USE OF COMPOSITIONS COMPRISING DESTRUCTURIZED STARCH IN A COMPLEXED FORM AS ABRASIVES AND/OR STRUCTURING AGENTS

Abstract

This invention relates to the use of microgranules comprising destructurized starch in a complexed form as abrasive and/or structuring agents in cosmetic, dermatological, detergent and cleansing formulations.

Claims

1. A composition selected from the group consisting of cosmetic, dermatological, detergent and cleansing formulations comprising, as abrasive and/or structuring agents, from 1 to 20% by weight, with respect to the total weight of the composition, of microgranules comprising destructurized starch in a complexed form with polymers containing hydrophilic groups intercalated with hydrophobic sequences, said microgranules being in the form of spheroidal particles of diameter between 1 and 100 μm.

2. The composition according to claim 1, wherein the water in said microgranules is that naturally present in the starch.

3. The composition according to claim 1, wherein said microgranules comprise, with respect to the total of components i-iv: i. 30-80% of destructurized starch; ii. 20-70% of polymers containing hydrophilic groups intercalated with hydrophobic sequences; iii. 0-25% of plasticizers; iv. 0-50% of water.

4. The composition according to claim 1, wherein said polymers containing hydrophilic groups intercalated with hydrophobic sequences are selected from: polyvinyl alcohol having a degree of hydrolysis of 10 to 100%; vinyl alcohol/vinyl acetate block copolymers; polyvinyl acetate in dry form and in a form emulsified in water; copolymers of ethylene with vinyl alcohol, vinyl acetate, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, glycidylmethacrvlate and mixtures thereof; aliphatic 6-6, 6-9 or 12 polyamides, aliphatic polyurethanes, aliphatic and aliphatic/aromatic polyesters, polyurethane: polyimide, polyurethane/polyether, polyurethane/polyester, polyamide/polyester, polyamide/polyether, polyester/polyether, polyurea/polyester, polyurea/polyether, polylactic acid, polyglycolic acid, polycaprolactone/urethane random and block copolymers, in which the molecular weight of the polycaprolactone blocks is between 300 and 3000.

5. The composition according to claim 4, wherein said polymers containing hydrophilic groups intercalated with hydrophobic sequences are polyvinyl alcohols having a degree of hydrolysis of between 10 and 100%.

6. The composition according to claim 4, wherein said polymers containing hydrophilic groups intercalated with hydrophobic sequences are vinyl alcohol/vinyl acetate block copolymers.

7. The composition according to claim 4, wherein said polymers containing hydrophilic groups intercalated with hydrophobic sequences are polyvinyl acetates.

8. The composition according to claim 4, wherein said polymers containing hydrophilic groups intercalated with hydrophobic sequences are copolymers of ethylene with vinyl alcohol and/or acrylic acid.

9. The composition according to claim 8, wherein said copolymers of ethylene with vinyl alcohol contain 20-50% in moles of ethylene units.

10. The composition according to claim 8, wherein said copolymers of ethylene with acrylic acid contain 70-99% by weight of ethylene units.

Description

EXAMPLE 1

[0061] 49.5 parts of native maize starch (containing 12% by weight of water), 32.2 parts of polyvinyl alcohol having a degree of hydrolysis of 88%, 7 parts of glycerine and 11.2 parts of water were fed to an TSA twin-screw extruder set in accordance with the following operating parameters:

[0062] Thermal Profile [0063] Feed zone (° C.): 60 [0064] Extrusion zone (° C.): 120-200×4-110-90 [0065] Throughput (kg/h)=3 [0066] SME (specific energy) (kWh/kg)=0.267

[0067] The composition so obtained was ground up at 25° C. and sieved to a particle size <250 μm and analysed in a Philips X'Pert θ/2θ X-ray spectrometer with Bragg-Brentano geometry using Cu K.sub.α X-ray radiation with λ=1.5416 Å and a power of 1.6 kW. The angular range used was from 5 to 60° (2θ) in steps of 0.03° (2θ) and an acquisition time of 2 seconds per step.

[0068] Analysis of the spectrum revealed the presence of diffraction peaks at 2θ=12.7-16.5-18.2-19.4-22.0 indicating formation of the complex between the starch and polyvinyl alcohol (VH form).

[0069] The composition was analysed using a Leitz Wetzlar Orthoplan model phase contrast optical microscope adjusted to the following parameters: [0070] Magnification 400× [0071] EF 40/0.65 Phaco 2 objective [0072] Phase ring no. 5

[0073] The composition showed that no residues of granular structure which could be attributed to the starch were present, thus revealing the destructurized nature of the starch.

[0074] The composition was then ground by grinding in a pin crusher in the presence of liquid nitrogen yielding a powder having dimensions <1 mm. The said powder was further ground by means of jet-mill technology thus obtaining two types of microgranules in the form of spheroidal particles having a mean diameter of 9 microns (Dv90=16 microns) and 12 microns (Dv90=21 microns).

EXAMPLE 2

[0075] 56.3 parts of native maize starch (containing 12% by weight of water), 24.8 parts of polyethylene acrylic acid containing 20% by weight of acrylic acid, 7.9 parts of glycerine and 10.1 parts of water were fed to an OMC twin-screw extruder set in accordance with the following operating parameters:

[0076] Thermal Profile [0077] Feed zone (° C.): 60 [0078] Extrusion zone (° C.): 145-170-180×4-150×2 [0079] Throughput (kg/h)=40 [0080] SME (specific energy) (kWh/kg)=0.232

[0081] The composition so obtained was ground up at 25° C. and sieved to a particle size <250 μm and analysed in a Philips X'Pert θ/2θ X-ray spectrometer with Bragg-Brentano geometry using Cu K.sub.α X-ray radiation with λ=1.5416 Å and a power of 1.6 kW. The angular range used was from 5 to 60° (2θ) in steps of 0.03° (2θ) and an acquisition time of 2 seconds per step.

[0082] Analysis of the spectrum revealed the presence of diffraction peaks at 20=6.8-11.8-13.1-18.1-20.7 indicating formation of the complex between the starch and the polyethylene acrylic acid (E.sub.H and V.sub.A forms).

[0083] The composition was analysed using a Leitz Wetzlar Orthoplan model phase contrast optical microscope adjusted to the following parameters: [0084] Magnification 400× [0085] EF 40/0.65 Phaco 2 objective [0086] Phase ring no. 5

[0087] The composition showed that no residues of granular structure which could be attributed to the starch were present, thus revealing the destructurized nature of the starch.

[0088] The composition was then ground by grinding in a pin crusher in the presence of liquid nitrogen yielding a powder having dimensions <1 mm. The said powder was further ground by means of jet-mill technology thus obtaining two types of microgranules in the form of spheroidal particles having a mean diameter of 9 microns (Dv90=16 microns) and 12 microns (Dv90=21 microns).

[0089] The microgranules were subsequently used as a replacement for conventional microbeads to produce some cosmetic formulations, for example base cream (Examples 3-6) and foundation (Examples 7-10).

EXAMPLES 3 (COMPARATIVE), 4 (COMPARATIVE), 5, 6: BASE CREAM FORMULATIONS

[0090] Different base cream formulations were produced and the compositions are reported in Table 1. For each cosmetic formulation, the ingredients are listed according to INCI nomenclature, and the amount of each ingredient is referred to the total weight of the formulation.

TABLE-US-00002 TABLE 1 Composition % wt Example 3 Example 4 Phase INCI name (comparative) (comparative) Example 5 Example 6 A Aqua 82.80 80.80 80.80  80.80 Disodium EDTA 0.10 0.10 0.10 0.10 Chlorophenesin 0.30 0.30 0.30 0.30 B Peg-8 Stearate, CetearylEthylhexanoate, 10.00 10.00 10.00  10.00 Glyceryl Stearate, StearylHeptanoate, CetylAlcohol, Butyl Stearate, Olive Glycerides, StearylCaprylate, CetylPalmitate, SorbitanSesquioleate, Stearic Acid, Aqua, Tocopherol, Potassium Hydroxide Triolein, Glyceryl Dioleate 6.00 6.00 6.00 6.00 TocopherylAcetate 0.50 0.50 0.50 0.50 O-cymen-5-ol 0.10 0.10 0.10 0.10 C Parfum 0.20 0.20 0.20 0.20 D Nylon-12 — 2.00 — — Microgranules according to Example 1 — — 2.00 — with Dv90 = 16 microns Microgranules according to Example 1 — — — 2.00 with Dv90 = 21 microns

[0091] Manufacturing Method:

the components of Phase A and Phase B were separately heated at 65° C. under stirring. Subsequently, Phase B was added to Phase A under mixing and maintained under this condition for 5 minutes. After cooling down to room temperature, Phase C and Phase D were added under stirring to the mixture.

[0092] The stability of base cream formulations according to Examples 3-6 was tested for 6 months at 25° C. (Table 2). No significant variations of Colour, Smell, Appearance, pH, Viscosity were noticed, thus confirming the stability of all the formulations.

[0093] Viscosity was measured by means of a Brookfield viscometer (RV) equipped with spindle n. 4 at 50 rpm and at 25° C.

TABLE-US-00003 TABLE 2 Example 3 Example 4 (comparative) (comparative) Example 5 Example 6 beginning 6 months beginning 6 months beginning 6 months beginning 6 months colour conform conform conform conform conform conform conform conform smell conform conform conform conform conform conform conform conform appearance conform conform conform conform conform conform conform conform pH 6.39 6.22 6.23 6.16 6.26 6.18 6.25 6.09 Viscosity mPas 1180 1190 1060 1060 1200 1210 1100 1090 (s = 4; 50 rpm)

[0094] The formulations prepared according to examples 3-6 were tested in terms of their softness, smoothness, greasiness, stickiness, film-forming and absorption rate by a panel of 20 volounteers (both men and women). The sensory analyses, determined 3 minutes after the application, were classified according to the following scale: [0095] 1=absolutely not good [0096] 2=not good [0097] 3=sufficiently good [0098] 4=good [0099] 5=very good.

[0100] The results are reported in Table 3.

TABLE-US-00004 TABLE 3 PANEL TEST Absorp- Soft- Smooth- Greasi- Sticki- Film- tion Example ness ness ness ness forming rate 3 4 4 5 5 3 3 (comparative) 4 5 4 5 5 4 5 (comparative) 5 5 5 5 5 5 5 6 5 5 5 5 5 5

[0101] 3 minutes after the application, the base cream formulations of the invention (Examples 5-6) showed improved Smoothness and Film-forming effect with respect to that comprising Nylon 12 (comparative Example 4), and a general improvement with respect to the basic formulation (comparative Example 3).

EXAMPLES 7 (COMPARATIVE), 8 (COMPARATIVE), 9, 10: FOUNDATION FORMULATIONS

[0102] Different foundation formulations were produced and the compositions are reported in Table 4.

TABLE-US-00005 TABLE 4 Composition % wt Example 7 Example 8 Phase INCI name (comparative) (comparative) Example 9 Example 10 A Aqua 66.25 62.25 62.25  62.25 Glycerin 4.00 4.00 4.00 4.00 Sodium Chloride 1.00 1.00 1.00 1.00 Chlorophenesin 0.30 0.30 0.30 0.30 B IsodecylNeopentanoate 3.00 3.00 3.00 3.00 Triolein, Glyceryl Dioleate 2.00 2.00 2.00 2.00 C15-19 Alkane 1.50 1.50 1.50 1.50 Cyclopentasiloxane 3.00 3.00 3.00 3.00 Isotridecyl Isononanoate 4.00 4.00 4.00 4.00 CetylPEG/PPG-10/1 Dimethicone 0.70 0.70 0.70 0.70 C10-18 Triglycerides 2.00 2.00 2.00 2.00 Cyclopentasiloxane, 2.00 2.00 2.00 2.00 DimethiconeCrosspolymer O-cymen-5-ol 0.10 0.10 0.10 0.10 C Titanium Dioxide, Cyclopentasiloxane, 7.00 7.00 7.00 7.00 PEG/PPG-18/18 Dimethicone, Isopropyl Titanium Triisostearate, TriethoxysilylethylPolydimethylsiloxyethylDi- methicone, DisteardimoniumHectorite, TocopherylAcetate Iron Oxides (C.I. 77492), Cyclopentasiloxane, 2.20 2.20 2.20 2.20 PEG/PPG-18/18 Dimethicone, Isopropyl Titanium Triisostearate, Triethoxysilylethyl Polydimethylsiloxyethyl Dimethicone, Disteardimonium Hectorite, Tocopheryl Acetate Iron Oxides (C.I. 77491), Cyclopentasiloxane, 0.70 0.70 0.70 0.70 PEG/PPG-18/18 Dimethicone, Isopropyl Titanium Triisostearate, Triethoxysilylethyl Polydimethylsiloxyethyl Dimethicone, Disteardimonium Hectorite, Tocopheryl Acetate Iron Oxides (C.I. 77499), Cyclopentasiloxane, 0.25 0.25 0.25 0.25 PEG/PPG-18/18 Dimethicone, Isopropyl Titanium Triisostearate, Triethoxysilylethyl Polydimethylsiloxyethyl Dimethicone, Disteardimonium Hectorite, Tocopheryl Acetate D Nylon-12 — 4.00 — — Microgranules according to Example 1 — — 4.00 — with Dv90 = 16 microns Microgranules according to Example 1 — — — 4.00 with Dv90 = 21 microns

[0103] Manufacturing Method:

[0104] Phase A was prepared at 25° C., while Phase B was heated at 80° C. Phase C was added to Phase B, and cooled down to 35° C. Subsequently Phase A was added very slowly under the turboemulsifier to the mixture of Phase B and C. The mixture was then cooled down to 25° C. and Phase D was finally added.

[0105] The stability of the foundation formulations according to Examples 7-10 was tested for 6 months at 25° C. (Table 5). No significant variations of Colour, Smell, Appearance, Viscosity were noticed, thus confirming the stability of all the formulations.

[0106] Viscosity was measured by means of a Brookfield viscometer (RV) equipped with spindle n. 4 at 50 rpm and at 25° C.

TABLE-US-00006 TABLE 5 Example 7 Example 8 (comparative) (comparative) Example 9 Example 10 beginning 6 months beginning 6 months beginning 6 months beginning 6 months colour conform conform conform conform conform conform conform conform smell conform conform conform conform conform conform conform conform appearance conform conform conform conform conform conform conform conform Viscosity mPas 28600 27900 29000 28950 28500 29650 29700 29320 (s = 4; 50 rpm)

[0107] The formulations prepared according to examples 7-10 were tested in terms of their softness, smoothness, greasiness, stickiness, film-forming and absorption rate by a panel of 20 volounteers (both men and women). The sensory analyses, determined 3 minutes after the application, were classified according to the following scale: [0108] 1=absolutely not good [0109] 2=not good [0110] 3=sufficiently good [0111] 4=good [0112] 5=very good.

[0113] The results are reported in Table 6.

TABLE-US-00007 TABLE 6 PANEL TEST Absorp- Soft- Smooth- Greasi- Sticki- Film- tion Example ness ness ness ness forming rate 7 3 3 5 4 3 3 (comparative) 8 4 4 4 4 4 3 (comparative) 9 5 5 5 5 5 4 10  5 5 5 5 5 4

[0114] The foundation formulations of the invention (Examples 9-10) showed a general improvement with respect to the basic formulation (comparative Example 7) and with respect to that comprising Nylon 12 (comparative Example 8).

[0115] In addition to the advantages reported above, the formulations containing the microgranules according to the present invention have a higher biodegradability with respect to common formulations including microgranules.

[0116] The microgranules according to the present invention were effectively used as a replacement for conventional microbeads to produce cosmetic formulations, with better performance than conventional microbeads.