyd of the alkyd mixture of step a) is from 0.01 to 0.

30.

20. The method according to the preceding claim 1, wherein the alkyd mixture of step a) is provided by mixing an alkyd with the suhfa.

21. The method of claim 1, wherein the temperature of the alkyd and the suhfa during mixing to provide the alkyd mixture of step a) is in the range of 10°C to 150°C.

22. The method according to the preceding claim 1, wherein the alkalizing agent is added in solid form, liquid form or dissolved form.

23. The method according to claim 1, wherein the alkalizing agent comprises one or more components selected from the group consisting of hydroxide salts, ammonia, amines and amino alcohols.

24. The method of claim 1, wherein forming the nanoemulsion of step c) comprises emulsifying an aqueous liquid into the alkyd mixture and causing a phase transition to occur, thereby providing a nanoemulsion comprising nanodroplets of the alkyd mixture.

25. The method according to the preceding claim 1, wherein forming the nanoemulsion of step c) comprises mixing the alkyd mixture with the aqueous liquid under mechanical shear.

26. The method according to the preceding claim 1, wherein the pH of the aqueous liquid of step c) is in the range of 5 to 13.

27. The method according to the preceding claim 1, wherein the temperature during mixing of step c) is in the range of 0°C to 200°C.

28. The method according to claim 1, wherein the hydrodynamic diameter of the nanodroplets containing the alkyd is at most 350 nm.

29. An alkyd mixture comprising a source of unsaturated hydroxy fatty acid and an alkyd, wherein the source comprises: i) Free unsaturated hydroxy fatty acids, free unsaturated hydroxy fatty acids are denoted as fuhfa, ii) oligoesters of unsaturated hydroxy fatty acids, which are denoted as ouhfa, or iii) a free ester of the fuhfa or the ouhfa with a hydroxycarboxylic acid having a molecular weight of at most 250 g / mol, wherein the free ester of the fuhfa or the ouhfa with a hydroxycarboxylic acid having a molecular weight of at most 250 g / mol is denoted as hcuhfa.

30. A nanoemulsion comprising nanodroplets of an alcoholic acid, the nanodroplets further comprising a source of an unsaturated hydroxy fatty acid, the source comprising: i) free unsaturated hydroxy fatty acids, ii) oligoesters of unsaturated hydroxy fatty acids, or iii) free esters of the free unsaturated hydroxy fatty acids or oligoesters of the unsaturated hydroxy fatty acids with hydroxy carboxylic acids having a molecular weight of up to 250 g / mol.

31. The nanoemulsion containing nanodroplets of an alkyd according to claim 30, obtained by the method according to any one of claims 1 to 28.

32. A nanodroplet containing an alcohol acid, the nanodroplet further comprising a source of unsaturated hydroxy fatty acids, the source comprising: i) free unsaturated hydroxy fatty acids, ii) oligoesters of unsaturated hydroxy fatty acids, or iii) free esters of the free unsaturated hydroxy fatty acids or oligoesters of the unsaturated hydroxy fatty acids with hydroxy carboxylic acids having a molecular weight of up to 250 g / mol.

33. The nanodroplets containing alkyd acid according to claim 32, obtained by the method according to any one of claims 1 to 28.

34. A method of producing a coating product comprising nanodroplets containing an alkyd acid dispersed in an aqueous solvent, the method comprising the steps of: 1) providing the nanoemulsion according to claim 30 or the nanoemulsion obtained by the method according to any one of claims 1 to 28 or the nanodroplets containing alkyd according to claim 32, 2) contacting the nanoemulsion or the nanodroplets with one or more additional ingredients to obtain a coating mixture, wherein the one or more additional ingredients include water, pigment, thickener, defoamer, desiccant, dispersant, silicone, thixotropic agent, anti-settling agent, bactericide, fungicide, algaecide, 3) optionally, subjecting the coating mixture to one or more further processing steps, including -mix - Degassing -filter, 4) Optionally, package the final product in a suitable container.

35. A coating product comprising the nanodroplets according to claim 32 and a drying agent.

36. The coating product of claim 35, comprising, based on the weight of the coating product: - a total amount of nanodroplets according to claim 32 in the range of 10% w / w to 50% w / w, - a total amount of water in the range of 10% w / w to 80% w / w, - a desiccant in a total amount in the range of at least 0.05% w / w, - a total amount of pigments in the range of 0% w / w to 40% w / w, - a total amount of defoamers in the range of 0% to 2%, - a total amount of thickeners in the range of 0% to 4%, - Total amount of preservatives in the range of 0% to 4%.

37. The coating product of claim 35, obtained by the method of claim 34.

38. Use of a suhfa as defined in claim 1 as an emulsifier in forming a nanoemulsion of an alkyd in an aqueous liquid.

39. The use according to claim 38, wherein the suhfa is used as the sole emulsifier.

40. The use according to claim 38, wherein the suhfa is used in combination with one or more additional emulsifiers and / or co-surfactants.

41. Use of an alkyd mixture according to claim 29 for producing a nanoemulsion.

42. Use of the nanodroplets containing alkyd according to claim 32 or the nanoemulsion according to claim 30 for producing a coating product.

43. An emulsifier composition comprising: a) One or more of the following: i) Free unsaturated hydroxy fatty acids, where free unsaturated hydroxy fatty acids are denoted as FUHFA, ii) oligoesters of unsaturated hydroxy fatty acids, wherein oligoesters of unsaturated hydroxy fatty acids are denoted as ouhfa, or iii) a free ester of said fuhfa or said ouhfa with a hydroxycarboxylic acid having a molecular weight of up to 250 g / mol, wherein The free ester of the fuhfa or the ouhfa with a hydroxycarboxylic acid having a molecular weight of up to 250 g / mol is denoted as hcuhfa, and b) Alkalizing agents containing basic nitrogen atoms.

44. The emulsifier composition according to claim 43, comprising a total amount of 20% w / w to 99% w / w of i) free unsaturated hydroxy fatty acids, ii) oligoesters of unsaturated hydroxy fatty acids, or iii) free esters of the free unsaturated hydroxy fatty acids or oligoesters of the unsaturated hydroxy fatty acids with hydroxy carboxylic acids having a molecular weight of up to 250 g / mol.

45. An emulsifier composition according to claim 43, comprising free unsaturated hydroxy fatty acids in a total amount ranging from 20% w / w to 99% w / w by weight of the emulsifier composition.

46. ​​The emulsifier composition according to claim 43, wherein the molecular weight of the alkalizing agent containing a basic nitrogen atom is at most 300 g / mol.

47. The emulsifier composition according to claim 43, wherein the alkalizing agent containing a basic nitrogen atom has a molecular weight of at most 150 g / mol.

48. The emulsifier composition according to claim 43, wherein the alkalizing agent containing a basic nitrogen atom comprises one or two hydroxyl groups.

49. The emulsifier composition of claim 43, wherein the alkalizing agent comprises one or more amino alcohols.

50. The emulsifier composition of claim 43, wherein the alkalizing agent containing a basic nitrogen atom comprises one or more of 1-amino-2-propanol or 1-amino-3-propanol or ethanolamine.

51. The emulsifier composition according to claim 43, comprising a total amount of an alkalizing agent containing a basic nitrogen atom in a range of 1% w / w to 30% w / w, based on the weight of the emulsifier composition.

52. The emulsifier composition according to claim 43, wherein the molar ratio between the total amount of the alkalizer containing a basic nitrogen atom and the sum of fuhfa and ouhfa of the emulsifier composition is in the range of 1:3 to 5:

1.

53. The emulsifier composition according to claim 43, wherein the molar ratio between the total amount of the alkalizer containing a basic nitrogen atom and the amount of fuhfa of the emulsifier composition is in the range of 1:3 to 5:

1.

54. The emulsifier composition according to claim 43, wherein the pH of the emulsifier composition is in the range of 4.8 to 11.

55. The emulsifier composition of claim 43, further comprising one or more additional emulsifiers.

56. A method for producing an emulsifier composition according to any one of claims 43 to 55, comprising the steps of: -combination: a) One or more of the following: i) free unsaturated hydroxy fatty acids, ii) oligoesters of unsaturated hydroxy fatty acids, or iii) the free esters of the free unsaturated hydroxy fatty acids or the oligoesters of the unsaturated hydroxy fatty acids with hydroxy carboxylic acids having a molecular weight of up to 250 g / mol, b) alkalizing agents containing basic nitrogen atoms, and c) optionally one or more further ingredients, - combining a), b) and optionally c) in amounts sufficient to obtain the emulsifier composition, and - Optionally packaging the emulsifier composition.

57. An emulsifier composition as claimed in any one of claims 43 to 55 as an emulsifier for forming an alkyd nanoemulsion in an aqueous liquid.

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