Resin, composition and use

Abstract

The present invention relates to an alkyd resin comprising the condensation product of at least the following components (A) a polybasic acid, (B) a polyhydric alcohol, and (C) a linear C.sub.12-C.sub.60 hydrocarbo monocarboxylic acid, and optionally (D) at least one component other than any of components A to C characterized in that at least a part of the polybasic acid (A) is a (optionally hydrogenated) Diels Alder adduct of citraconic acid with C.sub.4-C.sub.14 conjugated diene, a (optionally hydrogenated) Diels Alder adduct of citraconic anhydride with C.sub.4-C.sub.14 conjugated diene, a half ester of such a Diels Alder adduct and/or a diester of such a Diels Alder adduct.

Claims

1. An alkyd resin comprising the condensation product of at least the following components: (A) a polybasic acid, (B) a polyhydric alcohol, and (C) a linear C12-C60 hydrocarbo monocarboxylic acid, and optionally (D) at least one component other than the components (A) to (C), wherein at least a part of the polybasic acid (A) is a Diels Alder adduct of citraconic acid or citraconic anhydride with a C4-C14 conjugated diene, a half ester of the Diels Alder adduct and/or a diester of the Diels Alder adduct, and wherein the alkyd resin is free of rosin.

2. The alkyd resin according to claim 1, wherein the Diels Alder adduct is hydrogenated.

3. The alkyd resin according to claim 1, wherein the Diels Alder adduct is present in the alkyd resin in an amount of at least 25 wt. %, relative to total weight of the polybasic acid present in the alkyd resin.

4. The alkyd resin according to claim 1, which comprises is from 10 to 50% by weight of component (A), from 10 to 40% by weight of component (B), and from 1 to 80% by weight of component (C), wherein components (A) to (C) and optionally component (D) are present in a total amount of 100 wt. %.

5. The alkyd resin as claimed in claim 1, wherein component (C) is a fatty acid or a mixture of fatty acids.

6. The alkyd resin as claimed in claim 5, wherein the fatty acid comprises at least one double bond.

7. The alkyd resin as claimed in claim 5, wherein the fatty acids are obtained from natural sources selected from the group consisting of soyabean fatty acids, sunflower fatty acids, tall oil fatty acids, and linseed oil fatty acids.

8. The alkyd resin as claimed in claim 1, wherein component (B) is a polyalcohol with at least three hydroxyl groups selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, mannitol, sorbitol, sorbitan and mixtures thereof.

9. The alkyd resin as claimed in claim 1, wherein the component (A) comprises a polybasic acid selected from the group consisting of phthalic acid, maleic acid, fumaric acid, azelaic acid, succinic acid, itaconic acid, adipic acid, sebacic acid, furandicarboxylic acid, trimellitic acid, pyromellitic acid and mixtures thereof.

10. The alkyd resin as claimed in claim 1, wherein the C4-C14 conjugated diene is a conjugated diene that does not contain carboxylic acid functionality is selected from the group consisting of 1,3-butadiene, isoprene, terpenes containing conjugated double bonds and mixtures thereof.

11. The alkyd resin as claimed in claim 10, wherein the C4-C14 conjugated diene is myrcene and/or phellandrene.

12. The alkyd resin as claimed in claim 1, wherein the C4-C14 conjugated diene is isoprene, myrcene and/or limonene, and wherein the diene is treated with isomerization catalyst.

13. The alkyd resin as claimed in claim 1, wherein component (A) comprises a phthalic acid monomer in an amount which is lower than 25 wt. % relative to total weight amount of alkyd resin.

14. The alkyd resin as claimed in claim 1, wherein component (A) comprises an amount lower than 15 wt. %, relative to total weight of the alkyd resin, of a Diels Alder adduct of a conjugated diene and maleic acid and a Diels Alder adduct of a conjugated diene and maleic acid anhydride.

15. The alkyd resin as claimed in claim 1, wherein the alkyd resin is solvent borne or a solid.

16. A water borne alkyd emulsion comprising the alkyd resin as claimed in claim 1 and optionally at least one surfactant added either during or after the reaction of Components (A) to (D).

17. A process for preparing the alkyd resin as claimed in claim 1 comprising the steps of: (a) preparing the Diels Alder adduct; (b) optionally hydrogenating the Diels Alder adduct; and (c) reacting the Diels Alder adduct obtained in step (a) or the hydrogenated Diels Alder adduct obtained in step (b) directly after preparation or alternatively after collection and isolation in an esterification step with an alkyd prepolymer to form the alkyd resin.

18. A process for preparing the alkyd resin as claimed in claim 1, wherein the process comprises the steps of: (a) preparing the Diels Alder adduct; (b) optionally hydrogenating the Diels Alder adduct; and (c) reacting, in a (trans)esterification step, the Diels Alder adduct obtained in step (a) or the hydrogenated Diels Alder adduct obtained in step (b) directly after preparation or alternatively after collection and isolation with components (B), (C) and (D) and optionally with and additional polybasic acid of component (A) to form the alkyd resin.

19. A coating composition comprising the alkyd resin as claimed in claim 1.

20. A substrate or article having coated thereon the coating composition as claimed in claim 19.

21. A method for preparing a coated substrate or article comprising the steps of: (i) applying the coating composition as claimed in claim 19 onto a substrate or article; (ii) optionally drying the composition in situ; and/or (iii) optionally curing the composition in situ.

Description

EXAMPLES AND COMPARATIVE EXPERIMENTS

Example 1a

DMTHPA

(1) The adduct of isoprene and citraconic anhydride was prepared by mixing the monomers (isoprene in 5% excess) with 250 ppm hydroquinone in a stirred pressure reactor and heating to 85 C. for 12 hours. After a distillation step about 92% product was isolated as a mobile liquid and identified as a mixture of 2 isomers of dimethyl tetrahydrophthalic anhydride (DMTHPA) by H NMR. Purity was estimated 99.8% by GC.

Example 1b

Alkyd Resin from DMTHPA

(2) An alkyd resin was prepared by reacting 35.0 grams of DMTHPA prepared according to example 1a, 26.6 grams of pentaerythritol, 16.5 grams of benzoic acid and 37.1 grams of soyabean fatty acids at max 230 C. Esterification was conducted using azeotropic water removal until acid value below 15 mgKOH/g. The resin was cooled down, diluted in xylene and poured out. Resin properties are shown in table 1.

Comparative Examples Comp A to C

(3) A comparative alkyd resin A was prepared by reacting 168.2 grams of phthalic anhydride (PA), 155.4 grams of pentaerythritol, 96.2 grams of benzoic acid and 217 grams of soyabean fatty acids at max 230 C. Esterification was conducted by azeotropic water removal until acid value below 15 mgKOH/g. The resin was cooled down, diluted in xylene and poured out.

(4) Comparative resins B and C respectively were produced by replacing phthalic anhydride on a molar basis in the method described in comparative example A above with respectively tetrahydro phthalic anhydride (THPA) or Methyl tetrahydrophthalic anhydride (MTHPA). MTHPA is produced by Polynt SpA. Resin properties are shown in table 1.

Example 2a

DMHHPA

(5) DMTHPA prepared according to example 1a was hydrogenated using a supported palladium catalyst in a stirred pressure reactor to yield dimethylhexahydro phthalic anhydride (DMHHPA). H NMR showed conversion of the CC double bond, GC showed presence of 4 compounds being formed and mass spectrometry (using chemical ionization) showed that the MW of all 4 peaks is 182 (MW of Diels-Alder adduct starting material is 180). Further fragmentation pattern of all 4 peaks (using electron impact) indicated they are all isomers/diastereomers.

Example 2b

Alkyd Resin from DMHHPA

(6) An alkyd resin was prepared by reacting 45.6 grams of DMHHPA prepared according to example 2a, 34 grams of pentaerythritol, 21.1 grams of benzoic acid and 47.5 grams of soyabean fatty acids at max 230 C. Esterification was conducted using azeotropic water removal until acid value below 15 mgKOH/g. The resin was cooled down, diluted in xylene and poured out. Resin properties are shown in table 1.

Comparative Examples Comp D and E

(7) Comparative resins D and E respectively were produced by replacing phthalic anhydride on a molar basis in the method described in comparative example A above with respectively hexahydro phthalic anhydride (HHPA) or Methyl hexahydrophthalic anhydride (MHHPA). MHHPA is produced by Polynt SpA. Resin properties are shown in table 1.

Example 3a

Citraconic AnhydrideMyrcene Adduct

(8) The adduct of myrcene and citraconic anhydride was prepared by mixing the monomers in equivalent amounts at room temperature in a stirred reactor and heating to 180 C. for 2 hours. After a distillation step about 97% product was isolated as a slightly yellow mobile liquid of which identity was confirmed by H NMR.

Example 3b

Alkyd Resin from Citraconic AnhydrideMyrcene Adduct

(9) An alkyd resin was prepared by reacting 234 grams of adduct prepared according to example 3a, 137.7 grams of pentaerythritol, 80.1 grams of benzoic acid and 230.6 grams of soyabean fatty acids at max 240 C. Esterification was conducted using azeotropic water removal until acid value below 15 mgKOH/g. The resin was cooled down, diluted in xylene and poured out. Resin properties are shown in table 1.

Example 4a

Alkyd Resin from DMTHPA Adduct

(10) An alkyd resin was prepared by reacting 227.4 grams of adduct prepared according to example 1a, 170.5 grams of pentaerythritol, 105.6 grams of benzoic acid and 238.2 grams of soyabean fatty acids at max 240 C. Esterification was conducted using azeotropic water removal until acid value below 12 mgKOH/g. The resin was cooled down, and it was diluted with xylene. The resin was poured out.

Example 5a

Alkyd Resin from DMHHPA

(11) An alkyd resin was prepared by reacting 513 grams of adduct prepared according to example 2a, 361 grams of pentaerythritol, 178 grams of benzoic acid and 532 grams of soyabean fatty acids at max 250 C. Esterification was conducted using azeotropic water removal until acid value below 12 mgKOH/g. The resin was cooled down, and xylene was removed by vacuum distillation. The resin was poured out and used in example 5b.

Example 5b

Emulsion Resin from DMHHPA

(12) 302 grams of the solid resin from example 6a were emulsified as follows. The resin was heated to between 50-80 C. and 51 grams of a 30% solution of a highly branched alcohol based surfactant combining anionic and non-ionic components and 14 grams of demineralised water were added. The mixture was neutralised with a non-amine base and was stirred until homogeneous. Demineralised water was added during 2 hours until a solids content of 53% was obtained. The emulsion showed a milky appearance and was stable.

Example 6a

Alkyd Resin from Citraconic AnhydrideMyrcene Adduct

(13) An alkyd resin was prepared by reacting 351 grams of adduct prepared according to example 3a, 200 grams of pentaerythritol, 116 grams of benzoic acid and 335 grams of soyabean fatty acids at max 240 C. Esterification was conducted using azeotropic water removal until acid value below 12 mgKOH/g. The resin was cooled down, and xylene was removed by vacuum distillation. The resin was poured out and used in example 6b.

Example 6b

Emulsion Resin from Citraconic AnhydrideMyrcene Adduct

(14) 348 grams of the solid resin from example 6a were emulsified as follows. The resin was heated to between 50-80 C. and 59 grams of a 30% solution of a highly branched alcohol based surfactant combining anionic and non-ionic components and 25 grams of demineralised water were added. The mixture was neutralised with a non-amine base and was stirred until homogeneous. Demineralised water was added during 2 hours until a solids content of 51% was obtained. The emulsion showed a milky appearance and was stable.

Comparative examples Comp F and G

(15) A comparative adduct F was prepared using maleic anhydride and myrcene with the process of example 3a.

(16) A comparative alkyd resin G was prepared by replacing Citraconic anhydridemyrcene adduct on a molar basis in the method described in example 3b above with Maleic anhydridemyrcene adduct F. Resin properties are shown in table 1.

Comparative Example Comp H

(17) A resin containing rosincitraconic anhydride adduct as exemplified in WO2013/167662 was prepared as follows: 400 g of tall oil fatty acids, 450 g of tall rosin and 114 g of itaconic acid were charged to a reactor fitted with thermocouple, stirrer, nitrogen flow and Dean-Stark trap, and heated to 180 C. After 2 hours the reactor was cooled to 120 C. and 175 g of glycerol were charged to the reactor. The reactor was heated to 250 C. under xylene reflux conditions and the distillation was stopped when the acid value reached 10 mg KOH/g resin. The reactor was then cooled to 180 C. and vacuum distillation was started for removal of xylene azeotropic solvent. After cooling down to below 100 C. the resin was poured out. Resin properties are shown in table 1.

Comparative Example Comp J

(18) A resin containing rosincitraconic anhydride adduct as exemplified in WO2013/167662 was prepared as follows: 536 g of tall oil fatty acids, 203 g of tall rosin and 183 g of itaconic acid were charged to a reactor fitted with thermocouple, stirrer, nitrogen flow and Dean-Stark trap, and heated to 180 C. After 2 hours the reactor was cooled to 120 C. and 184 g of glycerol were charged to the reactor. The reactor was heated to 250 C. under xylene reflux conditions and the distillation was stopped when the acid value reached 15 mg KOH/g resin. The reactor was then cooled to 180 C. and vacuum distillation was started for removal of xylene azeotropic solvent. After cooling down to below 100 C. the resin was poured out. Resin properties are shown in table 1.

Comparative Example Comp K

Emulsion Resin

(19) Comparative emulsion K was prepared as follows: A sample of comparative alkyd resin Comp A was freed of xylene by distillation and used in the preparation procedure exemplified in Example 6b. The resulting emulsion had a solids content of 53%, showed a milky appearance and was stable.

(20) TABLE-US-00001 TABLE 1 Resin characteristics Acid value Mn Mw Example Resin based on: mgKOH/g Da kDa 1b DMTHPA 6 2760 12 2b DMHHPA 14 2310 9 3b Myrcenecitraconic anhydride 10 2960 20 adduct 4a DMTHPA 10 2980 36 5a DMHHPA 11 3700 40 6a Myrcenecitraconic anhydride 9 2960 16 adduct, oil length 40% Comp A PA 15 3050 19 Comp B THPA 11 3810 189 Comp C MTHPA 14 3150 40 Comp D HHPA 14 3140 26 Comp E MHHPA 13 3130 21 Comp G Myrcenemaleic anhydride adduct 12 3420 85 Comp H Rosincitraconic anhydride 8 1760 26 adduct, oil length 40% Comp J Rosincitraconic anhydride 16 1970 105 adduct, oil length 66%

Example 7

Paints

(21) Paints were produced by mixing in a Cowless dissolver resin solution (44 grams solid resin), 28 grams of Tioxide TR 92 (pigment) and 0.30 grams of Nuosperse FA 601 (dispersant) and milling them into a mill paste. To this paste were added under stirring 0.31 grams Borchi-Oxy-Coat (iron drier), 0.70 grams Calcium naphthenate (calcium drier), 1.83 grams Octasoligen Zirconium 12 (zirconium drier), 0.3 grams Borchinox M2 (antiskinning agent) and xylene to give application viscosity.

(22) These paints showed the following properties (table 2).

(23) TABLE-US-00002 Paint Paint A1 Paint B1 Paint C1 Ex 7 Example resin used in paint Comp A Comp B Comp C Ex 1b Resin based on: PA THPA MTHPA DMTHPA Cotton wool drying, 100 m wet dust free time (hr:min) 0.25 0.47 1.02 1.01 tack free time (hr:min) 2.25 2.17 4.02 4.01 Knig Hardness in sec, 100 m wet 1 day 31 19 19 20 7 days 49 34 28 48 14 days 66 40 40 63 28 days 77 45 59 87 Yellowing in the dark, 100 m wet b* Initial 2.11 2.21 2.47 2.42 db* after 14 days 50 C. 1.32 2.05 1.43 0.78 db* after 21 days 50 C. 1.87 3.16 2.04 1.13

(24) The results show that the paint (Example 7) formulated with a resin of the invention (Example 1b prepared from DMTHPA monomer (adduct of myrcene and citraconic anhydride) according to the inventionExample 1a) shows better final hardness and yellowing results in comparison with prior art Paints A1, B1 and C1 respectively formulated from comparative resins Comp A, B and C. Interestingly Example 7 is a better paint than Paint A1 prepared using a resin (Comp A) made from a phtalic anhydride PA monomer, having much better yellowing and comparable hardness development and even better final hardness. Furthermore it is particularly surprising that Example 7 also has much better properties than Paints B1 and C1 formulated from resins prepared from monomers of respectively THPA (Comp B) and MTHPA (Comp C), which are maleic anhydride based analogues of DMTHPA.

Example 8

Paints

(25) Paints were produced by mixing in a Cowless dissolver resin solution (44 grams solid resin), 28 grams of Tioxide TR 92 (pigment) and 0.30 grams of Nuosperse FA 601 (dispersant) and milling them into a mill paste. To this paste were added under stirring 0.31 grams Borchi-Oxy-Coat (iron drier), 0.70 grams Calcium naphthenate (calcium drier), 1.83 grams Octasoligen Zirconium 12 (zirconium drier), 0.3 grams Borchinox M2 (antiskinning agent) and xylene to give application viscosity.

(26) These paints showed the following properties (table 3).

(27) TABLE-US-00003 Paint Paint A2 Paint D1 Paint E1 Ex 8 Example resin used in paint Comp A Comp D Comp E Ex 2b Resin based on: PA HHPA MHHPA DMHHPA Cotton wool drying, 100 m wet dust free time (hr:min) 0:19 0:43 0:31 1:40 tack free time (hr:min) 4:57 5:21 5:04 5:19 Knig Hardness in sec, 100 m wet 1 day 33 19 23 24 7 days 49 28 34 40 14 days 63 40 49 54 28 days 65 42 52 55 Yellowing in the dark, 100 m wet b* Initial 2.35 2.27 2.08 2.42 db* after 14 days 50 C. 1.29 0.96 1.04 1.17 db* after 21 days 50 C. 1.51 1.25 1.27 1.31

(28) The results show that the paint (Example 8) formulated with a resin of the invention (Example 2b prepared from DMHHPA monomer (hydrogenated adduct of myrcene and citraconic anhydride) according to the inventionExample 2a) shows better hardness development results in comparison with prior art Paints D1 and E1 respectively formulated from comparative resins Comp D and E. Whereas all hydrogenated monomers (HHPA, MHHPA and DMHHPA) result in less yellowing paints compared to Paint A2 prepared using a resin (Comp A) made from a PA monomer, it is particularly surprising that Example 8 also has better hardness properties than Paints D1 and E1 formulated from resins prepared from monomers of respectively HHPA (Comp D) and MHHPA (Comp E), which are maleic anhydride based analogues of DMHHPA.

Example 9

Paints

(29) Paints were produced by mixing in a Cowless dissolver resin solution (44 grams solid resin), 28 grams of Tioxide TR 92 (pigment) and 0.30 grams of Nuosperse FA 601 (dispersant) and milling them into a mill paste. To this paste were added under stirring 0.31 grams Borchi-Oxy-Coat (iron drier), 0.70 grams Calcium naphthenate (calcium drier), 1.83 grams Octasoligen Zirconium 12 (zirconium drier), 0.3 grams Borchinox M2 (antiskinning agent) and xylene to give application viscosity.

(30) These paints showed the following properties (table 4).

(31) TABLE-US-00004 Paint Ex Paint Paint Paint Paint A3 9 G1 H1 J1 Example resin used Comp Ex Comp Comp Comp in paint A 3b G H J Resin based on: PA CA- MA- CA- CA- Myrcene Myrcene Rosin Rosin Cotton wool drying, 100 m wet dust free time (hr:min) 0:19 2:30 1:38 3:00 2:30 tack free time (hr:min) 4:57 6:24 4:49 >8:00 5:30 Knig Hardness in sec, 100 m wet 1 day 33 20 19 39 13 7 days 49 56 52 88 11 14 days 63 91 94 115 14 28 days 65 109 112 124 17 Yellowing in the dark, 100 m wet b* Initial 2.35 2.59 2.65 5.31 3.78 db* after 14 days 50 C. 1.29 2.25 2.70 4.40 4.71 db* after 21 days 50 C. 1.51 2.56 3.27 5.68 6.87

(32) The results show that the paint (Example 9) formulated with a resin of the invention (Example 3b prepared from a citraconic anhydrideMyrcene adduct of the invention Example 3a) shows comparable hardness development and much better yellowing results in comparison with prior art Paint G1 formulated from comparative resin Comp G. The paint of the invention also shows (at equal or better hardness) much better yellowing results in comparison with prior art paints H1 and J1 formulated from prior art resins Comp H and Comp J based on patent publication WO2013/167662. Furthermore example 9 is a better paint than Paint A3 prepared using a resin (Comp A) made from a phtalic anhydride PA monomer, having much better hardness development.

Examples 10-12

Paints

(33) Paints were produced by mixing in a Cowless dissolver resin solution (44 grams solid resin), 28 grams of Tioxide TR 92 (pigment) and 0.30 grams of Nuosperse FA 601 (dispersant) and milling them into a mill paste. To this paste were added under stirring 0.31 grams Borchi-Oxy-Coat (iron drier), 0.3 grams Exkin 2 (antiskinning agent) and xylene to give application viscosity.

(34) These paints showed the following properties (table 5).

(35) TABLE-US-00005 Paint Paint A4 Ex 10 Ex 11 Ex 12 Resin from example: Comp A 4a 5a 6a Drying Dust free time (hrs:min) 0:18 1:04 1:05 3:33 Drying Tack free time (hrs:min) 5:23 8:00 7:05 7:33 Knig Hardness 1 day 27 10 23 14 Knig Hardness 7 days 54 56 53 48 Knig Hardness 14 days 65 69 62 76 Knig Hardness 28 days 73 86 66 102 Yellowing in the dark, 150 m wet b* Initial 2.38 2.27 2.08 2.67 b* after 14 days 50 C. 1.13 0.75 0.95 2.64 b* after 21 days 50 C. 1.50 1.04 1.28 3.24

(36) The results in table 5 show that the paints formulated with resins of the invention (Examples 10 to 12) show either better final hardness or better yellowing results (or both) in comparison with prior art Paint A4 formulated from comparative resin Comp A, just as was found above for Examples 8 and 9 respectively.

Examples 13-14

Emulsion Paints

(37) A paste was produced by mixing in a Cowless dissolver 5.5 grams of demi water, 24 grams of Tioxide TR 92 (pigment), 1.2 grams of Disperbyk 2015 (dispersant), 1 gram of Rheolate 212 (thickener) and 0.2 grams of Byk 028 (antifoam agent) and milling them into a mill paste. To this paste were added under stirring resin emulsion (26.24 grams solid resin), 1.84 grams Borchi-Oxy-Coat 1101 diluted 9:1 in demi water (iron drier), 2.7 grams of Rheolate 644 (thickener) and demi water to give 100 grams of paint

(38) These emulsion paints showed the following properties (table 6).

(39) TABLE-US-00006 Paint Paint K1 Ex 13 Ex 14 Resin from example: Comp K 5b 6b Drying Dust free time (hrs:min) 0:30 2:00 3:30 Drying Tack free time (hrs:min) 4:00 7:00 7:30 Knig Hardness 1 day 23 10 10 Knig Hardness 7 days 29 13 26 Knig Hardness 14 days 33 16 42 Knig Hardness 28 days 36 13 55 Yellowing in the dark, 150 m wet b* Initial 2.34 2.24 2.80 b* after 14 days 50 C. 2.35 1.87 3.56 b* after 21 days 50 C. 3.09 2.42 4.29 Water resistance average value (1-5) 4.6 2.8 3.0 Gloss, 100 m wet after 1 day, 20 /60 89/96 70/87 89/97

(40) The results in table 6 show that the paints formulated with emulsions of the invention (Examples 13 and 14) show either better final hardness or yellowing results in comparison with an optimized commercially available prior art based paint.