CURABLE AQUEOUS POLYURETHANE DISPERSIONS MADE FROM RENEWABLE RESOURCES

Abstract

A curable aqueous polyurethane dispersion is formed by reacting a polyol component with a polyisocyanate. The polyol component comprises a1) at least one non-ionic polyol, a2) at least one polyol bearing at least one ionic or potentially ionic group comprising an acid group or salt thereof and a3) at least one ethylenically unsaturated monoalcohol or polyol. The polyol component contains carbon atoms from renewable resources. A method for making the curable aqueous polyurethane dispersion, uses of the aqueous polyurethane dispersion, cured polyurethanes and nail polish formulations comprising aqueous polyurethane dispersions are also disclosed.

Claims

1. A nail polish formulation comprising: a curable aqueous polyurethane dispersion; a photoinitiator; optionally a leveling agent and optionally a thickener wherein the formulation is free of non-reactive solvents and wherein said curable aqueous polyurethane dispersion is formed by the reaction of a) at least one polyol component comprising a1) a non-ionic polyol, a2) at least one polyol bearing at least one ionic or potentially ionic group comprising an acid group or salt thereof and a3) at least one ethylenically unsaturated monoalcohol or polyol, with b) at least one polyisocyanate, wherein the number of isocyanate (NCO) groups of the at least one polyisocyanate b) is in excess with respect to the number of hydroxyl (OH) groups of the at least one polyol component a), wherein said at least one polyol component a1) comprises carbon atoms from renewable resources, said acid group of polyol a2) being at least partly neutralized and said reaction being followed in a second step by an extension reaction with an isocyanate-reactive chain extender c).

2. The nail polish formulation of claim 1, wherein the at least one non-ionic polyol a1) comprises a polyol formed by reacting a 1,4:3,6-dianhydrohexitol in a polycondensation polymerization reaction with at least one diacid or higher functional carboxylic acid, by reacting a 1,4:3,6-dianhydrohexitol with a hydroxyl functional monocarboxylic acid or by reacting a 1,4:3,6-dianhydrohexitol with caprolactone.

3. The nail polish formulation of claim 2, wherein the 1,4:3,6-dianhydrohexitol is selected from the group consisting of isosorbide, isomannide and isoidide.

4. The nail polish formulation of claim 3, wherein the 1,4:3,6-dianhydrohexitol is isosorbide.

5. The nail polish formulation of claim 1, wherein the at least one non-ionic polyol a1) comprises a polyol formed by reacting a 1,4:3,6-dianhydrohexitol in a polycondensation polymerization reaction with at least one diol or polyol and at least one diacid or higher functional carboxylic acid, wherein the diol or polyol is selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,3-butanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,4- and 1,6-dimethylolcylcohexane, C.sub.36-dimer diol, hydroxypivaloyl hydroxyl pivalate and ethoxylated and/or propoxylated derivatives thereof and combinations thereof.

6. The nail polish formulation of claim 5, wherein the at least one diacid or higher functional carboxylic acid is selected from the group consisting of malonic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, glutaric acid, citric acid, adipic acid, pimelic acid, sebacic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, C.sub.36-dimer fatty acids, C.sub.54-trimer fatty acids (triacid) trimellitic acid, pyromellitic acid and anhydrides thereof and combinations thereof.

7. The nail polish formulation of claim 1, wherein said non-ionic polyol a1) is formed using a 1,4:3,6-dianhydrohexitol as a hydroxyl functional initiator molecule in a ring opening polymerization of lactide.

8. The nail polish formulation of claim 1, wherein said monoalcohol or polyol a3) is an isocyanate-reactive ethylenically unsaturated monoalcohol or polyol selected from the group consisting of polyester (meth)acrylates, epoxy (meth)acrylates, polyether (meth)acrylates, polyurethane (meth)acrylates and hydroxyl group-containing (meth)acrylates.

9. The nail polish formulation of claim 1, wherein said curable aqueous polyurethane dispersion and said nail polish formulation is a radiation- or peroxide-curable dispersion.

10. The nail polish formulation of claim 1, wherein the at least one polyol component a) has a content by weight of .sup.14C such that the .sup.14C/.sup.12C ratio is greater than 0.110.sup.12.

11. The nail polish formulation of claim 1, further comprising at least one coloring agent.

12. The nail polish formulation of claim 1, wherein the said nail polish formulation is UV curable.

13. The nail polish formulation of claim 1 to 12, wherein the formulation has a solids level of 20% to 30% w/w and a viscosity of 500 mPa.Math.s (500 cP) to 3000 mPa.Math.s (3000 cP) at room temperature.

14. The nail polish formulation of claim 1, wherein said chain extender c) bears two isocyanate-reactive groups from hydroxyl or amine.

15. A nail polish formulation comprising: an aqueous polyurethane dispersion formed in a reaction comprising at least one polyol component comprising carbon atoms from a renewable resource; a photoinitiator; optionally a leveling agent and optionally a thickener, wherein the formulation is free of non-reactive solvent.

16. A method of coating nails comprising using the nail polish formulation of claim 1.

17. A method of preparing a nail polish formulation comprising using the curable aqueous polyurethane dispersion of claim 1.

18. Nail coating resulting from the cure of a nail polish formulation of claim 1.

19. The nail polish formulation of claim 14, wherein said chain extender c) bears two isocyanate-reactive groups from amine and c) is a diamine.

Description

EXAMPLES

Example 1

[0097] A polyester polyol was made using the following procedure: 1,3-propanediol (177 g, from DuPont Tate&Lyle), isosorbide (681 g, from Roquette), succinic acid (551 g, from BioAmbe), which were all derived from renewable sources along with toluene (388 g) and 70% methanesulfonic acid in water (17 g) were charged to a reaction vessel with fitted with a side arm for collection of evolved water. The mixture was heated to 112 C. for 21 hours at which time production of water had substantially ceased. After removal of the toluene by vacuum distillation, the final polyester polyol product was a viscous liquid with hydroxyl number of 200 mg KOH/g.

[0098] All cited OH values are determined by Radiometer TitraLab TM865 Autotitrator. The detailed method is as follows:

[0099] A 4-5 g sample is dissolved in 25 ml acetonitrile (CH.sub.3CN), then 25 ml p-toluenesulfonyl isocyanate (TSI) reagent is added volumetrically and stirred for 10 minutes. The sample is then titrated with 0.25 M concentration tetrabutylammonium hydroxide. The results are reported in mg KOH/g by the autotitrator.

Example 2

[0100] A polyester polyol was prepared from isosorbide (98 g) and d,l-lactide (240 g) by heating to 120 C. for several hours in the presence of stannous octoate catalyst. The final polyester polyol product was a viscous liquid with hydroxyl number of 211 mg KOH/g.

Example 3

Preparation of a UV-Curable Polyurethane Dispersion (UV-PUD)

[0101] A reaction vessel suitable for polyurethane preparation was charged with di-trimethylol propane triacrylate with OH value=163 mg KOH/g (206 g), the polyester polyol of Example 1 (388 g), dimethylolpropionic acid (113 g), methyl hydroquinone MeHQ (4.8 g), dibutyltin dilaurate (3.2 g) and ethoxylated trimethylolpropane triacrylate (Sartomer SR454, 1603 g) and the mixture was heated to 50 C. Isophorone diisocyanate (888 g) was added over 30 minutes while increasing the temperature to 70 C. The reaction was held at 70 C. until the % NCO by titration was constant at which point the temperature was lowered to 55 C. Triethylamine (85 g) was added followed by, with vigorous agitation, de-ionized water (4577 g). After 5 minutes, ethylenediamine (92 gm) dissolved in de-ionized water (93 g) was added and agitation was continued for another 2 hours. After filtration through a 100 micron filter bag, the final dispersion had the following properties: w/w % solids=42.0, viscosity at 25 C.=6.1 mPa.Math.s (6.1 cP), average particle size=114 nm and pH=7.23.

Example 4

Preparation of a UV-Curable Polyurethane Dispersion (UV-PUD)

[0102] A reaction vessel suitable for polyurethane preparation was charged with di-trimethylol propane triacrylate with OH value=163 mg KOH/g (130 g), the polyester polyol of Example 1 (101 g), poly(1,3-propanediol) (product of DuPont, 1000MW, 200 g) dimethylolpropionic acid (78 g), MeHQ (3.3 g), dibutyltin dilaurate (2.2 g) and ethoxylated trimethylolpropane triacrylate (Sartomer SR454, 1110 g) and the mixture was heated to 50 C. Isophorone diisocyanate (590 g) was added over 30 minutes while increasing the temperature to 70 C. The reaction was held at 70 C. until the % NCO by titration was constant at which point the temperature was lowered to 55 C. Triethylamine (59 g) was added followed by, with vigorous agitation, de-ionized water (3135 g). After 5 minutes, ethylenediamine (58 g) dissolved in de-ionized water (64 g) was added and agitation was continued for another 2 hours. After filtration through a 100 micron filter bag, the final dispersion had the following properties: w/w % solids=41.3, viscosity at 25 C.=10.2 mPa.Math.s (10.2 cP), average particle size=126 nm and pH=7.2.

Example 5

Preparation of a UV-Curable Polyurethane Dispersion (UV-PUD)

[0103] The procedure of Example 4 was followed but the following recipe was used: dimethylolpropanetriacrylate with OH value=163 mg KOH/g (124 g), the polyester polyol of Example 1 (210 g), poly(1,3-propanediol) (product of DuPont, 1000MW, 140 g), dimethylolpropionic acid (84 g), MeHQ (3.6 g), dibutyltin dilaurate (2.4 g) and ethoxylated trimethylolpropane triacrylate (Sartomer SR454, 1195 g), isophorone diisocyanate (631 g), triethylamine (63 g), de-ionized water (3408 g) and ethylene diamine+water (68 g+70 g). After filtration through a 100 micron filter bag, the final dispersion had the following properties: w/w % solids=41.1, viscosity at 25 C.=10.2 mPa.Math.s (10.2 cP), average particle size=176 nm and pH=7.25.

Example 6

Preparation of a UV-Curable Polyurethane Dispersion (UV-PUD)

[0104] A reaction vessel suitable for polyurethane preparation was charged with dimethylolpropionic acid (85 g), MeHQ (2.8 g), dibutyltin dilaurate (1.9 g), ethoxylated trimethylolpropane triacrylate (Sartomer SR454, 1204 g) and isophorone diisocyanate (572 g) and the mixture was heated to 70 C. until the % NCO content by titration dropped to about 7.9%. Dimethylolpropanetriacrylate with OH value=163 mg KOH/g (98 g), the polyester polyol of Example 2 (145 g), poly(1,3-propanediol) (product of DuPont, 1000MW, 298 g) MeHQ (3.6 g) and an additional 1.9 g of dibutyltin dilaurate were then added and the temperature maintained at 70 C. until a constant % NCO content was achieved. The temperature was reduced to 55 C. and triethylamine (64 g) was added followed by, with vigorous agitation, de-ionized water (3359 g). After 5 minutes, ethylenediamine (49 g) dissolved in de-ionized water (120 g) was added and agitation continued for another two hours. After filtration through a 100 micron filter bag, the final dispersion had the following properties: w/w % solids=40.6, viscosity at 25 C.=12.6 mPa.Math.s (12.6 cP), average particle size=118 nm and pH=7.79.

Example 7

Use of the Prepared Curable Aqueous Polyurethane Dispersions in Nail Polish Formulation

[0105] 97.73 wt parts of the polyurethane dispersion of Example 4, which has been diluted with water to 35% solids, is mixed with 0.17 wt part of a leveling agent (BYK-346, available from BYK-CHEMIE GMBH), 1.74 wt part of a photoinitiator (Irgacure 500) and about 0.35 wt part of a thickener Acrysol RM825 to form a nail polish formulation (100 wt parts).

[0106] The formulation is coated on aluminum and cured under UV energy of 1 J/cm.sup.2. The 60 gloss is about 116.

[0107] The formulation is applied to acrylic artificial nails using a brush applicator. Once the water evaporates, a homogeneous film is formed without brush marks. After curing under UV energy of 1 J/cm.sup.2, the formulation is expected to produce a smooth, homogeneous, shiny film. The adhesion of the nail polish formulation on the acrylic artificial nails is excellent and unable to be peeled or cracked off using finger nails.