EFFICIENT MEKO-FREE ANTI-SKINNING AGENT

Abstract

A clear homogenous, efficient, MEKO-free anti-skinning composition, for use in alkyd-based coating materials containing metal carboxylate driers, contains a mixture of cyclohexanone oxime and/or a petroleum distillate soluble zinc carboxylate dissolved in methyl propyl ketoxmine.

Claims

1. A clear homogenous composition, for use as an anti-skinning composition with alkyd-based coating materials containing metal carboxylate driers, which comprises a mixture of cyclohexanone oxime and/or a petroleum distillate soluble zinc carboxylate dissolved in methyl propyl ketoxime, wherein the methyl propyl ketoxime comprises from 35 to 91% by weight of the composition.

2. (canceled)

3. The composition of claim 1, wherein the methyl propyl ketoxime comprises from 46 to 70% by weight of the composition.

4. The composition of claim 1, wherein the methyl propyl ketoxime comprises from 47 to 49% by weight of the composition.

5. The composition of claim 1, wherein the cyclohexanone oxime is present in concentrations of up to 15% by weight of the composition.

6. The composition of claim 1, wherein the cyclohexanone oxime is present in concentrations of 3.0 to 6.2% by weight of the composition.

7. The composition of claim 1, wherein the cyclohexanone oxime is present in concentrations of 5.8 to 6.2% by weight of the composition.

8. The composition of claim 1, wherein the cyclohexanone oxime is present in concentrations from 9% to 15% by weight of the composition.

9. The composition of claim 1, wherein the cyclohexanone oxime is present in concentrations from 9% to 11% by weight of the composition.

10. The composition of claim 1, further comprising up to 50% by weight of a petroleum distillate.

11. The composition of claim 10, wherein the petroleum distillate soluble zinc carboxylate comprises up to 7.0% by weight zinc metal content.

12. The composition of claim 10, wherein the petroleum distillate soluble zinc carboxylate comprises 1.8 to 7.0% by weight zinc content.

13. The composition of claim 10, wherein the petroleum distillate soluble zinc carboxylate comprises 4.5 to 4.7% by weight zinc content.

14. The composition of claim 10, wherein the petroleum distillate soluble zinc carboxylate comprises 0.9 to 3.5% by weight zinc content.

15. The composition of claim 10, wherein the petroleum distillate soluble zinc carboxylate comprises 2.2 to 2.4% by weight zinc content.

16. The composition of claim 11, wherein the petroleum distillate comprises mineral spirits or white spirits.

17. The composition of claim 11, wherein the petroleum distillate comprises 30 to 50% by weight of the composition.

18. The composition of claim 11, wherein the petroleum distillate comprises 34 to 46% by weight of the composition.

19. The composition of claim 11, wherein the petroleum distillate comprises 38 to 42% by weight of the composition.

20. A clear homogenous composition, for use as an anti-skinning composition with alkyd-based coating materials containing metal carboxylate driers, which comprises a mixture of cyclohexanone oxime and/or a petroleum distillate soluble zinc carboxylate dissolved in methyl propyl ketoxime, wherein the cyclohexanone oxime is present in concentrations of up to 15% by weight of the composition.

21. The composition of claim 20, wherein the cyclohexanone oxime is present in concentrations of 3.0 to 6.2% by weight of the composition.

22. The composition of claim 20, wherein the cyclohexanone oxime is present in concentrations of 5.8 to 6.2% by weight of the composition.

23. The composition of claim 20, wherein the cyclohexanone oxime is present in concentrations from 9% to 15% by weight of the composition.

24. The composition of claim 20, wherein the cyclohexanone oxime is present in concentrations from 9% to 11% by weight of the composition.

25. The composition of claim 20, further comprising up to 50% by weight of a petroleum distillate.

26. The composition of claim 25, wherein the petroleum distillate soluble zinc carboxylate comprises up to 7.0% by weight zinc metal content.

27. The composition of claim 25, wherein the petroleum distillate soluble zinc carboxylate comprises 1.8 to 7.0% by weight zinc content.

28. The composition of claim 25, wherein the petroleum distillate soluble zinc carboxylate comprises 4.5 to 4.7% by weight zinc content.

29. The composition of claim 25, wherein the petroleum distillate soluble zinc carboxylate comprises 0.9 to 3.5% by weight zinc content.

30. The composition of claim 25, wherein the petroleum distillate soluble zinc carboxylate comprises 2.2 to 2.4% by weight zinc content.

31. The composition of claim 26, wherein the petroleum distillate comprises mineral spirits or white spirits.

32. The composition of claim 26, wherein the petroleum distillate comprises 30 to 50% by weight of the composition.

33. The composition of claim 26, wherein the petroleum distillate comprises 34 to 46% by weight of the composition.

34. The composition of claim 26, wherein the petroleum distillate comprises 38 to 42% by weight of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0033] Solutions of cyclohexanone oxime and/or zinc carboxylates in MPKO perform as efficient MEKO-free anti-skinning compositions for use in an oil-based paint or ink coatings containing metal carboxylates as driers.

[0034] Skinning tendency was determined by weighing 100 g of the white alkyd enamel containing driers and anti-skinning agent into a clean glass jar. These jars were kept open and observed for skin formation. Results were quoted to the nearest day.

[0035] The invention will be further described by reference to the following non-limiting examples:

Example 1

[0036] In this example, a solution consisting of 90% MPKO and 10% CHO designated as 90:10 MPKO:CHO was used as the anti-skinning agent. Preparation of white alkyd enamel:

TABLE-US-00001 Raw Materials % by wt. Procedure Mill Base Long oil alkyd (S-10702) 20.00 Mix resin, dispersing additive, Pat-Add DA 707 dispersing 0.40 viscogel gelly and white spirit additive at 1000 RPM for 10 minutes. Viscogel b4 (10%) 3.00 White spirit 8.00 TiO.sub.2 (R-902) 22.00 Add under stirring and grind it until 10 ?m fineness. Let down Long oil alkyd (S-10702) 30.00 Add the remaining resin and White spirt 16.60 white spirit at 800 RPM and mix it for 15 minutes at 800 RPM. Total 100.00

Addition of Driers and Anti-Skinning Agent:

[0037]

TABLE-US-00002 Trial 1A Trial 2A Trial 3 Trial 4 Trial 5 Anti-skinning None MEKO 90:10 MPKO: CHO agent used White alkyd 100.00 100.00 100.00 100.00 100.00 enamel Patcham Cobalt 0.18 0.18 0.18 0.18 0.18 10% Patcham 0.58 0.58 0.58 0.58 0.58 Zirconium 18% Patcham Calcium 0.70 0.70 0.70 0.70 0.70 10% Dosage % of Anti- 0.20 0.20 0.18 0.16 skinning agent

Comparison of Skinning Tendency:

[0038]

TABLE-US-00003 Trial 1A Trial 2A Trial 3 Trial 4 Trial 5 Anti-skinning agent None MEKO 90:10 MPKO:CHO used Dosage of anti- 0.20 0.20 0.18 0.16 skinning agent Duration of 2 days 8 days 11 days 8 days 8 days complete skinning

Comparison of Physical Properties and Dry Times:

[0039]

TABLE-US-00004 Trial 1A Trial 2A Trial 3 Trial 4 Trial 5 Anti-skinning None MEKO 90:10 MPKO:CHO agent used Dosage of anti- 0.20 0.20 0.18 0.16 skinning agent L* 95.28 95.33 95.28 95.81 96.03 a* ?1.14 ?1.13 ?1.20 ?1.15 ?1.14 b* 1.79 1.83 2.08 2.12 2.05 Whiteness index 82 82 82 81 81 @C/10? Whiteness index 81 81 81 80 80 @D65/10? Yellowness index 2 3 3 3 3 @C/10? Yellowness index 2 3 3 3 3 @D65/10? Gloss @20? 72 70 76 81 81 Gloss @60? 87 89 90 91 91 Pendulum 24 25 24 24 24 hardness Drying times Surface dry 1:00 1:45 1:30 1:30 1:30 Hours:Minutes Tack free dry 3:00 2:00 2:00 3:00 3:00 Hours:Minutes Hard dry 4:00 5:00 6:15 4:45 5:00 Hours:Minutes

Remarks:

[0040] 90:10 MPKO:CHO showed better anti-skinning protection than MEKO at same dosage. [0041] 90:10 MPKO:CHO showed comparable anti-skinning protection to MEKO at 20% lower dosage. [0042] 90:10 MPKO:CHO showed comparable color values, gloss, pendulum hardness, whiteness index and yellowness index with MEKO in white alkyd enamel. [0043] 90:10 MPKO:CHO showed slightly longer hard dry times at equal use level but comparable hard dry times at 20% lower dosage.

Summary of Example I

[0044] A 10% solution of cyclohexanone oxime in methyl propyl ketoxime can be used in place of methyl ethyl ketoxime as an anti-skinning agent in alkyd paint containing metal carboxylate driers at 20% lower dose without imparting detrimental properties.

Example 2

[0045] In this example, a mixture consisting of 80% MPKO and 20% of Zinc Octoate (2 ethyl hexanoate) in 2 ethyl hexanoic acid at 23% zinc metal content (Zn23%) was used as a petroleum soluble zinc carboxylate, designated as 80:20 MPKO:Zn23% was used as the anti-skinning agent. This mixture contains 4.6% zinc metal content.

Preparation of White Alkyd Enamel:

[0046]

TABLE-US-00005 Raw Materials % by wt. Procedure Mill Base Long oil alkyd (S-10702) 20.00 Mix resin, dispersing additive, Pat-Add DA 707 0.40 viscogel gelly and white spirit dispersing additive at 1000 RPM for 10 minutes Viscogel b4 (10%) 3.00 White spirit 8.00 TiO.sub.2 (R-902) 22.00 Add under stirring and grind it until 10 ?m fineness Let down Long oil alkyd (S-10702) 30.00 Add the remaining resin and white White Spirit 16.60 spirit at 800 RPM and mix it for 15 minutes at 800 RPM Total 100.00

Addition of Driers and Anti-Skinning Agent:

[0047]

TABLE-US-00006 Trial Trial Trial Trial Trial Trial Trial 1A 2A 13 14 15 16 17 Anti-skinning None MEKO 80:20 MPKO:Zn23% agent used White alkyd 100.00 100.00 100.00 100.00 100.00 100.00 100.00 enamel Co 10% (lot 0.18 0.18 0.18 0.18 0.18 0.18 0.18 no. 1961-01- 2021) Zr 18% (lot 0.58 0.58 0.58 0.58 0.58 0.58 0.58 no. 140-02- 2021) Ca 10% (lot 0.70 0.70 0.70 0.70 0.70 0.70 0.70 no. 404-04- 2021) Dosage % of 0.20 0.20 0.18 0.16 0.14 0.12 Anti-skinning agent

Comparison of Skinning Tendency:

[0048]

TABLE-US-00007 Trial Trial Trial Trial Trial Trial Trial 1A 2A 13 14 15 16 17 Anti- None MEKO 80:20 MPKO:Zn23% skinning agent used Dosage of 0.20 0.20 0.18 0.16 0.14 0.12 anti-skinning agent Duration of 2 days 8 days 9 days 9 days 9 days 8 days 8 days complete skinning

Comparison of Physical Properties and Dry Times:

[0049]

TABLE-US-00008 Trial Trial Trial Trial Trial Trial Trial 1A 2A 13 14 15 16 17 Anti-skinning None MEKO 80:20 MPKO:Zn23% agent used Dosage of 0.2 0.2 0.18 0.16 0.14 0.12 anti-skinning agent Viscosity in 83 83 69 69 69 69 69 KU L* 95.28 95.33 95.77 95.7 95.59 95.68 95.51 a* ?1.14 ?1.13 ?1.12 ?1.12 ?1.1 ?1.12 ?1.11 b* 1.79 1.83 1.65 1.65 1.57 1.65 1.55 Whiteness 81 81 83 83 83 83 83 index @D65/10? Yellowness 2 3 2.2 2.3 2.2 2.1 2 index @D65/10? Gloss @20? 72 70 72 74 72 74 78 Gloss @60? 87 89 87 88 89 89 89 Pendulum 24 25 21 21 21 21 21 hardness Drying time Surface dry 1:00 1:45 1:30 1:30 1:30 1:30 1:30 Hours:Minutes Tack free dry 3:00 2:00 2:00 2:00 2:00 2:00 2:00 Hours:Minutes Hard dry 4:00 5:00 2:45 3:15 3:30 3:45 3:45 Hours:Minutes

Remarks:

[0050] 80:20 MPKO:Zn23% showed better anti-skinning protection than MEKO at same dosage. [0051] 80:20 MPKO:Zn23% showed comparable anti-skinning protection to MEKO at 40% lower dosage. [0052] 80:20 MPKO:Zn23% showed comparable color values, gloss, pendulum hardness and whiteness index compared with MEKO in white alkyd enamel. [0053] 80:20 MPKO:Zn23% showed slightly less yellowing compared to MEKO in white alkyd enamel. [0054] 80:20 MPKO:Zn23% showed comparable dry times at 40% lower dosage than MEKO.

Summary of Example 2

[0055] A 20% solution of a 23% metal content Zinc Octoate in methyl propyl ketoxime can be used in place of methyl ethyl ketoxime as an anti-skinning agent in alkyd paint containing metal carboxylate driers at 40% lower dose without imparting any detrimental properties.

Example 3

[0056] In this example, a mixture consisting of 80% MPKO 10% CHO and 10% Zn23% designated as 80:10:10 MPKO:CHO:Zn23% was used as the anti-skinning agent.

Preparation of White Alkyd Enamel:

[0057]

TABLE-US-00009 Raw Materials % by wt. Procedure Mill Base Long oil alkyd (S-10702) 20.00 Mix resin, dispersing additive, Pat-Add DA 707 dispersing 0.40 viscogel gelly and white spirit additive at 1000 RPM for 10 minutes Viscogel b4 (10%) 3.00 White spirit 8.00 TiO.sub.2 (R-902) 22.00 Add under stirring and grind it until 10 ?m fineness Let down Long oil alkyd (S-10702) 30.00 Add the remaining resin and White spirit 16.60 white spirit at 800 RPM and mix it for 15 minutes at 800 RPM Total 100.00

Addition of Driers and Anti-Skinning Agent:

[0058]

TABLE-US-00010 Trial Trial Trial Trial Trial Trial Trial 1B 2B 3B 4B 5B 6B 7B Anti- Blank MEKO 80:10:10 MPKO:CHO:Zn23% skinning agent used White alkyd 100.00 100.00 100.00 100.00 100.00 100.00 100.00 enamel Patcham 0.18 0.18 0.18 0.18 0.18 0.18 0.18 Cobalt 10% Patcham 0.58 0.58 0.58 0.58 0.58 0.58 0.58 Zirconium 18% Patcham 0.70 0.70 0.70 0.70 0.70 0.70 0.70 Calcium 10% Dosage % of - 0.2 0.2 0.18 0.16 0.14 0.12 Anti- skinning agent

Comparison of Skinning Tendency:

[0059]

TABLE-US-00011 Trial Trial Trial Trial Trial Trial Trial 1B 2B 3B 4B 5B 6B 7B Anti-skinning Blank MEKO 80:10:10 MPKO:CHO:Zn23% agent used Dosage of 0.2 0.2 0.18 0.16 0.14 0.12 anti-skinning agent Time for 1 7 9 8 8 8 7 complete skinning/days

Comparison of Physical Properties and Dry Times:

[0060]

TABLE-US-00012 Trial Trial Trial Trial Trial Trial Trial 1B 2B 3B 4B 5B 6B 7B Anti-skinning Blank MEKO 80:10:10 MPKO:CHO:Zn23% agent used Dosage of 0.2 0.2 0.18 0.16 0.14 0.12 anti-skinning agent L* 96.26 96.21 96.3 95.04 95.16 95.06 94.81 a* ?1.14 ?1.13 ?1.14 ?1.06 ?1.08 ?1.07 ?1.06 b* 1.96 1.99 2.08 1.3 1.28 1.29 1.25 Whiteness 83 83 83 83 83 83 83 index @D65/10? Yellowness 2.7 2.7 3 1.7 1.7 1.5 2 index @65/10? Gloss@20? 77 76 79 74 74 74 80 Gloss @60? 91 90 91 88 89 89 89 Pendulum 22 23 22 22 22 22 21 harness Drying time Surface dry 1:50 1:30 1:45 1:45 1:50 2:00 2:00 Hours:Mins Tack free dry 2:10 2:00 2:00 2:15 2:00 2:15 2:15 Hours:Mins Hard dry 4:00 3:00 3:30 3:45 4:00 4:00 3:45 Hours:Mins

Remarks:

[0061] 80:10:10 MPKO:CHO:ZN23% provided better protection against skin formation than MEKO at same dosage. [0062] 80:10:10 MPKO:CHO:ZN23% provided comparable protection against skin formation to MEKO at 40% lower dosage. [0063] 80:10:10 MPKO:CHO:ZN23% showed comparable color values, gloss, pendulum hardness and whiteness index compared with MEKO in white alkyd enamel. [0064] 80:10:10 MPKO:CHO:ZN23% showed marginally slower dry times at 40% lower dosage then MEKO.

Summary of Example 3

[0065] A mixture consisting of 80% MPKO 10% CHO and 10% Zn23% (2.3% zinc metal content) can be used, in alkyd based coatings containing metal carboxylate driers, as the anti-skinning agent in place of MEKO at a dose of approximately 40% less than that required for MEKO to provide comparable protection against skinning and comparable dry times for the resulting coating.

Example 4

[0066] In this example, a mixture consisting of 48% MPKO, 6% CHO, 6% Zinc 23% and 40% Petroleum distillate de-aromatized, >80? C. flash point (D80) designated as 48:6:6:40 MPKO:CHO:Zn23%:D80 was used as the anti-skinning agent.

Preparation of White Alkyd Enamel:

[0067]

TABLE-US-00013 Raw Materials % by wt. Procedure Mill Base Long oil alkyd (S-10702) 20.00 Mix resin, dispersing additive, Pat-Add DA 707 dispersing 0.40 viscogel gelly and white spirit additive at 1000 RPM for 10 minutes Viscogel b4 (10%) 3.00 White spirit 8.00 TiO.sub.2 (R-902) 22.00 Add under stirring and grind it until 10 ?m fineness Let down Long oil alkyd (S-10702) 30.00 Add the remaining resin and White spirit 16.60 white spirit at 800 RPM and mix it for 15 minutes at 800 RPM Total 100.00

Addition of Driers and Anti-Skinning Agent:

[0068]

TABLE-US-00014 Trial Trial Trial Trial Trial Trial Trial 1B 2B 18 19 20 21 22 Anti- Blank MEKO 48:6:640 MPKO:CHO:Zn23%:D80 skinning agent used White alkyd 100.00 100.00 100.00 100.00 100.00 100.00 100.00 enamel Patcham 0.18 0.18 0.18 0.18 0.18 0.18 0.18 Cobalt 10% Patcham 0.58 0.58 0.58 0.58 0.58 0.58 0.58 Zirconium 18% Patcham 0.70 0.70 0.70 0.70 0.70 0.70 0.70 Calcium 10% Dosage % of 0.2 0.2 0.18 0.16 0.14 0.12 Anti- skinning agent

Comparison of Skinning Tendency:

[0069]

TABLE-US-00015 Trial Trial Trial Trial Trial Trial Trial 1B 2B 18 19 20 21 22 Anti-skinning Blank MEKO 48:6:640 MPKO:CHO:Zn23%:D80 agent used Dosage of 0.2 0.2 0.18 0.16 0.14 0.12 anti-skinning agent Time for 1 7 7 6 6 6 5 complete skinning/days

Comparison of Physical Properties and Dry Times:

[0070]

TABLE-US-00016 Trial Trial Trial Trial Trial Trial Trial 1B 2B 18 19 20 21 22 Anti-skinning Blank MEKO 48:6:6:40 MPKO:CHO:Zn23%:D80 agent used Dosage of 0.2 0.2 0.18 0.16 0.14 0.12 anti-skinning agent L* 96.26 96.21 96.13 96.15 96.27 96.25 96.23 a* ?1.14 ?1.13 ?1.2 ?1.14 ?1.16 ?1.17 ?1.17 b* 1.96 1.99 1.99 2.01 2.11 2.07 2.17 Whiteness 83 83 83 83 83 83 83 index @D65/10? Yellowness 2.7 2.7 2.7 2.7 2.7 2.7 2.9 index @65/10? Gloss@20? 77 76 80 80 77 77 75 Gloss @60? 91 90 90 90 90 90 90 Pendulum 22 23 21 21 21 21 21 harness Drying time Surface dry 1:50 2:00 2:00 2:00 2:15 2:00 2:00 Hours:Mins Tack free dry 2:10 2:30 2:45 2:30 2:40 2:20 2:30 Hours:Mins Hard dry 4:00 4:45 4:30 4:30 4:40 4:30 4:45 Hours:Mins

Remarks:

[0071] 48:6:6:40 MPKO:CHO:ZN23%:D80 provided similar protection against skin formation as MEKO at same dosage. [0072] 48:6:6:40 MPKO:CHO:ZN23%:D80 showed comparable color values, gloss, pendulum 10 hardness and whiteness index compared with MEKO in white alkyd enamel. [0073] 48:6:6:40 MPKO:CHO:ZN23%:D80 showed comparable dry times to the alkyd enamel protected by MEKO at equal dose.

Summary of Example 4

[0074] A mixture consisting of 48% MPKO, 6% CHO, 6% Zn23% and 40% D80 can be used in alkyd based coatings containing metal carboxylate driers, as the anti-skinning agent in place of MEKO at the same dose level to provide similar protection against skin formation and comparable dry times for the resulting coating.