POLYUREA MICROCAPSULES AND LIQUID SURFACTANT SYSTEMS CONTAINING THEM

Abstract

Suggested are polyurea microcapsules obtainable or obtained by reacting di- and/or polyisocyanates and guanidine carbonate in the presence of chemically modified biopolymer colloidal protection agents. The capsules can be loaded for example with fragrances and show high resistance against agglomeration in unstructured (viscosity 10-300 cps), anionic surfactant based liquid products.

Claims

1. Polyurea microcapsules obtained according to the following steps: (a) providing an oil phase comprising at least one aliphatic and/or aromatic di- and/or polyisocyanate and optionally one or more actives for encapsulation and/or at least one oil component; (b) providing a first aqueous phase comprising at least one modified biopolymer colloidal protection agent and optionally at least one non-interfering emulsifier; (c) providing a second aqueous phase comprising guanidine carbonate and optionally at least one cationic surface active agent; (d) blending the oil phase and the first aqueous phase to form an emulsion; (e) adding the second aqueous phase to the emulsion formed in step (d) to form a dispersion of crude microcapsules (d); (f) curing the mixture; and optionally (g) removing the solvent(s) to obtain the microcapsules.

2. A process for making polyurea microcapsules, comprising the following steps: (a) providing an oil phase comprising at least one aliphatic and/or aromatic di- and/or polyisocyanate and optionally at least one oil component; (b) providing a first aqueous phase comprising at least one modified biopolymer colloidal protection agent; (c) providing a second aqueous phase comprising guanidine carbonate; (d) blending the oil phase and the first aqueous phase to form an emulsion; (e) adding the second aqueous phase to the emulsion formed in step (d) to form a dispersion of crude microcapsules; (f) curing the mixture; and optionally (g) removing the solvent(s) to obtain the microcapsules.

3. The process of claim 2, wherein said di- and/or polyisocyanate is selected from the group consisting of methylenediphenyl diisocyanate (MDI); toluol diisocyanate (TDI); hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI); 4,4-dicyclohexylmethan diisocyanate (H12MDI); and mixtures thereof.

4. The process of claim 2, said oil phase further comprising one or more actives for encapsulation.

5. The process of claim 4, wherein said active is a fragrance or perfume oil.

6. The process of claim 2, wherein said colloidal protection agent is selected from the group consisting of chemically modified biopolymers, preferably chemically modified starches, gum Arabic or cellulose, and mixtures thereof.

7. The process of claim 2, said first aqueous phase further comprising at least one non-interfering emulsifier.

8. The process of claim 6, wherein said emulsifier is selected from the group consisting of non-ionic, anionic, amphoteric, and cationic surfactants, and mixtures thereof.

9. The process of claim 2, wherein said emulsion is formed by subjecting the blend of said oil phase and said first aqueous phase to high-speed shearing.

10. The process of claim 2, wherein said emulsion is blended with said second aqueous phase and the mixture thus obtained is subjected to high-speed shearing.

11. The process of claim 2, said second aqueous phase further comprising at least one surface active agent.

12. The process of claim 2, wherein the curing takes place at elevated temperatures of from about 50 to about 90? C. over a period of from about 1 to about 12 hours.

13. A liquid surfactant system, preferably a liquid detergent composition comprising the microcapsules according to claim 1.

14. A method for manufacturing a liquid surfactant system, preferably a liquid detergent composition comprising the following steps: (i) providing components for manufacturing the composition, optionally in aqueous solution; (ii) providing the dispersion of microcapsules according to claim 1; and (iii) blending the components and the dispersion to obtain the final composition.

15. (canceled)

Description

EXAMPLES

Example 1

[0220] A microcapsule of this invention was prepared using guanidine carbonate as the multi-functional nucleophile and Capsul? starch as the capsule formation aid.

[0221] More specifically, 196 g of a fragrance, W-Cap (Symrise, Teterboro, NJ) was weighed out in a 250 ml beaker and combined with 10.4 g of hexamethylene diisocyanate (Desmodur N-3400, Covestro Corporation) to form an oil phase. In a separate 800 ml beaker, a solution (375 g) containing 2% of Capsul starch (commercially available from Ingredion Inc.) in water to form the aqueous phase. The oil phase was then emulsified into the aqueous phase to form the fragrance emulsion under shearing (Ultra Turrax, T-50, commercially available from IKA Werke) at 3500 rpm between 20 and 60 seconds.

[0222] The fragrance emulsion was placed with an overhead mixer and agitated at 600 rpm while 25 g of a 15% guanidine carbonate solution added incrementally. The capsule slurry was cured by heat at 70? C. for at least 3 hours.

[0223] The capsule slurry of this example was disbursed in commercially available unfragranced liquid laundry detergent at a dose of 0.3% w/w until homogeneous. The liquid laundry detergent contains no structuring agents. Samples were aged in an oven for 7 days at 40 C to simulate long term stability. This is shown in FIG. 2.

Example 2

[0224] A microcapsule of this invention was prepared using guanidine carbonate as the multi-functional nucleophile and Capsul? starch as the capsule formation aid.

[0225] More specifically, 98 g of a fragrance, Tomcap (Symrise, Teterboro, NJ) was weighed out in a 250 ml beaker and combined with 98 g of vegetable oil triglycerides and 10.4 grams of a mixture of hexamethylene diisocyanate and diphenylmethane diisocyanate (Desmodur N-3400 and Mondur M, both from Covestro Corporation) to form an oil phase. In a separate 800 ml beaker, a solution (375 g) containing 2% of Capsul? starch (commercially available from Ingredion Inc.) in water to form the aqueous phase. The oil phase was then emulsified into the aqueous phase to form the fragrance emulsion under shearing (Ultra Turrax, T-50, commercially available from IKA Werke) at 3500 rpm between 30 to 60 seconds. The particle size was measured on a Mastersizer?3000 (Malvern Instruments|117 Flanders Road, Westborough, MA) particle size analyzer to produce desired median size of 5 to 50 microns.

[0226] The fragrance emulsion was placed with an overhead mixer and agitated at 600 rpm while 25 g of a 15% guanidine carbonate solution added incrementally. The capsule slurry was cured by heat at 70? C. for 3 hours.

[0227] The capsule slurry of this example was disbursed in commercially available unfragranced liquid laundry detergent at a dose of 0.3% w/w until homogeneous. The liquid laundry detergent contains no structuring agents. Samples were aged in an oven for 7 days at 40 C to simulate long term stability. This is shown in FIG. 3.

Example 3

[0228] A microcapsule of this invention was prepared using guanidine carbonate as the multi-functional nucleophile and Hi-Cap? starch as the capsule formation aid.

[0229] More specifically, 98 g of a fragrance, Red Berry (Symrise, Teterboro, NJ) was weighed out in a 250 ml beaker and combined with 98 g of vegetable oil triglycerides and 10.4 grams of a mixture of hexamethylene diisocyanate and diphenylmethane diisocyanate (Desmodur N-3400 and Mondur M, both from Covestro Corporation) to form an oil phase. In a separate 800 ml beaker, a solution (375 g) containing 2% of HI-Cap?100 starch (commercially available from Ingredion Inc.) in water to form the aqueous phase. The oil phase was then emulsified into the aqueous phase to form the fragrance emulsion under shearing (Ultra Turrax, T-50, commercially available from IKA Werke) at 3500 rpm between 30 to 60 seconds. The particle size was measured on a Mastersizer?3000 (Malvern Instruments|117 Flanders Road, Westborough, MA) particle size analyzer to produce desired median size of 5 to 50 microns.

[0230] The fragrance emulsion was placed with an overhead mixer and agitated at 600 rpm while 25 g of a 15% guanidine carbonate solution added incrementally. The capsule slurry was cured by heat at 70? C. for 3 hours.

[0231] The capsule slurry of this example was disbursed in commercially available unfragranced liquid laundry detergent at a dose of 0.3% w/w until homogeneous. The liquid laundry detergent contains no structuring agents. Samples were aged in an oven for 7 days at 40 C to simulate long term stability. This is shown in FIG. 4.

Example 4

[0232] A microcapsule of this invention was prepared using guanidine carbonate as the multi-functional nucleophile and Capsul? starch as the capsule formation aid. A cationic quaternary was added during final process step.

[0233] More specifically, 98 g of a fragrance, Red Berry (Symrise, Teterboro, NJ) was weighed out in a 250 ml beaker and combined with 98 grams of vegetable oil triglycerides and 10.4 grams of a mixture of hexamethylene diisocyanate and diphenylmethane diisocyanate (Desmodur N-3400 and Mondur M, both from Covestro Corporation) to form an oil phase. In a separate 800 ml beaker, a solution (375 g) containing 2% of HI-Cap?100 starch (commercially available from Ingredion Inc.) in water to form the aqueous phase. The oil phase was then emulsified into the aqueous phase to form the fragrance emulsion under shearing (Ultra Turrax, T-50, commercially available from IKA Werke) at 3500 rpm between 30 to 60 seconds. The particle size was measured on a Mastersizer?3000 (Malvern Instruments|117 Flanders Road, Westborough, MA) particle size analyzer to produce desired median size of 5 to 50 microns.

[0234] The fragrance emulsion was placed with an overhead mixer and agitated at 600 rpm while 25 grams of a 15% Guanidine carbonate solution added incrementally. The capsule slurry was cured by heat at 70? C. for 3 hours. A cationic polymer (Salcare SC-60, BASF) was added to the capsule slurry as a solid powder or as a aqueous solution during final cure.

BRIEF DESCRIPTION OF THE FIGURES

[0235] FIG. 1

[0236] Symcap G Type (polyurea) microcapsules showing agglomeration in an unstructured liquid laundry base.

[0237] FIG. 2

[0238] Capsules prepared in Example 1 (right), disbursed in unstructured Liquid Laundry Detergent after 1 week at 40? C.

[0239] FIG. 3

[0240] Capsules prepared in Example 2 (right), disbursed in unstructured Liquid Laundry Detergent after 1 week at 40? C.

[0241] FIG. 4

[0242] Capsules prepared in Example 3 (right), disbursed in unstructured Liquid Laundry Detergent after 1 week at 40? C.

Consumer Product Formulations

[0243]

TABLE-US-00001 TABLE 1 Cleaner. APC liquid. alkaline pH 8-10 (Amounts in % b.w.) Ingredients (INCI) Amount Aqua 59.06 Tri Sodium Citrate Dihydrate 3.00 Sodium Laureth Sulfate 30.00 Trideceth-9 5.00 Ethanol 2.00 Citric Acid 10% solution 0.24 1,2-pentanediol (Hydrolite? 5) 0.50 Mixture of 5-Chloro-2-methyl-2H-isothiazol-3-one 0.10 and 2-Methyl-2H-isothiazol-3-one Microcapsules according to Example 4 0.30

TABLE-US-00002 TABLE 2 Fabric softener (Amounts in % b.w.) Ingredients (INCI) Amount Aqua 72.10 Dialkylester ammomium methosulfate 16.60 Polydimethylsiloxane 0.30 Magnesiumchloride 10.00 1,2-pentanediol (Hydrolite? 5) 0.60 Mixture of 5-Chloro-2-methyl-2H-isothiazol-3-one 0.10 and 2-Methyl-2H-isothiazol-3-one Microcapsules according to Example 4 0.40

TABLE-US-00003 TABLE 3 Liquid detergent (Amounts in % b.w.) Ingredients Amount Deionized water 39.60 Optical brightener 0.10 Coconut fatty acids (C12-C18) 7.50 Potassium hydroxide 50% solution 4.30 Propane-1.2-diol 5.00 Fatty alcohols C12-C15. 8 EO 12.00 Na-salt of secondary alkyl sulfonates (C13-C17) 17.00 Triethanolamine 2.00 Trisodium citrate dihydrate 5.00 Dequest 2066 Diethylenetriamine 3.00 penta(methylene phosphonic acid) Ethanol 3.00 Enzymes 0.70 1,2-pentanediol (Hydrolite? 5) 0.50 Microcapsules according to Example 4 1.00

TABLE-US-00004 TABLE 4 Liquid detergent concentrate (Amounts in % b.w.) Ingredients Amount Deionized water 12.9 Coconut fatty acids (C12-C18) 10.0 Fatty alcohols C12-C15. 8 EO 26.0 Na-salt of secondary alkyl sulfonates (C13-C17) 26.5 Triethanol amine 8.5 Na-salt of fatty alcohol sulfates C12-C14 3.0 Ethanol 5.5 Urea 4.5 Enzymes 0.9 Citric acid 1.0 1,2-pentanediol (Hydrolite? 5) 0.7 Microcapsules according to Example 4 0.8

TABLE-US-00005 TABLE 5 Toilet cleaner (Amounts in % b.w.) Ingredients Amount Water 93.0 Kelzan ASX-T 0.5 Parafin sulfonate. sodium salt 1.0 Citric acid 5.0 Colorant (FD & C Yellow No. 6) 0.1 1,2-pentanediol (Hydrolite? 5) 0.3 Preservative (Benzisothiazolinone. Glutaral) 0.05 Microcapsules according to Example 4 0.6

TABLE-US-00006 TABLE 6 Dish washing concentrate (Amounts in % b.w.) Ingredients Amount Sodium laurylsulfate 31.0 Propane-1.2-diole 6.0 Ethyl alcohol 96% 7.0 Palm tree glucosides 6.0 Coco betaine 18.0 1,2-pentanediol (Hydrolite? 5) 0.4 Microcapsules according to Example 4 0.5 Water 31.6

TABLE-US-00007 TABLE 7 Dish washing concentrate (Amounts in % b.w.) Ingredients Amount Palm tree glucosides 4.0 Sodium lauryl sulfate 45.0 Coco betaine 8.0 Ethyl alcohol 96% 1.0 Colorant (C.I. Pigment Blue 15) 0.05 1,2-pentanediol (Hydrolite? 5) 0.2 Microcapsules according to Example 4 0.7 Water Ad 100

TABLE-US-00008 TABLE 8 Solution for wet wipes (Amounts in % b.w.) Ingredients INCI Amount SymSol? PF-3 Water (Aqua). Pentylene Glycol. 2.00 Sodium Lauryl Sulfoacetate. SodiumOleoyl Sarcosinate. Sodium Chloride. Disodium Sulfoacetate. SodiumOleate. Sodium Sulfate Dragosantol? 100 Bisabolol 0.10 Glycerol 99.5 P. Glycerol 5.00 Water Water (Aqua) Ad 100 Hydrolite? 5 1,2-pentanediol 5.00 D-Panthenol 75 W Panthenol 0.80 DragoCalm? Water (Aqua). Glycerol. Avena 1.00 Sativa (Oat) Kernel Extract Witch Hazel-Distillate Hamamelis Virginiana (Witch Hazel) 1.00 Water. Water (Aqua). Alcohol Allplant Essence? Org. Pelargonium Graveolens 1.00 Rose Geranium P Flower/Leaf/Stem Water Preservative Phenoxyethanol 0.30 Microcapsules according 0.50 to Example 4