Aqueous dispersions of pre-crosslinked organopolysiloxanes

Abstract

In the present invention, the compound represented by the following general formula SiRO 2 / 2 -Y-SiRO 2 / 2 On average at least one structural unit of (I) and the following formula RSiO 2 / 2 Novel aqueous dispersions of pre-crosslinked organopolysiloxanes containing units of the formula (II) are described, wherein Y is -R 2 -[NR 3 -R 4 ] x -NR 3 -OC-[C(Z 1 )(H)] k1 -[C(Z 2 )(H)] k2 -CO-NR 3 -[R 4 -NR 3 ] a -R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -[NR 3 -R 4 ] a -NR 3 -OC-[C(Z 2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO-NR 3 -[R 4 -NR 3 ] x -R 2 -, R may be the same or different and represent a monovalent SiC-bonded hydrocarbon radical having 1 to 18 carbon atoms which may contain one or more heteroatoms from the group of N, P, S, O, and halogen, R 2 means a SiC-bonded divalent linear or branched hydrocarbon radical having 3 to 18 carbon atoms, R 3 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group, and R 4means a divalent hydrocarbon group having 1 to 6 carbon atoms, k1 is 0, 1, 2 or 3, k2 is 0, 1, 2 or 3, x is 0, 1, 2, 3 or 4, a is 0, 1, 2, 3 or 4, b is 0 or an integer of 1 to 500, and Z 1 is -OH, H or -NHR 3 means Z 2 is -OH, -H or -NHR 3 means.

Description

[Technical field]

[0001] The present invention relates to an aqueous dispersion of a pre-crosslinked organopolysiloxane, a pre-crosslinked organopolysiloxane, and a cosmetic composition comprising an aqueous dispersion of a pre-crosslinked organopolysiloxane.The present invention further relates to a process for producing the pre-crosslinked organopolysiloxane and its aqueous dispersion.The present invention further relates to the use of the cosmetic composition. [Background technology]

[0002] Organopolysiloxanes are used in cosmetic compositions, such as hair care products, for their conditioning properties, such as improved softness and smoothness, reduced combing force, gloss properties, improved perceived color, color protection properties, reduced instances of static electricity, protection properties related to thermal stress on the hair, or hydrophobization.

[0003] A review of selected organopolysiloxanes for the care of keratinous materials such as hair can be found in M. D. Berthiaume, Society of Cosmetic Chemists (ed.), monograph, Silicones in Hair Care, 1997 and in J. Sejpka, Silicones in Haarpflegeproducten [Silicones in Haircare Products] in the SOEFW-Journal, Vol. 118, No. 17, 1992, pp. 1065-1070.

[0004] In daily life, hair is exposed to numerous external influences that cause damage to the hair surface and thus impair its cosmetic properties, such as smoothness, softness, luster, and other parameters, compared to undamaged hair. Damage to the hair surface can be caused, for example, by chemical or mechanical treatments, by UV radiation, or by heat. Concomitant with the surface damage to hair is the destruction and partial removal of the lipid layer covering the cuticle, which is responsible for the highly hydrophobic quality of undamaged natural hair (R.A. Lodge, B.Bhusan, Wetting Properties of Human hair by Means of Dynamic Contact Angle Measurement, Journal of Applied Polymer Science, Vol. 102, 5255-5265, 2006, Wiley). Damaged hair is significantly more hydrophilic than undamaged hair, since the effective hair surface after destruction of the superficial lipid layer is a hydrophilic amino acid-based protein matrix.

[0005] Modified siloxanes with oxalamide ester-terminated organopolysiloxanes are known. Those described in WO2019 / 114953A1 are linear copolymers of oxalamide ester-terminated organopolysiloxanes and amino-terminated polyethers. They show significantly increased hydrophilicity compared to exclusively amino-functionalized organopolysiloxanes. However, their linear structure means that they have no elastic effect.

[0006] US7501184B2 describes copolymers obtained by reacting linear organopolysiloxanes terminated with oxalamide ester groups with organic diamines. Highly viscous to solid copolymers are obtained, which are used in adhesives, especially as hot melt adhesives. These high viscosity products are not stably emulsifiable and therefore cannot be used to treat fibrous substrates such as hair. Furthermore, their linear structure means that they have no elastic effect.

[0007] US7223385B2, US7485289B2, US7220408B2 and US7504094B2 describe cosmetic compositions for treating hair containing special aminosilicones and conditioning or thickening agents. The aminosilicones are dimethylpolysiloxanes with terminal alkoxy / hydroxy groups and non-crosslinked aminoethylaminopropylalkoxysiloxane or aminoethylaminopropylmethylsiloxane units.

[0008] WO2020 / 239229A1 describes aqueous dispersions of pre-crosslinked organopolysiloxanes that can be used in cosmetic compositions and preferably form an elastomeric film after removal of water. It has been found that cosmetic formulations for hair applications containing pre-crosslinked organopolysiloxanes exhibit specific care effects. Despite the properties of forming an elastomeric film, only a limited effect on the shaping of hair fibers is observed.

[0009] No. 5,039,738A discloses a process for producing modified aminoorganosiloxanes by reacting an aminoorganosiloxane in an aqueous emulsion with a dialkyl oxalate, a dialkyl pyrocarbonate, or a mixture thereof. Textile materials treated with the emulsion described have been found to exhibit reduced yellowing.

[0010] WO2015 / 024079A1 describes a cosmetic composition comprising an aminoorganopolysiloxane, a cationic surfactant, and a dialkyl ester of a dicarboxylic acid of formula R'-O-CO-R-CO-O-R', where R' is a C8 to C30 group.

[0011] According to WO2004 / 039930A2, fabrics treated with a composition consisting of a polycarboxylic acid and an aminoorganosiloxane exhibit improved resistance to curl and crease.

[0012] Crosslinkable compositions consisting of an aminoorganopolysiloxane and a crosslinker component which is an alkoxysilane or siloxane having at least one carboxylic acid anhydride group are described in US Pat. No. 5,399,652 A. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] International Publication No. 2019 / 114953 [Patent Document 2] U.S. Patent No. 7,501,184 [Patent Document 3] U.S. Patent No. 7,223,385 [Patent Document 4] U.S. Pat. No. 7,485,289 [Patent Document 5] U.S. Patent No. 7,220,408 [Patent Document 6] U.S. Patent No. 7,504,094 [Patent Document 7] International Publication No. 2020 / 239229 [Patent Document 8] U.S. Pat. No. 5,039,738 [Patent Document 9] International Publication No. 2015 / 024079 [Patent Document 10] International Publication No. 2004 / 039930 [Patent Document 11] U.S. Pat. No. 5,399,652 [Non-patent literature]

[0014] [Non-Patent Document 1] MDBerthiaume, Society of Cosmetic Chemists (ed.), monograph, Silicones in Hair Care, 1997 [Non-Patent Document 2] J. Sejpka, Silicones in Haarpflegeproductten [Silicones in Haircare Products] in SOFW-Journal, Vol. 118, No. 17, 1992, pp. 1065-1070 [Non-Patent Document 3] RALodge, B.Bhusan, Wetting Properties of Human hair by Means of Dynamic Contact Angle Measurement, Journal of Applied Polymer Science, Volume 102, 5255-5265, 2006, Wiley Summary of the Invention [Problem to be solved by the invention]

[0015] The object was to provide precrosslinked organopolysiloxanes, in particular aqueous dispersions of precrosslinked organopolysiloxanes, which preferably form an elastomeric film on removal of water and can be used in cosmetic compositions.A further object was to provide a cosmetic composition for treating keratinous fibers, such as hair, preferably for the cleaning and care thereof, which can be used to shape and condition keratinous fibers, such as hair, and in particular provide easier combing thereof. [Means for solving the problem]

[0016] The above object is achieved by the present invention.

[0017] The present invention relates to an aqueous dispersion, preferably an aqueous emulsion, comprising a pre-crosslinked organopolysiloxane, The pre-crosslinked organopolysiloxane comprises, on average, at least one structural unit, preferably at least two structural units, more preferably at least three structural units of the following general formula: SiRO 2 / 2 -Y-SiRO 2 / 2 (I) and units in the following formula: R2SiO 2 / 2 (II) [In the formula, Y represents a group of the formula: -R 2 -[NR 3 -R 4 ] x -NR 3 -OC-[C(Z 1 )(H)] k1 -[C(Z 2 )(H)] k2 -CO-NR 3 -[R 4 -NR 3 ] a -R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -[NR 3 -R 4 ] a -NR 3 -OC-[C(Z 2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO-NR 3 -[R 4 -NR 3 ] x -R 2 - R may be the same or different and represent a monovalent SiC-bonded hydrocarbon radical having 1 to 18 carbon atoms and which may contain one or more heteroatoms from the group of N, P, S, O, and halogens; R 2 may be the same or different and represent a SiC-bonded divalent linear or branched hydrocarbon group having 3 to 18 carbon atoms, preferably an alkylene group having 3 to 10 carbon atoms; R 3 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group such as an acetyl group, and preferably represents a hydrogen atom; R 4may be the same or different and represent a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms; k1 is 0, 1, 2 or 3, preferably 0; k2 is 0, 1, 2 or 3, preferably 0; x is 0, 1, 2, 3 or 4, preferably 0 or 1; a is 0, 1, 2, 3 or 4, preferably 0 or 1; b is 0 or an integer of 1 to 500, preferably 20 to 350; Z 1 is -OH, -H or -NHR 3 represents Z 2 is -OH, -H or -NHR 3 represents.] The present invention provides an aqueous dispersion, preferably an aqueous emulsion, comprising:

[0018] The present invention provides a pre-crosslinked organopolysiloxane comprising: Furthermore, on average at least one structural unit, preferably at least two structural units, more preferably at least three structural units of the following general formula: SiRO 2 / 2 -Y-SiRO 2 / 2 (I) and units in the following formula: R2SiO 2 / 2 (II) [In the formula, Y is a group of the formula -R 2 -[NR 3 -R 4 ] x -NR 3 -OC-[C(Z 1 )(H)] k1 -[C(Z 2 )(H)] k2 -CO-NR 3 -[R 4 -NR 3 ] a -R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2] b -R2SiO 1 / 2 -R 2 -[NR 3 -R 4 ] a -NR 3 -OC-[C(Z 2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO-NR 3 -[R 4 -NR 3 ] x -R 2 - R, R 2 , R 3 , R 4 , k1, k2, x, a, b, Z 1 , and Z 2 is as defined above.] The present invention provides a pre-crosslinked organopolysiloxane comprising:

[0019] The present invention further provides a process for preparing an aqueous dispersion of a pre-crosslinked organopolysiloxane, comprising the steps of: An aqueous dispersion, preferably an aqueous emulsion, of an aminoorganopolysiloxane (1) of the following formula: (R 1 O) d A e R 3-d-e SiO (SiARO) p (SiRO) q SiR 3-d-e A e (OR 1 ) d (IV) [In the formula, A is an amino group of the general formula: -R 2 -[NR 3 -R 4 -] x NR 3 2 R may be the same or different and represent a monovalent SiC-bonded hydrocarbon radical having 1 to 18 carbon atoms and which may contain one or more heteroatoms from the group of N, P, S, O, and halogens; R1 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, optionally interrupted by one or more distinct oxygen atoms, R 2 may be the same or different and represent a SiC-bonded divalent linear or branched hydrocarbon group having 3 to 18 carbon atoms, preferably an alkylene group having 3 to 10 carbon atoms; R 3 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group such as an acetyl group, and preferably represents a hydrogen atom; R 4 may be the same or different and represent a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms; d is 0 or 1; e is 0 or 1; p is an integer of at least 1, preferably at least 2, more preferably at least 3, and at most 1000, preferably at most 10; q is 0 or an integer of 1 to 2000, preferably 50 to 1000; x is 0, 1, 2, 3 or 4, preferably 0 or 1. The process for producing the compound is provided by reacting the compound with a reactive ester (2) of the formula: R 5 -O2C-[C(Z 1 )(H)] k1 -[C(Z 2 )(H)] k2 -CO-NR 3 -[R 4 -NR 3 ] a -R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -[NR 3 -R 4 ] a -NR 3 -OC-[C(Z2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO2-R 5 (V) [In the formula, R, R 2 , R 3 , and R 4 is as defined above, R 5 represents O-bonded saturated or unsaturated, linear or branched monovalent hydrocarbon radicals, which may be identical or different, having 1 to 20 carbon atoms per radical and which may contain one or more heteroatoms from the group of N, P, S, O and halogens, k1 is 0, 1, 2 or 3, preferably 0; k2 is 0, 1, 2 or 3, preferably 0; a is 0, 1, 2, 3 or 4, preferably 0 or 1; b is 0 or an integer of 1 to 500, preferably 20 to 350; Z 1 is -OH, -H or -NHR 3 represents Z 2 is -OH, -H or -NHR 3 represents.]

[0020] The present invention further provides a process for preparing a pre-crosslinked organopolysiloxane, comprising the steps of: Aminoorganopolysiloxane (1) of the following formula (R 1 O) d A e R 3-d-e SiO (SiARO) p (SiRO) q SiR 3-d-e A e (OR 1 ) d (IV) Reacting with a reactive ester (2) of the following formula: R 5 -O2C-[C(Z 1 )(H)] k1 -[C(Z 2 )(H)] k2-CO-NR 3 -[R 4 -NR 3 ] a -R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -[NR 3 -R 4 ] a -NR 3 -OC-[C(Z 2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO2-R 5 (V) [In the formula, A, R, R 1 , R 2 , R 3 , R 4 , R 5 , d, e, p, q, k1, k2, x, a, b, Z 1 and Z 2 is as defined above.] A manufacturing process is provided which is characterized in that the resulting pre-crosslinked organopolysiloxane is optionally subsequently emulsified in water.

[0021] In the process of the present invention, the aminoorganopolysiloxanes (1) of formula (IV) used are preferably those in which e is 0 and therefore contain only pendant amino groups A, which, upon reaction with the reactive esters (2), form crosslinks according to the structural units of formula (I).

[0022] When e is 0, the pre-crosslinked organopolysiloxane of the invention comprises not only structural units of formula (I) and siloxane units of formula (II), but also preferably siloxane units of the following formula: R 3-d (OR 1 ) d SiO 1 / 2 (III) [In the formula, R, R 1 and d is as defined above.]

[0023] However, it is also possible to use aminoorganopolysiloxanes (1) of formula (IV) which also contain terminal amino groups A, so that e is 1.

[0024] It is also possible to use mixtures of aminoorganopolysiloxanes (1) of formula (IV) where e is 0 and e is 1.

[0025] In the reaction with the reactive ester (2), bridges between the two terminal amino groups (formula (VI)) or between a terminal and a pendant amino group (formula (VII)) can in this case additionally be formed.

[0026] In addition to the aminoorganopolysiloxane (1), it is also possible to use aminoorganopolysiloxane (1a) containing only terminal amino groups of the following general formula: (R 1 O) f AR 2-f SiO(SiRO) n SiR 2-f A(OR 1 ) f (IVa) [Wherein, A, R, and R 1 is as defined above, f is 0 or 1; n is an integer of 1 to 1000, preferably 50 to 1000.]

[0027] Consequently, in addition to the structural units of formula (I) as crosslinks, the pre-crosslinked organopolysiloxanes of the invention contain structural units of the following formula: SiR2O 1 / 2 -Y-SiR2O 1 / 2 (VI) Or SiRO 2 / 2 -Y-SiR2O 1 / 2 (VII) Structural unit of Or it may further comprise a mixture of (VI) and (VII). [R and Y are as defined above.]

[0028] The pre-crosslinked organopolysiloxanes of the present invention preferably comprise siloxane units of formula (III) where d is 0 or 1, preferably 1.

[0029] The pendant and optionally terminal amino groups A in the aminoorganopolysiloxane (1) or optionally in the aminoorganopolysiloxane (1a) used in the present invention can also react with reactive esters (2) without forming crosslinks, so that the pre-crosslinked organopolysiloxanes have the following formula: SiRO 2 / 2 -R 2 -[NR 3 -R 4 ] x -NR 3 -OC-[C(Z 1 )(H)] k1 -[C(Z 2 )(H)] k2 -CO-NR 3 -[R 4 -NR 3 ] a -R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -[NR 3 -R 4 ] a -NR 3 -OC-[C(Z 2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO2-R 5 (VIIIa) and / or SiR2O 1 / 2 -R 2 -[NR 3 -R 4 ] x -NR 3 -OC-[C(Z 1 )(H)] k1 -[C(Z 2 )(H)] k2 -CO-NR 3 -[R4 -NR 3 ] a -R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -[NR 3 -R 4 ] a -NR 3 -OC-[C(Z 2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO2-R 5 (VIIIb) [In the formula, R, R 2 , R 3 , R 4 , R 5 , k1, k2, x, a, b, Z 1 , and Z 2 is as defined above.] It may further comprise structural units of the formula:

[0030] In the context of the present invention, formula (IV) refers to a compound having p units - (SiARO) - and q units - (SiR 2 It should be understood to mean that the (O)-- groups can be distributed in any manner in the aminoorganopolysiloxane molecule, for example as blocks or statistically.

[0031] Although not represented by formulas (IV) and (IVa), the aminoorganopolysiloxane (1) used in the present invention and the aminoorganopolysiloxane (1a) optionally used can also be represented by the following formula: RSiO 3 / 2 , (OR 1 )SiO 3 / 2 and SiO 4 / 2 (IXa-c) [Wherein, R and R 1 is as defined above.] and thus the pre-crosslinked organopolysiloxane of the present invention may also comprise siloxane units of formula (IXa-c). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] Preferably, R is a monovalent saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms.

[0033] Examples of hydrocarbon radicals R are alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl; hexyl radicals, such as n-hexyl; heptyl radicals, such as n-heptyl; octyl radicals, such as n-octyl and isooctyl radicals, such as 2,2,4-trimethylpentyl; nonyl radicals, such as n-nonyl; decyl radicals, such as n-decyl; dodecyl radicals, such as n-dodecyl; octadecyl radicals, cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl; alkenyl groups, such as vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl; aryl groups, such as phenyl, naphthyl, anthryl and phenanthryl; alkaryl groups, such as o-, m- and p-tolyl; xylyl and ethylphenyl; and aralkyl groups, such as benzyl and α- and β-phenylethyl.

[0034] Preferred as radicals R are methyl, ethyl, octyl and phenyl radicals, more preferably methyl and ethyl radicals.

[0035] Examples of substituted groups R are haloalkyl groups such as 3,3,3-trifluoro-n-propyl, 2,2,2,2',2',2'-hexafluoroisopropyl, heptafluoroisopropyl, and haloaryl groups such as o-, m-, and p-chlorophenyl.

[0036] Further examples of substituted groups R are polyalkyleneoxy groups, such as polyethyleneoxy, polypropyleneoxy or polyethyleneoxy / polypropyleneoxy groups.

[0037] base R 1 Examples of R are the alkyl groups listed above for R, and also the methoxyethyl, ethoxyethyl and hexoxyethyl groups, preferably the group R 1 is hydrogen, a methyl group, or an ethyl group.

[0038] Preferably, R 5 is C 1~20 It is a hydrocarbon group, which may be interrupted by one or more oxygen atoms.

[0039] Examples of the group R are the groups R 5 also applies.

[0040] Preferably, R 5 is C 1~4 An alkyl group is, for example, a methyl group or an ethyl group.

[0041] Examples of the group A are -(CH2)3NH2 -(CH2)3-NH-(CH2)2-NH2 -CH2CH(CH3)CH2-NH-(CH2)2-NH2 -(CH2)3-NH(cyclohexyl) -(CH2)3-NHCH3 -(CH2)3-N(CH3)2 -(CH2)3-NHCH2CH3 -(CH2)3-N(CH2CH3)2 -(CH2)4-NH2 -CH2CH(CH3)CH2-NH2 -(CH2)3-NH-(CH2)2-NHCH3 -(CH2)3-NH-(CH2)2-N(CH3)2 -(CH2)3-NH-(CH2)2-NHCH2CH3 -(CH2)3-NH-(CH2)2-N(CH2CH3)2 -(CH2)3[-NH-CH2CH2]2-NH2 and its partially or fully acetylated forms, e.g. -(CH2)3-NH(acetyl) (CH2)3-NH-(CH2)2-NH(acetyl), and -(CH2)3-N(acetyl)-(CH2)2-NH(acetyl).

[0042] Preferred examples of the group A are -(CH2)3NH2 -(CH2)3-NH-(CH2)2-NH2 -CH2CH(CH3)CH2-NH-(CH2)2-NH2 -(CH2)3-NHCH3.

[0043] Preferably, A is an amino group of the formula: -R 2 -[NH-CH2CH2-] x NH2 [In the formula, x is 0 or 1; R 2 is a group of formula -(CH2)3- or -CH2-CH(CH3)-CH2-.

[0044] Particularly preferred examples of the group A are -(CH2)3NH2 -(CH2)3-NH-(CH2)2-NH2 and -CH2CH(CH3)CH2-NH-(CH2)2-NH2.

[0045] Further examples of aminoorganopolysiloxanes (1) are commercially available functionalized siloxanes, such as amine oils, for example amine oils having 3-(2-aminoethyl)aminopropyl functional groups, and also glycol, phenyl or phenylmethyl oils containing amino groups.

[0046] In preparing the dispersions of the invention, it is possible to use one type of aminoorganopolysiloxane (1) or different types of aminoorganopolysiloxanes (1).

[0047] The aminoorganopolysiloxane (1) used to produce the dispersion of the present invention preferably has a viscosity of 1 mPa.s to 50,000,000 mPa.s at 25°C, more preferably 50 mPa.s to 10,000,000 mPa.s at 25°C, and particularly preferably 100 mPa.s to 500,000 mPa.s at 25°C.

[0048] The aminoorganopolysiloxane (1) used in the preparation of the dispersion of the present invention can be prepared, for example, as described in US Pat. No. 7,129,369 B2.

[0049] The dispersion of the present invention preferably comprises the pre-crosslinked organopolysiloxane of the present invention, an emulsifier (3), and water (4).

[0050] The dispersions of the pre-crosslinked organopolysiloxanes of the present invention can optionally be prepared using additional materials that do not directly participate in the reaction.

[0051] Upon drying (without the addition of a catalyst or change in pH), the dispersions of the present invention form a silicone network, preferably an elastomeric silicone network. The dispersions of the present invention preferably form an elastomeric film after removal of water.

[0052] In the process of the present invention, the reaction of aminoorganopolysiloxane (1) and optionally (1a) with reactive ester (2) according to the present invention, preferably no metal-containing catalyst is used.

[0053] Therefore, the dispersions of the present invention preferably do not contain a catalyst.

[0054] In the preparation of the pre-crosslinked organopolysiloxane of the present invention, an aminoorganopolysiloxane (1) and a reactive ester (2) are used, and these components preferably react with each other at room temperature. No additional metal-containing catalyst is required to assist this reaction, and therefore preferably no transition metals and their compounds from subgroup VIII of the periodic table, and no metals and their compounds from main groups III, IV and V of the periodic table are used. In this definition, the elements C, Si, N and P are not considered to be metals.

[0055] Furthermore, the reaction preferably proceeds in the neutral range, i.e., a pH range of about 4 to 8 provided by the components themselves. The high reactivity also means that there is no need for specifically controlled chemical reactions, and preferably no need for heating.

[0056] In preparing the dispersions of the invention, it is possible to use one type of aminoorganopolysiloxane (2) as crosslinker or different types of aminoorganopolysiloxanes (2) as crosslinkers.

[0057] The preferred esters (2) used are oxalamide ester terminated organopolysiloxanes of the formula: R 5 -O2C-CO-NH-R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -NH-OC-CO2-R 5 [In the formula, R is as defined above, R 2 is a group of formula -(CH2)3- or -CH2-CH(CH3)-CH2-, R 5 is as defined above, preferably a C1-4 alkyl group, in particular a methyl group or an ethyl group; b is 0 or an integer of 1 to 500, preferably 20 to 350.

[0058] Thus, Y is preferably a group of the formula: -R 2 -[NH-CH2CH2] x -NH-OC-CO-NH-R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R2-NH-OC-CO-NH-[CH2CH2-NH] x -R 2 - [In the formula, x is 0 or 1, b and R are as defined above. R2 is a group of formula -(CH2)3- or -CH2-CH(CH3)-CH2-.

[0059] Depending on the use of the crosslinker (2) or the linear, branched or resinous aminoorganopolysiloxane (1), the pre-crosslinked organopolysiloxane can have a branched or even highly branched or highly crosslinked structure along with a linear fraction.

[0060] In the process of the present invention, the nature and amount of the aminoorganopolysiloxane and ester are selected so that the organopolysiloxane in the resulting dispersion is precrosslinked.

[0061] The preferred aminoorganopolysiloxanes (1) used are those which contain, on average, at least one primary amino functional group among the pendant amino groups A, thus giving the pre-crosslinked organopolysiloxanes of the invention. It is also possible to use aminoorganopolysiloxanes (1a) which contain only terminal amino groups A with primary amino functional groups.

[0062] When the aminoorganopolysiloxane (1a) is used, it is preferably used in an amount of 10 to 300 parts by weight per 100 parts by weight of the aminoorganopolysiloxane (1).

[0063] Additionally, the use of a mixture of aminoorganopolysiloxane (1) and non-functional organopolysiloxane (1b) also results in the pre-crosslinked organopolysiloxane of the present invention.

[0064] Here, the non-functional organopolysiloxane (1b) is an organopolysiloxane that does not have an amino group A, and is preferably a linear organopolysiloxane of the following general formula: R 7 u R 6 3-u SiO[R 6 2SiO] v SiR 6 3-u R 7 u (X) [In the formula, R 6 is as defined for R, R 7 is R 6 or is an HO- group, u is 0 or 1; v is 0 or an integer from 1 to 2000.

[0065] Preferably, R 6 is C 1~18 Hydrocarbon group, preferably C 1~18 It is an alkyl group.

[0066] Examples of non-functional organopolysiloxanes (1b) are dialkylpolysiloxanes, preferably dimethylpolysiloxane.

[0067] When the non-functional organopolysiloxane (1b) is used, it is preferably used in an amount of 100 to 800 parts by weight per 100 parts by weight of the aminoorganopolysiloxane (1).

[0068] The degree of crosslinking here is determined by the ratio of the -OR group in the reactive ester (2) to the amino group A in the aminoorganopolysiloxane (1). 5 It depends on the ratio of equivalents of

[0069] To produce the dispersion of the present invention composed of an aminoorganopolysiloxane (1) and a reactive ester (2), the ester (2) preferably contains 0.1 to 10 equivalents of -OR per equivalent of amino group A in the aminoorganopolysiloxane (1). 5 , more preferably 0.2 to 5 equivalents of -OR 5 and particularly preferably 0.3 to 3 equivalents of -OR 5 is used in amounts of

[0070] The dispersions of the pre-crosslinked organopolysiloxanes of the present invention are prepared by vigorously mixing together the aminoorganopolysiloxane (1), the ester (2), the emulsifier (3) and water (4).

[0071] The production can be carried out batchwise or continuously.

[0072] The method of mixing the components used to prepare the dispersions of the present invention is not particularly critical and can be carried out in different orders.

[0073] For example, components (1) and (2) can be premixed with each other, then the emulsifier is added, followed by the incorporation of water (4). Another possibility is to continuously meter components (1) to (4) into an emulsifier. In special cases, for example due to the viscosity or reactivity of the aminoorganopolysiloxane (1) and optionally (1a) and optionally non-functional organopolysiloxane (1b) used, it may be advantageous to mix ester (2) with the aminoorganopolysiloxane and then incorporate a different aminoorganopolysiloxane or a non-functional organopolysiloxane, or vice versa, which achieves more favorable rheological properties for the processing of the components.

[0074] In addition, it is also possible to introduce an ester (2) as a crosslinking agent into the final emulsion of the aminoorganopolysiloxane (1) to achieve the desired reaction and crosslinking of the aminoorganopolysiloxane in the emulsion. In order to obtain a product free of volatile organic compounds, that is, a VOC-free product, the by-product alcohol R 5 OH(R 5 (wherein R is as defined above) can be completely or partially removed by any suitable known means, such as distillation, membrane processes, or other separation methods.

[0075] In producing the dispersion of the present invention, water (4) is used in an amount of preferably 1% by weight to 99% by weight, more preferably 25% by weight to 95% by weight, based on the total weight of all constituent components of the dispersion.

[0076] The aqueous dispersions of the pre-crosslinked organopolysiloxanes of the present invention are used as oil-in-water systems.

[0077] As emulsifiers (3) for producing aqueous dispersions of precrosslinked organopolysiloxanes, all anionic, nonionic, cationic or amphoteric emulsifiers known to date can be used, both individually and as mixtures of different emulsifiers, and it has also long been possible to produce aqueous dispersions, and more particularly aqueous emulsions, of organopolysiloxanes.

[0078] Examples of anionic emulsifiers are:

[0079] 1. Alkyl sulfates, especially those having a chain length of 8 to 18 carbon atoms, alkyl and alkaryl ether sulfates having 8 to 18 carbon atoms and 1 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units in the hydrophobic group.

[0080] 2. Sulfonates, in particular alkylsulfonates having 8 to 18 carbon atoms, alkylarylsulfonates having 8 to 18 carbon atoms, taurides, esters and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms (these alcohols or alkylphenols may also optionally be ethoxylated with 1 to 40 EO units).

[0081] 3. Alkali metal and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl group.

[0082] 4. Partial esters of phosphoric acid and their alkali metal and ammonium salts, in particular alkyl and alkaryl phosphates having 8 to 20 carbon atoms in the organic radical and alkyl ether phosphates and alkaryl ether phosphates having 8 to 20 carbon atoms and 1 to 40 EO units in the alkyl or alkaryl radical.

[0083] Examples of non-ionic emulsifiers are:

[0084] 5. Polyvinyl alcohol still having 5% to 50%, preferably 8% to 20%, vinyl acetate units and having a degree of polymerization of 500 to 3000.

[0085] 6. Alkyl polyglycol ethers, preferably those having 3 to 40 EO units and alkyl groups of 8 to 20 carbon atoms.

[0086] 7. Alkylaryl polyglycol ethers, preferably those having 5 to 40 EO units and 8 to 20 carbon atoms in the alkyl and aryl groups.

[0087] 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those having 8 to 40 EO or PO units.

[0088] 9. Addition products of alkylamines having alkyl groups of 8 to 22 carbon atoms with ethylene oxide or propylene oxide.

[0089] 10. Fatty acids having 6 to 24 carbon atoms.

[0090] 11. General formula R”-OZ o Alkyl polyglycosides (R" denotes a linear or branched, saturated or unsaturated alkyl group having an average of 8 to 24 carbon atoms; Z o is an oligoglycoside radical having an average of o=1-10 hexose or pentose units or a mixture thereof).

[0091] 12. Natural substances and their derivatives, such as lecithin, lanolin, saponin, cellulose; cellulose alkyl ethers and carboxyalkylcelluloses, the alkyl groups of which in each case have up to 4 carbon atoms.

[0092] 13. Linear organo(poly)siloxanes containing polar groups, in particular containing the elements O, N, C, S, P, Si, in particular linear organo(poly)siloxanes having alkoxy groups with up to 24 carbon atoms and / or up to 40 EO and / or PO groups.

[0093] Examples of cationic emulsifiers are as follows:

[0094] 14. Salts of primary, secondary and tertiary aliphatic amines having 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acid.

[0095] 15. Quaternary alkylammonium and alkylbenzeneammonium salts, especially those in which the alkyl group has from 6 to 24 carbon atoms, especially the halides, sulfates, phosphates and acetates.

[0096] 16. Alkylpyridinium, alkylimidazolinium, and alkyloxazolinium salts, especially those in which the alkyl chain has up to 18 carbon atoms, such as the halides, sulfates, phosphates, and acetates.

[0097] Particularly suitable amphoteric emulsifiers are:

[0098] 17. Salts of amino acids having long chain substituents, for example, N-alkyldi(aminoethyl)glycines or N-alkyl-2-aminopropionic acids.

[0099] 18. Betaine, e.g. C8~C 18 N-(3-acylamidopropyl)-N,N-dimethylammonium salts having acyl groups, and alkylimidazolinium betaines, or quaternized alkyl or substituted alkyl derivatives of N,N-dimethylglycine.

[0100] Preferred emulsifiers for preparing precrosslinked organopolysiloxanes for aqueous dispersion are the nonionic emulsifiers, especially the alkyl polyglycol ethers listed above under 6.k.

[0101] Component (3) may consist of one of the abovementioned emulsifiers or a mixture of two or more of the abovementioned emulsifiers, which can be used in pure form or in the form of a solution of one or more emulsifiers in water or in an organic solvent.

[0102] In the preparation of the dispersion of the present invention, the emulsifier (3) is preferably used in an amount of 0.1% by weight to 60% by weight, more preferably 0.5% by weight to 30% by weight, based in each case on the total weight of the aminoorganopolysiloxane (1) and the ester (2).

[0103] If the aminoorganopolysiloxane (1) or ester (2), or the resulting precrosslinked organopolysiloxane, itself acts as an emulsifier, there is no need to add a separate emulsifier (3).

[0104] The emulsification process for producing the dispersion is preferably carried out at a temperature below 120°C, more preferably between 5°C and 100°C, particularly preferably between 10°C and 80°C. The increase in temperature is preferably brought about by the introduction of mechanical shear energy required for the emulsification process. The increase in temperature is not necessary to accelerate chemical processes. Furthermore, the dispersion is preferably produced at ambient pressure, but may also be produced at higher or lower pressures.

[0105] The reaction between the aminoorganopolysiloxane (1) and the ester (2) in preparing the dispersion preferably proceeds within a few minutes to a few days.

[0106] Alcohol obtained as a condensation by-product in the preparation of the dispersion may remain in the product or may be removed, for example, by vacuum distillation, membrane processes or extraction.

[0107] The average particle size in the dispersion of the invention, measured by laser diffraction (using a Mastersizer 3000 particle size analyzer from Malvern Panalytical), is preferably in the range of 0.001 to 50 μm, preferably 0.005 to 20 μm, particularly preferably 0.01 to 10 μm.

[0108] The pH may vary from 1 to 14, preferably from 3 to 9, more preferably from 4 to 8.

[0109] The present invention provides a cosmetic composition comprising an aqueous dispersion, preferably an aqueous emulsion, of a pre-crosslinked organopolysiloxane.

[0110] The cosmetic composition of the present invention preferably comprises an aqueous dispersion of pre-crosslinked organopolysiloxane in an amount of from 0.2% to 65% by weight, more preferably from 0.5% to 50% by weight, in each case based on the total weight of the cosmetic composition.

[0111] The cosmetic compositions of the present invention preferably comprise water as a cosmetically acceptable medium.

[0112] The cosmetic composition of the present invention preferably comprises a conditioning agent. The term conditioning agent is used according to K. Krummel, Stephane Chiron, J. Jachowicz, Chapter 14 in "The Chemistry and Manufacture of Cosmetics", Vol. II, Formulating, 3rd Edition, Mitchell L. Schlossmann, 2000, pp. 359-396, to refer to cosmetic components that modify the hair surface and affect the condition of the hair. Cosmetic compositions that contain conditioning agents are used to modify or improve hair softness, increase detangling, reduce wet and dry combing forces, care for hair, prevent static buildup, provide easier sliding effect through hair and along the hair surface, improve hair gloss, preserve hair color fastness, reduce hair breakage, preserve hair shape, and for further cosmetic properties related to natural and healthy hair.

[0113] The cosmetic compositions of the present invention improve one or more of the above mentioned benefits, particularly the combability and deposition of silicone on the hair.

[0114] Examples of conditioning agents and their INCI names can be found in the International Cosmetic Ingredient Dictionary & Handbook edited by the Personal Care Product Council.

[0115] For reference, the World Wide Web-based "wINCI Web Based International Cosmetic Ingredient Dictionary & Handbook (http: / / online.personalcarecouncil.org / jsp / Home.jsp)" or the International Cosmetic Ingredient Dictionary & Handbook, 13th Edition, The Personal Care Products Council (formerly The Cosmetic, Toiletry, and Fragrance Association (CTFA)), 2010) can be used.

[0116] The conditioning agents used are preferably those selected from the following group: cationic polymers, Cationic surfactants, non-polymeric quaternary ammonium compounds, Organopolysiloxanes and organopolysiloxane copolymers different from pre-crosslinked organopolysiloxanes comprising structural units of general formula (I), Fatty acid esters and fatty acid alcohols, Natural or synthetic oils and waxes, and Panthenol, lipids, proteins, and hydrolyzed proteins, and mixtures thereof.

[0117] Preferred examples of conditioning agents are cationic polymers, which are understood to mean polymers which have pendant or terminal cationic groups or which have pendant or terminal groups which can be converted into cationic groups by ionization.

[0118] It is preferred to use cationic polymers which contain quaternary ammonium groups.

[0119] Examples of cationic polymers which are preferably used are published in the International Cosmetic Ingredient Dictionary & Handbook under the name Polyquaternium, each polymer being identified by a respective numerical abbreviation, for example Polyquaternium-1.

[0120] Further examples of cationic polymers are quaternary ammonium group-containing derivatives of modified polysaccharides, such as the polymers with the INCI name Cassia Hydroxypropyltrimonium Chloride, derivatives of modified cellulose and / or starch, such as the propylene glycol ether-modified Cyamopsis tetragonoloba (Cyamopsis niger) with the INCI name Guar Hydroxypropyltrimonium Chloride. quaternary ammonium derivatives of Tetragonoloba (guar) gum, or polymeric quaternary ammonium salts of the reaction product of hydroxyethylcellulose with trimethylammonium substituted epoxides, such as cellulose 2-hydroxyethyl 2-(2-hydroxy-3-(trimethylammonium)propoxy)ethyl 2-hydroxy-3-(trimethylammonio)propyl ether chloride, for example cellulose 2-hydroxyethyl 2-hydroxy-3-(trimethylammonium)propyl ether chloride, for example cellulose 2-hydroxyethyl 2-hydroxy-3-(trimethylammonium)propyl ether chloride, for example cellulose 2-[2-hydroxy-3-(trimethylammonium)propoxy]ethyl ether chloride, for example cellulose 2-[2-hydroxy-3-(trimethylammonium)propoxy]ethyl ether chloride, which has the INCI name Polyquaternium-10.

[0121] Further examples of cationic polymers are quaternary ammonium group-containing acrylic acid polymer derivatives, acrylic acid copolymer derivatives, methacrylic acid derivatives, and methacrylic acid copolymer derivatives, such as the polymer with the INCI name Polyquaternium-37.

[0122] Further examples of cationic polymers are quaternary ammonium group-containing copolymers of dimethyldiallylammonium chloride and acrylic acid, such as the polymer with the INCI name Polyquaternium-22.

[0123] Further examples of cationic polymers are quaternary ammonium group-containing copolymers of derivatives of vinylpyrrolidone, vinylimidazole and vinylimidazoline with methacrylic acid, such as the polymer with the INCI name Polyquaternium-86.

[0124] Further examples of cationic polymers are quaternary ammonium group-containing copolymers of acrylamide and dimethyldiallylammonium chloride, such as the polymer with the INCI name Polyquaternium-7.

[0125] Further examples of cationic polymers are quaternary ammonium group-containing copolymers of reaction products of diethyl sulfate with vinylpyrrolidone and dimethylaminoethyl methacrylate, such as the polymer with the INCI name Polyquaternium-11.

[0126] When a cationic polymer is used, the cosmetic composition of the present invention preferably contains the cationic polymer in an amount of 0.01 to 5% by weight, more preferably 0.05 to 4% by weight, and particularly preferably 0.10 to 3% by weight, based on the total weight of the cosmetic composition in each case.

[0127] Further preferred examples of conditioning agents are cationic surfactants. Examples of cationic surfactants preferably used correspond to the materials listed in items 14 to 16 under the examples of cationic emulsifiers. Examples are cetyltrimethylammonium salts or behenyltrimethylammonium salts. The anionic counterions present can be, for example, chloride, bromide, methosulfate.

[0128] INCI names of preferably used cationic surfactants are, for example, cetrimonium chloride, cetrimonium methosulfate, behentrimonium chloride, behentrimonium methosulfate, stearmonium bromide.

[0129] When a cationic surfactant is used, the cosmetic composition of the present invention preferably contains the cationic surfactant in an amount of 0.1 wt % to 7 wt %, more preferably 0.15 wt % to 6 wt %, and particularly preferably 0.2 wt % to 5 wt %, based on the total weight of the cosmetic composition in each case.

[0130] Further examples of conditioning agents are non-polymeric quaternary ammonium compounds, which term refers to non-polymeric ammonium compounds that exist in cationic form or can be converted to cationic groups by ionization.

[0131] Examples of non-polymeric quaternary ammonium compounds which are preferably used are dimethyldioctadecylammonium chloride, which has the INCI name distearyldimonium chloride, N-[3-(dimethylamino)propyl]octadecanamide, which has the INCI name stearamidopropyldimethylamine, or compounds which have the INCI name dicocoyl ethyl hydroxyethylmonium methosulfate or quaternium-87.

[0132] Further preferred examples of conditioning agents are organopolysiloxanes and organopolysiloxane copolymers different from the pre-crosslinked organopolysiloxanes having structural units of formula (I) present in the aqueous dispersion. The organopolysiloxanes can be present in the form of oils, waxes, gums or resins, or in the form of an emulsion.

[0133] Examples of such organopolysiloxanes which are different from the pre-crosslinked organopolysiloxanes having structural units of formula (I) are: Cyclic organopolysiloxanes of the formula: [R *2SiO] x’ [In the formula, x' is an integer of 4 to 8.] A linear organopolysiloxane of the following general formula: R * 3SiO[R * 2SiO] y SiR * 3 or HOSiR * 2O[R * 2SiO] y SiR * 2OH [In the formula, y is 0 or an integer of 1 to 2000.] and resinous organopolysiloxanes of the general formula: R * t SiO (4-t) / 2 [In the formula, R * In both cases, R, R 1 or for A, preferably R and R 1 is as defined above, t is 0, 1, 2 or 3. The organopolysiloxane resin is thus composed of M, D, T and / or Q units, with both predominantly or exclusively combinations of D and T units and predominantly or exclusively combinations of M and Q units being preferred; in the case of a resin composed predominantly or exclusively of D and T units, the T units are preferably present in a molar ratio T / [M+D+T+Q] of 0.45 to 1, more preferably 0.55 to 1.0, and the number of M and Q units is in both cases preferably zero; in the case of an organopolysiloxane resin composed predominantly or exclusively of M and Q units, the Q units are preferably present in a molar ratio Q / [M+D+T+Q] of 0.25 to 0.9, more preferably 0.35 to 0.7, and the number of D and T units is in both cases preferably zero.

[0134] Examples of organopolysiloxanes present in the form of oils are the polydimethylsiloxanes and the INCI designations disiloxane and dimethicone having a viscosity of 0.65 to 2,000,000 mPas (25° C.).

[0135] Further examples of organopolysiloxanes present in the form of oils or waxes are functionalized organopolysiloxanes, for example polyalkylsiloxanes in which at least one alkyl group is different from methyl, for example organopolysiloxanes with the INCI names stearyl dimethicone, cetyl dimethicone or C26-28 alkyl dimethicone, or for example polyarylsiloxanes and polyarylalkylsiloxanes, for example organopolysiloxanes with the INCI names phenyl trimethicone, trimethylsiloxyphenyl dimethicone or dimethylphenyl dimethicone. or organopolysiloxanes having organic functional groups, such as, for example, aminopropyl, aminopropylaminoethyl, aminopropylaminoisobutyl groups, for example organopolysiloxanes having the INCI name amodimethion, or organopolysiloxanes having, for example, polyethylene glycol or polyalkylene glycol groups, for example organopolysiloxanes having the INCI names PEG12 Dimethicone, PEG / PPG-25,25-Dimethicone or Cetyl PEG / PPG-15 / 15 Butyl Ether Dimethicone.

[0136] Further examples of organopolysiloxanes are silicone resins having the INCI name trimethylsiloxysilicate or polymethylsilsesquioxane.

[0137] When such organopolysiloxanes or organopolysiloxane copolymers are used, the cosmetic composition of the present invention preferably comprises the organopolysiloxanes and organopolysiloxane copolymers different from the pre-crosslinked organopolysiloxanes having structural units of formula (I) present in the aqueous dispersion in an amount of from 0.1% to 40% by weight, more preferably from 0.2% to 30% by weight, particularly preferably from 0.3% to 20% by weight, in each case based on the total weight of the cosmetic composition.

[0138] Further preferred examples of conditioning agents are fatty acid esters and fatty acid alcohols.

[0139] Examples of fatty acid alcohols are alcohols with a C8 to C28 carbon chain, such as the fatty alcohol 1-octadecanol with the INCI name stearyl alcohol, 1-hexadecanol with the INCI name cetyl alcohol, or the fatty alcohols with the INCI names cetearyl alcohol, myristyl alcohol, capryl alcohol, lauryl alcohol, decyl alcohol, and oleyl alcohol.

[0140] In addition to their conditioning properties, fatty acid alcohols also provide a structuring, thickening effect in cosmetic compositions.

[0141] Further examples of fatty acid esters are the esters of fatty acids having the INCI names palmitic acid, oleic acid, linolic acid and linoleic acid, caprylic acid, myristic acid, stearic acid, for example the fatty acid esters having the INCI names isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate, isopropyl stearate.

[0142] When a fatty acid ester and a fatty acid alcohol are used, the cosmetic composition of the present invention preferably contains the fatty acid ester and the fatty acid alcohol in an amount of 0.1 wt % to 15 wt %, more preferably 0.3 wt % to 12 wt %, and particularly preferably 0.5 wt % to 10 wt %, based on the total weight of the cosmetic composition in each case.

[0143] Further preferred examples of conditioning agents are natural or synthetic oils and waxes.

[0144] Examples of preferred oils and waxes are hydrocarbons having a linear or branched, saturated or unsaturated C4 to C60 carbon chain, such as oils and waxes having the INCI names isododecane, hydrated polyisobutylene, hydrated polydecene, paraffin and isoparaffin.

[0145] Further examples of preferred oils and waxes are carnauba wax, beeswax, wool wax, microcrystalline wax, jojoba oil, rice oil, calendula oil, sunflower oil, soybean oil, palm oil, olive oil, and almond oil.

[0146] When natural or synthetic oils and waxes are used, the cosmetic composition of the present invention preferably contains the oils and waxes in an amount of 0.1% by weight to 10% by weight, more preferably 0.2% by weight to 7% by weight, and particularly preferably 0.3% by weight to 5% by weight, in each case based on the total weight of the cosmetic composition.

[0147] Further preferred examples of conditioning agents are panthenol, lipids such as ceramides, proteins, and hydrolyzed proteins such as hydrolyzed collagen, hydrolyzed wheat protein, and hydrolyzed silk.

[0148] The cosmetic composition optionally further comprises additives customary in cosmetics, such as, for example, surfactants, thickeners, gelling agents, film-forming agents, moisturizers, UV filters, pearlescent pigments, vitamins, antioxidants, caffeine, antidandruff active ingredients or preservatives.

[0149] Examples of further additives customary in cosmetology and their INCI names are found in the "International Cosmetic Ingredient Dictionary & Handbook" of the Personal Care Product Council.

[0150] The cosmetic composition optionally further comprises cosmetically customary additives such as surfactants.

[0151] Examples of cosmetically customary surfactants are also described in K. Schrader, A. Domsch, Cosmetology-Theory and Practice, Vol. II, pages II-8 to II-22, Verlag für chemische Industrie, 2005, and also under examples of emulsifiers, items 1. to 18.

[0152] Examples of anionic surfactants which are preferably used correspond to the materials listed in items 1. to 3. under the examples of anionic emulsifiers.

[0153] INCI names of preferably used anionic surfactants are, for example, sodium lauryl sulfate, ammonium laureth sulfate, sodium laureth sulfate, disodium 2-sulfolaurate, disodium lauryl sulfosuccinate or disodium laureth-sulfosuccinate.

[0154] When an anionic surfactant is used, the cosmetic composition of the present invention preferably contains the anionic surfactant in an amount of 1 wt % to 30 wt %, more preferably 5 wt % to 25 wt %, and particularly preferably 7 wt % to 20 wt %, based on the total weight of the cosmetic composition in each case.

[0155] Examples of preferably used nonionic surfactants correspond to the materials listed in items 5. to 13. under Examples of nonionic emulsifiers.

[0156] INCI names of preferably used non-ionic surfactants are, for example, coco glucoside, lauryl glucoside, decyl glucoside, PEG-40 hydrogenated castor oil, polysorbate 80 or PEG-7 glyceryl cocoate.

[0157] When a nonionic surfactant is used, the cosmetic composition of the present invention preferably contains the nonionic surfactant in an amount of 1 wt % to 15 wt %, more preferably 2 wt % to 12 wt %, and particularly preferably 3 wt % to 10 wt %, based on the total weight of the cosmetic composition in each case.

[0158] Examples of amphoteric surfactants which are preferably used correspond to the materials listed under examples of nonionic emulsifiers in points 17. and 18. Further preferred examples are compounds from the classes of the alkylamidobetaines, alkylamphoacetates and alkylamphopropionates.

[0159] INCI names of preferably used non-ionic surfactants are, for example, cocamidopropyl betaine, cetyl betaine, cocamide MEA, cocamide DEA, cocamide MIPA, sodium cocoamphoacetate or sodium cocoamphopropionate.

[0160] When an amphoteric surfactant is used, the cosmetic composition of the present invention preferably contains the amphoteric surfactant in an amount of 1 wt % to 15 wt %, more preferably 2 wt % to 12 wt %, and particularly preferably 3 wt % to 10 wt %, based on the total weight of the cosmetic composition in each case.

[0161] The cosmetic composition optionally further comprises additives customary in cosmetics, such as thickeners.

[0162] Examples of thickeners which are preferably used are modified polysaccharides, such as starch, cellulose, gum arabic and guar gum, for example polymers with the INCI names cellulose gum, guar gum, xanthan gum or cassia gum.

[0163] Further examples of thickening agents are hydrophobically modified non-ionic cellulose derivatives, such as the cellulose derivative with the INCI name hydroxyethyl cellulose.

[0164] Further examples of thickeners are crosslinked acrylic and methacrylic acid polymers and derivatives of crosslinked acrylic and methacrylic acid polymers, such as the polymers with the INCI name Carbomer.

[0165] Further examples of thickening agents are agents which achieve a thickening effect in combination with surfactants. Examples are monoglycerides of fatty acids, mono / diglycerides of ethoxylated fatty acids, and ethoxylated fatty alcohols.

[0166] The INCI names of thickeners preferably used in combination with surfactants to achieve a thickening effect are PEG-120 methyl glucose dioleate, PEG-150 distearate, myristyl glycol, PEG-200 glyceryl palmitate, laureth-4 or PEG-200 glyceryl palmitate.

[0167] Further examples of thickening agents are salts, such as the salt with the INCI name sodium chloride.

[0168] When a thickening agent is used, the cosmetic composition of the present invention preferably comprises the thickening agent in an amount of from 0.1% to 10% by weight, in each case based on the total weight of the cosmetic composition.

[0169] The cosmetic composition optionally further comprises cosmetically customary additives, such as film-forming agents.

[0170] A preferred example of a film-forming agent is a polymer.

[0171] Examples of preferably used film-forming polymers are described in the Personal Care Product Council's "International Cosmetic Ingredient Dictionary & Handbook."

[0172] Examples of preferred film-forming polymers are acrylic acid polymer derivatives, acrylic acid copolymer derivatives, methacrylic acid derivatives, and methacrylic acid copolymer derivatives.

[0173] Examples of preferred anionic polymers are copolymers of vinyl acetate and one or more acrylic acid monomers, methacrylic acid monomers or esters thereof, such as polymers having the INCI name Acrylates / VA Copolymers.

[0174] Further examples of preferred film-forming polymers are copolymers of vinylpyrrolidone with one or more acrylic acid monomers, methacrylic acid monomers or esters thereof, such as polymers having the INCI name Acrylates / VP Copolymer.

[0175] Further examples of preferred film-forming polymers are copolymers of tert-butylacrylamide and one or more acrylic acid monomers, methacrylic acid monomers or esters thereof, such as polymers having the INCI name Acrylates / t-butylacrylamide Copolymer.

[0176] Further examples of preferred film-forming polymers are copolymers of vinyl acetate, crotonic acid, and vinyl neodecanoate monomers, such as the polymer having the INCI name VA / crotonic acid / vinyl neodecanoate copolymer.

[0177] Further examples of preferred film-forming polymers are copolymers of vinyl acetate, crotonic acid, and vinyl neodecanoate monomers, such as the polymer with the INCI name Crotonic Acid / Vinyl C8-C12 Isoalkyl Ester / VA / Bis-Vinyl Dimethicone Copolymer.

[0178] When a film-forming polymer is used, the cosmetic composition of the present invention preferably contains the film-forming polymer in an amount of 0.1% by weight to 15% by weight, more preferably 0.2% by weight to 10% by weight, and particularly preferably 0.3% by weight to 7% by weight, in each case based on the total weight of the cosmetic composition.

[0179] The cosmetic composition optionally further comprises cosmetically customary additives, such as moisturizers.

[0180] Examples of humectants which are preferably used are glycerol, sorbitol, xylitol, polyethylene glycol, propane-1,2-diol, propane-1,3-diol or polypropylene glycol.

[0181] When a moisturizing agent is used, the cosmetic composition of the present invention preferably contains the moisturizing agent in an amount of 0.1 wt % to 10 wt %, more preferably 0.2 wt % to 8 wt %, and particularly preferably 0.3 wt % to 6 wt %, based on the total weight of the cosmetic composition in each case.

[0182] The cosmetic composition optionally further comprises additives customary in cosmetics, such as pearlescent agents.

[0183] Examples of preferably used pearlescent agents are pearlescent pigments or glycol distearate.

[0184] When a pearlescent agent is used, the cosmetic composition of the present invention preferably contains the pearlescent agent in an amount of 0.1% to 7% by weight, more preferably 0.2% to 6% by weight, and particularly preferably 0.3% to 5% by weight, in each case based on the total weight of the cosmetic composition.

[0185] The cosmetic composition is preferably prepared by mixing at least one aqueous dispersion of the pre-crosslinked organopolysiloxane of the present invention in a cosmetically acceptable medium, preferably water, optionally with at least one conditioning agent and optionally further cosmetically customary additives.

[0186] The individual components can be mixed together in a hot / hot, hot / cold, or cold / cold process.

[0187] In the preparation of the cosmetic compositions according to the invention, the dispersions of pre-crosslinked organopolysiloxanes according to the invention are preferably added at a temperature of at most 50° C., more preferably at a temperature of at most 40° C., particularly preferably at a temperature of at most 35° C. They are preferably added at a temperature of at least 5° C., more preferably at least 10° C.

[0188] The cosmetic composition of the present invention may be in the form of an emulsion, suspension, solution, cream, lotion, mousse, stick, soap bar, paste, or gel.

[0189] The cosmetic composition according to the invention in the form of an emulsion may be in the form of a W / O emulsion (water-in-oil emulsion), an O / W emulsion (oil-in-water emulsion) or as a multiple emulsion.

[0190] If the aim is to produce a cosmetic composition comprising an aqueous dispersion of the pre-crosslinked organopolysiloxane of the invention in the form of an emulsion having a translucent or transparent appearance, it is preferred to use an aqueous dispersion of the pre-crosslinked organopolysiloxane of the invention having a particle size of less than 700 nm, more preferably less than 400 nm, particularly preferably less than 300 nm.

[0191] The present invention further provides the use of the cosmetic composition of the present invention for treating keratinous fibers such as hair. The cosmetic composition is preferably used for cleaning and caring for keratinous fibers such as hair or for shaping keratinous fibers such as hair.

[0192] Examples of products for washing and caring for the hair are hair shampoos, hair rinses (rinse-off conditioners), hair treatments, hair masks, hair serums, hair mousses, hair styling sprays, hair creams, hair gels, hair oils, hair end fluids, and hair dyes.

[0193] The present invention further provides the use of the cosmetic composition according to the invention for conditioning keratinous fibres, such as hair, in particular for the purpose of making the keratinous fibres easier to comb.

[0194] The present invention further provides a process for treating keratinous fibers, preferably hair, by applying the cosmetic composition of the present invention to the keratinous fibers, preferably hair, and then optionally rinsing with water. EXAMPLES

[0195] In the examples described below, all amounts reported in parts and percentages are by weight unless otherwise specified. Furthermore, all viscosity data refer to a temperature of 25°C. Unless otherwise specified, the following examples are carried out at ambient pressure, i.e., about 1020 hPa, at room temperature, i.e., about 20°C, or at the temperature that occurs when the reactants are combined at room temperature without supplemental heating or cooling.

[0196] <Synthesis of oxalamide-ethyl-ester terminated organopolysiloxanes S1 and S2> <Synthesis of oxalamide-ethyl-ester terminated organopolysiloxane S1> An apparatus consisting of a 4 L three-neck flask equipped with a magnetic stir bar, magnetic stirrer, reflux condenser, internal thermometer and dropping funnel was inerted with nitrogen gas. The flask was then initially charged with 2679 g (18.45 mol) of diethyl oxalate (M = 146.14 g / mol, CAS number 95-92-1, available from Sigma-Aldrich, Munich, Germany) under a continuous flow of nitrogen, to which 600 g (4.07 mol) of (3-aminopropyl)dimethylmethoxysilane (M = 147.29 g / mol, CAS number 31024-26-7, available from Gelest, Morrisville, USA) was added dropwise with continuous stirring at such a rate that the temperature of the reaction mixture was maintained below 50°C throughout. This resulted in a slightly yellowish transparent liquid, which was stirred at room temperature for an additional hour after the addition was complete. The excess diethyl oxalate was then distilled off under reduced pressure (2 mbar). 1995 g of diethyl oxalate (13.65 mol) were obtained as a colorless, transparent liquid. The liquid distillation residue was fractionated at an internal temperature of 160 °C. In a boiling range of 136-141 °C / 2 mbar vacuum, 949 g (3.84 mol) of the desired main product ethyl 2-((3-(methoxydimethylsilyl)propyl)amino)-2-oxoacetate (EtO-CO-CO-HN-CH2CH2CH2-Si-Me2(OMe))P1 (M = 247.37 g / mol) was distilled as a colorless, transparent liquid. The yield was 94% based on the (3-aminopropyl)dimethylmethoxysilane used.

[0197] First, a 2 L round-bottom flask was charged with 164.95 g (0.66 mol) of P1 and 740 g (10.00 mol Si) of α,ω-OH terminated linear dimethylsiloxane (CAS number 70131-67-8) with a viscosity of 50 mPas. The round-bottom flask containing the reaction mixture was heated under rotation in a rotary evaporator in an oil heating bath at 130° C. and a vacuum of 6 mbar for 30 minutes. The vacuum was then released, 0.02 g of a 40% solution of PNCl2 in ethyl acetate was added, and the mixture was heated under reduced pressure in a rotary evaporator (oil bath at 130° C., vacuum at 6 mbar) for 1 hour. The vacuum was then released again, 0.02 g of a 40% solution of PNCl2 in ethyl acetate (10 ppm of PNCl2) was added, and the mixture was heated under reduced pressure in a rotary evaporator (oil bath at 130° C., vacuum at 6 mbar) for an additional hour. The vacuum was then released again, 0.02 g of a 40% solution of PNCl2 in ethyl acetate (10 ppm PNCl2) was added, and the mixture was heated under reduced pressure on a rotary evaporator (oil bath at 130° C., vacuum at 6 mbar) for 4 hours. After cooling to room temperature, 8 g of magnesium oxide (heavy MgO, CAS number 1309-48-4, available from Sigma-Aldrich, Munich, Germany) was added to the flask contents, and the mixture was stirred at room temperature for 1 hour. The suspension was then filtered through a Seitz® T-120 depth filter (available from Pall Corporation, New York, USA) under a pressure of 6 mbar. This gave 793 g of a clear, colorless oil with a viscosity of about 95 mPas.

[0198] <Synthesis of oxalamide-ethyl-ester terminated organopolysiloxane S2> A stirred flask apparatus consisting of a 1 L three-neck flask equipped with a heating mantle, mechanical stirrer, internal thermometer and water separator with reflux condenser was initially charged with 400 g (5.41 mol Si) of α,ω-OH terminated linear dimethylsiloxane (CAS number 70131-67-8) with a viscosity of 50 mPas and 19.8 g (0.08 mol) of P1 and heated to 80° C. with stirring. After adding 50 mg of PNCl2 (100%), the pressure was reduced (10 mbar) and the flask contents were heated to 100° C. The water formed was removed with a water separator. After 5 min, the vacuum was adjusted to 40 mbar and the mixture was stirred under these conditions for 30 min. The vacuum was then released and another 25 mg of PNCl2 (100%) was added and the mixture was heated to 100° C. and 40 mbar with stirring. The vacuum was then released again, 25 mg of PNCl2 (100%) was added and the mixture was further heated at 100 °C and 40 mbar with stirring. The vacuum was then released, the mixture was cooled to an internal temperature of 70-80 °C and the flask contents were neutralized by adding 2.5 g of anhydrous soda (light sodium carbonate, CAS number 497-19-8, available from Sigma-Aldrich, Munich, Germany). The mixture was stirred for a further 30 min and then filtered. This yielded a clear oil with a viscosity of about 525 mPas.

[0199] <Preparation of Amino Silicone Oil Emulsions E1 to E3> <Preparation of Amino Silicone Oil Emulsion E1> 4.9 g of an 80% aqueous solution of isotridecyl decaethoxylate, commercially available under the name Lutensol TO10 (from BASF), and 1.6 g of demineralized water are premixed at 4000 rpm using an Ultra-Turrax T50 emulsifier (from Janke & Kunkel / IKA). 234.9 g of hydroxy / methoxy-terminated copolymer having a viscosity of 1 / sec (25° C.) is added in three portions at a shear rate of 4000 rpm to give a relatively stiff phase as a pre-emulsion, which is diluted with 57.5 g of demineralized water added in small portions at low shear to obtain the desired emulsion, which is then mixed with 0.20 g of 80% acetic acid and 0.9 g of 2-phenoxyethanol.

[0200] This gives a smooth, low viscosity, white silicone oil emulsion E1 having a solids content of 39.8% and a pH of 5.0.

[0201] Measurement of the particle size distribution gives a D50 value of 160 nm.

[0202] <Preparation of Amino Silicone Oil Emulsion E2> 30.0 g of an 80% aqueous solution of isotridecyldecaethoxylate commercially available under the trade name Lutensol TO 10 (from BASF), composed of 3-(2-aminoethylamino)propyl-methylsiloxy units and dimethylsiloxy units, with an amine number of 0.6 equivalents / g and a viscosity of 2500 mm 2 / sec (at 25°C), 81.7 g of trimethylsilyl-terminated copolymer with a viscosity of 60000 mm 2 86.3 g of trimethylsilyl-terminated polydimethylsiloxane at 25° C. / sec (at 25° C.) are premixed in a container of a lab planetary mixer (model Labmax, manufactured by Molteni) at 500 rpm. 39.6 g of demineralized water and 1.4 g of 80% acetic acid are added (at 500 rpm) and the mixture is homogenized at a shear rate of 2500 rpm for three cycles to obtain a soft to medium-hard solid phase as a pre-emulsion. This is diluted with 157.4 g of demineralized water, added in small portions at relatively low shear, to obtain the desired emulsion, which is mixed with 3.6 g of 2-phenoxyethanol.

[0203] This gives a smooth, fluid, white silicone oil emulsion E2 having a solids content of 48.9% and a pH of 5.5.

[0204] Measurement of the particle size distribution gives a D50 value of 180 nm.

[0205] <Preparation of Amino Silicone Oil Emulsion E3> 32.0 g of an 80% aqueous solution of isotridecyldecaethoxylate commercially available under the trade name Lutensol TO10 (from BASF), composed of 3-(2-aminoethylamino)propyl-methylsiloxy units and dimethylsiloxy units, with an amine value of 0.14 equivalents / g and a viscosity of 4000 mm 2 / sec (at 25°C), 44.0 g of hydroxy / methoxy terminated copolymer with a viscosity of 60000 mm 2 132.0 g of trimethylsilyl-terminated polydimethylsiloxane at 25° C. / sec (at 25° C.) is premixed in a container of a lab planetary mixer (model Labmax, manufactured by Molteni) at 500 rpm. 20.0 g of demineralized water and 0.3 g of 80% acetic acid are added (at 500 rpm) and the mixture is homogenized at a shear rate of 2500 rpm for three cycles to obtain a firm solid phase as a pre-emulsion. This is diluted with 168.1 g of demineralized water, added in small portions at relatively low shear, to obtain the desired emulsion, which is mixed with 3.6 g of 2-phenoxyethanol.

[0206] This gives a smooth, mobile, white silicone oil emulsion E3 having a solids content of 51.3% and a pH of 5.0.

[0207] Measurement of the particle size distribution gives a D50 value of 257 nm.

[0208] [Examples 1 to 4] The following Examples 1-4 represent preparation methods for the synthesis of the inventive aqueous dispersions of pre-crosslinked organopolysiloxanes used to prepare the inventive cosmetic compositions.

[0209] [Example 1] <Emulsion B1-a=B1-b> 92.26 g of aminosilicone oil emulsion E1 are homogenized with 7.74 g of oxalamido-ethyl-ester-terminated organopolysiloxane S1 within 1 minute at 5000 rpm using an Ultra-Turrax T50 emulsifier (from Janke & Kunkel / IKA).

[0210] This gives a smooth, low-viscosity, white silicone oil emulsion B1-a (=B1-b) with a solids content of 44.5% and a pH of 5.0. Measurement of the particle size distribution gives a D50 value of 141 nm.

[0211] After a drying time of 24 hours at 25° C., the emulsion is evaporated to give a pronounced whitish, slightly soft, elastic film that is slightly tacky on the surface.

[0212] <Emulsion B1-c> 96.16 g of aminosilicone oil emulsion E1 are homogenized with 3.84 g of oxylamido-ethyl-ester-terminated organopolysiloxane S1 within 1 minute at 5000 rpm using an Ultra-Turrax T50 emulsifier (from Janke & Kunkel / IKA).

[0213] This gives a smooth, low viscosity, white silicone oil emulsion B1-c with a solids content of 42.1% and a pH of 5.5. Measurement of the particle size distribution gives a D50 value of 123 nm.

[0214] After a drying time of 24 hours at 25° C., the emulsion is evaporated to give a pronounced, whitish, slightly soft and elastic film.

[0215] [Example 2] <Emulsion B2> 96.08 g of the aminosilicone oil emulsion E2 are homogenized with 3.92 g of the oxalamidoethyl-ester-terminated organopolysiloxane S1 within 1 minute at 5000 rpm using an Ultra-Turrax T50 emulsifier (from Janke & Kunkel / IKA).

[0216] This gives a smooth, fluid, white silicone oil emulsion B2 with a solids content of 50.9% and a pH of 6.5. Measurement of the particle size distribution gives a D50 value of 230 nm.

[0217] After a drying time of 24 hours at 25° C., the emulsion is evaporated to give a pronounced, whitish, slightly soft and elastic film.

[0218] [Example 3] <Emulsion B3> 98.22 g of aminosilicone oil emulsion E3 are homogenized with 1.78 g of oxalamidoethyl-ester-terminated organopolysiloxane S1 within 1 minute at 5000 rpm using an Ultra-Turrax T50 emulsifier (from Janke & Kunkel / IKA).

[0219] This gives a smooth, mobile, white silicone oil emulsion B3 with a solids content of 52.2% and a pH of 4.5. Measurement of the particle size distribution gives a D50 value of 210 nm.

[0220] After a drying time of 24 hours at 25° C., the emulsion is evaporated to give a pronounced, whitish, slightly soft, elastic film that is slightly tacky on the surface.

[0221] [Example 4] <Emulsion B4> 85.69 g of aminosilicone oil emulsion E1 are homogenized with 14.31 g of oxalamido-ethyl-ester-terminated organopolysiloxane S2 within 1 minute at 5000 rpm using an Ultra-Turrax T50 emulsifier (from Janke & Kunkel / IKA).

[0222] This gives a smooth, low viscosity, white silicone oil emulsion B4 with a solids content of 48.4% and a pH of 5.5. Measurement of the particle size distribution gives a D50 value of 192 nm.

[0223] After a drying time of 24 hours at 25° C., the emulsion is evaporated to give a pronounced, whitish, slightly soft and elastic film.

[0224] [Comparative Experiment V1] The following comparative experiment V1 represents a manufacturing process for the synthesis of a non-inventive aqueous emulsion (crosslinking with non-inventive diethyl oxalate according to US Pat. No. 5,039,738A).

[0225] 99.6 g of amino silicone oil emulsion E1 are homogenized with 0.4 g of diethyl oxalate within 1 minute at 5000 rpm using an Ultra-Turrax T50 emulsifier (Janke & Kunkel / IKA).

[0226] This gives a smooth, low-viscosity, white silicone oil emulsion V1 with a solids concentration of 40.0% and a pH of 4.5. Measurement of the particle size distribution gives a D50 value of 71 nm.

[0227] After a drying time of 24 hours at 25° C., the emulsion is evaporated to give a white opaque paste-like layer that shows a weak bond to glass and aluminum.

[0228] [Comparative experiment V2] The following comparative experiment V2 represents a manufacturing process for the synthesis of a non-inventive aqueous emulsion (crosslinking with non-inventive diethyl-L-tartrate according to WO20239229A).

[0229] 99.4 g of amino silicone oil emulsion E1 are homogenized with 0.6 g of diethyl-L-tartrate using an Ultra-Turrax T50 emulsifier (Janke & Kunkel / IKA) at 5000 rpm within 1 minute.

[0230] This gives a smooth, low viscosity, white silicone oil emulsion V2 with a solids content of 40.2% and a pH of 5.5. Measurement of the particle size distribution gives a D50 value of 135 nm.

[0231] After a drying time of 24 hours at 25° C., the emulsion is evaporated to give a soft, milky, elastic film with a slightly tacky surface.

[0232] <Rheology of elastomer films after removal of water> A Teflon ring with an inner diameter of 40 mm is placed on a circular glass plate with a diameter of 65 mm to prepare a casting mold. Into this ring, 2.5 g of the emulsion to be measured is weighed onto the glass plate, avoiding air bubbles. The cast emulsion is then dried at 25°C and 101.425 kPa. It must be ensured that the casting mold with the cast emulsion is located on a flat surface that is leveled during drying, so that a film of uniform thickness can be developed. After drying, a film of about 0.5 mm thickness is obtained here.

[0233] After a standing time of one week at 25°C, the obtained films are subjected to rheological analysis. The measurements were carried out using an MCR302 rheometer from Anton Paar, using a PP12.5 plate / plate measuring system and a gap height of 0.5 mm. The instrument was calibrated with standard oil 10000 from Physikalisch-Technische Bundesanstalt [German Federal Physical-Technical Institute]. The measurement temperature is 25.00°C ± 0.05°C.

[0234] The values ​​listed in Table 1 for the storage modulus G', loss modulus G" and loss factor tan δ can be calculated by applying a sinusoidal deformation and measuring the shear stress τ and phase shift angle δ. The measurements in Table 1 were measured at a frequency of 1 Hz and a deformation of 0.1%. When subjected to deformation, the measured samples are within the linear viscoelastic measurement range.

[0235] The following relationship applies here: tan δ=G″ / G′. If tan δ<1, the elastic properties of the sample dominate, and if tan δ>1, the viscous properties of the sample dominate.

[0236] The results of rheological measurements of the elastomeric films of Inventive Examples B1-B4, Comparative Experiments V1 and V2, and Non-Crosslinked Amino Silicone Oil Emulsions E1-E3 are summarized in Table 1.

[0237] [Table 1]

[0238] Table 1 demonstrates that emulsions B1-B4 of the present invention, each containing oxalamidoethyl-ester terminated organopolysiloxanes S1 and S2 as crosslinker components, form elastic films after removal of water, since tan δ<1.

[0239] Non-inventive emulsion V1 has a tan δ greater than 1 and therefore does not show any elastic film formation after removal of the water.

[0240] The non-inventive emulsion V2, which contains diethyl-L-tartrate as a crosslinker component, has a tan δ<1 and therefore shows the formation of an elastic film after removal of water according to WO20239229A1.

[0241] The evaporated pure amino silicone oil emulsions E1-E3 do not show film formation after removal of the water as the tan δ is in all cases significantly greater than 1. This indicates that the addition of a crosslinker is necessary to achieve film formation.

[0242] <Test methods for evaluating the effects of cosmetic compositions> Natural Hair The application behavior of the cosmetic composition and its effect on combing power and softness were evaluated on Caucasian hair available from Kerling International Haarfabrik GmbH. Prior to use, undamaged tresses of natural hair are washed and, if appropriate, damaged by bleaching in a further process step.

[0243] Basic Cleaning For washing, the undamaged hair tress is placed in a solution of methyl isobutyl ketone for 1 hour and shaken. After removing the solvent mixture, the hair tress is washed twice with 3 ml of ammonium lauryl sulfate solution (25%), STEPANOL® ALS25 from the STEPAN Company, then with demineralized water having a temperature of 30° C. The tress is detangled using a coarse-toothed comb. The tress is then placed in a large beaker of demineralized water for 1 hour, removed and rinsed again under running demineralized water. After the basic wash and before further use, the tress is conditioned for at least 12 hours at 23° C. and 50% humidity and combed before use.

[0244] Hair bleaching - production of damaged hair Damaged hair is produced by bleaching washed natural hair tresses (Euro-natural hair, color 6 / 0, 20 cm, tress weight 2 g, from Kerling International Haarfabrik GmbH). This is done by placing 5 tresses in a solution composed of 30% hydrogen peroxide and 25% ammonia (ratio 33.5:1) for 30 minutes in each case. The hair is then thoroughly rinsed with demineralized water and washed twice with 3 ml of ammonium lauryl sulfate solution (25%), STEPANOL® ALS25 from the STEPAN Company, and demineralized water having a temperature of 30° C. The tresses are then placed in a large beaker of demineralized water for 1 hour, removed and rinsed again under running demineralized water. Before further processing, the bleached tresses are conditioned for at least 12 hours at 23° C. and 50% humidity and combed before being used.

[0245] Combing force measurement The combing force of wet and dry hair was determined using bleached or unbleached hair tresses (Euro-natural hair, color 6 / 0, 20 cm, tress weight 2 g, from Kerling International Haarfabrik GmbH). The combing force was measured by the double combing method of YK Kamath and Hans-Dietrich Weigmann, J. Soc. Cosmet. Chem., 37, 111-124, 1986, using an Instron 3343 tensile tester. First, the wet and dry combing force is determined along a measured cross section of the untreated tress. The tress is then treated with the cosmetic composition of the invention and the force absorption during the combing procedure is determined. The reported measurement is the reduction in combing force (work) along the measured cross section obtained between the treated and untreated tresses. The average value from the five tresses is calculated. The reduction in combing force is reported as a percentage.

[0246] Flexibility / softness (by tensile test) The softness of the hair was determined using bleached or unbleached hair tresses (Kerling International Haarfabrik GmbH, Euro-natural hair, color 6 / 0, 20 cm, tress weight 2 g). The softness of the hair in the dry state was determined using an Instron 3343 tensile tester by correlating the required pulling force with the parameters of bending stiffness and surface roughness of the hair bundle. These two parameters in turn correlate with the softness of the hair. For this purpose, the untreated hair tress was fixed in a measuring assembly consisting of five bars arranged opposite each other with an offset. The shape of the hair tress in this starting position is a kind of double S. After this preparation, the hair tress is pulled out of the measuring assembly in one direction and the required force is evaluated as work along the measured cross section. The hair tress is then treated with the cosmetic composition of the invention and the force absorption when pulling the hair tress through the measuring assembly is determined along the measured cross section. The reported measurement is the reduction in tensile force (work) along the measured cross section obtained between treated and untreated tresses. A larger reduction in tensile force (work) corresponds to a good soft feel / high flexibility. The average value from 5 tresses is calculated.

[0247] Softness (by panel test) To assess the softness of the hair tresses, their tactile properties are evaluated by experts (trained panelists). The tresses are in each case compared in pairs, for example shampoo-treated hair compared with untreated hair. The number of pairs of tresses evaluated is at least 3 and the number of panelists is at least 5. The evaluation was based on hair tresses from Kerling International Haarfabrik GmbH (Euro-natural hair, color 6 / 0, 20 cm, tress weight 2 g).

[0248] Washing procedure, shampoo 0.2 g of shampoo per 1 g of hair is applied to the clean, wet tress. The shampoo is massaged in the direction of the ends for 30 seconds. The tress is then rinsed for 30 seconds under running demineralized water and detangled using a wide-toothed comb. This procedure is repeated twice. Finally, the rinsing process is extended to 60 seconds. The tress is then dried for at least 12 hours at a humidity of 50% and a temperature of 23°C.

[0249] Washing instructions, conditioner 0.3 g of rinse-off conditioner per gram of hair is applied to clean, wet tresses. The rinse-off conditioner is massaged in the direction of the ends for 120 seconds. The tress is then rinsed for 60 seconds under running demineralized water and detangled using a wide-toothed comb. This procedure is then repeated. The tress is then dried for at least 12 hours at 50% humidity and 23°C.

[0250] Determination of the amount of silicon (ppm) attached to the hair surface (silicone attachment) The amount of silicone deposited on the hair surface is measured using an energy dispersive x-ray fluorescence spectrometer (AMETEK, XEPOS). The hair tress is placed in a specially manufactured sample holder with a circular measurement area of ​​12 mm diameter. The hair surface in the region of the measurement area is smooth and the hairs are aligned parallel. The sample is excited under helium atmosphere using a palladium tube (17.05 kV, 2.0 mA). The excitation time is 300 s. A control sample (natural hair tress) is subjected to periodic measurements. In case of deviations, drift correction is performed using a glass tablet. The calibration standards used were hair tresses painted with polydimethylsiloxane in the range of 50-2000 ppm (control by atomic absorption spectroscopy).

[0251] To determine the effectiveness of silicone deposition, the amount of Si (ppm) on a clean tress is first determined and taken as the blank value. The same tress is then treated, for example by washing with shampoo. Again, the amount of Si (ppm) = sample value. The amount of deposited Si (ppm) is obtained by performing the following subtraction: sample value - blank value. Each tress is measured in the center on the opposite side and on the back side. The reported results are the average value from three tresses.

[0252] Simulation of shampooing by agitating hair tresses in a surfactant solution Many users wish to maintain the cosmetic benefits, such as improved hair softness, reduced wet combing force, and hair color retention, after the use of a hair conditioning product, despite multiple subsequent washes with shampoo. In order to evaluate the persistence of the cosmetic benefits after treating hair with the cosmetic composition of the present invention, a method was developed that constitutes a simulation of continuous shampooing. For this purpose, a treated hair tress in a 100 ml jar with a screw cap is treated with 50 ml of a 5 percent solution of ammonium lauryl sulfate, thermally equilibrated at 40° C. and obtained by diluting STEPANOL® ALS25 from STEPAN Company, and the treated tress is shaken for a specified time at a speed of 250 rpm in an incubation shaker (from Heidolph Unimax 1010+ incubator 1000) thermally equilibrated at 40° C. After shaking, the tress is rinsed for 1 minute with demineralized water having a temperature of 30° C. and dried.

[0253] Curl retention test at high humidity The humidity curl retention test allows the evaluation of care and styling products with respect to the shaping properties of hair fibers. In this model for determining hair fixation, the percentage change from the initial to the final length of a hair tress curled in a defined manner is recorded against the length of the subsequent tress. The humidity curl retention properties of hair care and styling products are monitored over a period of 7 hours at 23°C and 90% relative humidity.

[0254] Brown European hair strands 15 cm long are assembled into bundles of 3.5 g, tied with thread and permanently fixed with a suitable adhesive. The strands are washed twice with 3 ml of ammonium lauryl sulfate solution (25%), STEPANOL® ALS25 from the STEPAN Company, then with demineralized water having a temperature of 30° C. The strands are combed and dried. The dried strands are sprayed with 20 puffs of a 3% active pump spray, combed once, then wound around a plastic rod with a diameter of 1.4 cm, temporarily fixed with a cover and dried overnight at 50° C.

[0255] The curled tress is carefully removed from the plastic rod. After a short cooling period, the curled tress is attached to a scaled suspension device in a climate chamber at 23° C. and 90% relative humidity. The initial length of the curled tress is predetermined and recorded. At defined time intervals, the length of the curled tress, i.e. the change from the initial length, is read over a period of 7 hours.

[0256] The value is calculated according to formula (GI).

[0257]

number

[0258] The higher the curl retention after time t, the better the shaping / fixing properties of the cosmetic formulation. The uncurling of curly hair tresses is less pronounced.

[0259] <Examples of cosmetic compositions> The pre-crosslinked emulsion is preferably an emulsion which forms an elastic film after removal of water and has a tan δ<1 in rheological measurements.

[0260] [Examples A1-a, A1-c, and A2-a (rinse-off conditioner)] The following examples represent the cosmetic compositions A1-a, A1-c, and A2-a of the present invention, including the pre-crosslinked emulsions B1-a, B1-c, and B2 from the corresponding examples shown in Table 2. The active content of the organopolysiloxane in the cosmetic composition is 0.5%.

[0261] Preparation Instructions Heat the initial charge of water to 75°C with stirring. Add 2.0 parts of hydroxyethyl cellulose. Once 65°C is reached, add 0.5 parts of polysorbate 80, 0.5 parts of stearyl alcohol, 0.5 parts of cetyl alcohol, and 0.2 parts of behentrimonium chloride. Stir the mixture until it reaches 75°C, bringing the components into solution. The mixture is then cooled. During the cooling process, add 0.1 parts of citric acid and 0.2 parts of tetrasodium EDTA. At 35°C, add 0.9 parts of phenoxyethanol and ethylhexylglycerin. Continue stirring and add the emulsion from Example. Homogenize the composition with stirring for 15 minutes.

[0262] [Table 2]

[0263] The raw materials listed in Table 2 are available under the following trade names: 1) Hydroxyethylcellulose: Natrosol 250 HR, Ashland 2) Cetyl alcohol: Cetyl alcohol, Merck KGaA 3) Polysorbate 80: Tween® 80, Croda GmbH 4) Behentrimonium chloride: Genamin® KDMP, Clariant GmbH 5) Stearyl alcohol: Stearyl alcohol, Merck KGaA 6) Citric acid: Citric acid, Sigma 7) Tetrasodium EDTA: EDETA® B Powder, BASF Corporation 8) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schuelke & Mayr

[0264] [Comparative Experiments VA1 and VA2 (Rinse-off Conditioner (Rinse))] The following comparative experiments VA1 and VA2 represent non-inventive cosmetic compositions containing the non-precrosslinked aqueous dispersions E1 and E2 from the corresponding examples. The active content of organopolysiloxane in the cosmetic composition is 0.5%.

[0265] For the preparation of the cosmetic compositions of Comparative Experiments VA1 and VA2, the procedures of Examples A1-a, A1-c, and A2-a were repeated, but with the modification that uncrosslinked emulsions E1 and E2 were used instead of emulsions B1-a, B1-c, and B2 (emulsions of pre-crosslinked organopolysiloxanes according to the invention).

[0266] Preparation Instructions The initial charge of water is heated to 75°C with stirring. 2.0 parts of hydroxyethyl cellulose are added. Once 65°C is reached, 0.5 parts of polysorbate 80, 0.5 parts of stearyl alcohol, 0.5 parts of cetyl alcohol, and 0.2 parts of behentrimonium chloride are added. The mixture is stirred until 75°C is reached, bringing the components into solution. The mixture is then cooled. During the cooling process, 0.1 parts of citric acid and 0.2 parts of tetrasodium EDTA are added. At 35°C, 0.9 parts of phenoxyethanol and ethylhexylglycerin are added. Stirring is continued and the emulsion shown in Table 3 for the comparative experiment is added. The composition is homogenized with stirring for 15 minutes.

[0267] [Table 3]

[0268] The raw materials listed in Table 3 are available under the following trade names: 1) Hydroxyethylcellulose: Natrosol 250 HR, Ashland 2) Cetyl alcohol: Cetyl alcohol, Merck KGaA 3) Polysorbate 80: Tween® 80, Croda GmbH 4) Behentrimonium chloride: Genamin® KDMP, Clariant GmbH 5) Stearyl alcohol: Stearyl alcohol, Merck KGaA 6) Citric acid: Citric acid, Sigma 7) Tetrasodium EDTA: EDETA® B Powder, BASF Corporation 8) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schuelke & Mayr

[0269] [Comparative experiment VA1-DEO (rinse-off conditioner (rinse))] The following comparative experiment VA1-DEO represents a non-inventive cosmetic composition comprising an aqueous dispersion of a pre-crosslinked organopolysiloxane. The active content of the organopolysiloxane in the cosmetic composition is 0.5%.

[0270] For the preparation of the cosmetic composition of Comparative Experiment VA1-DEO, the procedure of Examples VA1 and VA2 was repeated, but with the modification of using precrosslinked non-inventive emulsion V1 instead of emulsions E1 and E2 (emulsions of non-precrosslinked organopolysiloxanes).

[0271] Preparation Instructions The initial charge of water is heated to 75°C with stirring. 2.0 parts of hydroxyethyl cellulose are added. Once 65°C is reached, 0.5 parts of polysorbate 80, 0.5 parts of stearyl alcohol, 0.5 parts of cetyl alcohol, and 0.2 parts of behentrimonium chloride are added. The mixture is stirred until 75°C is reached, bringing the components into solution. The mixture is then cooled. During the cooling process, 0.1 parts of citric acid and 0.2 parts of tetrasodium EDTA are added. At 35°C, 0.9 parts of phenoxyethanol and ethylhexylglycerin are added. Stirring is continued and the emulsion shown in Table 4 for the comparative experiment is added. The composition is homogenized with stirring for 15 minutes.

[0272] [Table 4]

[0273] The raw materials listed in Table 4 are available under the following trade names: 1) Hydroxyethylcellulose: Natrosol 250 HR, Ashland 2) Cetyl alcohol: Cetyl alcohol, Merck KGaA 3) Polysorbate 80: Tween® 80, Croda GmbH 4) Behentrimonium chloride: Genamin® KDMP, Clariant GmbH 5) Stearyl alcohol: Stearyl alcohol, Merck KGaA 6) Citric acid: Citric acid, Sigma 7) Tetrasodium EDTA: EDETA® B Powder, BASF Corporation 8) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schuelke & Mayr

[0274] Comparison of rinse-off conditioners of invention examples A1-a, A1-c, and A2-a with comparative experiments VA1 and VA2 The examples and comparative experiments described differ in that, in the case of Examples A1-a, A1-c and A2-a, an aqueous dispersion according to the invention of a precrosslinked organopolysiloxane was used, whereas in the comparative experiments VA1 and VA2, a similar aqueous dispersion of the corresponding non-precrosslinked organopolysiloxane was used in each case. The active content of the organopolysiloxane in the cosmetic composition is 0.5%.

[0275] In a direct comparison, the following examples / comparative experiments are correlated. Example A1-a - Comparative Experiment VA1 Example A1-c - Comparative Experiment VA1 Example A2-a - Comparative Experiment VA2

[0276] <Wet combing power (lasting effect) after treating damaged hair with rinse-off conditioner and after simulating multiple shampoo treatments by agitating hair in aqueous surfactant solution> [Examples A1-a and A1-c - Comparative Experiment VA1] The use of the aqueous dispersions B1-a and B1-c of pre-crosslinked organopolysiloxanes of the invention in rinse-off conditioners (Examples A1-a and A1-c) results in improved conditioning properties, such as reduced wet combing force, compared to the non-inventive rinse-off conditioner from Example VA1, which contains a dispersion of non-pre-crosslinked organopolysiloxane E1. A further object of the rinse-off conditioners of the invention is to retain the care properties even after multiple shampooings of the hair. In this example, the shampooing process is simulated by stirring the hair tresses treated with the rinse-off conditioner in a surfactant solution for 4 hours. Details of this treatment are given above under the test methods.

[0277] The results of the wet comb force determination are set forth below in Table 5 for the rinse-off conditioners of Examples A1-a, A1-c, and VA1.

[0278] [Table 5]

[0279] By treatment with the rinse-off conditioner of the invention (Example A1-a) containing an aqueous emulsion of pre-crosslinked organopolysiloxane B1-a, it is possible to achieve a significant reduction in the measured wet combing force of the hair tress, with a value of 84%. In particular, the high conditioning effect is retained after stirring the treated hair in the surfactant solution, which is reflected in a sustained reduction in the wet combing force of 39%. Similarly, treatment with the rinse-off conditioner of the invention (Example A1-c) containing an aqueous emulsion of pre-crosslinked organopolysiloxane B1-c achieves a high measured reduction in the wet combing force of the hair tress, with a value of 81%. After stirring the treated hair in the surfactant solution, a sustained reduction in the wet combing force of 31% is achieved.

[0280] Hair treated with a non-inventive rinse-off conditioner containing emulsion E1 (Comparative Example VA1) shows a slightly reduced drop in wet combing force of 79%. However, the drop in wet combing force of 21% after surfactant treatment is significantly lower than in Examples A-1a and A-1c. Treatment of hair in a surfactant solution represents a simulation of washing hair multiple times with shampoo, demonstrating that the rinse-off conditioner of the present invention shows better wash resistance and the conditioning properties are maintained longer than when hair is treated with a non-inventive rinse-off conditioner.

[0281] Comparison of silicone deposition after treating damaged hair with a rinse-off conditioner and after simulating multiple shampooings by agitating the hair in an aqueous surfactant solution for 4 hours. [Example A2-a - Comparative Experiment VA2] As an additional criterion, the efficiency of silicone deposition on damaged hair after treatment with a rinse-off conditioner was evaluated, plus the amount of conditioning organopolysiloxane remaining on the hair surface after simulating shampoo treatment by agitating the hair in a surfactant solution for 4 hours. The results are summarized in Table 6. The determination of silicone deposition is described above under the test methods.

[0282] [Table 6]

[0283] Table 6 shows that deposition of silicone in inventive example A2-a (even after shampooing) is more effective and more resistant to shampooing compared to non-inventive comparative experiment VA2.

[0284] <Comparison between invention example A1-a rinse-off conditioner and comparative example VA1-DEO> The described examples and comparative experiments differ in that, in the case of Example A1-a, an inventive aqueous dispersion of a precrosslinked organopolysiloxane was used, whereas in Comparative Experiment VA1-DEO, a similar non-inventive aqueous dispersion of the corresponding precrosslinked organopolysiloxane was used. The active content of the organopolysiloxane in the cosmetic composition is 0.5%.

[0285] <Wet combing force (lasting effect) after treating damaged hair with rinse-off conditioner and after simulating multiple shampooings by agitating hair in aqueous surfactant solution> [Example A1-a - Comparative Experiment VA1-DEO] The use of the aqueous dispersion B1-a of pre-crosslinked organopolysiloxane of the present invention in a rinse-off conditioner (Example A1-a) results in improved conditioning properties, such as reduced wet combing force, compared to a non-inventive rinse-off conditioner from Example VA1-DEO, which contains a dispersion of pre-crosslinked organopolysiloxane (Comparative Experiment V1). A further object of the rinse-off conditioner of the present invention is to retain the care properties even after multiple shampooings of the hair. In this example, the shampooing process is simulated by stirring a hair tress treated with the rinse-off conditioner in a surfactant solution for 4 hours. Details of this treatment are given above under the test methods.

[0286] The results of the wet comb force determination are set forth below in Table 7 for the rinse-off conditioners of Examples A1-a and VA1-DEO.

[0287] [Table 7]

[0288] By treatment with the rinse-off conditioner of the invention (Example A1-a) containing an aqueous emulsion of pre-crosslinked organopolysiloxane B1-a, it is possible to achieve a significant reduction in the measured wet combing force of the hair tress, with a value of 84%. In particular, the high conditioning effect is retained after stirring the treated hair in the surfactant solution, which is reflected in a sustained reduction in the wet combing force of 39%.

[0289] Hair treated with non-inventive rinse-off conditioner VA1-DEO containing emulsion from Comparative Example V1 shows a slightly reduced drop in wet combing force of 77%.However, the drop in wet combing force of 20% after surfactant treatment is significantly lower than that of Example A-1a.The treatment of hair in surfactant solution represents a simulation of multiple hair washings with shampoo, demonstrating that the rinse-off conditioner of the present invention shows better wash resistance and maintains conditioning properties longer than when hair is treated with non-inventive rinse-off conditioner.

[0290] [Example A3-a] Cosmetic composition: shampoo The following example represents a cosmetic composition A3-a of the present invention containing emulsion B3. Comparative example VA3 is a 60000 mm 2 The present invention represents a commercial shampoo formulation containing an emulsion of dimethicone (dimethylpolysiloxane, BELSIL® DM5102E, available from Wacker Chemie) having a viscosity of 1.0 µg / sec (25°C). The active content of organopolysiloxane in the cosmetic composition is 1.3%.

[0291] The composition of the shampoo is summarized in Table 8.

[0292] Preparation Instructions An initial charge of 32.11 parts water is heated to 50°C with stirring. During this time, 0.20 parts guar hydroxypropyltrimonium chloride, 6.06 parts sodium lauryl sulfate, 29.90 parts sodium laureth sulfate, 0.05 parts citric acid, and 5.0 parts cocamidopropyl betaine are added. The mixture is stirred until 50°C is reached, bringing the components into solution. The mixture is then cooled. In a separate vessel, 20.0 parts water is placed and 0.60 parts carbomer are added with stirring, and stirring is continued until a homogeneous mixture is obtained. 0.06 parts lactic acid is then added. This mixture is added to the initial mixture. At 40°C, 0.95 parts phenoxyethanol and ethylhexylglycerin are added. Continue stirring and add 0.30 parts of C12-13 alkyl lactate, 2.91 parts of inventive emulsion B3 or 2.60 parts of non-inventive dimethicone emulsion BELSIL® DM5102E, 0.40 parts of sodium hydroxide, and 0.66 parts of sodium chloride. The pH can be adjusted to the required value of 6.5 by adding sodium hydroxide as necessary.

[0293] [Table 8]

[0294] <Comparison between shampoo of Example A3-a and Comparative Experiment VA3> The described examples and comparative experiments differ in that, in the case of Example A-3a, an aqueous dispersion of pre-crosslinked organopolysiloxane was used. Comparative experiment VA3 used the commercially available aqueous dimethylpolysiloxane emulsion BELSIL® DM5102E (Wacker Chemie), which has a 60,000 mm 2 The cosmetic composition contains dimethicone (dimethylpolysiloxane) having a viscosity of 1.5 g / s. The active content of organopolysiloxane in the cosmetic composition is 1.3%.

[0295] The results of the cosmetic effects of the shampoo are summarized in Table 9.

[0296] [Table 9]

[0297] The shampoo of Example A-3a containing the emulsion of the present invention exhibits substantially higher reduced wet combing force and significantly improved softness (by tensile test) compared to the shampoo of Comparative Experiment VA3 containing a commercial dimethicone emulsion.

[0298] [Example A3-b] Cosmetic Compositions - Shampoo The following example represents a cosmetic composition comprising Emulsion B3.

[0299] The active content of the organopolysiloxane in the cosmetic composition is 1.0%.

[0300] The composition of the shampoo is summarized in Table 10.

[0301] Preparation Instructions 0.30 parts of guar hydroxypropyltrimonium chloride are dispersed in water. 41.50 parts of sodium laureth sulfate are slowly stirred and the mixture is gradually heated to 75°C. In the course of heating, 0.20 parts of PEG-150 distearate are added at 50°C and 0.50 parts of glycol distearate are added at 65°C. The mixture is then cooled. When 35°C is reached, phenoxyethanol, 0.90 parts of ethylhexylglycerin and the emulsion corresponding to the example are added and the mixture is stirred for 5 minutes. Finally, 13.4 parts of cocamidopropyl betaine are added and the mixture is stirred for another 10 minutes.

[0302] Damaged hair treated with the shampoo of Example A3-b is softer than damaged untreated hair according to the panel test.

[0303] [Table 10]

[0304] [Example A3-c] Cosmetic Compositions - Shampoo The following example represents a cosmetic composition comprising Emulsion B3.

[0305] The active content of the organopolysiloxane in the cosmetic composition is 1.0%.

[0306] The shampoo composition is summarized in Table 11.

[0307] [Table 11]

[0308] Damaged hair treated with the shampoo of Example A3-c is softer than damaged untreated hair according to the panel test.

[0309] [Examples A1-b and A2-b] Rinse-off conditioner The following examples represent cosmetic compositions A1-b and A2-b containing emulsions B-1b and B2, the active content of organopolysiloxane in the cosmetic compositions being 2.0%.

[0310] The compositions of the rinse-off conditioners are summarized in Table 12.

[0311] Preparation Instructions The initial charge of water is heated to 75°C with stirring. 1.1 parts of hydroxyethyl cellulose are added. Once 65°C is reached, 0.5 parts of stearamidopropyl dimethylamine, 1.0 parts 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, bringing the components into solution. The mixture is then cooled. During the cooling process, 0.2 parts of citric acid and 0.2 parts of tetrasodium EDTA are added. At 35°C, 0.9 parts of phenoxyethanol and ethylhexylglycerin are added. Stirring is continued and the emulsion from Example is added. The composition is homogenized with stirring for 15 minutes.

[0312] [Table 12]

[0313] The raw materials listed in Table 12 are available under the following trade names: 1) Hydroxyethylcellulose: Natrosol 250 HR, Ashland 2) Cetyl alcohol: Cetyl alcohol, Merck KGaA 3) Polysorbate 80: Tween® 80, Croda GmbH 4) Behentrimonium chloride: Genamin® KDMP, Clariant GmbH 5) Stearamidopropyl dimethylamine, Incromine® SB, Croda GmbH 6) Stearyl alcohol: Stearyl alcohol, Merck KGaA 7) Citric acid: Citric acid, Sigma 8) Tetrasodium EDTA: EDETA® B Powder, BASF Corporation 9) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schuelke & Mayr

[0314] Damaged hair treated with the rinse-off conditioners from Examples A1-b and A2-b is softer than damaged untreated hair according to the panel test.

[0315] [Example A4] Cosmetic composition: Nourishing styling spray The following example illustrates a cosmetic composition A4 according to the invention that includes emulsion B1-a.

[0316] To prepare cosmetic composition A4, 9.3 g of emulsion B1-a are diluted with 90.7 g of water. The active content of organopolysiloxane in the cosmetic composition is 3.0%.

[0317] [Comparative Example VA4] Cosmetic composition: Nourishing styling spray Comparative experiment VA4 represents a non-invention cosmetic composition containing the aqueous dispersion V2 of pre-crosslinked organopolysiloxane.

[0318] To prepare the cosmetic composition of comparative experiment VA4, the procedure of example A4 was repeated, with the change that the pre-crosslinked non-inventive emulsion V2 was used. 8.7 g of emulsion V2 was diluted with 91.3 g of water. The active content of organopolysiloxane in the non-inventive cosmetic composition VA4 was 3.0%.

[0319] <Comparison between the nourishing styling spray of invention example A4 and comparative experiment VA4> To examine the styling properties of the nourishing styling sprays on hair, curls were created as in the "Curl Retention in High Humidity" section, 0.2 g of each spray was sprayed, and curl retention was determined.

[0320] [Table 13]

[0321] As a result, the curled tresses of hair treated with the inventive styling spray of Example A4 showed a curl retention of 73% after 7 hours. The curled tresses of hair were pleasantly soft and retained their shape even after combing. It was possible to comb the curled tresses of hair without resistance. A curl retention of 30% was determined for the curled tresses of hair treated with the spray from non-inventive comparative example VA4. Thus, curl retention at high humidity is significantly lower for these curled tresses of hair than for the curled tresses of hair treated with the spray of inventive example A4.

Claims

1. 1. An aqueous dispersion, preferably an aqueous emulsion, comprising a pre-crosslinked organopolysiloxane, The pre-crosslinked organopolysiloxane has on average at least one structural unit of the general formula: SiRO ２／２ -Y-SiRO ２／２ () and units in the following formula: R ２ Yes ２／２ (II) [In the formula, Y represents a group of the formula: -R ２ -[NR ３ -R ４ ] ｘ -NR ３ -OC-[C(Z １ )(H)] ｋ１ -[C(Z ２ )(H)] ｋ２ -CO-NR ３ -[R ４ -NR ３ ] ａ -R ２ -R ２ SiO １／２ -[R ２ SiO ２／２ ] ｂ -R ２ SiO １／２ -R ２ -[NR ３ -R ４ ] ａ -NR ３ -OC-[C(Z ２ )(H)] ｋ２ -[C(Z １ )(H)] ｋ１ -CO-NR ３ -[R ４ -NR ３ ] ｘ -R ２ - R may be the same or different and represent monovalent SiC-bonded hydrocarbon radicals having 1 to 18 carbon atoms and which may contain one or more heteroatoms from the group of N, P, S, O, and halogen; R ２ represent, which may be the same or different, a SiC-bonded divalent linear or branched hydrocarbon radical having 3 to 18 carbon atoms, preferably an alkylene radical having 3 to 10 carbon atoms; R ３ may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group such as an acetyl group, preferably a hydrogen atom; R ４ may be the same or different and represent a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms; k1 is 0, 1, 2 or 3, preferably 0; k2 is 0, 1, 2 or 3, preferably 0; x is 0, 1, 2, 3 or 4, preferably 0 or 1; a is 0, 1, 2, 3 or 4, preferably 0 or 1; b is 0 or an integer of 1 to 500, preferably 20 to 350; Z １ is -OH, H or -NHR ３ represents Z ２ is -OH, -H or -NHR ３ represents.] An aqueous dispersion, preferably an aqueous emulsion, comprising:

2. 2. The aqueous dispersion of claim 1, wherein the pre-crosslinked organopolysiloxane comprises siloxane units of the formula: R ３－ｄ (OR １ ) ｄ SiO １／２ (III) [In the formula, R is as defined in claim 1; R １ represents, which may be the same or different, a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, optionally interrupted by one or more separate oxygen atoms, d is 0 or 1.

3. 3. The aqueous dispersion according to claim 1, wherein Y is a group of the formula: -R ２ -[NH-CH ２ CH ２ ] ｘ -NH-OC-CO-NH-R ２ -R ２ SiO １／２ -[R ２ SiO ２／２ ] ｂ -R ２ SiO １／２ -R ２ -NH-OC-CO-NH-[CH ２ CH ２ -NH] ｘ -R ２ - [In the formula, R is as defined in claim 1; x is 0 or 1; b is 0 or an integer of 1 to 500, preferably 20 to 350; R ２ is represented by the formula -(CH ２ ) ３ -or-CH ２ -CH(CH ３ )-CH ２ - is a group.

4. 1. A process for producing an aqueous dispersion, preferably an aqueous emulsion, of a pre-crosslinked organopolysiloxane, comprising: An aqueous dispersion, preferably an aqueous emulsion, of an aminoorganopolysiloxane (1) of the following formula: (R １ O) ｄ A ｅ R ３－ｄ－ｅ SiO(SiARO) ｐ (SiR ２ O) ｑ SiR ３－ｄ－ｅ A ｅ (OR １ ) ｄ (IV) [In the formula, A is an amino group of the general formula: -R ２ -[NR ３ -R ４ -] ｘ NR ３ ２ R may be the same or different and represent monovalent SiC-bonded hydrocarbon radicals having 1 to 18 carbon atoms and which may contain one or more heteroatoms from the group of N, P, S, O, and halogen; R １ represents, which may be the same or different, a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, optionally interrupted by one or more separate oxygen atoms, R ２ represent, which may be the same or different, a SiC-bonded divalent linear or branched hydrocarbon radical having 3 to 18 carbon atoms, preferably an alkylene radical having 3 to 10 carbon atoms; R ３ may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group such as an acetyl group, preferably a hydrogen atom; R ４ may be the same or different and represent a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms; d is 0 or 1; e is 0 or 1; p is an integer of at least 1 and at most 1000; q is 0 or an integer from 1 to 2000; x is 0, 1, 2, 3 or 4, preferably 0 or 1. A process for producing the compound by reacting with a reactive ester (2) of the following formula: R ５ -O ２ C-[C(Z １ )(H)] ｋ１ -[C(Z ２ )(H)] ｋ２ -CO-NR ３ -[R ４ -NR ３ ] ａ -R ２ -R ２ SiO １／２ -[R ２ SiO ２／２ ] ｂ -R ２ SiO １／２ -R ２ -[NR ３ -R ４ ] ａ -NR ３ -OC-[C(Z ２ )(H)] ｋ２ -[C(Z １ )(H)] ｋ１ -CO ２ -R ５ (V) [In the formula, R, R ２ , R ３ , and R ４ is as defined above, R ５ represents O-bonded saturated or unsaturated, linear or branched monovalent hydrocarbon radicals, which may be identical or different, having 1 to 20 carbon atoms per radical and which may contain one or more heteroatoms from the group N, P, S, O and the halogens, k1 is 0, 1, 2 or 3, preferably 0; k2 is 0, 1, 2 or 3, preferably 0; a is 0, 1, 2, 3 or 4, preferably 0 or 1; b is 0 or an integer of 1 to 500, preferably 20 to 350; Z １ is -OH, -H or -NHR ３ represents Z ２ is -OH, -H or -NHR ３ represents.]

5. 5. The process of claim 4, wherein A is an amino group of the formula: -R ２ -[NH-CH ２ CH ２ -] ｘ NH ２ [In the formula, x is 0 or 1; R ２ is represented by the formula -(CH ２ ) ３ -or-CH ２ -CH(CH ３ )-CH ２ - is a group.

6. 6. The process according to claim 4 or 5, characterized in that the reactive esters (2) are oxalamido-methyl-ester terminated organopolysiloxanes and oxalamido-ethyl-ester terminated organopolysiloxanes.

7. On average, at least one structural unit, preferably at least two structural units, more preferably at least three structural units of the following general formula: SiRO ２／２ -Y-SiRO ２／２ () and units in the following formula: R ２ Yes ２／２ (II) [In the formula, Y represents a group of the formula: -R ２ -[NR ３ -R ４ ] ｘ -NR ３ -OC-[C(Z １ )(H)] ｋ１ -[C(Z ２ )(H)] ｋ２ -CO-NR ３ -[R ４ -NR ３ ] ａ -R ２ -R ２ SiO １／２ -[R ２ SiO ２／２ ] ｂ -R ２ SiO １／２ -R ２ -[NR ３ -R ４ ] ａ -NR ３ -OC-[C(Z ２ )(H)] ｋ２ -[C(Z １ )(H)] ｋ１ -CO-NR ３ -[R ４ -NR ３ ] ｘ -R ２ - R, R ２ , R ３ , R ４ , k1, k2, x, a, b, Z １ , and Z ２ is as defined in claim 1.

1. A pre-crosslinked organopolysiloxane comprising:

8. 8. The pre-crosslinked organopolysiloxane of claim 7, characterized in that it comprises siloxane units of the following formula: R ３－ｄ (OR １ ) ｄ SiO １／２ (III) [In the formula, R is as defined in claim 1; d and R １ is as defined in claim 2.

9. 1. A process for producing a pre-crosslinked organopolysiloxane comprising: Aminoorganopolysiloxane of the following formula (R １ O) ｄ A ｅ R ３－ｄ－ｅ SiO(SiARO) ｐ (SiR ２ O) ｑ SiR ３－ｄ－ｅ A ｅ (OR １ ) ｄ (IV) Reacting with a reactive ester of the formula: R ５ -O ２ C-[C(Z １ )(H)] ｋ１ -[C(Z ２ )(H)] ｋ２ -CO-NR ３ -[R ４ -NR ３ ] ａ -R ２ -R ２ SiO １／２ -[R ２ SiO ２／２ ] ｂ -R ２ SiO １／２ -R ２ -[NR ３ -R ４ ] ａ -NR ３ -OC-[C(Z ２ )(H)] ｋ２ -[C(Z １ )(H)] ｋ１ -CO ２ -R ５ (V) [In the formula, A, R, R １ , R ２ , R ３ , R ４ , R ５ , d, e, p, q, k1, k2, a, b, Z １ and Z ２ is as defined in claim 4. A manufacturing process characterized in that the resulting pre-crosslinked organopolysiloxane is then optionally emulsified in water.

10. 10. A cosmetic composition comprising an aqueous dispersion, preferably an aqueous emulsion, of a pre-crosslinked organopolysiloxane according to claim 1, 2 or 3 or a pre-crosslinked organopolysiloxane prepared as claimed in claim 4, 5 or 6, or a pre-crosslinked organopolysiloxane according to claim 7 or 8 or a pre-crosslinked organopolysiloxane prepared as claimed in claim 9.

11. 11. The cosmetic composition according to claim 10, further comprising a conditioning agent.

12. Use of a cosmetic composition according to claim 10 or 11 for treating keratin fibres, preferably for cleaning, caring for or shaping keratin fibres.

13. Use of a cosmetic composition according to claim 10 or 11 for conditioning keratin fibres, in particular for making them easier to comb.

14. 14. Use according to claim 12 or 13, characterized in that the keratin fibres are hair.

15. 12. A process for treating keratin-containing fibres, preferably hair, by applying a cosmetic composition according to claim 10 or 11 to the keratin fibres, preferably hair, and then optionally rinsing with water.

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