OIL-IN-WATER EMULSION AND USE THEREOF

Abstract

An oil-in-water emulsion which includes one or more amino polyorganosiloxanes (A1), one or more silicone resins (A2), a surfactant composition (B) and water. The oil-in-water emulsion forms a film having a higher degree of crosslinking and an improved strength. Additionally, the oil-in-water emulsion is usable within hair care products to make hairstyles hold and offer a smooth, non-sticky hand feel. Furthermore, the oil-in-water emulsion also has good storage stability.

Claims

1-15. (canceled)

16. A film-forming oil-in-water emulsion, comprising: one or more amino polyorganosiloxanes (A1), one or more silicone resins (A2), a surfactant composition (B) and water; wherein at least 80 mol % of units of the amino polyorganosiloxanes (A1) are selected from those having the following general formulas Ia, Ib II and III:
R.sup.1.sub.2SiO.sub.(4-a-b)/2  (Ia)
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4-a-b)/2  (Ib)
R.sup.3.sub.3SiO.sub.(1/2)  (II)
R.sup.3.sub.2R.sup.4SiO.sub.(1/2)  (III) wherein a has the value 0 or 1; wherein b has the value 1 or 2; wherein a+b is equal to 2; wherein R.sup.1 represents monovalent hydrocarbon groups having 1-40 carbon atoms; wherein R.sup.2 represents aminoalkyl groups of the general formula IV:
—R.sup.5—NR.sup.6R.sup.7  (IV) wherein R.sup.5 represents divalent hydrocarbon groups having 1-40 carbon atoms; wherein R.sup.6 represents divalent hydrocarbon groups having 1-40 carbon atoms, H, hydroxymethyl or alkanoyl; wherein R.sup.7 represents groups of the general formula V:
—(R.sup.8—NR.sup.6).sub.xR.sup.6  (V)  wherein x is 0 or an arbitrary integer from 1 to 40;  wherein R.sup.8 represents divalent groups of the general formula VI:
—(CR.sup.9.sub.2—).sub.y  (VI)  wherein y an arbitrary integer from 1 to 6;  wherein R.sup.9 represents H or hydrocarbon groups having 1-40 carbon atoms; wherein R.sup.3 represents optionally halogen-substituted hydrocarbon groups having 1-40 carbon atoms; wherein R.sup.4 represents —OR or —OH groups; wherein (Ia+Ib)/(II+III), meaning the average ratio of the sum of units of the general formulas Ia and Ib to the sum of units of the general formulas II and III, ranges from 0.5 to 1000, wherein II/III≤1, preferably II/III≤0.9, more preferably II/III≤0.5, even more preferably II/III≤0.3, most preferably II/III=0; wherein the amino polyorganosiloxanes (A1) have a viscosity of from 3,000 to 9,000 mPa.Math.s, more preferably from 3,000 to 7,000 mPa.Math.s, most preferably from 4,000 to 6,000 mPa.Math.s; wherein at least 80 mol % of units of the silicone resins (A2) are selected from those having the following general formulas VII, VIII, IX and X:
R.sup.10.sub.3SiO.sub.(1/2)  (VII)
R.sup.10.sub.2SiO.sub.(2/2)  (VIII)
R.sup.10SiO.sub.(3/2)  (IX)
SiO.sub.(4/2)  (X) wherein R.sup.10 represents hydrocarbon groups that have 1-40 carbon atoms and are optionally substituted by halogens, or H, —OR or —OH groups; wherein at least 20 mol % of the units are selected from those having the general formulas IX and X, wherein at most 30 wt % of R.sup.10 are —OR and/or —OH groups, based on the total weight of the silicone resins (A2); and wherein in the terminal groups of the amino polyorganosiloxanes (A1), the number of moles of hydroxyl groups is greater than that of alkoxy groups.

17. The film-forming oil-in-water emulsion of claim 16, further comprising a low-viscosity oil (A3) that contains a volatile one in an amount of greater than or equal to 80 wt %, preferably greater than or equal to 90 wt %, more preferably greater than or equal to 95 wt %, based on the total weight, as 100 wt %, of A3.

18. The film-forming oil-in-water emulsion of claim 16, wherein the silicone resins (A2), the amino polyorganosiloxanes (A1) and the low viscosity oil (A3) were mixed to form a transparent homogeneous phase.

19. The film-forming oil-in-water emulsion of claim 17, wherein the low-viscosity oil (A3) and the silicone resins (A2) are used in a mass ratio of from 1 to 20, preferably from 2 to 10, more preferably from 3 to 8, most preferably from 4.5 to 7.

20. The film-forming oil-in-water emulsion of claim 16, comprising: 10-20 wt % of one or more amino polyorganosiloxanes (A1), and/or 0.1-4 wt % of one or more silicone resins (A2), and/or 4-10 wt % of the surfactant composition (B), and water, based on the total weight, as 100 wt %, of the emulsion.

21. The film-forming oil-in-water emulsion of claim 16, wherein the silicone resins (A2) comprise at least 80 mol % of units, preferably at least 90 mol %, more preferably at least 95 mol % are selected from those having the general formulas VII and X, based on the total units, as 100 mol % of, the silicone resins (A2).

22. The film-forming oil-in-water emulsion of claim 16, comprising one or more silicone resins (A2) in an amount of from 0.1 to 2 w %, preferably from 0.2 to 0.8 w %, more preferably from 0.3 to 0.7 w %, most preferably from 0.41 to 0.6 w %, based on the total weight, as 100 wt %, of the emulsion.

23. The film-forming oil-in-water emulsion of claim 16, wherein the emulsion is used in leave-on or rinse-off hair care products, preferably in rinse-off hair care products.

24. The film-forming oil-in-water emulsion of claim 16, wherein the emulsion is used in leave-on or rinse-off hair care products to make hairstyles hold, particularly on hair that has been treated by a permanent or temporary hair styling method, and preferably to maintain the degree of curling of the said hair.

25. The film-forming oil-in-water emulsion of claim 23, wherein the rinse-off hair care products are conditioners or hair masks.

26. The film-forming oil-in-water emulsion of claim 23, wherein the leave-on hair care products are atmospheric-pressure hairstyling sprays or hairstyling gels.

27. The film-forming oil-in-water emulsion of claim 23, wherein the leave-on hair care product is applied to the hair to realize a temporary styling treatment thereon.

28. The film-forming oil-in-water emulsion of claim 23, wherein the leave-on hair care product is applied to dry hair that has been treated by a permanent or a temporary hair styling method.

29. The film-forming oil-in-water emulsion of claim 23, wherein the rinse-off hair care product is applied to wet hair that are subsequently treated by a permanent or a temporary hair styling method during and/or after a drying process.

30. The film-forming oil-in-water emulsion of claim 23, wherein the rinse-off hair care product is applied to wet hair and is then kept in contact with it for at least 1 minute, preferably to thermally treat the hair after this process.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0062] Unless otherwise specified, all parts and percentages in the examples are based on weight. Information on the components used in the examples is as follows:

[0063] Multiso 13/30, an iso-tridecanol polyoxyethylene ether (3 EO), with HLB=7.9, available from Sasol;

[0064] Multiso 13/120, an iso-tridecanol polyoxyethylene ether (12 EO), with HLB=14.5, available from Sasol;

[0065] Phenoxyethanol, available from Schulke;

[0066] Amino polyorganosiloxane 1, a side chain amino polyorganosiloxane terminated with hydroxyl and/or methoxy groups, having an amine number of 0.14 mmol/g and a viscosity of 5,000 mPa.Math.s measured according to DIN 53019, where II/III=0 and the number of moles of the terminal hydroxyl groups is less than that of alkoxy groups, tested by .sup.29Si NMR and .sup.1H NMR;

[0067] Amino polyorganosiloxane 2, a side chain amino polyorganosiloxane terminated with hydroxyl and/or methoxy groups, having an amine number of 0.12 mmol/g and a viscosity of 5,000 mPa.Math.s measured according to DIN 53019, where II/III=0 and the number of moles of the terminal hydroxyl groups is greater than that of alkoxy groups, tested by .sup.29Si NMR and .sup.1H NMR;

[0068] Amino polyorganosiloxane 3, WACKER® FINISH WR1300, a side chain amino polyorganosiloxane terminated with hydroxyl and/or methoxy groups, having an amine number of 0.3 mmol/g and a viscosity of 1,000 mPa.Math.s measured according to D IN 53019, where II/III=0.

[0069] The above amino polyorganosiloxanes are supplied by WACKER CHEMIE AG.

[0070] Low-viscosity silicone fluid 1, BELSIL® DM2, having a viscosity of 2 mm.sup.2/s measured according to DIN 51562, available from WACKER CHEMIE AG;

[0071] Low-viscosity silicone fluid 2, BELSIL® 0.65, having a viscosity of 0.65 mm.sup.2/s measured according to DIN 51562, available from WACKER CHEMIE AG;

[0072] BELSIL® TM 803, a white solid powder at room temperature and MQ silicone resin with an Mw of 7300 g/mol, all units selected from VII and X, where alkoxy and hydroxyl groups are present in a total amount of 3.3 wt % and the hydroxyl content is less than or equal to 0.3 wt %, based on the total weight of silicone resins, available from WACKER CHEMIE AG;

[0073] BELSIL® MK Powder, a white solid powder at room temperature and T-type silicone resin with methoxy and methyl functional groups, all units selected from IX, having an Mw of about 10,000 g/mol;

[0074] SILRES® MSE 100, a liquid at room temperature and oligomeric T-type silicone resin with methoxy and methyl functional groups, all units selected from IX, having a solvent content of less than 2%, an Mw of from 2,000 to 5,000 g/mol and a viscosity of from 20 to 35 mm.sup.2/s;

[0075] SILRES® IC368, a solvent-free liquid at room temperature and oligomeric T-type silicone resin with methoxy, methyl and phenyl functional groups, all units selected from IX, wherein the content of methoxy groups is 15 wt % and the molar ratio of phenyl to methoxy is 1, having an active substance content of 84%, an Mw of about 1,900 g/mol and a viscosity of from 280 to 320 mm.sup.2/s;

[0076] The above silicone resins are supplied by WACKER CHEMIE AG.

TABLE-US-00001 TABLE 1 BELSIL ® BELSIL ® Amino Silicone resins DM2 0.65 polyorganosiloxane (A2) (wt %) (wt %) (wt %) 1 (wt %) Evaluation 1 BELSIL TM 1 5 transparent 803 2 SILRES MSE 1 5 transparent 100 3 SILRES 1 5 transparent IC368 4 BELSIL MK 1 5 insoluble, powder deposited on the bottom 5 BELSIL MK 1 5 transparent 6 BELSIL TM 1 5 38 transparent 803 7 SILRES MSE 1 5 38 / 100 8 SILRES 1 5 38 very turbid IC368 9 BELSIL MK 1 5 38 / 10 BELSIL MK 1 5 38 translucent

[0077] Compatibility test herein refers to a test in which the substances were mixed at room temperature as shown in Table 1, and after 24 hours the compatibility was observed.

[0078] Preparation Method

[0079] The following examples and comparative examples were carried out at room temperature according to the ratios of the ingredients shown in Table 2.

[0080] (1) the surfactant composition, the polyorganosiloxanes, the silicone resins, the optional low-viscosity oil and phenoxyethanol were mixed to form mixture (I) with IKA Eurostar 60 Digital (800-1500 rpm) stirrer;

[0081] (2) an aqueous acetic acid solution (containing acetic acid and water) was slowly added to mixture (I) while being stirred to obtain mixture (II).

[0082] (3) the remaining water was uniformly added to the mixture from step (2) to obtain a transparent oil-in-water emulsion; and

[0083] (4) the pH value of the emulsion obtained in step (3) was adjusted to 5-5.5 with 10 wt % aqueous solution of NaOH.

[0084] The compositions used in the examples and comparative examples are shown in Table 2, and the test results are shown in Table 4.

TABLE-US-00002 TABLE 2 C. Ex. 0 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 C. Ex. 8 C. Ex. 9 Ex. 10 C. Ex. 11 C. Ex. 12 Multiso 13/30 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Multiso 13/120 2 2 2 2 2 2 2 2 2 2 2 2 2 Phenoxyethanol 1 1 1 1 1 1 1 1 1 1 1 1 1 Amino polyorgano- 16 16 16 16 16 16 16 16 16 16 16 siloxane 1 Amino polyorgano- 16 siloxane 2 Amino polyorgano- 16 siloxane 3 BELSIL TM 803 / 1.78 0.64 0.42 0.42 0.32 0.23 0.21 0.42 BELSIL ® MK / 0.21 0.42 0.42 SILRES ® MSE100 / 0.42 SILRES ® IC 368 / 0.42 BELSIL DM 2 2.11 8.9 3.2 2.11 2.11 1.6 1.14 2.11 2.11 2.11 2.11 2.11 BELSIL 0.65 2.11 Acetate Acid 10.15 10.15 10.15 10.15 10.15 10.15 10.15 10.15 10.15 10.15 10.15 10.15 10.15 solution Water 64.24 55.67 62.51 63.82 63.82 64.43 64.98 63.82 63.82 63.82 63.82 63.82 63.82 total 100 100 100 100 100 100 100 100 100 100 100 100 100

[0085] Film-Forming Experiment

[0086] 3 g of the transparent emulsions of examples and comparative examples were respectively spread on an A1 foil tart cups having a radius of 7.7 cm, and stored for drying at 25° C. and 70% r.h for 96 hours. Afterwards, a scraper was used to scratch the film and the degree of film formation is rated (see Table 3).

TABLE-US-00003 TABLE 3 Rating System Scoring 0 1 2 3 5 Observed Significant Solid film Solid film intact Solid film intact Solid film intact results wire drawing broken Significant Slight scratches No scratches but no wire scratches on on film surface on film surface drawing film surface

[0087] In Table 3, the higher the score, the higher the degree of crosslinking.

TABLE-US-00004 TABLE 4 C. Ex. 0 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 C. Ex. 8 C. Ex. 9 Ex. 10 C. Ex. 11 C. Ex. 12 Score No film 5 5 3 5 3 1 1 0 0 2 1 1 formed

[0088] In C.Ex.12, the viscosity of the amino polyorganosiloxane was too low to form a film having a high degree of crosslinking and a high score.

[0089] In C.Ex.8 and 9, in spite of a silicone resin with a higher Mw used, a film having a high degree of crosslinking and a high score was not formed yet. In contrast, through the Mw of the silicone resin used in Ex.10 is lower than that of the silicone resin used in C.Ex.8, a film having a higher score was formed.

[0090] The inventors of the present invention surprisingly found that, if II/III=0, when the amino polyorganosiloxanes (A1) having a higher viscosity and a higher molecular weight were used in combination with a solid MQ type silicone resin, a film having a high degree of crosslinking and a high score could be formed. Moreover, when the silicone resins (A2), the amino polyorganosiloxanes (A1) and the low viscosity oil (A3) were mixed to form a transparent homogeneous phase, a solid film having a higher strength and a higher score can be formed.

[0091] Hair Curl Test

[0092] The hair tresses (10 g, 20 cm) were washed with ether and then with a 5% ammonium lauryl sulfate solution. The hair tresses were completely wet with water. Afterwards, 0.7 ml of the sample was evenly applied to each tress, which was fully rubbed for 30 seconds, let stand for 30 seconds before rinsing with 35° C. warm water, and hung on the hair rack for air-drying for later use.

[0093] Basic Formulation of Conditioner

TABLE-US-00005 Phase Grade INCI wt % A Water q.s. to 100 Glycerol 3.00 Natrosol 250HHR Hydroxyethyl cellulose 1.50 Disodium EDTA 0.10 B Genamin KDMP Docosyltrimethylammonium 2.00 chloride Lanette O Cetearyl alcohol 5.00 C Microcare IT Isothiazolinone 0.10 D Water + emulsion of 10.00 examples

[0094] The amino polyorganosiloxanes (A1) and the silicone resins (A2) are present in the conditioner in a total amount of 1.5 wt %, based on the total weight, as 100 wt %, of the basic formulation of the conditioner.

[0095] A conditioner sample was applied, at 0.5 g per 1.5 g of hair, to the prepared hair tress wetted again with water, which was rubbed for 1 minute and let stand for 1 minute before rinsing with water for 30 seconds. The water was absorbed from the hair tress with a paper towel until no water drips. At 25° C. and 70% r.h., a curling iron was heated to and maintained at 170° C. The hair tress was wound 4 turns clockwise around a curling iron, and after 15 to 20 seconds let naturally relax to cool down at room temperature.

[0096] The hair tress was placed vertically, with the top end fixed, photographed and scored to obtain the initial degree of curling.

[0097] A spray bottle was used to spray water onto the upper, middle and lower parts of the aforesaid hair tress once, which was immediately combed twice from top to bottom with a plastic comb, and air-dried. The hair tress was photographed again and scored to obtain the final degree of curling. The initial and final degrees of curling were compared and scored in terms of tress length change, number of curls, and angle change.

TABLE-US-00006 TABLE 5 C. Ex. 0 Ex. 2 Ex. 3 Ex. 4 C. Ex. 8 C. Ex. 12 Hairstyle's hold Average Good Good Very Average Average (degree of curling good evaluation) Storage stability / 21 28 3 3 28*2 at 48° C. (d) Soft 2 0 1 0 1 2 Sticky 1 3 2 3 3 2

[0098] The inventors of the present invention surprisingly found that, if the conditioner comprised an emulsion having a high degree of crosslinking and a good film strength, the hair tress treated with this conditioner exhibited a good style's hold, and had a smooth, non-sticky hand feel.

[0099] Each hair tress was touched by a 9-person test panel to evaluate its softness and smoothness. Results were classified into 3 grades: 0=fair, 1=good, 2=very good.

[0100] In Table 5 above, the stickiness (hand feel) was evaluated in reference to the following:

The stickiness of lanolin wax was given 10 points (very sticky);
Jergens Aloe and Lanolin (commercial product) oil-in-water lotion was given 5 points (moderately sticky);
The stickiness of baby oil (pure mineral oil) was given 0 point (not significantly sticky).