OXIDIZING, IONIC AND SHORT OIL ALKYD RESINS FOR COATINGS WITH EXCELLENT BALANCE OF HARDNESS AND GLOSS

Abstract

The invention relates to an oxidizing, ionic and short oil alkyd resin. The invention further relates to various compositions comprising the oxidizing, ionic and short oil alkyd resin, cured compositions derived upon curing of said compositions, objects comprising the various cured or uncured compositions as well as various uses of the oxidizing, ionic and short oil alkyd resin, and of the various compositions of the invention as well as of the various objects of the invention.

Claims

1. An oxidizing, ionic and short oil alkyd resin (OSAR) comprising one or both of: i) conjugated ethylenic unsaturations, and ii) diallylic ethylenic unsaturations, and wherein the OSAR has: an acid value as determined titrimetrically by ISO 2114 of at most 20, preferably at most 10, more preferably at most 5 mg KOH/g, and a M.sub.n-OSAR as determined by Gel Permeation Chromatography (GPC) according to the description, of at least 1500 and at most 10000 Da, and a M.sub.w-OSAR as determined by GPC according to the description of at least 20000 and at most 400000 Da, and a polydispersity (D=M.sub.w-OSAR/M.sub.n-OSAR) of at least 5 and at most 100, and an oil length of at least 18 and at most 38, preferably at least 18 and at most 36, more preferably at least 20 and at most 36%, and wherein the OSAR is the reaction—preferably polycondensation reaction—product of at least the following components POC, PAC, MAC, FAC, IOC, and PALC as each of them is defined below, and wherein the OSAR comprises polycondensed residues of at least the following components POC, PAC, MAC, FAC, IOC, and PALC: a polyol component (POC) selected from the group consisting of trialcohols, tetralcohols, pentalcohols, hexalcohols and mixtures thereof, and wherein each of the trialcohols, tetralcohols, pentalcohols, and hexalcohols has a theoretical molecular weight of at most 400 Da, and wherein the amount of the polycondensed residue of POC in the OSAR is at least 10 and at most 35 mol %, and a polycarboxylic acid component (PAC) selected from the group consisting of C.sub.8-C.sub.12 cycloaliphatic polycarboxylic acids, C.sub.8-C.sub.12 cycloaliphatic polycarboxylic acid anhydrides, C.sub.10-C.sub.16 esters of cycloaliphatic polycarboxylic acids, C.sub.8-C.sub.12 aromatic polycarboxylic acids, C.sub.8-C.sub.12 aromatic polycarboxylic acid anhydrides, C.sub.10-C.sub.16 esters of aromatic polycarboxylic acids, and mixtures thereof, and wherein the amount of the polycondensed residue of PAC in the OSAR is at least 10 and at most 30 mol %, and a monocarboxylic acid component (MAC) selected from the group consisting of C.sub.7-C.sub.11 aromatic monocarboxylic acids, C.sub.8-C.sub.13 esters of aromatic monocarboxylic acids, C.sub.7-C.sub.11 saturated cycloaliphatic monocarboxylic acids, C.sub.8-C.sub.13 esters of saturated cycloaliphatic monocarboxylic acids, and mixtures thereof, and wherein the amount of the polycondensed residue of MAC in the OSAR is at least 20 and at most 50 mol %, and a fatty acid component (FAC) selected from the group consisting of fatty acids and mixtures thereof, and wherein the FAC comprises ethylenic unsaturations and has an iodine number (ION) as determined by DIN 53241-1, of at least 15 and at most 300 cg/g, and wherein the amount of the polycondensed residue of FAC in the OSAR is at least 1 and at most 30 mol %, an ionic component (IOC) selected from the group consisting of aromatic monocarboxylic acid sulfonate salts, aromatic monocarboxylic acid alkyl ester sulfonate salts, aromatic dicarboxylic acid sulfonate salts, aromatic dialkyl ester sulfonate salts, and mixtures thereof, and wherein the amount of the polycondensed residue of IOC in the OSAR is at least 1.2 and at most 3 mol %, and a polyalkylene component (PALC) selected from the group consisting of: i) polyalkylene glycols A1 according to formula A1 (PG-A1) ##STR00017## wherein n is an integer of at least 1 and at most 200, and k is an integer of at least 0 and at most 50, and R.sub.1 is either H or CH.sub.3, and R.sub.2 is selected from the group consisting of H, CH.sub.3, and C.sub.2-C.sub.10 optionally substituted hydrocarbyl having at most three substituents each of which is a hydroxyl group, and R.sub.3 is CH.sub.3, or a C.sub.2-C.sub.10 hydrocarbyl, and wherein the formula A1 has at least one and at most four, preferably has at least two and at most three hydroxyl groups, ii) polyalkylene glycols A2 according to formula A2 (PG-A2), ##STR00018## wherein m is an integer of at least 1 and at most 100, and v is an integer of at least 0 and at most 40, and R.sub.4 is either H or CH.sub.3, and R.sub.5 is CH.sub.3, or a C.sub.2-C.sub.10 hydrocarbyl, and R.sub.6 is selected from the group consisting of H, CH.sub.3, and C.sub.2-C.sub.10 optionally substituted hydrocarbyl having at most four substituents selected from the group consisting of hydroxyl and amino groups and at least one of them—preferably two—is a hydroxyl group, and wherein the formula A2 has at least one and at most four, preferably at least two and at most three hydroxyl groups, iii) polyether amines A1 according to formula PE1 (PE-A1), ##STR00019## wherein x ranges from 0 up to and including 30, and y ranges from 1 up to and including 100, and z ranges from 0 up to and including 30 when x is different than 0, and from 1 up to and including 40 when x is 0, and R.sub.7 is selected from the group consisting of CH.sub.3, and C.sub.2-C.sub.10 optionally substituted hydrocarbyl (preferably C.sub.2-C.sub.5 optionally substituted hydrocarbyl, more preferably C.sub.3 optionally substituted hydrocarbyl) having at most two substituents each of which is an amino group, preferably the C.sub.2-C.sub.10 optionally substituted hydrocarbyl (preferably C.sub.2-C.sub.5 optionally substituted hydrocarbyl, more preferably C.sub.3 optionally substituted hydrocarbyl) has one amino group as substituent, and R.sub.8 is CH.sub.3, or a C.sub.2-C.sub.10 hydrocarbyl, preferably CH.sub.3, and R.sub.9 is CH.sub.3, or a C.sub.2-C.sub.10 hydrocarbyl, preferably CH.sub.3, and R.sub.10 is NH.sub.2, and iv) mixtures thereof, and wherein each of the PG-A1, PG-A2 and PE-A1 has a theoretical molecular weight of at least 500 and at most 5000 Da, and wherein the amount of the polycondensed residue of PALC in the OSAR is at least 0.01 and at most 1 mol %, and wherein the sum (S.sub.1) of the amounts in mol % of the polycondensed residues of MAC, FAC, IOC and PALC components (S.sub.1=MAC.sub.mol %+FAC.sub.mol %+IOC.sub.mol %+PALC.sub.mol %) in the OSAR, is at least 40 and at most 70 mol %, and wherein the ratio (R.sub.1) of the amount of the polycondensed residue of MAC in mol % (MAC.sub.mol %) to the amount of the polycondensed residue of FAC in mol % (FAC.sub.mol %) (R.sub.1=MAC.sub.mol %/FAC.sub.mol %) in the OSAR is at least 1 and at most 5, and wherein the ratio (R.sub.2) of the sum of the amounts in mol % of the polycondensed residues of IOC and PALC components (IOC.sub.mol % and PALC.sub.mol %, respectively) to the amount of the polycondensed residue of FAC in mol % (R.sub.2=(IOC.sub.mol %+PALC.sub.mol %)/FAC.sub.mol %) in the OSAR, is at least 0.1 and at most 0.5, and wherein the ratio (R.sub.3) of the sum of the amounts in mol % of the polycondensed residues of PAC and MAC components to the amount of the polycondensed residue of PALC in mol % (R.sub.3=(PAC.sub.mol %+MAC.sub.mol %)/PALC.sub.mol %) in the OSAR, is at least 150, and at most 1500, and wherein the mol % is based on the OSAR.

2. The OSAR as claimed in claim 1, wherein the MAC is selected from the group consisting of C.sub.7-C.sub.11 aromatic monocarboxylic acids, C.sub.5-C.sub.9 saturated monocarboxylic acids, and mixtures thereof.

3. The OSAR as claimed in claim 1, wherein the FAC is selected from the group consisting of soybean oil fatty acids, sunflower oil fatty acids, tall oil fatty acids, linseed oil fatty acids, dehydrated castor oil fatty acids, cottonseed oil fatty acids, corn oil fatty acids, tung oil fatty acids, calendula oil fatty acids, safflower oil fatty acids, hemp oil fatty acids, and mixtures thereof.

4. The OSAR as claimed in claim 1, wherein the IOC is selected from the group consisting of aromatic dicarboxylic acid sulfonate salts.

5. The OSAR as claimed in claim 1, wherein the PALC is selected from the group consisting of polyalkylene glycols A1 according to formula A1, polyalkylene glycols A2 according to formula A2, and mixtures thereof.

6. The OSAR as claimed in claim 1, wherein the OSAR is substantially-free—preferably free—of one or any combination of i) to vii): i) polycondensed residues of silanols e.g. siloxane groups, ii) polycondensed residues of C.sub.3-C.sub.4 unsaturated monocarboxylic acids, iii) polycondensed residues of C.sub.3-C.sub.4 saturated monocarboxylic acids, iv) reacted residue of an acrylic resin, v) reacted residue of a polyurethane resin, vi) reacted residue of a urethane alkyd (uralkyd), and vii) reacted residue of a polysiloxane.

7. The OSAR as claimed in claim 1, wherein the OSAR has: an acid value of at most 20, preferably at most 10, more preferably at most 5 mg KOH/g, and a M.sub.n-OSAR of at least 2000 and at most 7000 Da, and a M.sub.w-OSAR of at least 20000 and at most 80000 Da, and a D of at least 8, preferably at least 10 and at most 35, and an oil length of at least 20, preferably at least 22 and at most 36%, and wherein the POC is selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and mixtures thereof, and wherein the amount of the polycondensed residue of POC in the OSAR is at least 15 and at most 33 mol %, preferably is at least 20 and at most 30 mol %, and the PAC is selected from the group consisting of isophthalic acid, terephthalic acid, phthalic acid, phthalic acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and wherein the amount of the polycondensed residue of PAC in the OSAR is at least 10 and at most 30 mol % preferably at least 12 and at most 28 mol %, and the MAC is selected from the group consisting of C.sub.7-C.sub.11 aromatic monocarboxylic acids, C.sub.5-C.sub.9 saturated cycloaliphatic monocarboxylic acids, and mixtures thereof, and wherein the amount of the polycondensed residue of MAC in the OSAR is at least 25 and at most 45 mol %, and the FAC has an ION of at least 80 and at most 200 cg/g, and wherein the amount of the polycondensed residue of FAC in the OSAR is least 5 and at most 26 mol %, preferably at least 10 and at most 25 mol %, and the IOC is selected from the group consisting of 5-(sulfo)isophthalic acid sodium salt, 5-(sulfo)isophthalic acid lithium salt and mixtures thereof, and wherein the amount of the polycondensed residue of IOC in the OSAR is at least 1.2 and at most 3 mol %, and the PALC is selected from the group consisting of: i) polyalkylene glycols A1 according to formula A1 (PG-A1) wherein n is an integer of at least 1 and at most 100, and k is an integer of at least 0 and at most 10, and R.sub.1 is either H or CH.sub.3, and R.sub.2 is selected from the group consisting of H, CH.sub.3, and C.sub.2-C.sub.10 optionally substituted hydrocarbyl having at most two substituents each of which is a hydroxyl group, and R.sub.3 is CH.sub.3, or a C.sub.2-C.sub.10 hydrocarbyl, and wherein the formula A1 has at least one and at most three, preferably has two hydroxyl groups, ii) polyalkylene glycols A2 according to formula A2 (PG-A2), wherein m is an integer of at least 1 and at most 50, and v is an integer of at least 0 and at most 20, and R.sub.4 is either H or CH.sub.3, and R.sub.5 is CH.sub.3, or a C.sub.2-C.sub.10 hydrocarbyl, and R.sub.6 is selected from the group consisting of H, CH.sub.3, and C.sub.2-C.sub.6 optionally substituted hydrocarbyl having at most three substituents selected from the group consisting of hydroxyl and amino groups and at least one of them—preferably two—is a hydroxyl group, and wherein the formula A2 has at least one and at most three, preferably at least one and at most two hydroxyl groups, iii) mixtures thereof, and wherein each of the PG-A1 and PG-A2 has a theoretical molecular weight of at least 800 and at most 2000, and wherein the amount of the polycondensed residue of PALC in the OSAR is at least 0.2 and at most 0.4 mol %, and wherein the S.sub.1 is at least 50 and at most 60 mol %, and wherein the R.sub.1 is at least 1 and at most 4, and wherein the R.sub.2 is at least 0.1, and at most 0.5, preferably at least 0.1 and at most 0.3, and wherein the R.sub.3 is at least 150 and at most 1500, preferably at most 800, more preferably at most 500, most preferably at most 400, especially at most 300, more especially at most 250, most especially at most 200.

8. A composition (C) comprising: i) a Binder-C selected from the group consisting of an OSAR as claimed in claim 1, and a mixture of an OSAR with an oxidizing alkyd resin other than the OSAR, and ii) a drier.

9. A liquid composition (LC) comprising: i) a Binder-LC selected from the group consisting of an OSAR as claimed in claim 1, and a mixture of an OSAR with an oxidizing alkyd resin other than the OSAR, and ii) one or both of water and an organic solvent.

10. The liquid composition as claimed in claim 9, wherein the liquid composition is a water-borne composition, preferably an aqueous dispersion or an emulsion.

11. The liquid composition as claimed in claim 9 further comprising: iii) a drier.

12. A cured composition (CR-C) obtained upon curing of a composition (C) as claimed in claim 8.

13. A cured composition (CR-LC) obtained upon curing of a liquid composition (LC) as claimed in claim 9.

14. An object or a kit-of-parts comprising: i) an article, and ii) one or any combination of: an OSAR as claimed in claim 1, a composition (C), a liquid composition (LC), a cured composition (CR-C), and a cured composition (CR-LC).

15. A use of one or any combination of a) to f): a) an OSAR as claimed in claim 1, b) a C, c) a LC, d) a CR-C, e) a CR-LC, and f) an object or a kit-of-parts, in paints, coatings, polishes, varnishes, inks, adhesives, pastes, compositions suitable for 3D-printing, 3D-printed objects, automotive applications, marine applications, aerospace applications, medical applications, defense applications, sports/recreational applications, architectural applications, bottling applications, household applications, machinery applications, can applications, coil applications, energy applications, textile applications, electrical applications, building and construction applications, packaging applications, telecommunications, and consumer goods.

Description

EXAMPLES

1. Chemicals & Raw Materials

[0608] Tetrahydrofuran (THF), was purchased from Biosolve and purified using an activated alumina purification system. Phthalic anhydride (>99.8%) was supplied by BASF. Benzoic acid (99.9%) was supplied by Brenntag. Pentaerythritol (>98%) and Ymer™ N120 were supplied by Perstorp. SSIPA (>98%) was supplied by Future Fuel Corporation; sulphuric acid impurities contained in SSIPA were stoichiometrically neutralized with lithium hydroxide monohydrate. Lithium hydroxide monohydrate (LiOH>56.5%) was supplied by Caldic. Butyl stannoic acid (>96.5%) was supplied by Chemtura. Soybean fatty acid (Radiacid® 121; ION 127-140 cg/g) and tall oil fatty acid (SYLFAT® FA2; ION 130 cg/g) were supplied by Oleon and Arizona Chemical, respectively. Methylcyclohexane (99.8%) was supplied by Möller Chemie. Acetone (99.9%) is supplied by Ineos. Byk® 028 is a defoamer supplied by Byk. Borchi® Oxy Coat 1101 (supplied by Borchers) is an organic metal compound (1% w/w solution in propane diol) wherein the metal of the metal cation of the organic metal compound is Fe (Borchi® Oxy Coat 1101 contains 800-1000 ppm of Fe) and it was used as a drier. Nuosperse® FX 610 (supplied by Elementis specialties) is a pigment dispersant with an active content of 25 wt %. Rheolate® 212 (supplied by Elementis Specialties) is a rheology modifier. Kronos® 2190 is a TiO.sub.2 white pigment supplied by Kronos. All the chemicals mentioned in this paragraph were used as supplied. Any other chemicals mentioned in the Examples and not explicitly mentioned in this paragraph, were supplied by Aldrich and they were used as supplied.

[0609] Glass plates of 3 mm in thickness (normal flat glass type, supplied by Boer Glas), Leneta Black Scrub Test Panels P121-10N.

2. Experimental Methods & Techniques

[0610] The acid value (AV) was determined titrimetrically according to ISO 2114. The AV is given as the mass of potassium hydroxide (KOH) in milligrams that is required to neutralize one gram of the tested substance and is used as a measure of the concentration of carboxyl groups present.

[0611] The oil length was calculated according to the equation shown in the section Definitions (see definition for the term ‘oil length’).

[0612] The number average molecular weight (M.sub.a) and the weight average molecular weight (M.sub.w) were determined via Gel Permeation Chromatography (GPC) calibrated with a set of polystyrene standards with a molecular weight range of from 162 up to 3.8×10.sup.6 Da, and using as eluent stabilized tetrahydrofuran (THF) modified with 0.5 (v/v %) acetic acid, 3 (v/v %) water and 0.1 (m/v %) LiBr, at a flow rate of 1 mL/min at 40° C. 50 mg of a resin dissolved in a suitable organic solvent e.g. acetone were diluted with 5 ml of eluent, and used for the measurement. The GPC measurements were carried out on a Waters Alliance system equipped with: i) a Waters Alliance 2414 refractive index detector at 40° C., and ii) a Waters Alliance 2695 separation module equipped with two consecutive PL-gel columns of Mixed-C type with 1/d=300/7.5 mm and filled with particles having a particle size of 20 micron (supplied by Agilent).

[0613] The polydispersity (D) was calculated according to the following equation: D=M.sub.w/M.sub.n.

[0614] The iodine number (ION) is determined according to the DIN 53241-1.

[0615] The chemical composition (mol %) of an OSAR or another alkyd resin can be determined by .sup.1H- and .sup.13C-NMR spectroscopy. The OSAR or the other alkyd resin is dissolved in a suitable deuterated organic solvent e.g. deuterated chloroform, once any other solvent(s) and/or water are removed from the OSAR or the other alkyd resin by for example drying in a vacuum oven.

[0616] Gloss measurements at 20° angle (reported in GU which stands for gloss units; (the GU scale of a glossmeter is based on a highly polished, reference black glass standard with a defined refractive index having a specular reflectance of 100 GU at 20° angle) were carried out with BYK micro-TRI-gloss glossmeter in accordance with the ASTM D523 89, on (cured) coatings which were derived upon curing under standard drying of films of 100 micron (1 micron=10.sup.−6 m) wet film thickness coated and cured on Leneta Black Scrub Test Panels P121-10N, within 1 h from the lapse of 24 h from their application. The higher the value of gloss20°, the glossier the coating.

[0617] The König hardness (reported in seconds) of the (cured) coatings was determined in accordance with the DIN 53157 [using a BYK pendulum hardness tester (Cat. No 5858] on (cured) coatings which were derived upon curing of films of 100-micron wet film thickness coated and cured on glass panels, within 1 h from the lapse of 24 h from their application. The higher the number of seconds, the higher the König hardness.

3. Example of Inventive Alkyd Resins (OSAR Series) and their Corresponding Emulsions (EM-OSAR Series)

3.1 Example 3.1: Preparation of the OSAR1

[0618] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 76.6 g of Ymer™ N120, 862.9 g of pentaerythritol, 946.3 g of benzoic acid, 134.3 g of SSIPA, and 1.75 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 210° C. whilst the water produced as the polycondensation reaction by-product, was being removed via distillation. The reaction mixture was maintained at 210° C. for as long as it was rendered transparent. Once the reaction mixture turned transparent, it was cooled down to 160° C. 762.7 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 174.9 g of tall oil fatty acids and 936.5 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 55 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.3 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the OSAR1 in order to afford a solution of the OSAR1 in acetone. This solution was discharged from the reactor and isolated.

[0619] A portion of the isolated acetone solution of the OSAR1 was used to characterize the OSAR1 by removing the acetone under vacuum evaporation.

[0620] The OSAR1 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 3.1EM: Preparation of the EM-OSAR1 (Emulsion of the OSAR1)

[0621] The inventive alkyd resin was emulsified (to 45% solids) as follows.

[0622] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 109.4 g of acetone were added to 435 g of the OSAR1 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.91 g of lithium hydroxide monohydrate. 415 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 47.6%, had a milky appearance and was stable (visual inspection by the completion of 2160 hours starting from the end of the preparation of the emulsion).

[0623] For use in a coating composition a sample was further diluted to 45% solids by adding demineralised water.

3.2 Example 3.2: Preparation of the OSAR7

[0624] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 92.5 g of Ymer™ N120, 1042 g of pentaerythritol, 1204 g of benzoic acid, 147.8 g of SSIPA, 0.8 g of lithium hydroxide monohydrate, and 2.1 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 185° C. Once the temperature reached 185° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 942.8 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 211.2 g of tall oil fatty acids and 996.1 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 60 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.9 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the OSAR7 in order to afford a solution of the OSAR7 in acetone. This solution was discharged from the reactor and isolated.

[0625] A portion of the isolated acetone solution of the OSAR7 was used to characterize the OSAR7 by removing the acetone under vacuum evaporation.

[0626] The OSAR7 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 3.2EM: Preparation of the EM-OSAR7 (Emulsion of the OSAR7)

[0627] The inventive alkyd resin was emulsified (to 45% solids) as follows.

[0628] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 109.4 g of acetone were added to 435 g of the OSAR7 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.91 g of lithium hydroxide monohydrate. 415 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 47.6%, had a milky appearance and was stable (visual inspection by the completion of 2160 hours starting from the end of the preparation of the emulsion).

[0629] For use in a coating composition a sample was further diluted to 45% solids by adding demineralised water.

3.3 Example 3.3: Preparation of the OSAR2

[0630] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 90.7 g of Ymer™ N120, 810.6 g of pentaerythritol, 258.6 g of trimethylolpropane, 941.5 g of benzoic acid, 159.1 g of SSIPA, 0.8 g of lithium hydroxide monohydrate, and 2.07 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 185° C. Once the temperature reached 185° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 971.6 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 217.4 g of tall oil fatty acids and 1164.5 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 55 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.4 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the OSAR2 in order to afford a solution of the OSAR2 in acetone. This solution was discharged from the reactor and isolated.

[0631] A portion of the isolated acetone solution of the OSAR2 was used to characterize the OSAR2 by removing the acetone under vacuum evaporation.

[0632] The OSAR2 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 3.3EM: Preparation of the EM-OSAR2 (Emulsion of the OSAR2)

[0633] The inventive alkyd resin was emulsified (to 45% solids) as follows.

[0634] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 150.5 g of acetone were added to 435 g of the OSAR2 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.66 g of lithium hydroxide monohydrate. 455 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 45.8%, had a milky appearance and was stable (visual inspection by the completion of 2160 hours starting from the end of the preparation of the emulsion).

[0635] For use in a coating composition a sample was further diluted to 45% solids by adding demineralised water.

3.4 Example 3.4: Preparation of the OSAR3

[0636] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 90.8 g of Ymer™ N120, 1023.5 g of pentaerythritol, 1122.4 g of benzoic acid, 159.4 g of SSIPA, 0.8 g of lithium hydroxide monohydrate, and 2.1 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 185° C. Once the temperature reached 185° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 915.7 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 207.4 g of tall oil fatty acids and 1110.8 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 55 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.5 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the OSAR3 in order to afford a solution of the OSAR3 in acetone. This solution was discharged from the reactor and isolated.

[0637] A portion of the isolated acetone solution of the OSAR3 was used to characterize the OSAR3 by removing the acetone under vacuum evaporation.

[0638] The OSAR3 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 3.4EM: Preparation of the EM-OSAR3 (Emulsion of the OSAR3)

[0639] The inventive alkyd resin was emulsified (to 45% solids) as follows.

[0640] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 260.4 g of acetone were added to 730 g of the OSAR3 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.67 g of lithium hydroxide monohydrate. 750 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 45.5%, had a milky appearance and was stable (visual inspection by the completion of 2160 hours starting from the end of the preparation of the emulsion).

[0641] For use in a coating composition a sample was further diluted to 45% solids by adding demineralised water.

3.5 Example 3.5: Preparation of the OSAR5

[0642] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 57.0 g of Ymer™ N120, 630.7 g of pentaerythritol, 722.5 g of benzoic acid, 73.7 g of SSIPA, 0.53 g of lithium hydroxide monohydrate, and 1.33 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 185° C. Once the temperature reached 185° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 601.7 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 132.8 g of tall oil fatty acids and 702.9 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 45 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 4.1 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the OSAR5 in order to afford a solution of the OSAR5 in acetone. This solution was discharged from the reactor and isolated.

[0643] A portion of the isolated acetone solution of the OSAR5 was used to characterize the OSAR5 by removing the acetone under vacuum evaporation.

[0644] The OSAR5 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 3.5EM: Preparation of the EM-OSAR5 (Emulsion of the OSAR5)

[0645] The inventive alkyd resin was emulsified (to 45% solids) as follows.

[0646] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 333.1 g of acetone were added to 480 g of the OSAR solution in acetone isolated previously in order to obtain an acetone solution of 43 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.67 g of lithium hydroxide monohydrate. 483 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 45.3%, had a milky appearance and was stable (visual inspection by the completion of 2160 hours starting from the end of the preparation of the emulsion).

[0647] For use in a coating composition a sample was further diluted to 45 solids by adding demineralised water.

3.6 Example 3.6: Preparation of the OSAR4

[0648] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 57.3 g of Ymer™ N120, 400.1 g of pentaerythritol, 255.2 g of dipentaerythritol, 816.2 g of benzoic acid, 100.4 g of SSIPA, 0.43 g of lithium hydroxide monohydrate, and 1.06 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N.sub.2 and under N.sub.2 flow the reaction mixture was stirred and heated up to 185° C. Once the temperature reached 185° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 463.2 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 143.8 g of tall oil fatty acids and 685.7 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 55 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.9 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the OSAR4 in order to afford a solution of the OSAR4 in acetone. This solution was discharged from the reactor and isolated.

[0649] A portion of the isolated acetone solution of the OSAR4 was used to characterize the OSAR4 by removing the acetone under vacuum evaporation.

[0650] The OSAR4 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 3.6EM: Preparation of the EM-OSAR4 (Emulsion of the OSAR4)

[0651] The inventive alkyd resin was emulsified (to 45% solids) as follows.

[0652] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 162.3 g of acetone were added to 400 g of the OSAR4 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.38 g of lithium hydroxide monohydrate. 428 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 45.2%, had a milky appearance and was stable (visual inspection by the completion of 2160 hours starting from the end of the preparation of the emulsion).

[0653] For use in a coating composition a sample was further diluted to 45% solids by adding demineralised water.

3.7 Example 3.7: Preparation of the OSAR6

[0654] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 61.1 g of Ymer™ N120, 667.6 g of pentaerythritol, 863.5 g of benzoic acid, 91.0 g of SSIPA, 0.54 g of lithium hydroxide monohydrate, and 1.35 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 185° C. Once the temperature reached 185° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 604.8 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 135.5 g of tall oil fatty acids and 423.7 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 55 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 5.5 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the OSAR6 in order to afford a solution of the OSAR6 in acetone. This solution was discharged from the reactor and isolated.

[0655] A portion of the isolated acetone solution of the OSAR6 was used to characterize the OSAR6 by removing the acetone under vacuum evaporation.

[0656] The OSAR6 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 3.7EM: Preparation of the EM-OSAR6 (Emulsion of the OSAR6)

[0657] The inventive alkyd resin was emulsified (to 45% solids) as follows.

[0658] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 137.6 g of acetone were added to 410 g of the OSAR6 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 1.37 g of 25% ammonia solution. 418 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 45.9%, had a milky appearance and was stable (visual inspection by the completion of 2160 hours starting from the end of the preparation of the emulsion).

[0659] For use in a coating composition a sample was further diluted to 45% solids by adding demineralised water.

4. Examples of Comparative Alkyd Resins (AR Series) and their Corresponding Emulsions (EM-AR Series)

4.1 Example 4.1: Preparation of the AR1

[0660] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 57 g of Ymer™ N120, 586.2 g of pentaerythritol, 472.8 g of benzoic acid, 160.6 g of SSIPA, and 2.2 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N.sub.2 and under N.sub.2 flow the reaction mixture was stirred and heated up to 210° C. whilst the water produced as the polycondensation reaction by-product, was being removed via distillation. The reaction mixture was maintained at 210° C. for as long as it was rendered transparent. Once the reaction mixture turned transparent, it was cooled down to 160° C. 485.4 g of phthalic anhydride were added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 113.2 g of tall oil fatty acids and 978.7 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 60 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 4.1 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the AR1 in order to afford a solution of the AR1 in acetone. This solution was discharged from the reactor and isolated.

[0661] A portion of the isolated acetone solution of the AR1 was used to characterize the AR1 by removing the acetone under vacuum evaporation. The AR1 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 4.1EM: Preparation of the EM-AR1 (Emulsion of the AR1)

[0662] The comparative alkyd resin was emulsified (to 45% solids) as follows. In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 85.4 g of acetone were added to 435 g of the AR1 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.35 g of lithium hydroxide monohydrate. 400 of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 45%, had a milky appearance and was stable (visual inspection by the completion of 240 hours starting from the end of the preparation of the emulsion).

4.2 Example 4.2: Preparation of the AR2

[0663] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 57.4 g of Ymer™ N120, 633.2 g of pentaerythritol, 731.3 g of benzoic acid, 53.8 g of SSIPA, and 1.3 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 210° C. whilst the water produced as the polycondensation reaction by-product, was being removed via distillation. The reaction mixture was maintained at 210° C. for as long as it was rendered transparent. Once the reaction mixture turned transparent, it was cooled down to 160° C. 614 g of phthalic anhydride were added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 128.3 g of tall oil fatty acids and 703.3 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 120 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 4 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the AR2 in order to afford a solution of the AR2 in acetone. This solution was discharged from the reactor and isolated.

[0664] A portion of the isolated acetone solution of the AR2 was used to characterize the AR2 by removing the acetone under vacuum evaporation. The AR2 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 4.2EM: Preparation of the EM-AR2 (Emulsion of the AR2)

[0665] An effort has been made to emulsify the comparative alkyd resin (to 45% solids) as follows.

[0666] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 145.6 g of acetone were added to 380 g of the AR2 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.51 g of lithium hydroxide monohydrate. 400 of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. By the completion of the removal of acetone the mixture had turned into an unworkable whitish semi-solid mass, failing to afford an emulsion.

[0667] The AR2 failed to provide an aqueous dispersion. Thus, no liquid (aqueous) coating composition and no coatings were prepared from the AR2.

4.3 Example 4.3: Preparation of the AR3

[0668] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 57.1 g of Ymer™ N120, 591.5 g of pentaerythritol, 479.3 g of benzoic acid, 92.1 g of SSIPA, 0.48 g of lithium hydroxide monohydrate, and 1.2 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 195° C. Once the temperature reached 195° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 529.2 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 119.9 g of tall oil fatty acids and 1030.4 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 55 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.8 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the AR3 in order to afford a solution of the AR3 in acetone. This solution was discharged from the reactor and isolated.

[0669] A portion of the isolated acetone solution of the AR3 was used to characterize the AR3 by removing the acetone under vacuum evaporation.

[0670] The AR3 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 4.3EM: Preparation of the EM-AR3 (Emulsion of the AR3)

[0671] The comparative alkyd resin was emulsified (to 45% solids) as follows. In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 300 g of acetone were added to 350 g of the AR3 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.32 g of lithium hydroxide monohydrate. 360 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared had a white appearance and was unstable (visual inspection by the completion of 48 hours starting from the end of the preparation of the emulsion).

4.4 Example 4.4: Preparation of the AR4

[0672] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 23.8 g of Ymer™ N120, 582.4 g of pentaerythritol, 484.5 g of benzoic acid, 126.0 g of SSIPA, 0.47 g of lithium hydroxide monohydrate, and 1.18 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 185° C. Once the temperature reached 185° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 497.5 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 118.0 g of tall oil fatty acids and 985.9 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 55 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.7 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the AR4 in order to afford a solution of the AR4 in acetone. This solution was discharged from the reactor and isolated.

[0673] A portion of the isolated acetone solution of the AR4 was used to characterize the AR4 by removing the acetone under vacuum evaporation.

[0674] The AR4 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 4.4EM: Preparation of the EM-AR4 (Emulsion of the AR4)

[0675] The comparative alkyd resin was emulsified (to 45% solids) as follows. In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 117 g of acetone were added to 400 g of the AR4 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. 393 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 45%, had a milky appearance and was stable (visual inspection by the completion of 240 hours starting from the end of the preparation of the emulsion).

4.5 Example 4.5: Preparation of the AR5

[0676] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 116.3 g of Ymer™ N120, 654.9 g of pentaerythritol, 844.1 g of benzoic acid, 41.9 g of SSIPA, 0.53 g of lithium hydroxide monohydrate, and 1.33 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 195° C. Once the temperature reached 195° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 627.8 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 132.7 g of tall oil fatty acids and 422.4 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 60 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.4 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the AR5 in order to afford a solution of the AR5 in acetone. This solution was discharged from the reactor and isolated.

[0677] A portion of the isolated acetone solution of the AR5 was used to characterize the AR5 by removing the acetone under vacuum evaporation.

[0678] The AR5 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 4.5EM: Preparation of the EM-AR5 (Emulsion of the AR5)

[0679] The comparative alkyd resin was emulsified (to 45% solids) as follows.

[0680] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 128.3 g of acetone were added to 401 g of the AR5 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and 400 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared was unstable (visual inspection by the completion of 48 hours starting from the end of the preparation of the emulsion).

4.6 Example 4.6: Preparation of the AR6

[0681] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 186.6 g of Ymer™ N120, 633.7 g of pentaerythritol, 816.8 g of benzoic acid, 41.9 g of SSIPA, 0.51 g of lithium hydroxide monohydrate, and 1.28 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 195° C. Once the temperature reached 195° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 617.7 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 128.4 g of tall oil fatty acids and 408.7 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 55 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.7 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the AR6 in order to afford a solution of the AR6 in acetone. This solution was discharged from the reactor and isolated.

[0682] A portion of the isolated acetone solution of the AR6 was used to characterize the AR6 by removing the acetone under vacuum evaporation.

[0683] The AR6 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 4.6EM: Preparation of the EM-AR6 (Emulsion of the AR6)

[0684] The comparative alkyd resin was emulsified (to 45% solids) as follows. In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 115.9 g of acetone were added to 405.5 g of the AR6 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.62 g of 25% ammonia solution. 395 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 68%, had a low viscosity and white colour and was unstable (visual inspection by the completion of 48 hours starting from the end of the preparation of the emulsion).

4.7 Example 4.7: Preparation of the AR7

[0685] A reaction vessel (reactor) equipped with a thermocouple, a nitrogen inlet, a mechanical stirrer and a distillation column was charged with 87.3 g of Ymer™ N120, 657.7 g of pentaerythritol, 850.5 g of benzoic acid, 130 g of SSIPA, 0.53 g of lithium hydroxide monohydrate, and 1.33 g of butyl stannoic acid (catalyst). Subsequently, the reactor was flashed with N2 and under N2 flow the reaction mixture was stirred and heated up to 185° C. Once the temperature reached 185° C., the distillation of water started; subsequently the reaction mixture was heated up to 210° C. At that point the reaction mixture became clear; once this happened the reaction mixture was cooled down to 160° C. 577.5 g of phthalic anhydride was added and afterwards the reaction mixture was heated up to 210° C. Subsequently a mixture of 133.3 g of tall oil fatty acids and 409.8 g of soybean fatty acids were dosed to the precursor resin over one hour making sure that the temperature did not exceed 210° C. After the dosing was completed the reaction mixture was heated up to 235° C.; at that point 55 g of methylcyclohexane (azeotropic agent) was introduced and the polyesterification reaction was conducted using azeotropic water removal (with methylcyclohexane) until an acid value of 3.7 mg KOH/g was obtained. The reaction mixture was then cooled down to 200° C. while vacuum was applied to remove the methylcyclohexane. Once the methylcyclohexane was removed, the reaction mixture was cooled down to room temperature and during this cooling down and already from a temperature of about 150° C. and up until about 50° C., an amount of acetone was added to the AR7 in order to afford a solution of the AR7 in acetone. This solution was discharged from the reactor and isolated.

[0686] A portion of the isolated acetone solution of the AR7 was used to characterize the AR7 by removing the acetone under vacuum evaporation.

[0687] The AR7 was isolated as a highly viscous liquid and its properties are shown in Table 1.

Example 4.7EM: Preparation of the EM-AR7 (Emulsion of the AR7)

[0688] The comparative alkyd resin was emulsified (to 45% solids) as follows.

[0689] In a glass reactor equipped with a nitrogen inlet, a mechanical stirrer and a distillation column, 84 g of acetone were added to 405 g of the AR7 solution in acetone isolated previously in order to obtain an acetone solution of 55 wt % solids. This solution was heated up to 45° C. and was neutralised with 0.47 g of 25% ammonia solution. 370 g of demineralised water were slowly added under stirring at 45° C. Subsequently, 0.22 g of Byk® 028 were added to the mixture, and the acetone was removed by vacuum distillation. The emulsion thus prepared, with a solids content of 45.0%, had a milky appearance and was stable (visual inspection by the completion of 240 hours starting from the end of the preparation of the emulsion).

5. Examples of Inventive Liquid (Aqueous) Coating Compositions (Series InvLC) and Comparative (Aqueous) Coating Composition (Series CompLC)

[0690] General Process (GP1)

[0691] A Getzman Dispermat Cowles dissolver was charged with:

a1. 5.30 parts of demineralized water,
b1. 0.30 parts of Byk® 028 (defoamer),
c1. 1.15 parts of Nuosperse® FX-610 (pigment dispersant),
d1. 0.95 parts of Rheolate® 212 (rheology modifier), and
e1. 22.65 parts of Kronos® 2190 (TiO.sub.2 white pigment).
This mixture was mixed up until a fineness—which was determined according to ISO 1524—of <10-micron Hegman was reached. The mixture with a fineness of <10-micron Hegman, is referred as Mixture A.

[0692] A propeller mixer Janke & Kunkel RW20 DZM with three-blade propeller was charged with:

a2. 9.88 parts of demineralized water,
b2. 30.35 parts of Mixture A,
c2. 56.12 parts of an emulsion of 45% solids (corresponding to 25.25 parts of a solid alkyd resin),
d2. 3.35 parts of Rheolate® 212 (rheology modifier), and
e2. 0.30 parts of Borchi® Oxy-Coat 1101 (Fe-drier).

[0693] This mixture was mixed for a total of 5 minutes to produce a liquid (aqueous) coating composition which was either inventive or comparative depending on the c2.

Example 5.1: Preparation of the Inventive Liquid (Aqueous) Coating Composition InvLC1

[0694] The general process (GP1) disclosed above was used to prepare the inventive liquid (aqueous) coating compositions:

InvLC1 using as c2 the EM-OSAR1,
InvLC2 using as c2 the EM-OSAR2,
InvLC3 using as c2 the EM-OSAR3,
InvLC4 using as c2 the EM-OSAR4,
InvLC5 using as c2 the EM-OSAR5,
InvLC6 using as c2 the EM-OSAR6,
InvLC7 using as c2 the EM-OSAR7.

Example 5.1a: Preparation of the Comparative Liquid (Aqueous) Coating Composition CompLC1

[0695] The general process (GP1) disclosed above was used to prepare the comparative liquid (aqueous) coating compositions:

CompLC1 using as c2 the EM-AR1,
CompLC4 using as c2 the EM-AR4,
CompLC7 using as c2 the EM-AR7.

6. Examples of Inventive Coatings (Series InvCR-LC) and Comparative Coatings Series (CompCR-LC Series)

[0696] The comparative liquid (aqueous) coating compositions (CompLC1, CompLC4 and CompLC7) and the inventive paint composition (InvLC1-InvLC7) were used to prepare coatings according to the following general process (GP2): an amount of each of the comparative or inventive liquid (aqueous) coating composition was applied on:

[0697] i) a glass plate [intended for the determination of the König hardness (KH)], and

[0698] ii) on a Leneta Black Scrub Test Panel P121-10N (intended for the determination of the gloss20°), using a Bird Film Applicator® with a slit of 100 micron, to afford uncured (‘wet’) films which were comparative or inventive depending on the liquid (aqueous) coating composition used to prepare them.

[0699] The wet films thus prepared were left to cure and dry under standard curing conditions, for a total time period of 24 h starting from the point in time these films were applied on the above-mentioned substrates, to ultimately afford the comparative (cured) coatings CompCR-LC1, CompCR-LC4 and CompCR-LC7; and the inventive (cured) coatings InvCR-LC1, InvCR-LC2, InvCR-LC3, InvCR-LC4, InvCR-LC5, InvCR-LC6, and InvCR-LC7. The film thickness of any one of the comparative and inventive (cured) coatings after 24 h of drying was estimated to be 25±5 micron.

[0700] The König hardness and the gloss20° were determined within 1 hour from the completion of the 24 h of drying.

[0701] The balance of KH and gloss20° (BKHG) was calculated as mentioned in the specification from the individual recorded values of KH and gloss20° for each of the paint compositions.

[0702] The Table 2 presents the results of the BKHG, along with those of KH and gloss20°.

TABLE-US-00001 TABLE 1 The inventive alkyd resins (OSAR) and the comparative alkyd resins (AR): composition and characterization. Polycondensed residue of OSAR1 OSAR2 OSAR3 OSAR4 OSAR5 OSAR6 OSAR7 POC (% mol) pentaerythritol 26.6 28.3 26.6 23 25.8 26.6 26.5 PAC (% mol) phthalic anhydride 21.9 23.6 21.9 18.2 22.7 22.1 22.1 MAC (% mol) benzoic acid 32.5 27.8 32.5 39.0 33.0 38.3 34.2 FAC (% mol) mixture of tall oil fatty acid & 16.6 21.9 16.6 17.3 16.6 10.8 14.9 soyabean oil fatty acid IOC (% mol) 5-(sulfo)isophtalic acid sodium salt 2.1 2.1 2.1 2.2 1.5 1.8 1.9 PALC (% mol) polyethylene glycol (Ymer ™ N120) 0.32 0.33 0.32 0.33 0.32 0.33 0.32 S.sub.1 (see claim 1) 51.5 52.1 51.5 58.8 51.4 51.3 51.3 R.sub.1 (see claim 1) 2.0 1.27 1.96 2.25 1.99 3.55 2.29 R.sub.2 (see claim 1) 0.15 0.11 0.15 0.15 0.11 0.20 0.15 R.sub.3 (see claim 1) 169 157 169 171 175 183 175 Oil length (%) 32.5 34 32.5 32.5 32.7 22.6 29.8 AV (mg KOH/g) 3.1 3.0 3.1 2.8 2.7 4.9 3.5 M.sub.n (Da) 2510 2835 2771 2495 2922 2369 2659 M.sub.w (Da) 68500 61754 56905 25627 49323 45889 41365 D (=M.sub.w/M.sub.n) 27.3 21.8 20.5 10.3 16.9 19.4 15.6 Polycondensed residue of AR1 AR2 AR3 AR4 AR5 AR6 AR7 POC (% mol) pentaerythritol 26.6 25.8 26.6 26.7 26.4 26.2 26.5 PAC (% mol) phthalic anhydride 20.2 23 21.9 20.9 23.3 23.5 21.4 MAC (% mol) benzoic acid 23.9 33.3 24.0 24.7 37.9 37.6 38.3 FAC (% mol) mixture of tall oil fatty acid & 25.2 16.4 25.1 24.6 10.9 10.8 10.7 soyabean oil fatty acid IOC (% mol) 5-(sulfo)isophtalic acid sodium salt 3.7 1.1 2.1 2.9 0.9 0.9 2.7 PALC (% mol) polyethylene glycol (Ymer ™ N120) 0.35 0.32 0.35 0.15 0.64 1.05 0.48 S.sub.1 (see claim 1) 53.1 51.1 51.5 52.4 50.3 3.5 52.1 R.sub.1 (see claim 1) 0.95 2.0 0.96 1.01 3.49 3.49 3.59 R.sub.2 (see claim 1) 0.16 0.09 0.10 0.13 0.14 0.18 0.29 R.sub.3 (see claim 1) 125 176 132 308 96 58 124 Oil length (%) 44.7 32.5 44.9 44.5 22.4 21.7 21.9 AV (mg KOH/g) 3.4 2.1 2.6 3.1 2.6 2.9 2.7 M.sub.n (Da) 2980 3480 3264 2981 2344 2338 2393 M.sub.w (Da) 124700 78800 54789 37978 20553 17273 49201 D (=M.sub.w/M.sub.n) 41.8 22.6 16.8 12.7 8.8 7.4 20.6

TABLE-US-00002 TABLE 2 The inventive and the comparative coatings their properties & characterization (for convenience it contains also the references to their corresponding alkyd resins, emulsions, and liquid coating compositions) Alkyd Resin OSAR1 OSAR2 OSAR3 OSAR4 OSAR5 OSAR6 OSAR7 Emulsion EM-OSAR1 EM-OSAR2 EM-OSAR3 EM-OSAR5 EM-OSAR4 EM-OSAR6 EM-OSAR7 Liquid (Aqueous) Coating Composition InvLC1 InvLC2 InvLC3 InvLC4 InvLC5 InvLC6 InvLC7 Coating Property & Characterization InvCR-LC1 InvCR-LC2 InvCR-LC3 InvCR-LC4 InvCR-LC5 InvCR-LC6 InvCR-LC7 BKHG (GU .Math. s) 1218  1116  1222  1369  1575  1260  1380  BKHG (Excellent or Poor) Excellent Excellent Excellent Excellent Excellent Excellent Excellent Gloss20° (GU) 29 36 26 37 35 15 23 KH (s) 42 31 47 37 45 84 60 KH (Good or Poor) Good Good Good Good Good Good Good Alkyd Resin AR1 AR2 AR3 AR4 AR5 AR6 AR7 Emulsion EM-AR1 n.p.p Unstable EM-AR4 Unstable Unstable EM-AR7 Liquid (Aqueous) Coating Composition CompLC1 n.p.p n.p. CompLC4 n.p. n.p. CompLC7 Coating Property & Characterization CompCR-LC1 n.p.p n.p. CompCR-LC4 n.p. n.p. CompCR-LC7 BKHG (GU .Math. s) 528  n.a. n.p. 713  n.p. n.p. 948  BKHG (Excellent or Poor) Poor n.a. n.p. Poor n.p. n.p. Poor Gloss20° (GU) 22 n.a. n.p. 23 n.p. n.p. 12 KH (s) 24 n.a. n.p. 31 n.p. n.p. 79 KH (Good or Poor) Poor n.a. n.p. Good n.p. n.p. Good n.p.p: not possible to prepare (because it was not possible to even prepare an emulsion). n.p.: not prepared (because the emulsion was unstable). BKHG: balance of KH and gloss20° (BKHG = KH × gloss20°) KH: könig hardness

[0703] The object of the invention was to provide for coatings which are prepared from aqueous coating compositions comprising a stable aqueous dispersion or a stable emulsion of oxidizing alkyd resins, the coatings having at least an excellent balance of König hardness (KH) and gloss20° with the proviso that the coatings maintain also a good König hardness and a gloss20° of at least 5.

[0704] By the term ‘good König hardness’ (referring to a coating) is meant in the specification that the König hardness (KH)—as this is determined as disclosed in the specification—is at least 25 s, preferably at least 27 s, more preferably at least 29 s.

[0705] By the term ‘poor König hardness’ (referring to a coating) is meant in the specification that the König hardness (KH)—as this is determined as disclosed in the specification—is lower than 25 s.

[0706] By the term ‘balance of König hardness (KH) and gloss20° ’ (referring to a coating) (abbreviated as BKHG) is meant in the specification the multiplication product of the KH and gloss20° values of a coating—as each of KH and gloss20° is determined in the specification-. In other words, the BKHG of a coating is calculated by the following equation:

BKHG=KH×gloss20°

[0707] By the term ‘excellent balance of König hardness (KH) and gloss20° ’ (referring to a coating) is meant in the specification that the BKHG is at least 1000, preferably at least 1050, more preferably at least 1100 GU.Math.s (wherein ‘GU’ represents gloss unit—as defined in the specification, and ‘s’ represents second).

[0708] By the term ‘poor balance of König hardness (KH) and gloss20° ’ (referring to a coating) is meant in the specification that the BKHG is lower than 1000 GU.Math.s.

[0709] Each of the comparative alkyd resins AR1 to AR7 either failed to even produce an emulsion (case of the AR2), or failed to produce a stable emulsion (case of the AR3, AR5 and AR6), or failed to afford coatings having at least an excellent balance of König hardness (KH) and gloss20° with the proviso that the coatings maintain also a good König hardness and a gloss20° of at least 5 (case of the AR1, AR4 and AR7). The comparative coating CompCR-LC1 had a poor balance of KH and gloss20° (poor BKHG), and a poor KH. Each of the comparative coatings CompCR-LC4 and CompCR-LC7 had a poor balance of KH and gloss20° (poor BKHG).

[0710] It was surprisingly found that the object of the invention was achieved only by an oxidizing, ionic and short oil alkyd resin (OSAR) as disclosed in the specification. The inventive coatings (InvCR-LC1 to InvCR-LC7) prepared from the aqueous coating compositions comprising a surprisingly stable emulsion of the OSAR of the invention, had surprisingly an excellent balance of König hardness (KH) and gloss20° (excellent BKHG) and at the same time surprisingly maintained also a good KH and a gloss20° of at least 5.