Resin, composition and use

Abstract

Low VOC, unsaturated alkyd resins are obtained by reacting (A) to (E): (A) optionally from 0 to 30% w/w naturally occurring Rosin, comprising from 40 to 80 w/w parts per hundred of Rosin of an unsaturated mono carboxylic acid with at least one C.sub.15-25cyclohydrocarbo moiety capable of a Diels Alder or Ene reaction (preferred monoacids being abietic acid, palustric acid, levopimaric acid, sandaracopimaric acid, and/or anhydrides thereof); (B) from 25 to 80% w/w of a linear C.sub.12-60hydrocarbo carboxylic acid with at least one (preferably at least two conjugated) CC bonds (=unsaturated fatty acid); (C) optionally from 1 to 30% w/w of an ethylenically unsaturated C.sub.5-6hydrocarbo dicarboxylic acid and/or anhydride thereof, being reactive as a dienophile and/or enophile with A and/or B (preferred for C are itaconic acid, citraconic acid and/or anhydrides thereof); (D) from 1 to 40% w/w of at least one polyol; (E) optionally at least one monomer other than A to Dthe total of A to E being 100%. There is a further optional step (II) where more or new (C) may be blended with the alkyd resin; the amount of C in blend being from 1 to 30 parts w/w of 100 parts of monomers (A) to (E)and where (C) is at least used as a monomer and/or as a diluent in the blend and where alkyd resin (i) has acid value of <50 KOH/g of alkyd; (ii) Mn of >=1200 g/mol (iii) oil length <80; (iv) optionally biorenewable content >=50%.

Claims

1. A low VOC unsaturated alkyd resin P obtained by reaction in a process (III) between the following components: (A) Optional Component A comprising from 0 to 30% by weight of naturally occurring Rosin, the Rosin comprising from 40 to 80 parts per hundred by weight of Rosin of an unsaturated mono carboxylic acid comprising at least one C.sub.15-25cyclohydrocarbo moiety capable of undergoing a Diels Alder or Ene reaction; (B) Component B comprising from 25 to 80% by weight of a linear C.sub.12-60 hydrocarbo carboxylic acid comprising at least one conjugated ethylenically unsaturated double bond; (C) Component C comprising from 5 to 30% by weight of an ethylenically unsaturated C.sub.5-6hydrocarbo dicarboxylic acid, ester thereof, and/or anhydride thereof, being reactive as a dienophile and/or enophile with Component B and/or Component A where present; (D) Component D comprising from 1 to 40% by weight of at least one polyhydric alcohol (polyol); (E) Optional Component E comprising at least one monomer other than any of Components A to D; the total of Components A to E being 100%; to obtain the alkyd resin P and wherein the alkyd resin P obtained from the process (III) has: (i) an acid value of no more than 50 mg KOH per g of the solid alkyd resin; (ii) a number average molecular weight (M.sub.n) of at least 1200 g/mol; (iii) an oil length from 60 to 78; and (iv) optionally a renewable content of at least 50% by weight of components (A) to (E) where present; and wherein low VOC denotes that the total amount of organic compounds that have a boiling point from 50 to 250 C. that are present in the composition is less than 100 g/l.

2. The low VOC alkyd resin P as claimed in claim 1, wherein the alkyd resin P obtained from the process (III) has an oil length from 65 to 78.

3. The low VOC alkyd resin P as claimed in claim 1, which is capable of being water borne.

4. The low VOC alkyd resin P as claimed in claim 1, which is capable of being solvent borne.

5. The low VOC alkyd resin P as claimed in claim 1, in which Component A is selected from the group consisting of: abietic acid, palustric acid, levopimaric acid, sandaracopimaric acid and/or mixtures thereof and the amount of Component A is from 5% to 28% of the total monomer A to E; and in which Component B is selected from the group consisting of palmitoleic acid, ricinoleic acid, oleic acid, myristoleic acid, erucic acid, gadoleic acid, linoleic acid, linolenic acid, (alpha)-eleostearic acid (ELA), (beta)-eleostearic acid, (alpha)-linolenic acid (ALA), licanic acid, arachidonic acid, eicosapentaenoic acid (EPA), clupanodonic acid (DPA), osbond acid, docosahexaenoic acid (DHA) and/or esters and/or mixtures thereof; and wherein the amount of Component B is from 30% to 75% of the total monomer A to E; and in which Component C is selected from itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and/or mixtures thereof; and the amount of Component C as a monomer is from 5% to 28% of the total monomer A to E; and in which Component D is selected from glycerol; pentaerythritol; mannitol, sorbitol, isosorbide, sorbitan and/or mixtures thereof; and the amount of Component D is from 5% to 28% of the total monomer A to E.

6. The low VOC alkyd resin P as claimed in claim 1, wherein the process (III) comprises a cyclo-addition step and an esterification step that said steps may be performed in any order, wherein the cyclo-addition step of process (III) comprises cyclo-reacting Component (C) which is reactive as a dienophile and/or enophile and comprises ethylenically unsaturated C.sub.5-6hydrocarbo dicarboxylic acid, ester thereof, and/or anhydride thereof, with at least one dienophile and/or enophile reactive component selected from the group consisting of: Component (A) comprising a naturally occurring Rosin comprising from 40 to 80 parts per hundred by weight of Rosin of an unsaturated mono carboxylic acid comprising at least one C.sub.15-25cyclohydrocarbo moiety capable of undergoing a Diels Alder or Ene reaction; Component (B) comprising a linear C.sub.12-60hydrocarbo carboxylic acid comprising at least one conjugated ethylenically unsaturated double bond; an alkyd adduct formed by reacting Component (D) comprising a polyol with at least one of Component (A) and Component (B); and wherein the esterification step of process (III) comprises reacting at least one acid functional component selected from the group consisting of: an acid functional alkyd adduct formed by reacting Component (D) with at least one of Component (A) and Component (B); Component (A); and Component (B); with at least one hydroxy functional component selected from the group consisting of: a hydroxyl functional alkyd adduct formed by reacting a Component (D) with at least one of the Component (A) and the Component (B); and Component D; wherein the Component (B) is present in at least one of the cyclo-addition step and the esterification step; and the Component (D) is present in at least one of the cyclo-addition step and the esterification step.

7. The low VOC alkyd resin P as claimed in claim 6, in which Component A is selected from the group consisting of: abietic acid, palustric acid, levopimaric acid, sandaracopimaric acid and/or mixtures thereof and the amount of Component A is from 5% to 28% of the total monomer A to E; and in which Component B is selected from the group consisting of palmitoleic acid, ricinoleic acid, oleic acid, myristoleic acid, erucic acid, gadoleic acid, linoleic acid, linolenic acid, (alpha)-eleostearic acid (ELA), (beta)-eleostearic acid, (alpha)-linolenic acid (ALA), licanic acid, arachidonic acid, eicosapentaenoic acid (EPA), clupanodonic acid (DPA), osbond acid, docosahexaenoic acid (DHA) and/or esters and/or mixtures thereof; and wherein the amount of Component B is from 30% to 75% of the total monomer A to E; and in which Component C is selected from itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and/or mixtures thereof; and the amount of Component C as a monomer is from 5% to 28% of the total monomer A to E; and in which Component D is selected from glycerol; pentaerythritol; mannitol, sorbitol, isosorbide, sorbitan and/or mixtures thereof; and the amount of Component D is from 5% to 28% of the total monomer A to E.

8. The low VOC alkyd resin P as claimed in claim 1, which is a solid.

9. The low VOC alkyd resin P as claimed in claim 3, which further comprises at least one surfactant which is added during the reaction of Components A to E.

10. The low VOC alkyd resin P as claimed in claim 9, wherein the at least on surfactant comprises a mixture of nonionic and ionic surfactants.

11. The low VOC alkyd resin P as claimed in claim 5, wherein Component B comprises a glycerol ester of at least one compound selected from the group consisting of palmitoleic acid, ricinoleic acid, oleic acid, myristoleic acid, erucic acid, gadoleic acid, linoleic acid, linolenic acid, (alpha)-eleostearic acid (ELA), (beta)-eleostearic acid, (alpha)-linolenic acid (ALA), licanic acid, arachidonic acid, eicosapentaenoic acid (EPA), clupanodonic acid (DPA), osbond acid, docosahexaenoic acid (DHA).

12. The low VOC alkyd resin P as claimed in claim 7, wherein Component B comprises a glycerol ester of at least one compound selected from the group consisting of palmitoleic acid, ricinoleic acid, oleic acid, myristoleic acid, erucic acid, gadoleic acid, linoleic acid, linolenic acid, (alpha)-eleostearic acid (ELA), (beta)-eleostearic acid, (alpha)-linolenic acid (ALA), licanic acid, arachidonic acid, eicosapentaenoic acid (EPA), clupanodonic acid (DPA), osbond acid, docosahexaenoic acid (DHA).

13. A coating composition comprising an alkyd resin as claimed in claim 1.

14. A coating composition comprising an alkyd resin as claimed in claim 2.

15. A coating composition comprising an alkyd resin as claimed in claim 5.

16. The coating composition as claimed in claim 13 which is water borne.

17. The coating composition as claimed in claim 13 which is solvent borne.

18. The coating composition as claimed in claim 13 which is a powder coating composition.

19. A substrate and/or article having coated thereon a coating composition, optionally cured, of claim 13.

20. A method preparing a coating composition which comprises using the low VOC unsaturated alkyd resin P as claimed in claim 1.

21. A method for preparing a coated substrate and/or article comprising the steps of applying a coating composition as claimed in claim 13 to a substrate and/or article; optionally drying the composition in situ and/or optionally curing the composition in situ to form a coating thereon.

Description

EXAMPLES

(1) The present invention will now be described in detail with reference to the following non limiting examples which are by way of illustration only. Unless otherwise specified all parts, percentages and ratios are on a weight basis.

Preparation of a Sebacate Alkyd Resin (Resin A, Comparative=Comp I)

(2) 696 g of soybean fatty acid and 176 g of pentaerythritol were charged to a reactor fitted with thermocouple, stirrer, nitrogen flow and Dean-Stark trap, and heated to 240 C. under xylene reflux conditions. The temperature was maintained at 240 C. for 3 hours, when an acid value of less than 3 mg KOH/g was reached. The reactor was cooled to 60 C. and 220 g of sebacic acid was charged to the reactor. The reactor was heated to 230 C. under azeotropic conditions and the distillation was stopped when the acid value reached 8.5 mg KOH/g resin. The reactor was then cooled to 170 C. and vacuum distillation was started for removal of xylene azeotropic solvent. After cooling down to below 100 C. the resin was poured out.

Preparation of an Itaconate Alkyd Resin (Resin B) (=Example 1 of Invention)

(3) 717 g of soybean fatty acid and 181 g of pentaerythritol were charged to a reactor fitted with thermocouple, stirrer, nitrogen flow and Dean-Stark trap, and heated to 240 C. under xylene reflux conditions. The temperature was maintained at 240 C. for 3 hours, when an acid value of less than 3 mg KOH/g was reached. The reactor was cooled to 60 C. and 133 g of sebacic acid and 54 g of itaconic acid were charged to the reactor. The reactor was heated to 185 C. and kept at this temperature for 2 hours. The reactor was heated to 230 C. under azeotropic conditions and the distillation was stopped when the acid value reached 9.7 mg KOH/g resin. The reactor was then cooled to 170 C. and vacuum distillation was started for removal of xylene azeotropic solvent. After cooling down to below 100 C. the resin was poured out.

Preparation of a Maleate Alkyd Resin (Resin C, Comparative)=Comp II

(4) 720 g of soybean fatty acid and 183 g of pentaerythritol were charged to a reactor fitted with thermocouple, stirrer, nitrogen flow and Dean-Stark trap, and heated to 240 C. under xylene reflux conditions. The temperature was maintained at 240 C. for 3 hours, when an acid value of less than 3 mg KOH/g was reached. The reactor was cooled to 60 C. and 133 g of sebacic acid and 41 g of maleic anhydride were charged to the reactor. The reactor was heated to 185 C. and kept at this temperature for 2 hours. The reactor was heated to 230 C. under azeotropic conditions and the distillation was stopped when the acid value reached 12.8 mg KOH/g resin. The reactor was then cooled to 170 C. and vacuum distillation was started for removal of xylene azeotropic solvent. After cooling down to below 100 C. the resin was poured out.

Preparation of an Itaconate Alkyd Resin (Resin D) (Example 2 of Invention)

(5) 750 g of soybean fatty acid and 190 g of pentaerythritol were charged to a reactor fitted with thermocouple, stirrer, nitrogen flow and Dean-Stark trap, and heated to 240 C. under xylene reflux conditions. The temperature was maintained at 240 C. for 3 hours, when an acid value of less than 3 mg KOH/g was reached. The reactor was cooled to 120 C. and 150 g of itaconic acid were charged to the reactor. The reactor was heated to 185 C. and kept at this temperature for 2 hours. The reactor was heated to 230 C. under azeotropic conditions and the distillation was stopped when the acid value reached 14 mg KOH/g resin. The reactor was then cooled to 170 C. and vacuum distillation was started for removal of xylene azeotropic solvent. After cooling down to below 100 C. the resin was poured out.

Preparation of a Maleate Alkyd Emulsion (Resin E, Comparative)=Comp III

(6) 875 g of tall oil fatty acids, 241 g of tall rosin and 115 g of maleic anhydride 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 218 g of glycerol were charged to the reactor. The reactor was heated to 230 C. under xylene reflux conditions and the distillation was stopped when the acid value reached 9 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.

(7) 550 g of the resin was then emulsified as follows. The resin was heated to between 50-70 C. and 92 g of a 30% solution of a highly branched alcohol based surfactant combining anionic and non ionic components and was neutralised with a non-amine base and the mixture was stirred until homogeneous. Demineralised water was added during 2 hours until a solids content of 52% was obtained. The emulsion showed particle size of 217 nm; pH of 7.7 and viscosity of 188 mPas.

Preparation of an Itaconate Alkyd Emulsion (Resin F)=Example 3 of Invention

(8) 875 g of tall oil fatty acids, 241 g of tall rosin and 217 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 218 g of glycerol were charged to the reactor. The reactor was heated to 230 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.

(9) 550 g of the resin was emulsified as described for Resin E and diluted until solids content of 55% was obtained. The emulsion showed particle size of 283 nm, pH of 7.5 and viscosity of 212 mPas.

(10) TABLE-US-00001 TABLE 1 Resin characteristics Oil Resin length Acid value Mn Mw Example code Resin based on: (%) mgKOH/g Da kDa Comp I A* Sebacic acid 72 7.3 4131 87 Ex 1 B Sebacic & 75 9.0 3352 25 itaconic acid Comp II C* Sebacic acid & 75 12.7 3341 27 Maleic anhydride Ex 2 D Itaconic acid 78 11.6 3802 128 Comp III E* Maleic anhydride 66 8 2020 65 Ex 3 F Itaconic acid 66 14 2026 121 *Resins A, C and E are comparative resins
Preparation of Non-Volatile Diluents

(11) A dipenta ester diluent was prepared according to the following process: 1108 g of soya fatty acid, 160 g of dipentaerythritol and 50 g of xylene were charged to a reactor and heated to 250 C. under azeotropic conditions. Distillation was stopped when the acid value reached 10 mg KOH/g. Finally, the xylene was stripped under vacuum conditions at 200 C. Thereafter, the resulting dipenta ester diluent was discharged and used for the examples.

(12) A dioctylfumarate diluent (also referred to herein as DOF) was prepared according to the following process: 459 g of 2-ethylhexanol, 205 g of fumaric acid and 50 g of xylene were charged to a reactor and heated to 190 C. under azeotropic conditions, using 1000 ppm Fascat 4101 tin catalyst. Distillation was stopped when the acid value reached 1 mg KOH/g. Finally, the xylene was stripped under vacuum conditions at 170 C. Thereafter, the resulting DOF diluent was discharged and used for the examples.

(13) A dioctylmaleate diluent (also referred to herein as DOM) was prepared according to the following process: 382 g of 2-ethylhexanol, 144 g of maleic anhydride and 50 g of xylene were charged to a reactor and heated to 190 C. under azeotropic conditions, using 1000 ppm Fascat 4101 tin catalyst. Distillation was stopped when the acid value reached 1 mg KOH/g. Finally, the xylene was stripped under vacuum conditions at 170 C. Thereafter, the resulting DOM diluent was discharged and used for the examples.

(14) A dioctylitaconate diluent (also referred to herein as DOIt) was prepared according to the following process: 367 g of 2-ethylhexanol, 183 g of itaconic acid and 50 g of xylene were charged to a reactor and heated to 190 C. under azeotropic conditions, using 1000 ppm Fascat 4101 tin catalyst. Distillation was stopped when the acid value reached 1 mg KOH/g. Finally, the xylene was stripped under vacuum conditions at 170 C. Thereafter, the resulting DOIt diluent was discharged and used for the examples.

Example 4 and Comp IV

(15) Coating compositions were obtained by mixing with a normal lab stirrer 50 g of solid resin Compl (from resin A) or Example 1 (from resin B) with 35 g xylene, 2.87 g Nuodex Ca 5 (Elementis: metal drier), 0.42 g Nuodex Co 10 (Elementis: metal drier), 2.18 g Nuodex Zr 12 (Elementis: metal drier) and 0.6 g Exkin 2 (Elementis: anti-skinning agent). Yellowing and drying properties were determined as described herein and are given in Table 2.

(16) TABLE-US-00002 TABLE 2 Yellowing behaviour Drying rate Initial After 1 After 2 Resin Dust free Tack free value week weeks Example code hours hours b b b Comp IV A 2:00 2:00 0.51 2.09 3.25 Ex 4 B 3:00 3:00 0.53 1.67 2.54

(17) It can be seen from Table 2 that although only 5% of the resin in Example 4 comprises an itaconic acid monomer, the yellowing behaviour has decreased by some 20% compared to comparative example Comp IV prepared without an itaconate monomer.

Example 5, Comp V and Comp VI

(18) More coating compositions were obtained by mixing with a normal lab stirrer 50 g of respectively solid resin A (Comp V), B (Ex 5) or C (Comp VI) with 35 g xylene, 2.87 g Nuodex Ca 5, 0.42 g Nuodex Co 10, 2.18 g Nuodex Zr 12 and 0.6 g Exkin 2. Yellowing properties were determined as described herein and are given in Table 3:

(19) TABLE-US-00003 TABLE 3 Yellowing behaviour Resin Initial value After 1 week After 3 weeks Example code b b b Comp V A 0.88 1.54 3.47 Ex 5 B 1.00 1.30 2.94 Comp VI C 0.92 1.64 3.82

(20) It can be seen from Table 3 that although only 5% of the resin in Example 5 comprises itaconic acid monomer, as before the yellowing behaviour has decreased by 15-25% compared to either of the comparative examples (Comp V and Comp VI) which were not prepare using itaconic acid monomer. Comp VI was prepared from maleate alkyd (Resin C). It is particularly surprising that despite having a similar structure to maleic acid, compositions prepared from itaconic acid have especially advantageous yellowing properties. Compositions prepared using itaconic acid (and/or esters and/or anhydrides thereof) are particularly preferred embodiments of this invention.

Examples 6, 7 and Comp VII and VIII

(21) Further coating compositions were obtained by mixing with a normal lab stirrer 40 g of respectively solid resin A (Comp VII), B (Ex 6), C (Comp VIII) or D (Ex 7) with 35 g xylene, 0.32 g Nuodex Co 10, and 0.4 g Exkin 2. Yellowing properties were determined as described herein and are given in Table 4:

(22) TABLE-US-00004 TABLE 4 Yellowing behaviour Drying rate Initial After 1 After 4 Resin Dust free Tack free value week weeks Example code hours hours b b b Comp VII A 3:30 4:00 0.32 2.55 6.27 Ex 6 B 3:30 4:00 0.66 2.30 5.35 Comp VIII C 3:00 3:30 0.54 2.68 6.41 Ex 7 D 3:30 4:00 0.85 1.58 3.48

(23) It can be seen from Table 3 that although only 5% of resin B comprises itaconic acid monomer, the yellowing behaviour has decreased by some 10-20% compared to either of the comparative examples (Comp VII and Comp VIII) which were not prepared using itaconic acid monomer. Resin D is based on 15% of itaconic acid and decreases yellowing by about 45% compared to Comp VII or Comp VIII.

Example 8 and Comp IX and X

(24) A Solid Resin derived from a commercially available product was prepared by stripping off the solvent from Uralac HS 233 (from DSM under that registered trademark) by vacuum distillation. Some more coating compositions were then obtained by mixing with a normal lab stirrer 24 g of the Solid Resin (obtained above) with 13 g dipenta ester diluent and 8 g of different diluents respectively DOF (Comp IX), DOM (Comp X) or DOIt (Example 8), 2.0 g Nuodex Ca 5, 0.4 g Nuodex Co 10, 2.0 g Nuodex Zr 12, and 0.4 g Exkin 2. Resulting paints had a VOC content of 51 g/l (calculated). Yellowing properties were determined with the following results:

(25) TABLE-US-00005 TABLE 5 Yellowing behaviour Diluent Initial value After 1 week After 2 weeks Example code b b b Comp IX DOF 5.67 1.40 2.90 Comp X DOM 5.93 1.30 2.89 Ex 5 DOIt 6.08 0.21 1.26

(26) It can be seen from Table 5 that although only 6% or the total binder in Example 5 comprises itaconic acid monomer, and although it is present unreacted as a diluent, the yellowing behaviour of the resultant coating has decreased by more than 50% compared to either of the comparative examples (ComplX or CompX) which were not prepared using itaconic acid as a diluent. The advantage compared to maleate and fumarate diluents is surprising given their similar structures. Compositions prepared from itaconic acid as diluent have especially advantageous yellowing properties and so are particularly preferred embodiments of this invention.

Example 9 and Comp XI

(27) A waterborne mill base (WB Mill Base) was prepared by mixing 20 parts of demineralised water, 3.5 parts Disperbyk 2015 (Byk: dispersant), 0.25 parts Byk 024 (Byk; defoamer), 1.3 parts Rheolate 644 (Elementis; thickener) and 60 parts Tioxide TR 92 (Huntsman; pigment) using a high speed stirrer. Further coating compositions were obtained from the WB Mill Base (obtained as described above) by mixing with a normal lab stirrer 24.8 g of respectively solid resin E (Comp XI) or F (Example 9) with 30.8 g WB Mill Base, 3.4 g Rheolate 644, 0.32 g Borchi OxyCoat 1101 (Borchers; metal drier), and remainder demineralised water to obtain 100 g of paint. Yellowing and drying properties were determined with the following results set out in Tables 6 and 7 below:

(28) TABLE-US-00006 TABLE 6 Knig Hardness Gloss Drying behaviour Resin After 2 weeks After 1 week Dust free Dust free Example code seconds 20/60 hours hours Comp XI E 11 75/85 3:30 3:30 Ex9 F 10 79/87 4:15 4:15

(29) TABLE-US-00007 TABLE 7 Yellowing behaviour Resin Initial value After 1 week After 4 weeks Example code b b b Comp XI E 1.87 2.59 4.29 Ex9 F 1.23 1.73 2.78

(30) It can be seen from Tables 6 and 7 that the aqueous coating composition Example 9 comprising Resin F based on 15% of itaconic acid forms a coating that has reduced yellowing by about 35% compared to a comparative example (CompXI) not prepared using itaconic acid. Thus it can be seem that waterborne emulsions of the invention also show strongly improved yellowing whilst the applicant has found that other properties remain comparable to known resins.