AQUEOUS DISPERSIONS OF PRE-CROSSLINKED ORGANOPOLYSILOXANES

Abstract

An aqueous of pre-crosslinked organopolysiloxanes and process for producing the same. The aqueous dispersion is preferably aqueous emulsion, including pre-crosslinked organopolysiloxanes which contains on average at least one structural unit of the general formula SiRO.sub.2/2—Y—SiRO.sub.2/2 and units of the formula R.sub.2SiO.sub.2/2. Where Y is a radical of the formula

—R.sup.2—[NR.sup.3—R.sup.4—].sub.x—NR.sup.3—OC—[C(Z.sup.1)(H)].sub.k1—[C(Z.sup.2)(H)].sub.k2—CO—NR.sup.3—[R.sup.4—NR].sub.x—R.sup.2

and where R, R.sup.2, R.sup.3, R.sup.4, k1, k2, x, Z.sup.1 and Z.sup.2 have a definition a set forth within herein. Additionally, the sum of k1+k2 is ≥1, the that at least one radical Z.sup.1 or Z.sup.2 is a hydroxyl or NHR.sup.3 group, preferably a hydroxyl group, and so the bridging group Y contains at least one hydroxyl or NHR.sup.3 group, preferably at least one hydroxyl group.

Claims

1.-15. (canceled)

16. An aqueous dispersion, comprising: wherein the aqueous dispersion is preferably aqueous emulsion, comprising pre-crosslinked organopolysiloxanes which contain on average at least one structural unit of the general formula
SiRO.sub.2/2—Y—SiRO.sub.2/2  (I) and units of the formula
R.sub.2SiO.sub.2/2  (II), wherein Y is a radical of the formula
—R.sup.2—[NR.sup.3—R.sup.4—].sub.x—NR.sup.3_OC—[C(Z.sup.1)(H)].sub.k1—[C(Z.sup.2)(H)].sub.k2—CO—NR.sup.3—[R.sup.4—NR.sup.3].sub.x—R.sup.2, wherein R may be identical or different and denotes a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may contain one or more heteroatoms from the group of N, P, S, O, and halogen; wherein R.sup.2 denotes an SiC-bonded, divalent linear or branched hydrocarbon radical having 3 to 18 carbon atoms, preferably an alkylene radical having 3 to 10 carbon atoms; wherein R.sup.3 denotes a hydrogen atom, an alkyl radical having 1 to 8 carbon atoms or an acyl radical, such as acetyl radical, and preferably is a hydrogen atom; wherein R.sup.4 denotes a divalent hydrocarbon radical having 1 to 6 carbon atoms, preferably an alkylene radical having 1 to 6 carbon atoms; wherein k1 is 0, 1, 2 or 3; wherein k2 is 0, 1, 2 or 3; wherein x is 0, 1, 2, 3 or 4, preferably 0 or 1; wherein Z.sup.1 is —OH, H or —NHR.sup.3; wherein Z.sup.2 is —OH, H or —NHR.sup.3; and wherein the sum k1+k2 is ≥1 and that at least one radical Z.sup.1 or Z.sup.2 is a hydroxyl or NHR.sup.3 group, preferably a hydroxyl group, and so the bridging group Y contains at least one hydroxyl or NHR.sup.3 group, preferably at least one hydroxyl group.

17. The aqueous dispersion of claim 16, wherein the pre-crosslinked organopolysiloxanes comprise siloxane units of the formula
R.sub.3-d(OR.sup.1).sub.dSiO.sub.1/2  (III), wherein R has the definition indicated for it in claim 16; wherein R.sup.1 may be identical or different and denotes a hydrogen carbon or an alkyl radical which has 1 to 18 carbon atoms and which may be interrupted by one or more separate oxygen atoms; and wherein d is 0 or 1.

18. The aqueous dispersion of claim 16, wherein Y is a radical of the formula
—R.sup.2—[NH—CH.sub.2CH.sub.2-].sub.x′—NH—OC—CH(OH)—CH(OH)—CO—NH—[CH.sub.2CH.sub.2—NH].sub.x′—R.sup.2— wherein x′ is 0 or 1; and wherein R.sup.2 is a radical of the formula —(CH.sub.2).sub.3— or —CH.sub.2—CH(CH.sub.3)—CH.sub.2—.

19. The aqueous dispersion of claim 16, wherein the aqueous dispersion is a cosmetic composition.

20. The aqueous dispersion of claim 19, wherein the cosmetic composition further comprises one or more conditioning agents.

21. The aqueous dispersion of claim 19, wherein the cosmetic composition is used for treating keratinic fibers, preferably for cleansing and caring for keratinic fibers; or wherein the cosmetic composition is used for conditioning keratinic fibers, more particularly for facilitating the combability of keratinic fibers.

22. The aqueous dispersion of claim 21, wherein the keratinic fibers are hair.

23. A process for producing the aqueous dispersion of pre-crosslinked organopolysiloxanes, comprising the steps of: reacting an aqueous dispersion, preferably aqueous emulsion, of aminoorganopolysiloxanes (1) of the formula
(R.sup.1O).sub.dA.sub.cR.sub.3-d-cSiO(SiARO).sub.p(SiR.sub.2O).sub.qSiR.sub.3-d-cA.sub.c(OR.sup.1).sub.d  (IV); wherein A is an amino radical of the general formula
—R.sup.2—[NR.sup.3—R.sup.4—].sub.xNR.sup.3.sub.2, wherein R may be identical or different and denotes a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may contain one or more heteroatoms from the group of N, P, S, O, and halogen; wherein R.sup.1 may be identical or different and denotes a hydrogen atom or an alkyl radical which has 1 to 18 carbon atoms and may be interrupted by one or more separate oxygen atoms; wherein R.sup.2 denotes an SiC-bonded, divalent linear or branched hydrocarbon radical having 3 to 18 carbon atoms, preferably an alkylene radical having 3 to 10 carbon atoms; wherein R.sup.3 denotes a hydrogen atom, an alkyl radical having 1 to 8 carbon atoms or an acyl radical, such as acetyl radical, and preferably is a hydrogen atom; wherein R.sup.4 denotes a divalent hydrocarbon radical having 1 to 6 carbon atoms; preferably an alkylene radical having 1 to 6 carbon atoms, wherein d is 0 or 1; wherein e is 0 or 1; wherein p is an integer of at least one and at most 1000; wherein q is 0 or an integer from 1 to 2000; and wherein x is 0, 1, 2, 3 or 4, preferably 0 or 1; with reactive esters (2) of the formula
R.sup.5O.sub.2C—[C(Z.sup.1)(H)].sub.k1[C(Z.sup.2)(H)].sub.k2—CO.sub.2R.sup.5  (V), wherein R.sup.5 may be identical or different and denotes an O-bonded, saturated or unsaturated, linear or branched, monovalent hydrocarbon radical which has 1-20 carbon atoms per radical and may contain one or more heteroatoms from the group of N, P, S, O and halogen; wherein k1 is 0, 1, 2 or 3; wherein k2 is 0, 1, 2 or 3; wherein Z.sup.1 is —OH, H or —NHR.sup.3; wherein Z.sup.2 is —OH, H or —NHR.sup.3; with the provisos that the sum k1+k2 is ≥1 and that at least one radical Z.sup.1 or Z.sup.2 is a hydroxyl or NHR.sup.3 group, preferably a hydroxyl group.

24. The process of claim 23, wherein A is an amino radical of the formula
—R.sup.2—[NH—CH.sub.2CH.sub.2-].sub.x′—NH.sub.2 wherein x′ is 0 or 1; and wherein R.sup.2 is a radical of the formula —(CH.sub.2).sub.3— or —CH.sub.2—CH(CH.sub.3)—CH.sub.2—.

25. The process of claim 23, wherein the reactive esters (2) are dimethyl tartrates and diethyl tartrates.

26. The process of claim 23, wherein the aqueous dispersion is a cosmetic composition.

27. The process of claim 26, wherein the cosmetic composition further comprises one or more conditioning agents.

28. The process of claim 26, wherein the cosmetic composition is used for treating keratinic fibers, preferably for cleansing and caring for keratinic fibers; or wherein the cosmetic composition is used for conditioning keratinic fibers, more particularly for facilitating the combability of keratinic fibers.

29. The process of claim 28, wherein the keratinic fibers are hair.

30. The process of claim 26, further comprising the step of applying the cosmetic composition to keratinic fibers, preferably hair, and then optionally rinsing with water.

31. A pre-crosslinked organopolysiloxane composition, comprising: wherein the pre-crosslinked organopolysiloxane contains on average at least one structural unit, preferably at least two structural units, more preferably at least three structural units, of the general formula
SiRO.sub.2/2—Y—SiRO.sub.2/2  (I) and units of the formula
R.sub.2SiO.sub.2/2  (II), wherein Y is a radical of the formula
[NR.sup.3.sub.x—NR.sup.3—OC—C(Z.sup.1)(H)].sub.k1—[C(Z.sup.2)(H)].sub.k2—CO—NR.sup.3-[x-R.sup.4—NR.sup.3].sub.x—R.sup.2— wherein R may be identical or different and denotes a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may contain one or more heteroatoms from the group of N, P, S, O, and halogen; wherein R.sup.2 denotes an SiC-bonded, divalent linear or branched hydrocarbon radical having 3 to 18 carbon atoms, preferably an alkylene radical having 3 to 10 carbon atoms; wherein R.sup.3 denotes a hydrogen atom, an alkyl radical having 1 to 8 carbon atoms or an acyl radical, such as acetyl radical, and preferably is a hydrogen atom; wherein R.sup.4 denotes a divalent hydrocarbon radical having 1 to 6 carbon atoms, preferably an alkylene radical having 1 to 6 carbon atoms; wherein k1 is 0, 1, 2 or 3; wherein k2 is 0, 1, 2 or 3; wherein Z.sup.1 is —OH, H or —NHR.sup.3; wherein Z.sup.2 is —OH, H or —NHR.sup.3; and wherein the sum k1+k2 is ≥1 and that at least one radical Z.sup.1 or Z.sup.2 is a hydroxyl or NHR.sup.3 group, preferably a hydroxyl group, and so the bridging group Y contains at least one hydroxyl or NHR.sup.3 group, preferably at least one hydroxyl group.

32. The pre-crosslinked organopolysiloxane composition of claim 31, wherein the siloxane units have the formula
R.sub.3-d(OR.sup.1).sub.dSiO.sub.1/2  (III) wherein R and Y have the definition indicated for them in claim 31; wherein R.sup.1 may be identical or different and denotes a hydrogen carbon or an alkyl radical which has 1 to 18 carbon atoms and which may be interrupted by one or more separate oxygen atoms; and wherein is 0 or 1.

33. The composition of claim 31, wherein the composition is a cosmetic composition.

34. The composition of claim 33, wherein the cosmetic composition further comprises one or more conditioning agents.

35. The composition of claim 33, wherein the cosmetic composition is used for treating keratinic fibers, preferably for cleansing and caring for keratinic fibers; or wherein the cosmetic composition is used for conditioning keratinic fibers, more particularly for facilitating the combability of keratinic fibers.

36. The composition of claim 35, wherein the keratinic fibers are hair.

37. A process for producing a pre-crosslinked organopolysiloxane composition, comprising the steps of: providing an amino-organopolysiloxanes of the formula
(R.sup.1O).sub.dA.sub.cR.sub.3-d-cSiO(SiARO).sub.p(SiR.sub.2O).sub.qSiR.sub.3-d-cA.sub.c(OR.sup.1).sub.d  (IV) reacted with reactive esters of the formula
R.sup.5O.sub.2C—[C(Z.sup.1)(H)].sub.k1—[C(Z.sup.2)(H)].sub.k2—CO.sub.2R.sup.5  (V) wherein A is an amino radical of the general formula
—R.sup.2—[NR.sup.3—R.sup.4—].sub.xNR.sup.3.sub.2, wherein R may be identical or different and denotes a monovalent hydrocarbon radical which has 1 to 18 carbon atoms and may contain one or more heteroatoms from the group of N, P, S, O, and halogen; wherein R.sup.1 may be identical or different and denotes a hydrogen atom or an alkyl radical which has 1 to 18 carbon atoms and may be interrupted by one or more separate oxygen atoms; wherein R.sup.5 may be identical or different and denotes an O-bonded, saturated or unsaturated, linear or branched, monovalent hydrocarbon radical which has 1-20 carbon atoms per radical and may contain one or more heteroatoms from the group of N, P, S, O and halogen; wherein k1 is 0, 1, 2 or 3; wherein k2 is 0, 1, 2 or 3; wherein Z.sup.1 is —OH, H or —NHR.sup.3; wherein Z.sup.2 is —OH, H or —NHR.sup.3; wherein the sum k1+k2 is ≥1 and that at least radical Z.sup.1 or Z.sup.2 is a hydroxyl or NHR.sup.3 group, preferably a hydroxyl group; and wherein the resulting pre-crosslinked organopolysiloxanes are optionally subsequently emulsified in water.

38. The process of claim 37, wherein the composition is a cosmetic composition.

39. The process of claim 38, wherein the cosmetic composition further comprises one or more conditioning agents.

40. The process of claim 38, wherein the cosmetic composition is used for treating keratinic fibers, preferably for cleansing and caring for keratinic fibers; and/or wherein the cosmetic composition is used for conditioning keratinic fibers, more particularly for facilitating the combability of keratinic fibers.

41. The process of claim 40, wherein the keratinic fibers are hair.

42. The process of claim 38, further comprising the step of applying the cosmetic composition to keratinic fibers, preferably hair, and then optionally rinsing with water.

Description

EXAMPLES 1-6

[0313] Examples 1-6 below represent production processes for the synthesis of aqueous dispersions of precrosslinked organopolysiloxanes according to the invention, which are used for producing cosmetic compositions of the invention.

Example 1: Emulsion B1

[0314] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 5000 rpm, 98.9 g of the aminosilicone oil emulsion E1 are homogenized with 1,1 g of diethyl L-tartrate over the course of a minute.

[0315] This gives a smooth white silicone oil emulsion B1 of low viscosity, having a solids content of 41% and a pH of 5. The particle size distribution is monomodal with a D50 of 110 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0316] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, gelatinous film which has a tacky surface and adheres weakly to glass and aluminum.

Example 2: Emulsion B2

[0317] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 5000 rpm, 98.9 g of the aminosilicone oil emulsion E2 are homogenized with 1,1 g of diethyl L-tartrate over the course of a minute.

[0318] This gives a smooth white silicone oil emulsion B2 of low viscosity, having a solids content of 41% and a pH of 6.5. The particle size distribution is bimodal with a D50 of 110 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0319] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, elastic film which has a nontacky surface and adheres well to glass and aluminum.

Example 3: Emulsion B3

[0320] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 5000 rpm, 98.9 g of the aminosilicone oil emulsion E3 are homogenized with 1,1 g of diethyl L-tartrate over the course of a minute.

[0321] This gives a smooth white silicone oil emulsion B3 of low viscosity, having a solids content of 41% and a pH of 6.5. The particle size distribution is bimodal with a D50 of 110 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0322] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, elastic film which has a nontacky surface and adheres well to glass and aluminum.

Example 4: Emulsion B4

[0323] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 5000 rpm, 98.9 g of the aminosilicone oil emulsion E4 are homogenized with 1,1 g of diethyl L-tartrate over the course of a minute.

[0324] This gives a smooth translucent emulsion B4 of low viscosity, having a solids content of 33% and a pH of 6.5. The particle size distribution is monomodal with a D50 of 56 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0325] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, elastic film which has a nontacky surface and adheres well to glass and aluminum.

Example 5: Emulsion B5

[0326] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 5000 rpm, 98.9 g of an emulsion E5 are homogenized with 1,1 g of diethyl L-tartrate over the course of a minute. This gives a smooth white silicone oil emulsion B5 of low viscosity, having a solids content of 41% and a pH of 5. The particle size distribution is monomodal with a D50 of 186 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0327] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, gelatinous film which has a tacky surface and adheres weakly to glass and aluminum.

Example 6: Emulsion B6

[0328] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 5000 rpm, 98.9 g of an emulsion E6 are homogenized with 1,1 g of diethyl L-tartrate over the course of a minute. This gives a smooth white silicone oil emulsion B6 of medium viscosity, having a solids content of 41% and a pH of 5. The particle size distribution is multimodal with a D50 of 171 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0329] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, gelatinous film which has a tacky surface and adheres weakly to glass and aluminum.

Example 7: Emulsion B7

[0330] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 5000 rpm, 98.9 g of an emulsion E7 are homogenized with 1,1 g of diethyl L-tartrate over the course of a minute. This gives a smooth white silicone oil emulsion B7 of low viscosity, having a solids content of 41% and a pH of 5. The particle size distribution is bimodal with a D50 of 115 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0331] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, gelatinous film which has a tacky surface and adheres weakly to glass and aluminum.

Example 8

[0332] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 4000 rpm, 4.9 g of an 80% aqueous solution of isotridecyldecaethoxylate, available commercially under the tradename Lutensol TO 10 (from BASF), and 2.4 g of fully demineralized water are premixed. 34.4 g of a hydroxy/methoxy-terminated copolymer composed of 3-(2-aminoethyl-amino)propylmethylsiloxy and dimethylsiloxy units, having an amine number of 0.13 and a viscosity of 4000 mm.sup.2/s (at 25° C.), are added in three portions with shearing of 4000 rpm, to give a relatively firm stiff phase. This stiff phase is further prediluted with 4.9 g of fully demineralized water. At this point 1.1 g of diethyl L-tartrate are incorporated further at 4000 rpm.

[0333] Dilution is carried out with 51.2 g of fully demineralized water in portions, with gentle shearing, to form the desired emulsion, and 0.20 g of 80% acetic acid and 0.9 g of 2-phenoxyethanol are added.

[0334] This gives a smooth white silicone oil emulsion B8 of low viscosity, having a solids content of 40% and a pH of 5. The particle size distribution is monomodal with a D50 of 105 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0335] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, gelatinous film which has a tacky surface and adheres weakly to glass and aluminum.

Example 9

[0336] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 4000 rpm, 5.5 g of an 80% aqueous solution of isotridecyldecaethoxylate, available commercially under the tradename Lutensol TO 10 (from BASF), and 5.5 g of fully demineralized water are premixed. A mixture of 33.76 g of a copolymer composed of 3-(2-aminoethylamino)propylmethylsiloxy and dimethylsiloxy units, having an amine number of 0.13 and a viscosity of 4000 mm.sup.2/s (at 25° C.), and 1.04 g of diethyl L-tartrate are added in three portions with shearing of 4000 rpm, to give a relatively firm stiff phase as a preliminary emulsion. Dilution is carried out with 53.1 g of fully demineralized water in portions, with gentle shearing, to form the desired emulsion, and 0.20 g of 80% acetic acid and 0.9 g of 2-phenoxyethanol are added.

[0337] This gives a smooth white silicone oil emulsion B9 of low viscosity, having a solids content of 40% and a pH of 5. The particle size distribution is bimodal with a D50 of 134 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0338] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, gelatinous film which has a tacky surface and adheres weakly to glass and aluminum.

Example 10

[0339] A mixture of 97.0 g of a hydroxy/methoxy-terminated copolymer composed of 3-(2-aminoethylamino)propylmethylsiloxy and dimethylsiloxy units, having an amine number of 0.13 and a viscosity of 4000 mm.sup.2/s (at 25° C.), and 3.0 g of diethyl L-tartrate are homogenized thoroughly with a paddle stirrer on a stirring apparatus from IKA. Immediately thereafter a film is cast, as described below. This gives a transparent elastomer film.

[0340] Comparative Experiments V1 and V2:

[0341] Comparative experiments V-1 and V-2 below represent production processes for the synthesis of noninventive aqueous emulsions.

[0342] Comparative Experiment V1 (Crosslinking with Noninventive Diethyl Succinate):

[0343] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 5000 rpm, 99.91 g of the aminosilicone oil emulsion E1 are homogenized with 0.9 g of diethyl succinate over the course of a minute.

[0344] This gives a smooth white silicone oil emulsion V1 of low viscosity, having a solids content of 40% and a pH of 5. The particle size distribution is monomodal with a D50 of 110 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0345] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, pasty layer which adheres weakly to glass and aluminum.

[0346] Comparative Experiment V2 (Crosslinking with Noninventive Diethyl Oxalate as Per U.S. Pat. No. 5,039,738 A):

[0347] Using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel/IKA), at 5000 rpm, 99.91 g of the aminosilicone oil emulsion E1 are homogenized with 0.9 g of diethyl oxalate over the course of a minute.

[0348] This gives a smooth white silicone oil emulsion V2 of low viscosity, having a solids content of 40% and a pH of 5. The particle size distribution is monomodal with a D50 of 110 nm. The emulsion is still uniform and stable after 4-week storage at 50° C.

[0349] Evaporation of the emulsion produces, after a drying time of 24 hours at 25° C., a white-opaque, pasty layer which adheres weakly to glass and aluminum.

[0350] Rheology of Elastomer Films after Removal of Water:

[0351] Production of Films for Rheology Measurements:

[0352] A Teflon ring having an internal diameter of 40 mm is placed onto a circular glass plate having a diameter of 65 mm, to form a casting mold. Into this ring, 2.5 g of the emulsion under measurement are weighed out onto the glass plate without bubbles. The cast emulsion is then left to dry at 25° C. and 101.425 kPa. It should be ensured that the casting mold with the cast emulsion for drying is located on a leveled planar surface, to allow a film of uniform thickness to develop. In this case, after drying, a film around 0.5 mm thick is obtained.

[0353] After a standing time of 1 week at 25° C., the films obtained undergo rheological analysis. The measurements were made using an MCR 302 rheometer from Anton Paar, employing a PP12.5 plate/plate measurement system and a gap height of 0.5 mm. The instrument was calibrated using standard oil 10 000 from the Physikalisch-Technische Bundesanstalt. The measuring temperature is 25.00° C. +/−0.05° C.

[0354] The values listed in table 1 for the storage modulus G′, the loss modulus G″ and the loss factor tan δ can be computed by applying a sinusoidal deformation to measure the shear stress and the phase shift angle δ. The measured values listed in table 1 were measured at a frequency of 1 Hz and a deformation of 0.1%. Under deformation, the measured samples are in the linear viscoelastic measuring range. The following relationship applies: tan δ=G″/G′. If tan δ<1, the elastic character of the sample is predominant; if tan δ>1, the viscous character of the sample is predominant.

[0355] The results of the rheology measurements for the elastomer films of inventive examples B1 to B10, of comparative experiments V-1 and V-2 and also of the uncrosslinked aminosilicone oil emulsions E1 to E7 are collated in table 1.

TABLE-US-00001 TABLE 1 Rheological data of the elastomer films Ex./ Storage modulus Loss modulus comp. Ex. G′ [Pa] G″ [Pa] tan δ B1 20 600 5930 0.29 B2 10 600 2630 0.25 B3 37 900 7890 0.21 B4   2060 1290 0.63 B5 15 600 1880 0.12 B6 29 100 5080 0.18 B7   9020 4010 0.45 B8 13 200 4190 0.32 B9 13 200 4190 0.32 B10 53 200 16 300   0.31 V-1   231  725 3.13 V-2 11 900 7860 0.66 E1    53  319 6.05 E2   405  723 1.78 E3     18.1  248 13.6 E4    12  211 18.1 E5     1.3    19.6 15.3 E6   100  451 4.5 E7   143  765 5.4

[0356] Table 1 shows that the inventive emulsions B1 to B9 with diethyl L-tartrate as crosslinker component form elastic films following removal of water, since tan δ<1. In example 10 as well an elastic film is formed.

[0357] The noninventive emulsion V2 (containing diethyl oxalate as crosslinker) likewise forms an elastic film on removal of water.

[0358] In contrast, the noninventive emulsion V1, containing diethyl succinate rather than diethyl L-tartrate, does not form a film. This is shown by the loss factor of 3.13.

[0359] The evaporated, pure aminosilicone oil emulsions E1 to E7 likewise show no filming on removal of water, since in all cases tan δ is greater than 1. This shows that the addition of a crosslinker is necessary in order to achieve filming.

[0360] These results show, surprisingly, that filming occurs as a result of the addition of the hydroxy-functional crosslinker diethyl L-tartrate according to the invention, but not by the addition of the noninventive, unfunctionalized diester, such as diethyl succinate.

[0361] Test Methods for Assessing the Effect of Cosmetic Compositions:

[0362] Natural Hair

[0363] The application behavior of the cosmetic composition and its effect in terms of combing force and softness were assessed on Caucasian hair, available from Kerling International Haarfabrik GmbH. Before being used, undamaged tresses of natural hair are cleaned and where appropriate, in a further process step, damaged by bleaching.

[0364] Basic Cleaning

[0365] For cleaning, the undamaged hair tresses are placed for an hour in a solvent mixture composed of equal parts of toluene and isobutyl ketone, and shaken. Following removal of the solvent mixture, the hair tresses are washed in each case twice with 3 ml of ammonium lauryl sulfate solution (25%), STEPANOL® ALS 25, from STEPAN Company, and then with fully demineralized water having a temperature of 30° C. The tresses are detangled using a coarse-tooth comb. The hair tresses are placed subsequently for an hour in a large beaker of fully demineralized water, withdrawn, and additionally rinsed under running, fully demineralized water. After the basic cleaning, and before being used further, the tresses are conditioned for at least 12 hours at 23° C. and 50% humidity and are combed before being used.

[0366] Bleaching of Hair—Generation of Damaged Hair

[0367] Damaged hair is generated by bleaching of cleaned natural hair tresses. This is done by placing five hair tresses in each case for 30 minutes into a solution composed of 30% hydrogen peroxide and 25% ammonia (ratio 33.5:1). The hair is subsequently thoroughly rinsed off with fully demineralized water and washed twice with 3 ml of ammonium lauryl sulfate solution (25%), STEPANOL® ALS 25, from STEPAN Company, and with fully demineralized water having a temperature of 30° C. Thereafter the hair tresses are placed for an hour in a large beaker of fully demineralized water, withdrawn, and further rinsed under running, fully demineralized water. Prior to further treatment, the bleached tresses are conditioned for at least 12 hours at 23° C. and 50% humidity and are combed before being used.

[0368] Combing Force Measurement:

[0369] The combing force on wet and dry hair was determined using hair tresses of damaged Caucasian hair from Kerling International Haarfabrik GmbH (hair tresses degree of damage B, double-drawn) having a weight of 2 g and a length of 20 cm. The combing force was measured by the double comb method of Y. K. Kamath and Hans-Dietrich Weigmann, J. Soc. Cosmet. Chem., 37, 111-124, 1986, using an Instron 3343 tension-elongation machine. First of all the wet and dry combing force is determined along the measurement section on untreated hair tresses. The hair tresses are then treated with an inventive cosmetic composition and the force absorption during the combing procedure is determined. The measurement value reported is the reduction in combing force along the measurement section (work) that arises between the treated and untreated hair tress. The mean value from five hair tresses is formed. The combing force reduction is reported as a percentage.

[0370] Smoothness/Softness (According to Tensile Testing):

[0371] The softness of the hair was determined using hair tresses from Kerling International Haarfabrik GmbH (Caucasian hair, double-drawn) having a weight of 2 g and a length of 20 cm. The hair softness in the dry state was determined using an Instron 3343 tensile testing machine, by correlating the required tensile force with the parameters of flexural stiffness and surface roughness of the hair bundle. These two parameters correlate in turn with the hair softness. For this purpose, an untreated hair tress was clamped into a measurement setup consisting of five rods lying opposite one another with an offset. The shape of the hair tress in this initial position is a kind of double S. Following this preparation, the hair tress is pulled out of the measurement setup in one direction and the force required is evaluated along the measurement section, as work. The hair tresses are then treated with an inventive cosmetic composition and the force absorption on pulling of the hair tress through the measurement setup is determined along the measurement section. The measurement value reported is the reduction in tensile force along the measurement section (work) which arises between the treated and untreated hair tress. A large reduction in tensile force (work) corresponds to a good soft feel/high smoothness. The mean is formed from five hair tresses.

[0372] Softness (According to Panel Test):

[0373] For assessing the softness of hair tresses, their tactile properties are assessed by experts (trained panelists). The hair tresses are compared in pairs in each case—for example, shampoo-treated hair as compared with untreated hair. The number of pairs of tresses assessed is at least three, the number of panelists at least five. The evaluation was based on hair tresses from Kerling International Haarfabrik GmbH (Caucasian hair, double-drawn) having a weight of 2 g and a length of 20 cm.

[0374] Washing Procedure, Shampoo:

[0375] Shampoo is applied at 0.2 g per g of hair to a cleaned, wetted hair tress. The shampoo is massaged in for 30 seconds in the direction of the hair ends. The hair tress is then rinsed for 30 s under running, fully demineralized water, and detangled using a coarse-tooth comb. The procedure is repeated twice. On the last occasion, the rinsing process is extended to 60 s. The hair tress is then dried for at least 12 h at an atmospheric humidity of 50% and a temperature of 23° C.

[0376] Washing Procedure, Conditioner:

[0377] Rinse-off conditioner is applied at 0.3 g/g of hair to a cleaned, wetted hair tress. The rinse-off conditioner is massaged in for 120 seconds in the direction of the hair ends. The hair tress is then rinsed for 60 s under running, fully demineralized water, and detangled using a coarse-tooth comb. The procedure is repeated. The hair tress is then dried for at least 12 h at an atmospheric humidity of 50% and a temperature of 23° C.

[0378] Determination of the Amount of Si Deposited on the Hair Surface in Ppm (Silicone Deposition):

[0379] The amount of silicone deposited on the hair surface is determined using an energy-dispersive x-ray fluorescence spectrometer (AMETEK, XEPOS). The hair bundles are placed in a specially manufactured sample holder, having a circular measurement area of 12 mm in diameter. The hair surface in the region of the measurement area is smooth, and the hairs are aligned in parallel. The sample is excited under the helium atmosphere, using a palladium tube (17.05 kV, 2.0 mA). The excitation time is 300 s. Control samples (natural hair tresses) are subjected to regular measurement. In the event of deviations, a drift correction takes place using glass tablets. The calibration standards used were hair tresses loaded with polydimethylsiloxane in the 50 to 2000 ppm range (control by atomic absorption spectroscopy).

[0380] To determine the effectiveness of the silicone deposition, a determination is made first of the amount of Si in ppm on a cleaned hair bundle=blank value. The same hair bundle is subsequently treated, by being washed with a shampoo, for example. The amount of Si in ppm is determined again=sample value. The amount of Si in ppm deposited is obtained by performing the following subtraction: sample value—blank value. Each hair tress is measured centrally on the facing and reverse sides. The result reported is the mean value from three hair tresses.

[0381] Simulation of Shampooing by Stirring Hair Tresses in a Surfactant Solution:

[0382] Many users desire cosmetic effects such as improved hair softness, reduction in wet combing force and retention of hair color to persist following application of a hair-conditioning product, in spite of multiple subsequent washes with shampoo. To assess the persistence of cosmetic effects following treatment of hair with an inventive cosmetic composition, a method was developed which constitutes a simulation of successive shampooings. For this purpose a treated hair tress in a 100 ml jar with screw-top lid is admixed with 50 ml of a five percent solution of ammonium lauryl solvate, this solution having been conditioned to 40° C. and obtained by diluting Stepanol® ALS 25, from Stepan Company, and the treated tress is shaken for a mandated time in an incubation shaker (Heidolph Unimax 1010+Incubator 1000) conditioned to 40° C., with a speed of 250 rpm. After having been shaken, the tresses are rinsed for a minute with fully demineralized water having a temperature of 30° C., and dried.

[0383] Color Protection/Color Measurement:

[0384] The inventive cosmetic composition was assessed for color protection effect on keratin fibers, using colored real hair. This was done using hair tresses having a weight of 4 g and a length of 20 cm, composed of damaged, Caucasian hair from Kerling International Haarfabrik GmbH (dense adhesive tress of European hair, bleaching stage A, mixture 79). The hair tresses were colored red. The shade used was Koleston Perfect® 77/44 from Wella or Majirel Mix Rouge from L′Oreal. 50 ml of hair coloring paste were mixed with 80 ml of six percent hydrogen peroxide solution. The paste was applied evenly to the hair tresses (1.6 g of paste/g of hair). After a contact time of 40 minutes at room temperature, the coloring paste was washed out of the hair tresses. Following treatment of the hair tress with a surfactant solution (Stepanol® ALS 25, from Stepan Company, diluted to 5% active content) and drying of the tresses, the coloring operation was repeated when using Koleston Perfect® 77/44.

[0385] Color measurement is performed on the smooth surface of the hair bundles, using the Spectro Guide colorimeter from Byk-Gardner. The color parameters L, a, b (Lab color space) are recorded.

[0386] Assessment of Color Protection by Hair Treatment with Inventive Cosmetic Compositions:

[0387] Colored hair undergoes a change in perceived color after washing with shampoo. The change in perceived color may be described by the □E value, which is defined as:

□E=((L1-Lo).sup.2+(a1-a0).sup.2+(b1-b0).sup.2).sup.1/2

[0388] L0, a0, b0 are the color values for a colored, untreated hair bundle.

[0389] L1, a1 and b1 are the color values for the hair bundle after simulation of shampooings, by stirring of hair tresses in a surfactant solution. A low □E value is an indicator of relatively low color change or enhanced persistence.

Examples of Cosmetic Compositions

Examples A1 to A4 (Rinse-Off Conditioners (Rinse)) A1-A4

[0390] The examples below represent inventive cosmetic compositions A1-A4 according to table 2, comprising the emulsions B1 and B2 from examples 1 and 2. The active content—the amount of precrosslinked organopolysiloxane in the cosmetic composition—is 0.5% to 2%.

[0391] Preparation instructions:

[0392] Water is introduced and heated to 75° C. with stirring. 1.3 parts of hydroxyethylcellulose are added. When 65° C. is attained, 0.5 part of Polysorbate 80, 0.5 part of Stearyl Alcohol, 0.5 part of Cetyl Alcohol and 0.2 part of Behentrimonium Chloride are added. The mixture is stirred until 75° C. is reached and the ingredients are in solution. The mixture is then cooled. In the course of cooling, 0.1 part of Citric Acid and 0.2 part of Tetrasodium EDTA are added. At 35° C., 0.9 part of Phenoxyethanol, and ethylhexylglycerin are added. With further stirring, the emulsion from the examples is added. The composition is homogenized with stirring for 15 minutes.

TABLE-US-00002 TABLE 2 Rinse-off conditioners A1-A4 Ex. A1 Ex. A2 Ex. A3 Ex. A4 Constituents [Parts [Parts [Parts [Parts (INCI name) by wt] by wt] by wt] by wt] Water ad 100 ad 100 ad 100 ad 100 Hydroxyethylcellulose.sup.1) 1.3 1.3 1.3 1.3 Cetyl Alcohol .sup.2) 0.5 0.5 0.5 0.5 Polysorbate 80 .sup.3) 0.5 0.5 0.5 0.5 Behentrimonium 0.2 0.2 0.2 0.2 Chloride .sup.4) Stearyl Alcohol .sup.5) 0.5 0.5 0.5 0.5 Citric Acid .sup.6) 0.1 0.1 0.1 0.1 Tetrasodium EDTA .sup.7) 0.2 0.2 0.2 0.2 Emulsion B1 from 5.71 ex. 1 Emulsion B1 from 1.43 ex. 1 Emulsion B2 from 5.71 ex. 2 Emulsion B2 from 1.43 ex. 2 Phenoxyethanol, 0.9 0.9 0.9 0.9 Ethylhexylglycerin .sup.8) The raw materials stated in table 2 are available under the following tradenames: .sup.1) Hydroxyethylcellulose: Natrosol 250 HR, Ashland .sup.2) Cetyl alcohol: cetyl alcohol, Merck KGaA .sup.3) Polysorbate 80: Tween ™ 80, Croda GmbH .sup.4) Behentrimonium Chloride: Genamin ® KDMP, Clariant GmbH .sup.5) Stearyl alcohol: stearyl alcohol, Merck KGaA .sup.6) Citric Acid: citric acid, Sigma .sup.7) Tetrasodium EDTA: EDETA ® B Powder, BASF Corporation .sup.8) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

Comparative Experiments V-A1 to V-A5 (Rinse-Off Conditioners (Rinse) V-A1-V-A5, not Inventive)

[0393] Comparative experiments V-A1 to V-A5 below represent noninventive cosmetic compositions V-A1-V-A4 comprising an aqueous dispersion of a non-precrosslinked organopolysiloxane or a noninventive cosmetic composition comprising a precrosslinked aqueous dispersion using the noninventive diethyl oxalate. The active content—the amount of organopolysiloxane—is 0.5 to 2 wt %. For the preparation of the cosmetic compositions of comparative experiments V-A1 to V-A5, the procedure for examples A1-A4 was repeated, with the modification that instead of the emulsions B1 and B2 from examples 1 and 2 (emulsions of inventive precrosslinked organopolysiloxane), the uncrosslinked emulsions E1 and E2 or the emulsions of the noninventive comparative experiment V2 are used. Emulsions of comparative experiments E1 and E2 contain organopolysiloxanes which are analogous in terms of initial viscosity to examples B1 and B2, but are uncrosslinked. The emulsion of comparative experiment V2 is precrosslinked with the noninventive diethyl oxalate rather than with the inventive diethyl L-tartrate.

TABLE-US-00003 TABLE 3 Rinse-off conditioners V-A1-VA5 Comp. Comp. Comp. Comp. Comp. exp. exp. exp. exp. exp. V-A1 V-A2 V-A3 V-A4 V-A5 Constituents [parts [parts [parts [parts [parts (INCI name) by wt.] by wt.] by wt.] by wt.] by wt.] Water ad 100 ad 100 ad 100 ad 100 ad 100 Hydroxyethyl- 1.3 1.3 1.3 1.3 1.3 cellulose .sup.1) Cetyl Alcohol .sup.2) 0.5 0.5 0.5 0.5 0.5 Polysorbate 80 .sup.3) 0.5 0.5 0.5 0.5 0.5 Behentrimonium 0.2 0.2 0.2 0.2 0.2 Chloride .sup.4) Stearyl Alcohol .sup.5) 0.5 0.5 0.5 0.5 0.5 Citric Acid .sup.6) 0.1 0.1 0.1 0.1 0.1 Tetrasodium 0.2 0.2 0.2 0.2 0.2 EDTA .sup.7) Emulsion E1 5.71 from ex. 1 Emulsion E1 1.43 from ex. 1 Emulsion E2 5.71 from ex. 2 Emulsion E2 1.43 from ex. 2 Emulsion V2 5.71 from comp. Exp. V2 Phenoxyethanol, 0.9 0.9 0.9 0.9 0.9 Ethylhexyl- glycerin.sup.8) The raw materials stated in table 3 are available under the following tradenames: .sup.1) Hydroxyethylcellulose: Natrosol 250 HR, Ashland .sup.2) Cetyl alcohol: cety l alcohol, Merck KGaA .sup.3) Polysorbate 80: Tween ™ 80, Croda GmbH .sup.4) Behentrimonium Chloride: Genamin ® KDMP, Clariant GmbH .sup.5) Stearyl alcohol: stearyl alcohol, Merck KGaA .sup.6) Citric Acid: citric acid, Sigma .sup.7) Tetrasodium EDTA: EDETA ® B Powder, BASF Corporation .sup.8)Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0394] Preparation Instructions:

[0395] Water is introduced and heated to 75° C. with stirring. 1.3 parts of hydroxyethylcellulose are added. When 65° C. is attained, 0.5 part of Polysorbate 80, 0.5 part of Stearyl Alcohol, 0.5 part of Cetyl Alcohol and 0.2 part of Behentrimonium Chloride are added. The mixture is stirred until 75° C. is reached and the ingredients are in solution. The mixture is then cooled. In the course of cooling, 0.1 part of Citric Acid and 0.2 part of Tetrasodium EDTA are added. At 35° C., 0.9 part of Phenoxyethanol, ethylhexylglycerin are added. With further stirring, the emulsion according to table 3 for the comparative experiment is added. The composition is homogenized with stirring for 15 minutes.

[0396] Comparison of the Rinse-Off Conditioners of Inventive Examples A1-A4 with the Comparative Experiments V-A1 to V-A4

[0397] The recited examples and comparative experiments differ in that in the case of examples A1-A4, inventive aqueous dispersions of precrosslinked organopolysiloxanes were used, while comparative experiments V-A1 to V-A4 used in each case analogous aqueous dispersions of the corresponding non-precrosslinked organopolysiloxanes. The active content—the amount of organopolysiloxane in the cosmetic composition—is 0.5 wt %.

[0398] The following examples/comparative experiments correlate in a direct comparison:

[0399] Example A1—Comparative experiment V-A1

[0400] Example A2—Comparative experiment V-A2

[0401] Example A3—Comparative experiment V-A3

[0402] Example A4—Comparative experiment V-A4

[0403] Wet Combing Force after Treatment of Damaged Hair with Rinse-Off Conditioner and after Simulation of Multiple Shampooings by Stirring the Hair in an Aqueous Surfactant Solution (Persistence Effect)

Example A2—Comparative Experiment V-A2

[0404] The use of the aqueous dispersion B1 of inventively precrosslinked organopolysiloxanes in the rinse-off conditioner (example A2) leads to an improvement in conditioning properties, such as the reduction of the combing forces in the wet state, for example, in comparison to the noninventive rinse-off conditioner from example V-A2, which contains the non-precrosslinked organopolysiloxane E1. An additional aim of the rinse-off conditioners of the invention is that the caring properties are retained even after multiple shampooing of the hair. The operation of shampooing is simulated in this example by the stirring of hair bundles, treated with rinse-off conditioner, for four hours in a surfactant solution. The details of this treatment are described above under Test Methods.

[0405] The results of the determination of the combing force in the wet state are set out below for the rinse-off conditioners of examples A2 and V-A2 in table 4.

TABLE-US-00004 TABLE 4 Rinse-off conditioners/results for reduction in wet combing force on damaged Caucasian hair after treatment with an inventive rinse- off conditioner in comparison to a noninventive conditioner and after simulation of multiple shampooings by four-hour stirring of the hair in an aqueous surfactant solution. All results refer to the comparison relative to untreated hair tresses. Reduction in wet combing force after conditioner treatment and subsequent Reduction in wet combing stirring of the hair in an Ex./ force after conditioner aqueous surfactant solution Comp. treatment [%] (persistence test) [%] A2 89 47 V-A2 85 34

[0406] By treatment with the inventive rinse-off conditioner containing an aqueous emulsion of a precrosslinked organopolysiloxane B1 (example A2) it is possible to measure, at 89%, a significant reduction in the wet combing force for the hair tresses. In particular, a very high conditioning effect is retained after stirring of the treated hair in a surfactant solution, and this is reflected in a persistent wet combing force reduction of 47%. Hair treated with a noninventive rinse-off conditioner containing the emulsion E1 (comparative example V-A2) exhibits a slightly reduced reduction in wet combing force, of 85%. Following the surfactant treatment, however, the reduction in wet combing force, of 34%, is much lower by comparison with example A2. The treatment of the hair in surfactant solution represents a simulation of multiple hair washes with shampoo, and demonstrates that the inventive rinse-off conditioner exhibits better wash resistance and that the conditioning properties are retained for longer than in the case of hair treatment with a noninventive rinse-off conditioner.

[0407] Comparison of Silicone Deposition after Treatment of Damaged Hair with Rinse-Off Conditioner and after Simulation of Multiple Shampooings by Four-Hour Stirring of the Hair in an Aqueous Surfactant Solution

[0408] Example A2—Comparative experiment V-A2

[0409] Example A4—Comparative experiment V-A4

[0410] In analogy to the determination of the reduction in wet combing force, the efficiency of silicone deposition on damaged hair by treatment with conditioners was studied. A study was also carried out into how much of the conditioning organopolysiloxane remains on the hair surface after simulation of shampooings by four-hour stirring of the hair in a surfactant solution. The results are collated in table 5. The determination of silicone deposition is described above under Test Methods.

TABLE-US-00005 TABLE 5 Rinse-off conditioners/silicone deposition Silicone deposition after stirring of the hair in an Ex./ Silicone aqueous surfactant solution Comp. deposition [ppm] (persistence test) [ppm] A2 65 55 V-A2 47 41 A4 79 42 V-A4 67 32

[0411] Table 5 shows that the deposition of the silicone—even after shampooing—is more durable for the inventive examples A2 and A4 by comparison with the noninventive comparative experiments V-A2 and V-A4, respectively.

[0412] Color Retention after Treatment of Red-Colored Hair with Rinse-Off Conditioner and Simulation of Multiple Shampooings by 10-Minute Stirring of the Hair in an Aqueous Surfactant Solution

Example A2—Comparative Experiment V-A2

[0413] The color protection was determined on hair which had been colored red using the Wella hair color Koleston Perfect® 77/44 (see above under Test methods). The colored hair was subsequently treated with an inventive rinse-off conditioner as per example A2 or with a noninventive conditioner as per comparative experiment V-A2. The initial color of the hair after treatment with the two conditioners was the same. To assess the color protection effect of the applied conditioners, the hair was shaken for 10 minutes each case in a surfactant solution, corresponding to a simulation of multiple shampooings. Then the change in color was determined in comparison to the initial color (see table 6). The color measurement and the assessment of the color protection are described above under Test methods.

TABLE-US-00006 TABLE 6 Rinse-Off conditioners/results of the color protection measurements after treatment of the colored hair with an inventive rinse- off conditioner in comparison to treatment with a noninventive conditioner, which does not contain a dispersion of a nonprecrosslinked organopolysiloxane, and subsequent simulation of multiple shampooings by 10-minute stirring of the hair in an aqueous surfactant solution. All results in comparison to freshly colored hair. Ex./comp. □E □L A2 5.7 3.6 V-A2 8.0 6.2

[0414] The change in color as a result of shaking of the hair in surfactant solution to simulate multiple shampooings is lower on treatment of the hair with inventive conditioner A2, at □E=5.7, than in the case of the noninventive conditioner V-A2, at □E=8.0. The change in lightness is lower on hair treatment with inventive conditioner A2, □L=3.6, than in the case of hair treatment with noninventive conditioner V-A2, at □L=6.2. Both parameters emphasize that the inventive precrosslinked organopolysiloxanes produce better color protection than the uncrosslinked organopolysiloxanes.

[0415] Care properties and color protection effect of conditioners comprising organopolysiloxanes precrosslinked with inventive esters, in comparison to conditioners comprising organopolysiloxanes precrosslinked with diethyl oxalate (not inventive).

[0416] Comparison of the Rinse-Off Conditioners of Inventive Examples A1 and A3 with the Comparative Experiment V-A5 (Diethyl Oxalate Crosslinking)

[0417] The recited examples and comparative experiments differ in that in the case of examples A1 and A3, aqueous dispersions of organopolysiloxanes precrosslinked with inventive esters were used, while in comparative experiment V-A5, analogous organopolysiloxanes but precrosslinked with diethyl oxalate (not inventive) were used. The active content—the amount of organopolysiloxane in the cosmetic composition—is 2 wt %.

[0418] Wet Combing Force after Treatment of Damaged Hair with Rinse-Off Conditioner and after Simulation of Multiple Shampooings by Four-Hour Stirring of the Hair in an Aqueous Surfactant Solution

[0419] The use of the inventive aqueous dispersion B1 in the rinse-off conditioner leads to an improvement in conditioning properties such as, for example, the reduction of the combing forces in the wet state in comparison to the corresponding organopolysiloxane dispersion V-A5, precrosslinked noninventively with diethyl oxalate. An additional aim of the rinse-off conditioners of the invention is that the caring properties are retained even after multiple shampooings of the hair. The operation of shampooing in this example is simulated by four-hour stirring of hair bundles, treated with rinse-off conditioner, in a surfactant solution. The details of this treatment are described above under Test methods.

[0420] The results are set out below for the rinse-off conditioners of example A1 and also of comparative experiment V-A5, in table 7.

TABLE-US-00007 TABLE 7 Rinse-off conditioners/results of the reduction in wet combing force after treatment with an inventive rinse-off conditioner in comparison to a noninventive conditioner and after simulation of multiple shampooings by four-hour stirring of the hair in an aqueous surfactant solution. All results relate to the comparison relative to untreated hair tresses. Reduction in wet combing force after stirring of Ex./ Reduction in wet the hair in an aqueous comp. combing force[%] surfactant solution [%] A1 85 48 V-A5 82 26

[0421] By treatment with a rinse-off conditioner containing an aqueous emulsion of a precrosslinked organopolysiloxane B1, it is possible to measure a significant reduction in the wet combing force for the hair tresses, of 85%. In particular, a very high conditioning effect is retained after stirring of the treated hair in a surfactant solution, and this is reflected in a reduction of 48% in wet combing force for example A1. Hair treated with a noninventive rinse-off conditioner as per comparative experiment V-A5 exhibits a reduction in wet combing force of 82%, but after the surfactant treatment the reduction in wet combing force drops to 26%. The treatment of the hair in surfactant solution represents a simulation of multiple hair washes with shampoo, and demonstrates that an inventive rinse-off conditioner exhibits better wash resistance and that the conditioning properties are retained for longer than in the case of hair treatment with a noninventive rinse-off conditioner.

Example A5: Use of Inventive Emulsions for Pretreatment in Hair Coloring

[0422] The coloring of hair with oxidative colors results in severe damage to the hair fibers. Not only the structure of the hair interior but also the hair surface are modified by the hair coloring procedure, in comparison to natural hair, and this is to the detriment of the cosmetic properties such as soft hair feel and combability. These negative effects can be counteracted by pretreating the hair with inventive cosmetic formulations prior to the coloring operation.

[0423] Pretreatment was carried out by immersing highly bleached hair (dense adhesive tress of European hair, bleaching level A) for one minute in a 0.1 percent solution of the emulsion B1 (from example 1) in water. The hair is then taken from the aqueous solution and blown dry with a hair dryer for five minutes. After this pretreatment, the hair is colored as described above under Test Methods, using the hair color L′Oreal Majirel Mix Rouge.

[0424] After the coloring and drying of the hair at 22° C. and 50% atmospheric humidity, the softness of pretreated hair was compared, in a panel test, with that of hair not treated before the coloring operation. The pretreated hair was consistently rated as being softer. There was no visually perceptible difference in color between pretreated and untreated hair after the coloring operation. Subsequently, in order to simulate multiple shampooings, both the pretreated hair and the unpretreated hair were stirred in an aqueous surfactant solution as described above (under Test Methods) for ten minutes. After the hair had dried, the panel test for assessing the softness of the hair tresses was repeated. After the surfactant treatment as well, the pretreated hair was consistently rated as being softer. This indicates a high persistence of the cosmetic effect after pretreatment of the hair with inventive cosmetic emulsions/compositions.

[0425] In addition, the change in color □E of the colored hair after the surfactant treatment was determined by comparison with the initial value, using the Spectro Guide colorimeter from Byk-Gardner. For the pretreated hair tresses, the color change □E=4.6 is lower than for unpretreated hair tresses, at □E=7.3. Pretreatment of the hair with inventive cosmetic emulsions/compositions leads to better color retention.

Examples A6 and A7 and Comparative Experiment V-A6

[0426] Cosmetic Composition: Shampoo

[0427] The examples below represent inventive cosmetic compositions comprising emulsions B4 from example 4 and B7 from example 7. The comparative example V-A6 represents a standard commercial shampoo formulation containing an emulsion of a dimethicone (dimethylpolysiloxane; Belsil® DM 5102 E, available from Wacker Chemie AG) having a viscosity of 60 000 mm.sup.2/s (at 25° C.).

[0428] The active content—the amount of organopolysiloxane in the cosmetic composition—is 1.3%. The composition of the shampoos is summarized in table 8.

[0429] Preparation Instructions:

[0430] 32.11 parts of water are introduced and heated to 50° C. with stirring. During this time, 0.20 part of Guar Hydroxylpropyltrimonium Chloride, 6.06 parts of Sodium Lauryl Sulfate, 29.90 parts of Sodium Laureth Sulfate, 0.05 part of Citric Acid and 5.0 parts of Cocamidopropyl Betaine are added. The mixture is stirred until 50° C. has been reached and the ingredients are present in solution. The mixture is then cooled. A separate vessel is charged with 20.0 parts of water; 0.60 part of Carbomer is added with stirring, and stirring is continued until the mixture is homogeneous. Then 0.06 part of lactic acid is added. This mixture is added to the first mixture. At 40° C., 0.95 part of Phenoxyethanol, Ethylhexylglycerin are added. Added with further stirring are 0.30 part of C12-13 Alkyl Lactate, 3.71 parts of inventive emulsions B4 and B7, or 2.60 parts of the noninventive Dimethicone Emulsion Belsil® DM 5102 E, 0.40 part of Sodium Hydroxide and 0.66 part of Sodium Chloride. The required pH of 6.5 can be set where necessary by adding sodium hydroxide.

TABLE-US-00008 TABLE 8 Shampoo formulations A6, A7 and V-A6 Comparative Example Example experiment A6 A7 V-A6 Constituents [parts [parts [parts (INCI Name) by wt.] by wt.] by wt.] Citric Acid.sup.1) 0.05 0.05 0.05 Cocamidopropyl Betaine.sup.2) 5.00 5.00 5.00 Sodium Laureth Sulfate.sup.3) 29.90 29.90 29.90 Guar Hydroxypropyl- 0.20 0.20 0.20 trimonium Chloride.sup.4) Sodium Lauryl Sulfate.sup.5) 6.06 6.06 6.06 Aqua (DI Water) 32.11 32.11 32.11 Carbomer.sup.6) 0.60 0.60 0.60 Lactic Acid.sup.7) 0.06 0.06 0.06 Aqua (DI Water) 20.00 20.00 20.00 Phenoxyethanol, 0.95 0.95 0.95 Ethylhexylglycerin.sup.8) C12-13 Alkyl Lactate.sup.9) 0.30 0.30 0.30 Emulsion B4 from Ex. 4 3.71 Emulsion B7 from Ex. 7 3.71 Belsil ® DM 5102 E.sup.10) 2.60 (Dimethicone Emulsion) Sodium Hydroxide.sup.11) 0.40 0.40 0.40 Sodium Chloride.sup.12) 0.66 0.66 0.66 .sup.1)Citric Acid: citric acid, Sigma .sup.2)Cocamidopropyl Betaine: Genagen CAB 818 30%, Clariant .sup.3)Sodium Laureth Sulfate: Genapol ® LRO 26.5%, Clariant .sup.3)Glycol Distearate: Genapol ® PMS, Clariant GmbH .sup.4)Guar Hydroxypropyltrimonium Chloride: N-Hance ® BF 13, Ashland .sup.5)Sodium Lauryl Sulfate: Texapon K 12 G, BASF .sup.6)Carbomer: Carbopol 980, Lubrizol .sup.7)Lactic Acid: L-(+)Lactic Acid, 90%, Bernd Kraft GmbH .sup.8)Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr .sup.9)C12-13 Alkyl Lactate: Ceraphyl ™ 41 ester, Ashland .sup.10)Belsil ® DM 5102 E, available from Wacker Chemie AG .sup.11)Sodium Hydroxide: Sodium Hydroxide, Sigma-Aldrich .sup.12)Sodium Chloride: Sodium Chloride ultrapure, Bernd Kraft GmbH

[0431] Comparison of the Shampoos of Inventive Examples A6 and A7 with Comparative Experiment V-A6

[0432] The recited examples and comparative experiments differ in that in the case of examples A6 and A7, aqueous dispersions of precrosslinked organopolysiloxanes were used. In comparative experiment V-A6, the commercial aqueous dimethylpolysiloxane emulsion Belsil® DM 5102 E (Wacker Chemie AG) is used, which as active conditioning ingredient comprises a dimethicone (dimethylpolysiloxane) with the viscosity of 60 000 mm.sup.2/s. The active content—the amount of organopolysiloxane in the cosmetic compositions—is 1.3 wt %.

[0433] The results for the cosmetic effect of the shampoos are collated in table 9.

TABLE-US-00009 TABLE 9 Shampoo/results for reduction in wet combing force. Improvement in the softness and amount of silicone deposited on damaged hair after treatment with shampoo. All results in comparison to untreated hair tresses. Silicone Reduction in Improvement deposition on Ex./ wet combing in softness hair surface comp. force [%] [%] [ppm] Ex. A6 67 28 126 Ex. A7 68 55 140 Comparative 20 2 46 experiment V-A6*) *)Belsil ® DM 5102 E (dimethicone emulsion), available from Wacker Chemie AG

[0434] The shampoos of examples A6 and A7 with the inventive emulsions exhibit a substantially higher reduction in wet combing force, a significantly improved softness (according to tensile testing) and a substantially higher deposition of the silicone on the hair, in comparison to the shampoo as per comparative experiment V-A6 with the commercial dimethicone emulsion.

Examples A8 and A9: Cosmetic Composition—Shampoo

[0435] Example A8 below represents a cosmetic composition comprising the emulsion B4 from example 4; example A9 is a cosmetic composition comprising the emulsion B1 in combination with the dimethylpolysiloxane emulsion Belsil® DM 5102 E (available from Wacker Chemie AG). The active content—the amount of organopolysiloxane in the cosmetic compositions—is 1.3%.

[0436] The compositions of the shampoos are summarized in table 10.

[0437] Preparation Instructions:

[0438] 0.30 part of Guar Hydroxypropyltrimonium Chloride is dispersed in water. 41.50 parts of Sodium Laureth Sulfate are stirred in slowly and the mixture is heated to 75° C. in stages. In the course of the heating, at 50° C., 0.20 part of PEG-150 Distearate is added, and at 65° C. 0.50 part of Glycol Distearate is added. The mixture is subsequently cooled. When 35° C. is reached, 0.90 part of Phenoxyethanol, Ethylhexylglycerin and the emulsions corresponding to the examples are added, followed by stirring for 5 minutes. Lastly, 13.4 parts of Cocamidopropyl Betaine are added and stirring is continued for 10 minutes.

[0439] A determination was made of the improvement in the softness of damaged hair tresses (in comparison to untreated hair tresses) after treatment with the shampoo formulations of examples A8 and A9. The results are collated in table 11.

TABLE-US-00010 TABLE 10 Shampoo formulations A8 and A9 (amounts in parts by weight) Constituents (INCI name) Ex. A8 Ex. A9 Aqua (Water VES) ad 100 ad 100 Guar Hydroxy-propyltrimonium Chloride .sup.1) 0.30 0.30 Sodium Laureth Sulfate .sup.2) 41.50 41.50 Glycol Distearate .sup.3) 0.50 0.50 PEG-150 Distearate .sup.4) 0.20 0.20 Emulsion B1 from example 1 1.43 Belsil ® DM 5102 E .sup.5) 1.60 (Dimethicone Emulsion) Emulsion B4 from example 4 3.71 Cocamidopropyl Betaine .sup.6) 13.33 13.33 Phenoxyethanol, Ethylhexylglycerin .sup.7) 0.90 0.90 .sup.1) Guar Hydroxypropyltrimonium Chloride: N-Hance ® 3196, Ashland. .sup.2) Sodium Laureth Sulfate: Genapol ® LRO 26.5%, Clariant GmbH .sup.3) Glycol Distearate: Hallstar ® EGDS, The Hallstar Company .sup.4) PEG-150 Distearate: Eumulgin ® EO 33, BASF AG .sup.5) Belsil ® DM 5102 E, available from Wacker Chemie AG .sup.6) Cocamidopropyl Betaine: Genagen ® CAB 30%, Clariant GmbH .sup.7) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

TABLE-US-00011 TABLE 11 Shampoo/improvement in softness. All results in comparison to untreated hair tresses. Ex. Improvement in softness [%] A8 45 A9 46

[0440] Damaged hair treated with the shampoos from examples A8 and A9 is rated in a test for assessing the softness (according to tensile testing) as being significantly softer than damaged, untreated hair.

Example A10: Cosmetic Composition—Shampoo

[0441] The example below represents a cosmetic composition comprising the emulsion B7 from example 7. The active content—the amount of organopolysiloxane in the cosmetic composition—is 1.0%.

[0442] The composition of the shampoos is summarized in table 12.

TABLE-US-00012 TABLE 12 Shampoo formulation A10 (figures in parts by weight) Constituents (INCI name) Ex. A10 Aqua (Water FD) ad 100 Polyquaternium-10 .sup.1) 0.10 Sodium Laureth Sulfate .sup.2) 52.80 PEG-150 Distearate .sup.3) 0.25 Cocamide MEA .sup.4) 1.00 Emulsion B7 from example 7 2.85 Cocamidopropyl Betaine .sup.5) 10.06 Phenoxyethanol, Ethylhexylglycerin .sup.6) 0.95 .sup.1) Polyquaternium-10: UCARE Polymer JR 400, Dow Chemical. .sup.2) Sodium Laureth Sulfate: Genapol ® LRO 26.5%, Clariant GmbH .sup.3) PEG-150 Distearate: Eumulgin ® EO 33, BASF AG .sup.4) Cocamide MEA: Comperlan 100, BASF AG .sup.5) Cocamidopropyl Betaine: Genagen ® CAB 30%, Clariant GmbH .sup.7) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mavr

[0443] Damaged hair treated with the shampoo from example A10 is softer (according to panel testing) than damaged untreated hair.

Example A11-A14

[0444] The examples below represent inventive cosmetic compositions A11-A14 according to table 13, comprising the emulsions B4, B5, B6 and B7 from examples 4 to 7. The active content—the amount of precrosslinked organopolysiloxane in cosmetic composition—is 2%.

TABLE-US-00013 TABLE 13 Rinse-off conditioners A11 to A14 Example Example Example Example A11 A12 A13 A14 Constituents [parts [parts [parts [parts (INCI name) by wt.] by wt.] by wt] by wt.] Water ad 100 ad 100 ad 100 ad 100 Hydroxyethyl- 1.3 1.3 1.3 1.3 cellulose.sup.1) Cetyl Alcohol.sup.2) 0.5 0.5 0.5 0.5 Polysorbate 80.sup.3) 0.5 0.5 0.5 0.5 Behentrimonium 0.2 0.2 0.2 0.2 Chloride.sup.4) Stearyl Alcohol.sup.5) 0.5 0.5 0.5 0.5 Citric Acid.sup.6) 0.1 0.1 0.1 0.1 Tetrasodium 0.2 0.2 0.2 0.2 EDTA.sup.7) Emulsion B4 5.71 from ex. 4 Emulsion B5 5.71 from ex. 5 Emulsion B6 5.71 from ex. 6 Emulsion B7 5.71 from ex. 7 Phenoxyethanol, 0.9 0.9 0.9 0.9 Ethylhexylglycerin.sup.8) The raw materials stated in table 13 are available under the following tradenames: .sup.1)Hydroxyethylcellulose: Natrosol 250 HR, Ashland .sup.2) Cetyl alcohol: cetyl alcohol, Merck KGaA .sup.3)Polysorbate 80: Tween ™ 80, Croda GmbH .sup.4) Behentrimonium Chloride: Genamin ® KDMP, Clariant GmbH .sup.5) Stearyl alcohol: Stearyl alcohol, Merck KGaA .sup.6) Citric Acid: citric acid, Sigma .sup.7)Tetrasodium EDTA: EDETA ® B Pulver, BASF Corporation .sup.8)Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0445] Preparation Instructions:

[0446] Water is introduced and heated to 75° C. with stirring. 1.3 parts of hydroxyethylcellulose are added. When 65° C. is attained, 0.5 part of Polysorbate 80, 0.5 part of Stearyl Alcohol, 0.5 part of Cetyl Alcohol and 0.2 part of Behentrimonium Chloride are added. The mixture is stirred until 75° C. is reached and the ingredients are in solution. The mixture is then cooled. In the course of cooling, 0.1 part of Citric Acid and 0.2 part of Tetrasodium EDTA are added. At 35° C., 0.9 part of Phenoxyethanol, ethylhexylglycerin are added. With further stirring, the emulsion from the examples is added. The composition is homogenized with stirring for 15 minutes.

[0447] Wet Combing Force after Treatment of Damaged Hair with Rinse-Off Conditioner and after Simulation of Multiple Shampooings by Four-Hour Stirring of the Hair in an Aqueous Surfactant Solution

TABLE-US-00014 TABLE 14 Rinse-off conditioners/results of the reduction in wet combing force after treatment with an inventive rinse-off conditioner and after simulation of multiple shampooings by four-hour stirring of the hair in an aqueous surfactant solution. All results relate to the comparison relative to untreated hair tresses. Reduction in wet combing force after conditioner treatment and subsequent Reduction in wet combing stirring of the hair in an force after conditioner aqueous surfactant solution Ex. treatment [%] (persistence test) [%] A11 78 37 A12 82 63 A13 83 69 A14 87 44

[0448] By treatment with rinse-off conditioners comprising an aqueous emulsion of a precrosslinked organopolysiloxane B4, B5, B6 and B7, respectively, it is possible to achieve a significant reduction in the wet combing force for the hair tresses, in the region of 78% to 87%. In particular, a very high conditioning effect is retained after stirring of the treated hair in a surfactant solution, and this is reflected in a reduction in wet combing force of 37% for example A11, 44% for example A14, and values of 63% and 69% for examples A12 and A13.

Example A15—Rinse-Off Conditioner

[0449] The example below represents an inventive cosmetic composition A15 according to table 15, comprising the emulsion B3 from example 3. The active content—the amount of precrosslinked organopolysiloxane in the cosmetic composition—is 0.5%.

[0450] Preparation Instructions:

[0451] Water is introduced and heated to 75° C. with stirring. 1.3 parts of hydroxyethylcellulose are added. When 65° C. is attained, 0.5 part of Stearamidopropyl Dimethylamine, 1.0 part of Polysorbate 80, 3.0 parts of Stearyl Alcohol, 2.0 parts of Cetyl Alcohol and 1.8 parts of Behentrimonium Chloride are added. The mixture is stirred until 75° C. is reached and the ingredients are in solution. The mixture is then cooled. In the course of cooling, 0.2 part of Citric Acid and 0.2 part of Tetrasodium EDTA are added. At 35° C., 0.9 part of Phenoxyethanol, ethylhexylglycerin are added. With further stirring, the emulsion from the example is added. The composition is homogenized with stirring for 15 minutes.

TABLE-US-00015 TABLE 15 Rinse-off conditioner A15 Constituent Example A15 (INCI name) [parts by wt.] Water ad 100 Hvdroxyethyl-cellulose .sup.1) 1.3 Cetyl Alcohol .sup.2) 2.0 Polysorbate 80 .sup.3) 1.0 Behentrimonium Chloride .sup.4) 1.8 Stearamidopropyl Dimethvlamine .sup.5) 0.5 Stearyl Alcohol .sup.6) 3.0 Citric Acid .sup.7) 0.2 Tetrasodium EDTA .sup.8) 0.2 Emulsion B3 from ex. 3 1.87 Phenoxyethanol, Ethylhexylglycerin .sup.9) 0.9 The raw materials stated in table 15 are available under the following tradenames: .sup.1) Hydroxyethylcellulose: Natrosol 250 HR, Ashland .sup.2) Cetyl alcohol: Cetyl alcohol, Merck KGaA .sup.3) Polysorbate 80: Tween ™ 80, Croda GmbH .sup.4) Behentrimonium Chloride: Genamin ® KDMP, Clariant GmbH .sup.5) Stearamidopropyl Dimethylamine, Incromine ™ SB, Croda GmbH .sup.6) Stearyl alcohol: Stearyl alcohol, Merck KGaA .sup.7) Citric Acid: Citric Acid, Sigma .sup.8) Tetrasodium EDTA: EDETA ® B Pulver, BASF Corporation .sup.9) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0452] By treating damaged hair with the inventive rinse-off conditioner from example A15, comprising an aqueous emulsion of a precrosslinked organopolysiloxane B3 (example 3), it is possible to achieve a significant reduction in the wet combing force for the hair tresses (in comparison to untreated hair tresses).