Aqueous dispersions of pre-crosslinked organopolysiloxanes

Abstract

Novel aqueous dispersions of pre-crosslinked organopolysiloxanes are described, the pre-crosslinked organopolysiloxanes containing on average at least one structural unit of general formula (I): SiR2 / 2-Y-SiR2 / 2 and a unit of formula (II): R2SiO2 / 2, where Y refers to a group of formula-R2-[NR3-R4] x-NR3-OC-[C (Z1) (H)] k1-[C (Z2) (H)] k2-CO-NR3-[R4-NR3] a-R2SiO1 / 2-[R2SiO2 / 2] b-R2SiO1 / 2-[NR3-R4] a-NR3-OC-[C (Z2) (H)] k2-[C (Z1) (H)] k1-CO-NR3-[R4-NR3 The present invention relates to a method for producing a SiC-bonded hydrocarbon group, which may contain one or more heteroatoms from the group N, P, S, O, and halogen, R2 is a SiC-bonded divalent linear or branched hydrocarbon group having 3 to 18 carbon atoms, R3 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an acyl group, R4 is 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, and n is 0, 1, 2, 3, or 4. A is 0, 1, 2, 3 or 4, b is 0 or an integer from 1 to 500, Z1 represents-OH, H or-NHR3, and Z2 represents-OH, H or-NHR3.

Description

Technical Field

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

[0002] Organopolysiloxanes are used in cosmetic compositions, for example in hair care products, due to their conditioning properties, such as improving softness and smoothness, reducing combing forces, shine properties, improving sensory color, color protection properties, reducing static conditions, protective properties related to thermal stress on the hair, or hydrophobizing.

[0003] An overview of selected organopolysiloxanes for the care of keratin materials such as hair is given in - MD Berthiaume, Society of Cosmetic Chemists (ed.), monograph, Silicones in Hair Care, 1997 and J. Sejpka, Silicone in Haarpflegeprodukten [Silicones in Haircare Products] in Journal, volume 118, No. 17, 1992, pp. 1065-1070.

[0004] Hair is exposed in everyday life to a variety of external influences that lead to damage to the hair surface and thus to impairment of aesthetic properties such as smoothness, softness, shine, and other parameters compared to undamaged hair. Damage to the hair surface can be caused, for example, by chemical or mechanical treatments, UV radiation or heat. Accompanying surface hair damage is the disruption and partial removal of the lipid layer covering the stratum corneum, which is responsible for the highly hydrophobic quality of undamaged natural hair (RALodge, 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 disruption of the surface lipid layer is a hydrophilic, amino acid-based protein matrix.

[0005] Modified siloxanes using oxalamidoester-terminated organopolysiloxanes are known. Those described in WO 2019 / 114953 A1 are linear copolymers of oxalamidoester-terminated organopolysiloxanes and amino-terminated polyethers. Compared to amino-functionalized organopolysiloxanes alone, they exhibit significantly increased hydrophilicity. However, their linear structure means that they do not have an elastic effect.

[0006] US 7501184 B2 describes copolymers obtained by reacting linear organopolysiloxanes terminated with oxalylamino ester groups with organic diamines. Highly viscous to solid copolymers are obtained which are used in adhesives, especially hot melt adhesives. These highly viscous products cannot be emulsified stably and therefore cannot be used to treat fibrous substrates such as hair. In addition, their linear structure means that there is no elastic effect.

[0007] US 7223385 B2, US 7485289 B2, US 7220408 B2 and US 7504094 B2 describe cosmetic compositions for treating hair comprising special aminosilicones and conditioning agents or thickeners. Aminosilicones are dimethylpolysiloxanes with terminal alkoxy / hydroxyl groups and with uncrosslinked aminoethylaminopropylalkoxysiloxane units or aminoethylaminopropylmethylsiloxane units.

[0008] WO 2020 / 239229 A1 describes aqueous dispersions of pre-crosslinked organopolysiloxanes which can be used in cosmetic compositions and preferably form elastomeric films after removal of water. It was found that cosmetic preparations for hair application comprising pre-crosslinked organopolysiloxanes exhibited specific care effects. Despite the elastomeric film-forming properties, only a limited effect on the shaping of the hair fibers was observed.

[0009] US 5039738 A 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. It was found that textile materials treated with the described emulsion exhibit reduced yellowing.

[0010] WO 2015 / 024079 A1 describes cosmetic compositions comprising aminoorganopolysiloxanes, cationic surfactants, and dialkyl esters of dicarboxylic acids of the formula R′—O—CO—R—CO—O—R′, wherein R′ is a C8-C30 group.

[0011] According to WO 2004 / 039930 A2, fabrics treated with a composition consisting of a polycarboxylic acid and an aminoorganosiloxane exhibit enhanced resistance to curling and wrinkling.

[0012] No. 5,399,652 A describes crosslinkable compositions composed of aminoorganopolysiloxanes and a crosslinker component which is an alkoxysilane or siloxane having at least carboxylic anhydride groups. Summary of the invention

[0013] The object is to provide precrosslinked organopolysiloxanes, especially aqueous dispersions of precrosslinked organopolysiloxanes, which preferably form elastomeric films upon removal of water and which can be used in cosmetic compositions. Another object is to provide cosmetic compositions for treating keratin fibers such as hair, preferably for cleaning and caring for them, which can be used for conditioning and shaping keratin fibers such as hair and in particular to provide easier combability thereof.

[0014] This object is achieved by the present invention.

[0015] The present invention provides an aqueous dispersion, preferably an aqueous emulsion, comprising a pre-crosslinked organopolysiloxane, wherein the pre-crosslinked organopolysiloxane comprises, on average, at least one structural unit of the following general formula, preferably at least two structural units, more preferably at least three structural units

[0016] SiRO 2 / 2 -Y-SiRO 2 / 2 (I)

[0017] And the following unit

[0018] R2SiO 2 / 2 (II)

[0019] in

[0020] Y represents a group having the formula

[0021] -R 2 -[NR 3 -R 4 ] x -NR 3 -OC-[C(Z 1 )(H)] k1 -[C(Z 2 )(H)] k2 -CO-NR 3

[0022] -[R 4 -NR 3 ] a -R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -[NR3 -R 4 ] a -

[0023] NR 3 -OC-[C(Z 2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO-NR 3 -[R 4 -NR 3 ] x -R 2 -

[0024] R may be the same or different and represents a monovalent SiC-bonded hydrocarbon radical having 1 to 18 carbon atoms and which may contain one or more heteroatoms selected from the group of N, P, S, O and halogen,

[0025] 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,

[0026] R 3 may be identical 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 is preferably a hydrogen atom,

[0027] 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,

[0028] k1 is 0, 1, 2 or 3, preferably 0,

[0029] k2 is 0, 1, 2 or 3, preferably 0,

[0030] x is 0, 1, 2, 3 or 4, preferably 0 or 1,

[0031] a is 0, 1, 2, 3 or 4, preferably 0 or 1,

[0032] b is 0 or an integer from 1 to 500, preferably 20 to 350,

[0033] Z 1 Indicates -OH, -H or -NHR 3 ,as well as

[0034] Z 2 Indicates -OH, -H or -NHR 3 .

[0035] The present invention further provides a pre-crosslinked organopolysiloxane containing on average at least one structural unit of the following general formula, preferably at least two structural units, more preferably at least three structural units

[0036] SiRO 2 / 2 -Y-SiRO 2 / 2 (I)

[0037] And the following unit

[0038] R2SiO 2 / 2 (II)

[0039] in

[0040] Y represents a group having the formula

[0041] -R 2 -[NR 3 -R 4 ] x -NR 3 -OC-[C(Z 1 )(H)] k1 -[C(Z 2 )(H)] k2 -CO-NR 3

[0042] -[R 4 -NR 3 ] a -R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -[NR 3 -R 4 ] a -

[0043] NR 3 -OC-[C(Z 2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO-NR 3 -[R 4 -NR 3 ] x -R 2 -

[0044] and

[0045] R, R 2 , R 3 , R 4 , k1, k2, x, a, b, Z1 , and Z 2 is as defined above.

[0046] The present invention further provides a process for producing an aqueous dispersion of a pre-crosslinked organopolysiloxane, wherein

[0047] The aqueous dispersion, preferably aqueous emulsion, comprises an aminoorganopolysiloxane (1) of the formula:

[0048] (R 1 O) d A e R 3-d-e SiO(SiARO) p (SiR2O) q S i 3-d-e A e (OR 1 ) d (IV)

[0049] in

[0050] A is an amino group having the general formula

[0051] -R 2 -[NR 3 -R 4 -] x NR 3 2

[0052] R may be the same or different and represents a monovalent SiC-bonded hydrocarbon radical having 1 to 18 carbon atoms and which may contain one or more heteroatoms selected from the group of N, P, S, O and halogen,

[0053] R 1 which may be identical or different and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms and which may be interrupted by one or more independent oxygen atoms,

[0054] 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,

[0055] R 3 may be identical 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 is preferably a hydrogen atom,

[0056] 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,

[0057] d is 0 or 1

[0058] e is 0 or 1

[0059] 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, and

[0060] q is an integer from 0 or 1 to 2000, preferably from 50 to 1000,

[0061] x is 0, 1, 2, 3 or 4, preferably 0 or 1,

[0062] React with the reactive ester (2) of the following formula:

[0063]

[0064] Among them, R 2 , R 3 and R 4 As defined above,

[0065] R 5 may be identical or different and denote an O-bonded, saturated or unsaturated, linear or branched, monovalent hydrocarbon radical having 1 to 20 carbon atoms per radical and which may contain one or more heteroatoms from the group consisting of N, P, S, O and halogen,

[0066] k1 is 0, 1, 2 or 3, preferably 0,

[0067] k2 is 0, 1, 2 or 3, preferably 0,

[0068] a is 0, 1, 2, 3 or 4, preferably 0 or 1,

[0069] b is 0 or an integer from 1 to 500, preferably from 20 to 350,

[0070] Z 1 Indicates -OH, -H or -NHR 3 ,as well as

[0071] Z 2 Indicates -OH, -H or -NHR 3 .

[0072] The present invention further provides a process for producing pre-crosslinked organopolysiloxanes, characterized in that

[0073] Aminoorganopolysiloxane (1) of the following formula:

[0074] (R 1 O) d A e R 3-d-e SiO(SiARO)p (SiR2O) q S i 3-d-e A e (OR 1 ) d (IV)

[0075] React with the reactive ester (2) of the following formula:

[0076]

[0077] Among them, 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,

[0078] And the resulting pre-crosslinked organopolysiloxane is optionally subsequently emulsified in water.

[0079] In the process of the invention, the aminoorganopolysiloxanes (1) of the formula (IV) used are preferably those in which e is 0 and therefore contain only pendant amino groups A and in the reaction with the reactive esters (2) the structural units according to the formula (I) form bridges.

[0080] When e is 0, the pre-crosslinked organopolysiloxane of the present invention contains not only structural units of formula (I) and siloxane units of formula (II), but also preferably contains siloxane units of the following formula:

[0081] R 3-d (OR 1 ) d SiO 1 / 2 (III)

[0082] Among them, R 1 and d are as defined above.

[0083] However, it is also possible to use aminoorganopolysiloxanes (1) of the formula (IV) which also comprise terminal amino groups A, in which e is therefore 1.

[0084] It is also possible to use mixtures of aminoorganopolysiloxanes (1) of the formula (IV) in which e is 0 and e is 1.

[0085] In the reaction with the reactive ester (2), a bridge between the two terminal amino groups (formula (VI)) or between the terminal and the pendant amino group (formula (VII)) can additionally form in this case.

[0086] Furthermore, in addition to the aminoorganopolysiloxane (1), an aminoorganopolysiloxane (1a) containing only a terminal amino group of the following formula may be used:

[0087] (R 1 O) f AR 2-f SiO(SiR2O) n S i 2-f A(OR 1 ) f (IVa)

[0088] Among them, A, R, and R 1 is as defined above,

[0089] f is 0 or 1, and

[0090] n is an integer of 1 to 1,000, preferably 50 to 1,000.

[0091] Thus, as bridges, in addition to the structural units of formula (I), the pre-crosslinked organopolysiloxanes of the present invention may comprise further structural units of the formula

[0092] SiO2 1 / 2 -Y-SiR2O 1 / 2 (VI)

[0093] or

[0094] SiRO 2 / 2 -Y-SiR2O 1 / 2 (VII)

[0095] or a mixture of (VI) and (VII), wherein

[0096] R and Y are as defined above.

[0097] The precrosslinked organopolysiloxanes according to the invention preferably contain siloxane units of the formula (III) in which d is 0 or 1, preferably 1.

[0098] The pendant amino groups and optionally the terminal amino groups A in the aminoorganopolysiloxane (1) or optionally also the aminoorganopolysiloxane (1a) used in the present invention may also react with the reactive ester (2) without forming a bridge, and therefore the pre-crosslinked organopolysiloxane may additionally contain structural units of the formula:

[0099]

[0100] and / or

[0101]

[0102] in

[0103] R, R 2 , R 3 , R 4 , R 5 , k1, k2, x, a, b, Z 1 , and Z 2 is as defined above.

[0104] In the context of the present invention, formula (IV) is understood to mean that the p units -(SiARO)- and the q units -(SiR2O)- can be distributed in any manner, for example as blocks or statistically in the aminoorganopolysiloxane molecule.

[0105] Although not represented by formula (IV) and formula (IVa), respectively, the aminoorganopolysiloxane (1) used in the present invention and the aminoorganopolysiloxane (1a) optionally also used may also contain a siloxane unit selected from the group consisting of the following formulae:

[0106] R 3 / 2, (OR 1 )SiO 3 / 2 and SiO 4 / 2 (IXa-c)

[0107] in

[0108] R and R 1 As defined above,

[0109] The pre-crosslinked organopolysiloxanes according to the invention may therefore also comprise siloxane units of the formula (IXa-c).

[0110] Preferably, R is a monovalent, saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms.

[0111] 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 radicals; hexyl radicals such as n-hexyl radicals; heptyl radicals such as n-heptyl radicals; octyl radicals such as n-octyl radicals and isooctyl radicals such as 2,2,4-trimethylpentyl radicals; nonyl radicals such as n-nonyl radicals; decyl radicals such as n-decyl radicals; dodecyl radicals such as n-dodecyl radicals; octadecyl radicals The invention also includes but is not limited to cycloalkyl groups, such as n-octadecyl groups; cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl groups; alkenyl groups, such as vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl groups; aryl groups, such as phenyl, naphthyl, anthracenyl and phenanthryl groups; alkylaryl groups, such as o-, m-, and p-tolyl groups; xylyl groups and ethylphenyl groups; and aralkyl groups, such as benzyl groups and α- and β-phenylethyl groups.

[0112] Preferred radicals R are methyl, ethyl, octyl and phenyl radicals, more preferably methyl and ethyl radicals.

[0113] The example of the substituted radical R is a haloalkyl group, such as 3,3,3-trifluoro-n-propyl group, 2,2,2,2',2',2'-hexafluoroisopropyl group, heptafluoroisopropyl group, and a halogen aryl group, such as o-, m-, and p-chlorophenyl group. Other examples of the substituted radical R are polyalkylene oxides, such as polyethylene oxide, polypropylene oxide or polyethylene oxide / polypropylene oxide.

[0114] Group R 1 Examples are the alkyl groups mentioned above for R, as well as methoxyethyl, ethoxyethyl and hexyloxyethyl groups; preferably, the group R 1 is hydrogen, methyl or ethyl.

[0115] Preferably, R 5 It is C 1-20 A hydrocarbon radical which may be interrupted by one or more oxygen atoms.

[0116] The examples for the group R also apply to the group R 5 .

[0117] Preferably, R 5 It is C 1-4 An alkyl group, such as a methyl or ethyl group.

[0118] Examples of group A are

[0119] -(CH2)3NH2

[0120] -(CH2)3-NH-(CH2)2-NH2

[0121] -CH2CH(CH3)CH2-NH-(CH2)2-NH2

[0122] -(CH2)3-NH(cyclohexyl)

[0123] -(CH2)3-NHCH3

[0124] -(CH2)3-N(CH3)2

[0125] -(CH2)3-NHCH2CH3

[0126] -(CH2)3-N(CH2CH3)2

[0127] -(CH2)4-NH2

[0128] -CH2CH(CH3)CH2-NH2

[0129] -(CH2)3-NH-(CH2)2-NHCH3

[0130] -(CH2)3-NH-(CH2)2-N(CH3)2

[0131] -(CH2)3-NH-(CH2)2-NHCH2CH3

[0132] -(CH2)3-NH-(CH2)2-N(CH2CH3)2

[0133] -(CH2)3[-NH-CH2CH2]2-NH2

[0134] and its partially or fully acetylated forms, such as -(CH2)3-NH(acetyl)

[0135] -(CH2)3-NH-(CH2)2-NH(acetyl), and -(CH2)3-N(acetyl)-(CH2)2-NH(acetyl).

[0136] Preferred examples of group A are:

[0137] -(CH2)3NH2

[0138] -(CH2)3-NH-(CH2)2-NH2

[0139] -CH2CH(CH3)CH2-NH-(CH2)2-NH2

[0140] -(CH2)3-NHCH3

[0141] Preferably, A is an amino group of the formula

[0142] -R 2 -[NH-CH2CH2-] x NH2

[0143] in

[0144] x is 0 or 1, and

[0145] R 2 It is a group having the formula –(CH2)3- or –CH2-CH(CH3)-CH2-.

[0146] Particularly preferred examples of group A are

[0147] -(CH2)3NH2

[0148] -(CH2)3-NH-(CH2)2-NH2 and

[0149] -CH2CH(CH3)CH2-NH-(CH2)2-NH2.

[0150] Further examples of aminoorganopolysiloxanes (1) are commercially available functionalized siloxanes, such as amine oils, for example amine oils having 3-(2-aminoethyl)aminopropyl functionality, and also glycol oils, phenyl oils or phenyl methyl oils containing amino groups.

[0151] In the preparation of the dispersion of the present invention, one aminoorganopolysiloxane (1) or different kinds of aminoorganopolysiloxanes (1) can be used.

[0152] The aminoorganopolysiloxane (1) used for producing the dispersion of the invention preferably has a viscosity of 1 to 50 000 000 mPa.s at 25° C., more preferably 50 to 10 000 000 mPa.s at 25° C. and particularly preferably 100 to 500 000 mPa.s at 25° C.

[0153] The aminoorganopolysiloxanes (1) used for producing the dispersions according to the invention can be produced, for example, as described in US Pat. No. 7,129,369 B2.

[0154] The dispersion according to the invention preferably comprises the precrosslinked organopolysiloxane according to the invention,

[0155] Emulsifier (3), and

[0156] Water (4).

[0157] The dispersions of the precrosslinked organopolysiloxanes according to the invention can optionally be produced using further substances which do not directly participate in the reaction.

[0158] On drying (without addition of catalyst or pH change), the dispersions according to the invention form a silicone network, preferably an elastic silicone network. The dispersions according to the invention preferably form an elastomeric film after removal of water.

[0159] In the process according to the invention (reaction of the aminoorganopolysiloxane (1) and optionally (1a) with the reactive ester (2) according to the invention) preferably no metal-containing catalysts are used.

[0160] The dispersions according to the invention therefore preferably contain no catalyst.

[0161] In the production of the pre-crosslinked organopolysiloxanes of the invention, aminoorganopolysiloxanes (1) and reactive esters (2) are used, and these components are preferably reacted with one another at room temperature. No additional metal-containing catalyst is required to assist the reaction, and therefore preferably no transition metals from group VIII of the periodic table and their compounds, and no metals from main groups III, IV and V of the periodic table and their compounds are used; in this definition, the elements C, Si, N and P are not regarded as metals.

[0162] Furthermore, the reaction is preferably carried out in the neutral range, ie in the pH range of about 4 to 8, which is achieved by the components themselves. The high reactivity means that a particularly controlled chemical reaction is also not required and preferably also no heating is required.

[0163] In the production of the dispersions of the invention, one aminoorganopolysiloxane (2) or different kinds of aminoorganopolysiloxanes (2) can be used as crosslinkers.

[0164] The ester (2) preferably used is an oxalylaminoester-terminated organopolysiloxane of the following formula:

[0165] R 5 -O2C-CO-NH-R 2 -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -R 2 -NH-OC-CO2-R 5

[0166] in

[0167] R is as defined above,

[0168] R 2 is a group having the formula –(CH2)3- or –CH2-CH(CH3)-CH2-,

[0169] R 5 is as defined above, preferably C 1-4 an alkyl group, especially a methyl or ethyl group, and

[0170] b is 0 or an integer of 1-500, preferably 20-350.

[0171] Thus, Y is preferably a group having the formula

[0172] -R 2 -[NH-CH2CH2] x -NH-OC-CO-NH-R 2

[0173] -R2SiO 1 / 2 -[R2SiO 2 / 2 ] b -R2SiO 1 / 2 -

[0174] R 2 -NH-OC-CO-NH-[CH2CH2-NH] x -R 2 -

[0175] where x is 0 or 1,

[0176] b and R are as defined above, and

[0177] R 2 It is a group having the formula –(CH2)3- or –CH2-CH(CH3)-CH2-.

[0178] Depending on the use of the crosslinking agent (2) or the linear, branched or resinous aminoorganopolysiloxane (1), the precrosslinked organopolysiloxane may have a branched or even highly branched or highly crosslinked structure with linear portions.

[0179] In the process of the invention, the nature and amount of aminoorganopolysiloxane and ester are chosen such that the organopolysiloxane in the resulting dispersion is pre-crosslinked.

[0180] Preferably used aminoorganopolysiloxanes (1) are those which contain on average at least one primary amino function in the pendant amino groups A, thus providing the precrosslinked organopolysiloxanes of the invention. Furthermore, it is also possible to use aminoorganopolysiloxanes (1a) which contain only terminal amino groups A having primary amino functions.

[0181] When aminoorganopolysiloxanes (1a) are used, they are preferably used in an amount of 10 to 300 parts by weight per 100 parts by weight of aminoorganopolysiloxane (1).

[0182] Furthermore, the use of mixtures of aminoorganopolysiloxanes (1) and unfunctionalized organopolysiloxanes (1b) also provides the precrosslinked organopolysiloxanes of the invention.

[0183] The non-functional organopolysiloxane (1b) is an organopolysiloxane having no amino groups A, preferably a linear organopolysiloxane having the general formula

[0184] R 7 u R 6 3-u SiO[R 6 2SiO] v S i 63-u R 7 u (X)

[0185] Where R 6 is as defined for R, and

[0186] R 7 Is it like R 6 The defined or HO-group,

[0187] u is 0 or 1, and

[0188] v is 0 or an integer from 1 to 2000.

[0189] Preferably, R 6 It is C 1-18 Hydrocarbyl, preferably C 1-18 alkyl.

[0190] Examples of non-functional organopolysiloxanes (1b) are dialkylpolysiloxanes, preferably dimethylpolysiloxanes.

[0191] When non-functional organopolysiloxanes (1b) are used, they are preferably used in an amount of 100 to 800 parts by weight per 100 parts by weight of aminoorganopolysiloxane (1).

[0192] The degree of crosslinking here depends on the -OR 5 The ratio of the equivalent weight of to the amino groups A in the aminoorganopolysiloxane (1).

[0193] To produce the dispersion of the invention composed of aminoorganopolysiloxane (1) and reactive ester (2), the ester (2) is preferably present in an amount of 0.1 to 10 equivalents of -OR per equivalent of amino groups A in the aminoorganopolysiloxane (1). 5 , more preferably 0.2 to 5 equivalents of -OR 5 , particularly preferably 0.3 to 3 equivalents of -OR 5 Amount used.

[0194] The dispersion of the precrosslinked organopolysiloxane according to the invention is produced by intensively mixing the aminoorganopolysiloxane (1) with the ester (2), the emulsifier (3), and water (4) with one another.

[0195] Production can be carried out batchwise or continuously.

[0196] The manner in which the components for producing the dispersion of the invention are mixed is not particularly critical and can be carried out in a different order.

[0197] For example, components (1) and (2) can be premixed with one another, then the emulsifier and subsequently the water (4) can be added. Another possibility is to meter the components (1) to (4) in sequence into an emulsifying apparatus. In special cases, it may be advantageous (for example due to the viscosity or reactivity of the aminoorganopolysiloxane (1) and optionally (1a) and optionally the non-functionalized organopolysiloxane (1b) used) to mix the ester (2) with the aminoorganopolysiloxane and thereafter combine the different aminoorganopolysiloxanes or the non-functionalized organopolysiloxanes, or vice versa, depending on which achieves more favorable rheological properties for the processing components.

[0198] Furthermore, the esters (2) can also be introduced as crosslinkers into the final emulsion (1) of aminoorganopolysiloxanes in order thereby to achieve the desired reaction and crosslinking of the aminoorganopolysiloxanes in the emulsion. In order to obtain VOC-free products (these are products free of volatile organic compounds), the by-product alcohols R 5 OH (where R 5 is as defined above) can be completely or partially removed by suitable known measures such as distillation, membrane methods, or other separation methods.

[0199] In the preparation of the dispersions according to the invention, water (4) is preferably used in amounts of 1% to 99% by weight, more preferably 25% to 95% by weight, based in each case on the total weight of all constituents of the dispersion.

[0200] The aqueous dispersion of the precrosslinked organopolysiloxane according to the invention is used as an oil-in-water system.

[0201] As emulsifiers (3) for producing aqueous dispersions of precrosslinked organopolysiloxanes, it is possible to use all anionic, nonionic, cationic or amphoteric emulsifiers known hitherto, both alone or as mixtures of different emulsifiers, which have also been used previously for producing aqueous dispersions, more particularly aqueous emulsions of organopolysiloxanes.

[0202] Examples of anionic emulsifiers are as follows:

[0203] 1. Alkyl sulfates, in particular those having a chain length of 8 to 18 carbon atoms, alkyl and alkylaryl ether sulfates having 8 to 18 carbon atoms in the hydrophobic group and 1 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units.

[0204] 2. Sulfonates, in particular alkylsulfonates having 8 to 18 carbon atoms, alkylarylsulfonates having 8 to 18 carbon atoms, taurates, 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.

[0205] 3. Alkali metal and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl radical.

[0206] 4. Partial esters of phosphoric acid and its alkali metal and ammonium salts, in particular alkyl and alkaryl phosphates having 8 to 20 carbon atoms in the organic radical and alkyl and alkaryl ether phosphates having 8 to 20 carbon atoms and 1 to 40 EO units in the alkyl or alkaryl radical.

[0207] Examples of nonionic emulsifiers are as follows:

[0208] 5. Polyvinyl alcohol, again with 5 to 50%, preferably 8 to 20%, of vinyl acetate units and having a degree of polymerization of 500 to 3,000.

[0209] 6. Alkyl polyglycol ethers, preferably those having 3 to 40 EO units and an alkyl group with 8 to 20 carbon atoms.

[0210] 7. Alkylaryl polyglycol ethers, preferably those having 5 to 40 EO units and 8 to 20 carbon atoms in the alkyl and aryl groups.

[0211] 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those having 8 to 40 EO or PO units.

[0212] 9. Addition products of alkylamines having an alkyl radical having 8 to 22 carbon atoms with ethylene oxide or propylene oxide.

[0213] 10. Fatty acids having 6 to 24 carbon atoms.

[0214] 11. With the general formula R"-OZ o Alkyl polyglycosides, wherein R "represents a linear or branched, saturated or unsaturated alkyl group having an average of 8 to 24 carbon atoms, and Z o represents an oligoglycoside group having an average of o=1-10 hexose or pentose units or a mixture thereof.

[0215] 12. Natural substances and their derivatives, such as lecithin, lanolin, saponins, cellulose; cellulose alkyl ethers and carboxyalkylcelluloses, the alkyl radical of which has in each case up to 4 carbon atoms.

[0216] 13. Linear organo(poly)siloxanes containing polar groups, especially containing the elements O, N, C, S, P, Si, especially those with alkoxy groups having up to 24 carbon atoms and / or up to 40 EO and / or PO groups.

[0217] Examples of cationic emulsifiers are as follows:

[0218] 14. Salts of primary, secondary and tertiary aliphatic amines having 8 to 24 carbon atoms with acetic acid, sulphuric acid, hydrochloric acid and phosphoric acid.

[0219] 15. Quaternary alkylammonium and alkylanilinium salts, especially those in which the alkyl radical has 6 to 24 carbon atoms, especially the halides, sulfates, phosphates and acetates.

[0220] 16. Alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts, especially those in which the alkyl chain has up to 18 carbon atoms, especially the halides, sulfates, phosphates and acetates.

[0221] Particularly suitable amphoteric emulsifiers are as follows:

[0222] 17. Amino acids having long-chain substituents, such as salts of N-alkyldi(aminoethyl)glycine or N-alkyl-2-aminopropionic acid.

[0223] 18. Betaine, such as those having C8-C 18 Acyl N-(amidopropyl)-N,N-dimethylammonium salts, and alkyl imidazolinium betaines, or quaternized alkyl or substituted alkyl derivatives of N,N-dimethylglycine.

[0224] Preferred emulsifiers for producing pre-crosslinked organopolysiloxanes for aqueous dispersions are nonionic emulsifiers, especially the alkyl polyglycol ethers listed under 6. above.

[0225] Component (3) may consist of one of the above-mentioned emulsifiers or a mixture of two or more of the above-mentioned emulsifiers; it may be used in pure form or in the form of a solution of one or more emulsifiers in water or an organic solvent.

[0226] In the production of the dispersions according to the invention, the emulsifier (3) is preferably used in an amount of 0.1 to 60% by weight, more preferably 0.5 to 30% by weight, based in each case on the total weight of aminoorganopolysiloxane (1) and ester (2).

[0227] If the aminoorganopolysiloxane (1) or the ester (2), or the precrosslinked organopolysiloxane obtained, itself acts as an emulsifier, there is no need to add a separate emulsifier (3).

[0228] The emulsification process for producing the dispersion is preferably carried out at a temperature below 120° C., more preferably at 5° C. to 100° C., particularly preferably at 10° C. to 80° C. The increase in temperature preferably occurs by introducing mechanical shear energy, which is required for the emulsification process. It is not necessary to increase the temperature to accelerate chemical processes. Furthermore, the dispersion is preferably prepared at ambient atmospheric pressure, but can also be prepared at higher or lower pressures.

[0229] In the production of the dispersion, the reaction of the aminoorganopolysiloxane (1) with the ester (2) is preferably carried out within a few minutes to a few days.

[0230] The alcohol obtained as condensation by-product in the preparation of the dispersion can remain in the product or be removed, for example, by vacuum distillation, membrane processes or by extraction.

[0231] The average particle size measured by laser diffraction (using a Mastersizer 3000 particle size analyzer from Malvern Panalytical al) in the dispersions according to the invention is preferably in the range from 0.001 to 50 μm, preferably from 0.005 to 20 μm, particularly preferably from 0.01 to 10 μm.

[0232] The pH may be from 1 to 14, preferably from 3 to 9, more preferably from 4 to 8.

[0233] The present invention provides a cosmetic composition comprising an aqueous dispersion, preferably an aqueous emulsion, of a pre-crosslinked organopolysiloxane.

[0234] The cosmetic composition according to the invention comprises an aqueous dispersion of a pre-crosslinked organopolysiloxane, preferably in an amount of 0.2 to 65% by weight, more preferably 0.5 to 50% by weight, in each case based on the total weight of the cosmetic composition.

[0235] The cosmetic compositions of the present invention preferably comprise water as the cosmetically acceptable medium.

[0236] 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", volume II, Formulating, third edition by Mitchell L. Schlossmann, 2000, pp. 359-396, and refers to a cosmetic ingredient that modifies the surface of the hair and affects the condition of the hair. Cosmetic compositions comprising conditioning agents are used to change or improve the softness of the hair, easier untangling, reduced wet and dry combing forces, conditioning of the hair, prevention of static electricity, easier sliding effect through the hair and along the surface of the hair, improved hair shine, maintenance of hair color fastness, reduced hair breakage, maintenance of hair shape, and other cosmetic properties associated with natural and healthy hair.

[0237] The cosmetic compositions of the present invention improve one or more of the above mentioned effects, especially combability and silicone deposition on the hair.

[0238] Examples of conditioning agents and their INCI names are described in "International Cosmetic Ingredient Dictionary & Handbook" by Personal Care Product Council (ed.).

[0239] As a reference, the "wINCI Web Based International Cosmetic Ingredient Dictionary & Handbook" based on the World Wide Web (http: / / online.personalc recuncil.org / jsp / Home.jsp) or International Cosmetic Ingredient Dictionary & Handbook, 13th Edition, The Personal Care Products Council (formerly known as: The Cosmetic, Toiletry, and Fragrance Association (CTFA)), 2010 can be used.

[0240] The conditioning agents used are preferably those selected from the group consisting of:

[0241] Cationic polymers,

[0242] Cationic surfactants,

[0243] Non-polymeric quaternary ammonium compounds,

[0244] Organopolysiloxanes and organopolysiloxane copolymers, other than pre-crosslinked organopolysiloxanes comprising structural units of formula (I),

[0245] Fatty acid esters and fatty acid alcohols,

[0246] Natural or synthetic oils and waxes, and

[0247] Panthenol, lipids, proteins, and hydrolyzed proteins,

[0248] and mixtures thereof.

[0249] Preferred examples of conditioning agents are cationic polymers. These are understood to mean polymers which carry side chain or terminal cationic groups or carry side chain or terminal groups which can be converted into cationic groups by ionization.

[0250] Preference is given to using cationic polymers having quaternary ammonium groups.

[0251] Examples of cationic polymers that are preferably used are disclosed in the International Cosmetic Ingredient Dictionary & Handbook under the name Polyquaternium, wherein each polymer is identified by an individual numerical abbreviation (eg Polyquaternium-1).

[0252] Other examples of cationic polymers are derivatives of modified polysaccharides containing quaternary ammonium groups, for example the polymer with the INCI name Cassia Hydroxypropyltrimonium Chloride, derivatives of modified cellulose and / or starch, for example propylene glycol ether-modified guar gum (Cyamopsis tetragonalus) with the INCI name Guar Hydroxypropyltrimonium Chloride. Tetragonoloba) (guar gum), or polymeric quaternary ammonium salts of the reaction products of hydroxyethylcellulose with a trimethylammonium-substituted epoxide, such as cellulose 2-hydroxyethyl 2-(2-hydroxy-3-(trimethylammonium)propoxy)ethyl 2-hydroxy-3-(trimethylammonium)propyl ether chloride, such as cellulose 2-hydroxyethyl 2-hydroxy-3-(trimethylammonium)propyl ether chloride, such as cellulose 2-hydroxyethyl 2-hydroxy-3-(trimethylammonium)propyl ether chloride, such as cellulose 2-hydroxyethyl 2-hydroxy-3-(trimethylammonium)propyl ether chloride, such as cellulose 2-[2-hydroxy-3-(trimethylammonium)propoxy]ethyl ether chloride, such as cellulose 2-[2-hydroxy-3-(trimethylammonium)propoxy]ethyl ether chloride having the INCI name Polyquaternium-10.

[0253] Further examples of cationic polymers are acrylic acid polymer derivatives, acrylic acid copolymer derivatives, methacrylic acid derivatives and methacrylic acid copolymer derivatives containing quaternary ammonium groups, for example the polymer with the INCI name Polyquaternium-37.

[0254] Further examples of cationic polymers are copolymers of dimethyldiallylammonium chloride and acrylic acid containing quaternary ammonium groups, for example the polymer with the INCI name Polyquaternium-22.

[0255] Further examples of cationic polymers are copolymers of derivatives of vinylpyrrolidone, vinylimidazole and vinylimidazoline with methacrylic acid containing quaternary ammonium groups, for example the polymer with the INCI name Polyquaternium-86.

[0256] Further examples of cationic polymers are copolymers of acrylamide and dimethyldiallylammonium chloride containing quaternary ammonium groups, for example the polymer with the INCI name Polyquaternium-7.

[0257] Further examples of cationic polymers are copolymers containing quaternary ammonium groups of diethyl sulfate with reaction products of vinylpyrrolidone and dimethylaminoethyl methacrylate, for example the polymer with the INCI name Polyquaternium-11.

[0258] When a cationic polymer is used, the cosmetic composition of the present invention contains the cationic polymer in an amount of preferably 0.01 to 5% by weight, more preferably 0.05 to 4% by weight, particularly preferably 0.10 to 3% by weight, in each case based on the total weight of the cosmetic composition.

[0259] Further preferred examples of conditioning agents are cationic surfactants. Examples of cationic surfactants preferably used correspond to the materials listed in point 14 to the examples of cationic emulsifiers in point 16. Examples are hexadecyltrimethylammonium salts or behenyltrimethylammonium salts. Anionic counterions present may be, for example, chloride, bromide, methylsulfate.

[0260] INCI names of cationic surfactants which are preferably used are, for example, Cetrimonium chloride, Cetrimonium Methosulfate, Behrentimonium chloride, Behrentimonium Methosulfate, Steartrimonium bromide.

[0261] When cationic surfactants are used, the cosmetic compositions of the present invention contain cationic surfactants in an amount of preferably 0.1 to 7% by weight, more preferably 0.15 to 6% by weight, particularly preferably 0.2 to 5% by weight, in each case based on the total weight of the cosmetic composition.

[0262] Other examples of conditioning agents are non-polymeric quaternary ammonium compounds. This term refers to non-polymeric ammonium compounds which exist in cationic form or which can be converted into cationic groups by ionization.

[0263] Examples of non-polymeric quaternary ammonium compounds that are preferably used are dimethyldioctadecyl ammonium chloride having the INCI name distearyl dichloride, N-[3-(dimethylamino)propyl]octadecylamide having the INCI name stearamidopropyl dimethylamine, or the compound having the INCI name dimethylacetylethylhydroxyethylammonium methosulfate or Quaternium-87.

[0264] Further preferred examples of conditioning agents are organopolysiloxanes and organopolysiloxane copolymers which are different from the precrosslinked organopolysiloxanes having structural units of formula (I) present in the aqueous dispersion. The organopolysiloxanes may be present in the form of oils, waxes, gums or resins or in the form of an emulsion.

[0265] Examples of such organopolysiloxanes other than pre-crosslinked organopolysiloxanes having structural units of formula (I) are as follows:

[0266] Cyclic organopolysiloxane of the formula

[0267] [R*2SiO] x′

[0268] Wherein, x' is an integer from 4 to 8,

[0269] The following linear organopolysiloxane

[0270] R*3SiO[R*2SiO] y SiR*3 or

[0271] HOSiR*2O[R*2SiO] y SiR*2OH,

[0272] Where y is 0 or an integer from 1 to 2000,

[0273] And the following general formula resinous organopolysiloxane

[0274] R* t SiO (4-t) / 2

[0275] where R* is in each case the same as above for R, R 1 or A, preferably for R and R 1 defined, and

[0276] t is 0, 1, 2, or 3,

[0277] Therefore, the organopolysiloxane resin is composed of M, D, T and / or Q units, preferably mainly or only a combination of D and T units and mainly or only a combination of M and Q units; in the case of a resin mainly or only composed 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 in both cases is preferably zero, and, in the case of an organopolysiloxane resin mainly or only composed 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 in both cases is preferably zero.

[0278] Examples of organopolysiloxanes in oily form are polydimethylsiloxanes having a viscosity of 0.65 to 2 000 000 mPas (25° C.) and the INCI names disiloxane and dimethicone.

[0279] Other examples of organopolysiloxanes 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 polyaryl siloxanes and polyaryl alkyl siloxanes, for example with the INCI names Phenyl Trimethicone, Trimethylsiloxyphenyl Dimethicone or Trimethylsiloxyphenyl Dimethicone. Dimethicone) or Dimethylphenyl Dimethicone, or, for example, organopolysiloxanes with organofunctional groups such as aminopropyl, aminopropylaminoethyl, aminopropylaminoisobutyl groups, for example, organopolysiloxanes with the INCI name Amodimethicone, or, for example, organopolysiloxanes with polyethylene glycol or polyalkylene glycol groups, for example, organopolysiloxanes with the INCI names PEG 12 Dimethicone, PEG / PPG-25,25-Dimethicone or Cetyl PEG / PPG-15 / 15 Butyl Ether Dimethicone.

[0280] Further examples of organopolysiloxanes are silicone resins with the INCI name trimethylsiloxysilicate or polymethylsilsesquioxane.

[0281] When such organopolysiloxanes or organopolysiloxane copolymers are used, the cosmetic composition of the present invention comprises organopolysiloxanes and organopolysiloxane copolymers which are different from the pre-crosslinked organopolysiloxanes having structural units of formula (I) present in the aqueous dispersion in an amount of preferably 0.1 to 40% by weight, more preferably 0.2 to 30% by weight, particularly preferably 0.3 to 20% by weight, in each case based on the total weight of the cosmetic composition.

[0282] Other preferred examples of conditioning agents are fatty acid esters and fatty acid alcohols.

[0283] Examples of fatty acid alcohols are alcohols with a C8-C28 carbon chain, such as fatty alcohol 1-octadecyl alcohol with the INCI name Stearyl Alcohol, fatty alcohol with the INCI name Cetyl Alcohol, or fatty alcohols with the INCI names Cetearyl Alcohol, Myristyl Alcohol, Caprylyl Alcohol, Lauryl Alcohol, Decyl Alcohol, and Oleyl Alcohol.

[0284] In addition to conditioning properties, fatty acid alcohols also achieve structuring, thickening effects in cosmetic compositions.

[0285] Further examples of fatty acid esters are esters of fatty acids with the INCI names palmitic acid, oleic acid, linolenic acid, linoleic acid, caprylic acid, myristic acid, stearic acid, for example fatty acid esters with the INCI names isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate, isopropyl stearate.

[0286] When fatty acid esters and fatty acid alcohols are used, the cosmetic composition according to the invention preferably comprises the fatty acid esters and fatty acid alcohols in an amount of 0.1 to 15% by weight, more preferably 0.3 to 12% by weight, particularly preferably 0.5 to 10% by weight, in each case based on the total weight of the cosmetic composition.

[0287] Further preferred examples of conditioning agents are natural or synthetic oils and waxes.

[0288] Examples of preferred oils and waxes are hydrocarbons having a linear or branched, saturated or unsaturated C4-C60 carbon chain, such as the oils and waxes having the INCI names isododecane, hydrated polyisobutene, hydrated polydecene, paraffin and isoparaffin.

[0289] Other examples of preferred oils and waxes are carnauba wax, beeswax, wool wax, microcrystalline wax, jojoba oil, rice oil, calendula oil, sunflower oil, soybean oil, coconut oil, olive oil and almond oil.

[0290] When natural or synthetic oils and waxes are used, the cosmetic compositions according to the invention preferably comprise the oils and waxes in an amount of 0.1 to 10% by weight, more preferably 0.2 to 7% by weight, particularly preferably 0.3 to 5% by weight, in each case based on the total weight of the cosmetic composition.

[0291] Further preferred examples of conditioning agents are panthenol, lipids (eg, ceramides), proteins, and hydrolyzed proteins (eg, hydrolyzed collagen, hydrolyzed wheat protein, and hydrolyzed silk).

[0292] The cosmetic composition may optionally contain other cosmetic customary additives, such as surfactants, thickeners, gelling agents, film formers, moisturizers, UV filters, pearlescent pigments, vitamins, antioxidants, caffeine, anti-dandruff active ingredients or preservatives.

[0293] Examples of further additives customary in cosmetology and their INCI names are described in the "International Cosmetic Ingredient Dictionary & Handbook" by the Personal Care Product Council.

[0294] The cosmetic composition may optionally contain other cosmetic conventional additives such as surfactants.

[0295] Examples of surfactants customary in cosmetology are also described in K. Schrader, A. Domsch, Cosmetology—Theory and Practice, volume II, pages II-8 to II-22, Verlag fürchemische Industrie, 2005, and in points 1. to 18. under the example of emulsifiers.

[0296] Examples of the anionic surfactants preferably used correspond to the examples of the anionic emulsifiers listed in Point 1. to Point 3.

[0297] Anionic surfactants which are preferably used have the INCI name Sodium Lauryl Sulfate, Ammonium Lauryl Ether Sulfate, Sodium Lauryl Ether Sulfate, Disodium 2-Sulfolaurate, Disodium Lauryl Sulfosuccinate or Disodium Laureth-Sulfosuccinate.

[0298] When anionic surfactants are used, the cosmetic composition of the present invention contains the anionic surfactant, preferably in an amount of 1 to 30% by weight, more preferably 5 to 25% by weight, particularly preferably 7 to 20% by weight, in each case based on the total weight of the cosmetic composition.

[0299] Examples of nonionic surfactants that are preferably used correspond to the examples of nonionic emulsifiers listed in points 5 to 13. INCI names of nonionic surfactants that are preferably used are, for example, Coco Glucoside, Lauryl Glucoside, Decyl Glucoside, PEG-40 Hydrogenated Castor Oil, Polysorbate 80 or PEG-7 Glyceryl Cocoate.

[0300] When a nonionic surfactant is used, the cosmetic composition of the present invention contains the nonionic surfactant, preferably in an amount of 1 to 15% by weight, more preferably 2 to 12% by weight, particularly preferably 3 to 10% by weight, in each case based on the total weight of the cosmetic composition.

[0301] Examples of preferably used amphoteric surfactants correspond to the examples of nonionic emulsifiers listed in points 17 to 18. Other preferred examples are compounds from the class of the alkylamidobetaines, alkylamphoacetates and alkylamphopropionates. INCI names of preferably used nonionic surfactants are, for example, cocamidopropyl betaine, cetyl betaine, cocamide MEA, cocamide DEA, cocamide MIPA, sodium cocoamphoacetate or sodium cocoamphopropionate.

[0302] When an amphoteric surfactant is used, the cosmetic composition according to the invention preferably comprises the amphoteric surfactant in an amount of 1 to 15% by weight, more preferably 2 to 12% by weight, particularly preferably 3 to 10% by weight, in each case based on the total weight of the cosmetic composition.

[0303] The cosmetic composition may optionally contain other cosmetic conventional additives such as thickeners.

[0304] Examples of thickeners which are preferably used are modified polysaccharides such as starch, cellulose, gum arabic, and guar gum, for example polymers having the INCI names cellulose gum, guar gum, xanthan gum or tapioca gum.

[0305] Further examples of thickeners are hydrophobically modified nonionic cellulose derivatives, for example the cellulose derivative with the INCI name hydroxyethylcellulose.

[0306] Further examples of thickeners are crosslinked acrylic acid and methacrylic acid polymers and derivatives of crosslinked acrylic acid and methacrylic acid polymers, for example the polymers with the INCI name Carbomer.

[0307] Other examples of thickeners 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.

[0308] Preferred thickeners for achieving thickening in combination with surfactants are given the INCI names PEG-120 methyl glucose dioleate, PEG-150 distearate, myristyl glycol, PEG-200 palmitin glyceryl, laureth-4 or PEG-200 palmitin glyceryl.

[0309] Other examples of thickeners are salts, for example the salt with the INCI name sodium chloride.

[0310] When a thickener is used, the cosmetic composition according to the invention preferably comprises the thickener in an amount of 0.1% to 10% by weight, based in each case on the total weight of the cosmetic composition.

[0311] The cosmetic composition may optionally contain other cosmetic conventional additives such as film formers.

[0312] Preferred examples of film formers are polymers.

[0313] Examples of film-forming polymers that are preferably used are described in the "International Cosmetic Ingredient Dictionary & Handbook" by the Personal Care Product Council.

[0314] Examples of preferred film-forming polymers are acrylic acid polymer derivatives, acrylic acid copolymer derivatives, methacrylic acid derivatives, and methacrylic acid copolymer derivatives.

[0315] Examples of preferred anionic polymers are copolymers of vinyl acetate and one or more acrylic acid monomers, methacrylic acid monomers or esters thereof, for example the polymer having the INCI name Acrylates / VA Copolymer.

[0316] Further examples of preferred film-forming polymers are copolymers of vinyl pyrrolidone with one or more acrylic acid monomers, methacrylic acid monomers or esters thereof, for example polymers having the INCI name Acrylates / VP Copolymer.

[0317] Further examples of preferred film-forming polymers are copolymers of tert-butylacrylamide with one or more acrylic acid monomers, methacrylic acid monomers or esters thereof, for example the polymer having the INCI name Acrylates / tert-butylacrylamide Copolymer.

[0318] Other 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.

[0319] Other 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 Crotonic Acid / Vinyl C8-C12 Isoalkyl Esters / VA / Bis-Vinyl Dimethicone Copolymer.

[0320] When film-forming polymers are used, the cosmetic compositions according to the invention contain preferably an amount of 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, particularly preferably 0.3 to 7% by weight, based in each case on the total weight of the cosmetic composition.

[0321] The cosmetic composition may optionally contain other cosmetic customary additives such as moisturizers.

[0322] Examples of humectants which are preferably used are glycerol, sorbitol, xylitol, polyethylene glycol, propane-1,2-diol, propane-1,3-diol or polypropylene glycol.

[0323] When a moisturizer is used, the cosmetic composition according to the invention contains preferably an amount of 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, particularly preferably 0.3 to 6% by weight, based in each case on the total weight of the cosmetic composition.

[0324] The cosmetic composition may optionally contain other cosmetic conventional additives such as pearlescent agents.

[0325] Examples of the pearlescent agent preferably used are pearlescent pigments or ethylene glycol distearate.

[0326] When an agent imparting pearl luster is used, the cosmetic composition according to the invention contains the agent imparting pearl luster in an amount of preferably 0.1 to 7% by weight, more preferably 0.2 to 6% by weight, particularly preferably 0.3 to 5% by weight, based in each case on the total weight of the cosmetic composition.

[0327] The cosmetic composition is preferably produced by mixing at least one aqueous dispersion of the precrosslinked organopolysiloxane according to the invention with, optionally, at least one conditioning agent and optionally further cosmetically customary additives in a cosmetically acceptable medium, preferably water.

[0328] The individual ingredients can be mixed with each other in a hot / hot, hot / cold or cold / cold process.

[0329] In the production of the cosmetic composition according to the invention, the dispersions of the precrosslinked 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 a temperature of at least 10° C.

[0330] The cosmetic composition of the present invention may be in the form of an emulsion, a suspension, a solution, a cream, a lotion, a mousse, a stick, a soap bar, a paste, or a gel.

[0331] The cosmetic composition of the present invention in the form of an emulsion may be present 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.

[0332] When the aim is to produce a cosmetic composition comprising an aqueous dispersion of the precrosslinked organopolysiloxane according to the invention in the form of an emulsion having a translucent or transparent appearance, preference is given to using an aqueous dispersion of the precrosslinked organopolysiloxane according to the invention having a particle size of <700 nm, more preferably having a particle size of <400 nm, particularly preferably having a particle size of <300 nm.

[0333] The present invention further provides the use of a cosmetic composition according to the invention for treating keratin fibres such as hair. The cosmetic composition is preferably used for cleaning and caring for keratin fibres such as hair, or for shaping keratin fibres such as hair.

[0334] Examples of products for cleansing and caring for hair are shampoos, hair rinses (rinse-off conditioners), hair treatments, hair masks, hair sera, hair mousses, hair setting sprays, hair creams, hair sprays, hair oils, hair end fluids, and hair colorants.

[0335] The invention further provides the use of a cosmetic composition according to the invention for conditioning keratin fibres such as the hair, in particular for the purpose of making the keratin fibres easier to comb.

[0336] The invention further provides a method for treating keratin fibers, preferably the hair, by applying a cosmetic composition according to the invention to the keratin fibers, preferably the hair, and then optionally rinsing with water. DETAILED DESCRIPTION

[0337] In the examples described below, all reported parts and percentages are based on weight unless otherwise stated. Furthermore, all viscosity data relate to a temperature of 25° C. Unless otherwise stated, the following examples were carried out at ambient atmospheric pressure, i.e. about 1020 hPa, and at room temperature, i.e. at about 20° C., or at the temperature that would result when the reactants were combined at room temperature without supplementary heating or cooling.

[0338] Synthesis of Oxaloylamino-Ethyl Ester-Terminated Organopolysiloxane S1-S2

[0339] Synthesis of Oxalylamino-Ethyl Ester-Terminated Organopolysiloxane S1

[0340] The apparatus consisting of a 4L three-necked flask with a magnetic stirring bar, a magnetic stirrer, a reflux condenser, an internal thermometer and a dropping funnel was inertized with nitrogen. Then, initially 2679 g (18.45 mol) of diethyl oxalate (M = 146.14 g / mol; CAS No. 95-92-1; available from Sigma-Aldrich, Munich, Germany) were charged under a continuous nitrogen stream and 600 g (4.07 mol) of (3-aminopropyl) dimethylmethoxysilane (M = 147.29 g / mol; CAS No. 31024-26-7; available from Gelest, Morrisville, USA) were added dropwise thereto under continuous stirring at a rate such that the temperature of the reaction mixture was always maintained below 50 ° C. This provided a yellowish clear liquid, which was stirred at room temperature for another hour after the addition was completed. Excess diethyl oxalate was then distilled off under reduced pressure (2 mbar). 1995 g of diethyl oxalate (13.65 mol) was obtained as a colorless transparent liquid. The liquid distillation residue was fractionated at an internal temperature of 160° C. In the boiling range of 136 to 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(OMe))P1 (M=247.37 μg / mol) was distilled as a colorless clear liquid. Based on the (3-aminopropyl)dimethylmethoxysilane used, the yield was 94%.

[0341] A 2L round-bottom flask was initially 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 No. 70131-67-8) with a viscosity of 50 mPas. The round-bottom flask containing the reaction mixture was heated on a rotary evaporator in a 130°C oil heating bath under 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 on a rotary evaporator (130°C oil bath, 6 mbar vacuum) under reduced pressure for 1 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 on a rotary evaporator (130°C oil bath, 6 mbar vacuum) under reduced pressure for another 1 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 (130°C oil bath, 6 mbar vacuum) for 4 hours. After cooling to room temperature, 8 g of magnesium oxide (heavy MgO; CAS No. 1309-48-4; available from Sigma-Aldrich, Munich, Germany) were added to the flask contents and the mixture was stirred at room temperature for 1 hour. The suspension was then passed through a pressure of 6 mbar. The mixture was filtered through a T-120 depth filter (available from Pall Corporation, New York, USA). This gave 793 g of a colorless, clear oil having a viscosity of about 95 mPas.

[0342] Synthesis of Oxalylamino-Ethyl Ester-Terminated Organopolysiloxane S2

[0343] A stirred flask apparatus consisting of a 1 L three-necked flask with a heating jacket, a mechanical stirrer, an internal thermometer, and a water separator with a reflux condenser was initially charged with 400 g (5.41 mol Si) of α,ω-OH-terminated linear dimethylsiloxane (CAS No. 70131-67-8) with a viscosity of 50 mPas and 19.8 g (0.08 mol) of P1, and the mixture was heated to 80° C. while stirring. After the addition of 50 mg PNCl2 (100%), the pressure was reduced (10 mbar) and the flask contents were heated to 100° C. The water formed was removed by a water separator. After 5 minutes, the vacuum was adjusted to 40 mbar and the mixture was stirred for 30 minutes under these conditions. The vacuum was then released, a further 25 mg of PNCl2 (100%) was added, and the mixture was heated at 100° C. and 40 mbar while stirring. The vacuum is then released again, 25 mg of PNCl2 (100%) is added, and the mixture is further heated at 100°C and 40 mbar while stirring. The vacuum is then released, the mixture is cooled to an internal temperature of 70°C-80°C, and the flask contents are neutralized by adding 2.5 g of anhydrous soda (light sodium carbonate; CAS No. 497-19-8; available from Sigma-Aldrich, Munich, Germany). The mixture is stirred for a further 30 minutes and then filtered. This gives a clear oil with a viscosity of about 525 mPas.

[0344] Production of amino silicone emulsion E1-E3:

[0345] Production of amino silicone emulsion E1:

[0346] 4.9 g of an 80% aqueous solution of isotridecyldecaethoxylate commercially available under the trade name Lutensol TO 10 (from BASF) and 1.6 g of demineralized water were premixed at 4000 rpm using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA). 34.9 g of a hydroxyl / methoxy-terminated copolymer consisting of 3-(2-aminoethylamino)propylmethylsiloxy and dimethylsiloxy units and having an amine value of 0.14 meq / g and 4000 mm was added in three portions at a shear rate of 4000 rpm. 2 / s (at 25°C), resulting in a relatively stiff hard phase as a pre-emulsion. This was diluted with 57.5 g of demineralized water, added portionwise under low shear to provide the desired emulsion, and mixed with 0.20 g of 80% acetic acid and 0.9 g of 2-phenoxyethanol.

[0347] This afforded a smooth, low viscosity white silicone oil emulsion E1 having a solids content of 39.8% and a pH of 5.0.

[0348] Measurement of the particle size distribution gave a D50 value of 160 nm.

[0349] Preparation of amino silicone oil emulsion E2:

[0350] 30.0 g of an 80% aqueous solution of isotridecyl decaethoxylate commercially available under the trade name Lutensol TO 10 (from BASF), 81.7 g of a 1,2-dimethylsiloxy-1,2-dimethylsiloxy-1,2-dimethylsiloxane ...oxane-1,2-dimethylsiloxy-1,2-dimethylsiloxane-1,2-dimethylsiloxane-1,2-dimethylsiloxane-1,2-dimethylsiloxane-1,2-dimethylsiloxane-1,2-dimethylsiloxane 2 / s viscosity (at 25°C) of a trimethylsilyl-terminated copolymer and 86.3 g of a 60000 mm 2 / s viscosity (at 25 ° C) of trimethylsilyl-terminated polydimethylsiloxane was premixed. 39.6 g of demineralized water and 1.4 g of 80% acetic acid (at 500 rpm) were added and the mixture was homogenized at a shear rate of 2500 rpm in three cycles to produce a soft to medium-firm hard phase as a pre-emulsion. This was diluted with 157.4 g of demineralized water, added in portions with relatively low shear to provide the desired emulsion, and mixed with 3.6 g of 2-phenoxyethanol.

[0351] This afforded a smooth, mobile, white silicone oil emulsion E2 having a solids content of 48.9% and a pH of 5.5.

[0352] Measurement of the particle size distribution gave a D50 value of 180 nm.

[0353] Production of amino silicone emulsion E3:

[0354] 32.0 g of an 80% aqueous solution of isotridecyl decaethoxylate commercially available under the trade name Lutensol TO 10 (from BASF), 44.0 g of a 1,2-dimethylsiloxane-based silane having 3-(2-aminoethylamino)propylmethylsiloxane and dimethylsiloxane units and having an amine value of 0.14 meq / g and a 4000 mm 2 / s viscosity (at 25°C) of a hydroxyl / methoxy-terminated copolymer, and 132.0 g of a 60000 mm 2 / s viscosity (at 25 ° C) of trimethylsilyl-terminated polydimethylsiloxane was premixed. 20.0 g of demineralized water and 0.3 g of 80% acetic acid (at 500 rpm) were added and the mixture was homogenized at a shear rate of 2500 rpm in three cycles to produce a hard hard phase as a pre-emulsion. This was diluted with 168.1 g of demineralized water, added in portions with relatively low shear to provide the desired emulsion, and mixed with 3.6 g of 2-phenoxyethanol.

[0355] This afforded a smooth, free-flowing, white silicone oil emulsion E3 having a solids content of 51.3% and a pH of 5.0.

[0356] Measurement of the particle size distribution gave a D50 value of 257 nm.

[0357] Embodiment 1-4:

[0358] The following Examples 1 to 4 illustrate the production process of the aqueous dispersions according to the invention for the synthesis of pre-crosslinked organopolysiloxanes which are used to produce the cosmetic compositions according to the invention.

[0359] Example 1

[0360] Emulsion B1-a=B1-b.

[0361] 92.26 g of aminosilicone oil emulsion E1 and 7.74 g of oxalylamino-ethyl ester-terminated organopolysiloxane S1 were homogenized at 5000 rpm for one minute using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA).

[0362] This afforded a smooth, low-viscosity white silicone oil emulsion B1-a (= B1-b) having a solids content of 44.5% and a pH of 5.0. Measurement of the particle size distribution gave a D50 value of 141 nm.

[0363] After drying at 25°C for 24 hours, the emulsion evaporated to provide a pronounced, whitish, slightly soft elastic film which was slightly tacky on the surface.

[0364] Emulsion B1-c

[0365] 96.16 g of aminosilicone oil emulsion E1 and 3.84 g of oxalylamino-ethyl ester-terminated organopolysiloxane S1 were homogenized within one minute at 5000 rpm using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA).

[0366] This afforded a smooth, low viscosity white silicone oil emulsion B1-c having a solids content of 42.1% and a pH of 5.5. Measurement of the particle size distribution gave a D50 value of 123 nm.

[0367] After drying at 25°C for 24 hours, the emulsion was evaporated to give a pronounced, whitish, slightly soft elastic film.

[0368] Example 2

[0369] Lotion B2

[0370] 96.08 g of aminosilicone oil emulsion E2 and 3.92 g of oxalylamino-ethyl ester-terminated organopolysiloxane S1 were homogenized within one minute at 5000 rpm using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA).

[0371] This afforded a smooth, mobile, white silicone oil emulsion B2 having a solids content of 50.9% and a pH of 6.5. Measurement of the particle size distribution gave a D50 value of 230 nm.

[0372] After drying at 25°C for 24 hours, the emulsion was evaporated to give a pronounced, whitish, slightly soft elastic film.

[0373] Example 3

[0374] Lotion B3

[0375] 98.22 g of aminosilicone oil emulsion E3 and 1.78 g of oxalylamino-ethyl ester-terminated organopolysiloxane S1 were homogenized within one minute at 5000 rpm using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA).

[0376] This afforded a smooth, free-flowing, white silicone oil emulsion B3 having a solids content of 52.2% and a pH of 4.5. Measurement of the particle size distribution gave a D50 value of 210 nm.

[0377] After drying at 25°C for 24 hours, the emulsion evaporated to provide a pronounced, whitish, slightly soft elastic film which was slightly tacky on the surface.

[0378] Example 4

[0379] Lotion B4

[0380] 85.69 g of aminosilicone oil emulsion E1 and 14.31 g of oxalylamino-ethyl ester-terminated organopolysiloxane S2 were homogenized within one minute at 5000 rpm using an Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA).

[0381] This afforded a smooth, low viscosity white silicone oil emulsion B4 having a solids content of 48.4% and a pH of 5.5. Measurement of the particle size distribution gave a D50 value of 192 nm.

[0382] After drying at 25°C for 24 hours, the emulsion was evaporated to give a pronounced, whitish, slightly soft elastic film.

[0383] Comparative experiment V1:

[0384] The following comparative experiment V1 represents a production process for the synthesis of an aqueous emulsion not according to the invention (crosslinked with diethyl oxalate not according to the invention according to US Pat. No. 5,039,738 A):

[0385] 99.6 g of aminosilicone oil emulsion E1 were homogenized with 0.4 g of diethyl oxalate at 5000 rpm for one minute using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA).

[0386] This afforded a smooth, low-viscosity, white silicone oil emulsion V1 having a solids content of 40.0% and a pH of 4.5. Measurement of the particle size distribution gave a D50 value of 71 nm.

[0387] After a drying period of 24 hours at 25° C., the emulsion was evaporated to obtain a white opaque pasty layer showing weak adhesion to glass and aluminum.

[0388] Comparative experiment V2:

[0389] The following comparative experiment V2 represents a production method for synthesizing an aqueous emulsion not according to the invention (crosslinked with diethyl-L-tartaric acid ester not according to the invention according to WO20239229 A):

[0390] 99.4 g of aminosilicone emulsion E1 were homogenized with 0.6 g of diethyl-L-tartrate using Ultra-Turrax T 50 emulsifier (from Janke & Kunkel / IKA) at 5000 rpm for one minute.

[0391] This afforded a smooth, low viscosity, white silicone oil emulsion V2 having a solids content of 40.2% and a pH of 5.5. Measurement of the particle size distribution gave a D50 value of 135 nm.

[0392] After drying at 25°C for 24 hours, the emulsion was evaporated to give a soft, milky white, elastic film with a slightly tacky surface.

[0393] Rheology of the elastomeric film after removal of water:

[0394] A Teflon ring with an inner diameter of 40 mm is placed on a circular glass plate with a diameter of 65 mm to form a casting mold. 2.5 g of the emulsion to be measured are weighed out into the ring 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 lies on a flat, planar surface during drying so that a film of uniform thickness can be formed. After drying, a film of approximately 0.5 mm thickness is obtained here.

[0395] After standing for 1 week at 25° C., the resulting films were subjected to rheological analysis. The measurements were performed using an MCR 302 rheometer from Anton Paar, using a PP12.5 plate / plate measuring system and a gap height of 0.5 mm. The instrument was calibrated using standard oil 10000 from the Physikalisch-Technische Bundesanstalt [German Federal Physical-Technical Institute]. The measuring temperature was 25.00° C. ± 0.05° C.

[0396] The values ​​of storage modulus G', loss modulus G", and loss factor tanδ listed in Table 1 can be calculated by measuring shear stress τ and phase shift angle δ by applying sinusoidal deformation. The measured values ​​listed in Table 1 were measured at a frequency of 1 Hz and a deformation of 0.1%. When subjected to deformation, the measured sample is within the linear viscoelastic measurement range.

[0397] The following relationship applies here: tan δ=G″ / G′. If tan δ<1, the elastic properties of the sample are predominant; if tan δ>1, the viscous properties of the sample are predominant.

[0398] The results of rheological measurements of the elastomeric films of inventive examples B1 to B4, comparative experiments V1 and V2 and non-crosslinked aminosilicone oil emulsions E1 to E3 are summarized in Table 1.

[0399] Table 1: Rheological data of elastomeric films

[0400]

[0401] Table 1 shows that the inventive emulsions B1 to B4, which respectively comprise oxalylamino-ethyl ester-terminated organopolysiloxanes S1 and S2 as crosslinker components, form elastic films after removal of water, since tan δ <1.

[0402] Emulsion V1 not according to the invention does not show any elastic film formation after removal of the water, since tan δ is greater than 1.

[0403] Emulsion V2 not according to the invention which comprises diethyl-L-tartaric acid ester as crosslinker component shows the formation of an elastic film after removal of water according to WO 20239229 A1, since tan δ <1.

[0404] The evaporated pure aminosilicone oil emulsions E1 to E3 showed no film formation after removal of water, since in all cases tan δ was significantly greater than 1. This indicates that the addition of a crosslinker is necessary to achieve film formation.

[0405] Test methods for evaluating the effectiveness of cosmetic compositions:

[0406] Natural Hair

[0407] The application behavior of the cosmetic compositions and their effects on combing power and softness were evaluated on Caucasian hair available from Kerling International Haarfabrik GmbH. Prior to use, undamaged natural hair tresses were cleaned and, where appropriate, damaged by bleaching in a further process step.

[0408] Basic cleaning

[0409] For cleaning, undamaged tresses were placed in a methyl isobutyl ketone solution for 1 hour and shaken. After removal of the solvent mixture, the tresses were washed with in each case 3 ml of ammonium lauryl sulfate solution (25%), ALS25 (from the company STEPAN) was washed twice and then washed with demineralized water having a temperature of 30°C. The tresses were detangled using a coarse-toothed comb. The tresses were then placed in a large beaker of demineralized water for one hour, taken out, and rinsed again under running demineralized water. After alkaline cleaning, and before further use, the tresses were conditioned at 23°C and 50% humidity for at least 12 hours and combed before use.

[0410] Bleaching of hair – produces damaged hair

[0411] Damaged hair was produced by bleaching clean natural hair tresses (from Kerling International Haarfabrik GmbH, European natural hair, color 6 / 0, 20 cm, tress weight 2 g). This was done by placing five tresses in each case in a solution consisting of 30% hydrogen peroxide and 25% ammonia (ratio 33.5:1) for 30 minutes. The hair was then rinsed thoroughly with demineralized water and washed twice with 3 ml of ammonium lauryl sulfate solution (25%), STEPANOL (R) ALS25, from STEPAN Company, and with demineralized water at a temperature of 30° C. The tresses were then placed in a large beaker of demineralized water for one hour, removed and rinsed again under running demineralized water. Before further treatment, the bleached tresses were conditioned at 23° C. and 50% humidity for at least 12 hours and combed before use.

[0412] Combing force measurement:

[0413] The combing forces on wet and dry hair were determined using bleached or unbleached tresses (from Kerling International Haarfabrik GmbH, European natural hair, color 6 / 0, 20 cm, tress weight 2 g). The combing forces were measured by the double comb method of YK Kamathand Hans-Dietrich Weigmann, J. Soc. Cosmet. Chem., 37, 111-124, 1986, using an Instron 3343 tensile tester. First, the wet and dry combing forces were determined along a measuring section on an untreated tress. The tress was then treated with a cosmetic composition according to the invention and the force absorption during the combing procedure was determined. The reported measured value is the reduction in the combing force (work) obtained along the measuring section between the treated and untreated tresses. The average value from five tresses was calculated. The combing force reduction is reported as a percentage.

[0414] Compliance / Softness (Based on Tensile Test):

[0415] The softness of the hair was determined using bleached or unbleached hair tresses (from Kerling International Haarfabrik GmbH, European 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 tensile force with the parameters of the bending rigidity and surface roughness of the hair strand. These two parameters in turn correlate with the softness of the hair. For this purpose, the untreated hair tresses were clamped into a measuring assembly consisting of five rods positioned relative to each other with an offset. The shape of the hair tress in this starting position was a double S. After this preparation, the hair tresses were pulled out of the measuring assembly in one direction and the required force was evaluated along the measured cross section as work. The hair tresses were then treated with the cosmetic composition of the invention and the force absorption when pulling the hair tresses through the measuring assembly was determined along the measured cross section. The reported measured value is the reduction in tensile force (work) along the measured cross section obtained between the treated and untreated hair tresses. A substantial reduction in tension (work) corresponds to a good soft feel / high softness. The average value from five tresses was calculated.

[0416] Softness (based on panel test):

[0417] To assess the softness of the hair tresses, their tactile properties are assessed by experts (trained panelists). The hair tresses are compared in pairs in each case, e.g. hair treated with shampoo compared with untreated hair. The number of hair tress pairs evaluated is at least three, the number of panelists is at least five. The assessment is based on hair tresses from Kerling International Haarfabrik GmbH (European natural hair, color 6 / 0, 20 cm, tress weight 2 g).

[0418] Washing programs, shampoo:

[0419] 0.2 g shampoo / g hair is applied to a clean, moistened tress. The shampoo is massaged in the direction of the hair ends for 30 seconds. The tress is then rinsed under running demineralized water for 30 s and detangled using a coarse-toothed comb. This process is repeated twice. In the last case, the rinsing process is extended to 60 seconds. The tress is then dried at 50% humidity and a temperature of 23° C. for at least 12 h.

[0420] Washing programs, conditioner:

[0421] 0.3 g of rinse-out conditioner per g of hair is applied to a clean, wet tress. The rinse-out conditioner is massaged in the direction of the hair ends for 120 seconds. The tress is then rinsed in running demineralized water for 60 seconds and detangled using a coarse-toothed comb. The process is repeated. The tress is then dried at 50% humidity and a temperature of 23° C. for at least 12 h.

[0422] Determination of the amount of Si deposited on the hair surface in ppm (silicone deposition):

[0423] The amount of silicone deposited on the hair surface was determined using an energy dispersive X-ray fluorescence spectrometer (AMETEK, XEPOS). The hair strands were placed in a specially produced sample holder with a circular measuring area of ​​12 mm in diameter. The hair surface in the region of the measuring area was smooth and the hairs were aligned parallel. The samples were excited using a palladium tube (17.05 kV, 2.0 mA) under a helium atmosphere. The excitation time was 300 seconds. Conventional measurements were performed on control samples (natural hair strands). In the event of deviations, drift correction was performed using glass slides. The calibration standards used were hair strands loaded with polydimethylsiloxane in the range of 50 to 2000 ppm (controlled by atomic absorption spectroscopy).

[0424] To determine the effectiveness of silicone deposition, first determine the amount of Si on a clean tress in ppm = Blank value. Then treat the same tress by, for example, washing with shampoo. Determine again the amount of Si in ppm = Sample value. The amount of Si deposited in ppm is obtained by performing the following subtraction: Sample value - Blank value. Each tress is measured centered on the facing side and the reverse side. The reported results are the average from three tresses.

[0425] Simulate shampooing by agitating hair tresses in a surfactant solution:

[0426] Many users desire cosmetic effects such as improved hair softness, reduced wet combing forces, and persistence of hair color retention after the use of hair conditioning products despite multiple subsequent shampooings. In order to evaluate the persistence of cosmetic effects after treatment of hair with the cosmetic compositions of the invention, a method constituting a simulation of consecutive shampoos was developed. For this purpose, treated hair tresses in 100 ml bottles with screw-top caps were treated with 50 ml of a 5% ammonium lauryl sulfate solution which had been thermally equilibrated at 40° C. and diluted by 1% shampoo. ALS25 (from STEPAN Company) was obtained and the treated tresses were shaken for a defined time at 40° C. at a speed of 250 rpm in a thermo-equilibrated incubation shaker (from Heidolph Unimax 1010 + Incubator 1000). After shaking, the tresses were rinsed with demineralized water at a temperature of 30° C. for one minute and dried.

[0427] Curl retention test under high humidity:

[0428] The curl retention test at high humidity allows the evaluation of the shaping properties of care and styling products with respect to the hair fiber. In this model for determining hair hold, the percentage change from the initial to the final length of a lock of hair curled in a defined manner is recorded compared to the subsequent lock length. The curl retention properties of hair care and styling products at high humidity are monitored over a period of seven hours at 23°C and 90% relative humidity.

[0429] 15 cm long locks of European brown hair were assembled into bundles of 3.5 g, tied with thread and permanently fixed with a suitable adhesive. The locks were in each case treated with 3 ml of ammonium lauryl sulfate solution (25%) from STEPAN Company. ALS25, then washed twice with demineralized water at a temperature of 30°C. The tresses were combed and dried. Tresses of 20 strands were spray-dried with a 3% active pump spray, combed once, then wound on a plastic rod with a diameter of 1.4 cm, temporarily fixed with a cap, and dried at 50°C overnight.

[0430] The curled hair tresses were carefully removed from the plastic rods. After brief cooling, the curled hair tresses were attached to a scaled hanging device in a climate chamber at 23° C. and 90% relative humidity. The initial length of the curled hair tresses had been previously determined and recorded. At defined time intervals, the length of the curled hair tresses, i.e. the change from the initial length, was read over a period of 7 hours.

[0431] According to the equation (GI), the value is calculated.

[0432]

[0433] in

[0434] L = length of the hair strand

[0435] L o = Initial length of the curled hair strands

[0436] L t =Measure the length of the curled hair strands before / during

[0437] The higher the percentage of curl retention after time t, the better the shaping / fixing properties of the cosmetic formulation. The unwinding of the curled hair locks is less noticeable.

[0438] Examples of cosmetic compositions:

[0439] The pre-crosslinked emulsion is preferably an emulsion which forms an elastic film after removal of water and in rheological measurements has a tan δ<1.

[0440] Examples A1-a, A1-c, and A2-a (Rinse-off Conditioners)

[0441] The following examples represent cosmetic compositions A1-a, A1-c, and A2-a of the present invention shown in Table 2, which include pre-crosslinked emulsions B1-a, B1-c, and B2 from the corresponding examples. The active content of the organopolysiloxane in the cosmetic composition is 0.5%.

[0442] Preparation Instructions:

[0443] The initially charged water is heated to 75°C with stirring. 2.0 parts of hydroxyethylcellulose are added. When 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 biscitamide chloride are added. The mixture is stirred until 75°C is reached and the ingredients are in solution. The mixture is then cooled. During cooling, 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 of the example is added. The composition is homogenized for 15 minutes with stirring.

[0444] Table 2: Rinse Conditioners A1-a, A1-c and A2-a

[0445]

[0446]

[0447] The raw materials listed in Table 2 are available under the following trade names:

[0448] 1) Hydroxyethylcellulose: Natrosol 250HR, Ashland

[0449] 2) Cetyl alcohol: Cetyl alcohol, Merck KGaA

[0450] 3) Polysorbate 80: Tween TM 80, Croda GmbH

[0451] 4) Dicitamide chloride: KDMP, Clariant GmbH

[0452] 5) Stearyl alcohol: Stearyl alcohol Merck KGaA

[0453] 6) Citric acid: Citric acid, Sigma

[0454] 7) Tetrasodium EDTA: B powder, BASF Corporation

[0455] 8) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0456] Comparative experiment VA1 and VA2 (rinsing conditioner (lotion))

[0457] The following comparative experiments VA1 and VA2 represent cosmetic compositions not according to the invention comprising the non-precrosslinked aqueous dispersions E1 and E2 from the corresponding examples. The active content of organopolysiloxane in the cosmetic composition was 0.5%.

[0458] To prepare the cosmetic compositions of comparative experiments VA1 and VA2, the procedures of Examples A1-a, A1-c, and A2-a were repeated, 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 of the present invention).

[0459] Preparation Instructions:

[0460] The initially charged water is heated to 75°C with stirring. 2.0 parts of hydroxyethylcellulose are added. When 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 biscitamide chloride are added. The mixture is stirred until 75°C is reached and the ingredients are in solution. The mixture is then cooled. During cooling, 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 emulsions for comparative experiments shown in Table 3 are added. The composition is homogenized for 15 minutes with stirring.

[0461] Table 3: Rinse Conditioners VA1 and VA2

[0462]

[0463] The raw materials listed in Table 3 are available under the following trade names:

[0464] 1) Hydroxyethylcellulose: Natrosol 250HR, Ashland

[0465] 2) Cetyl alcohol: Cetyl alcohol, Merck KGaA

[0466] 3) Polysorbate 80: Tween TM 80, Croda GmbH

[0467] 4) Dicitamide chloride: KDMP, Clariant GmbH

[0468] 5) Stearyl alcohol: Stearyl alcohol Merck KGaA

[0469] 6) Citric acid: Citric acid, Sigma

[0470] 7) Tetrasodium EDTA: B powder, BASF Corporation

[0471] 8) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0472] Comparative experiment VA1-DEO (rinsing conditioner (lotion))

[0473] The following comparative experiment VA1-DEO represents a cosmetic composition not according to the invention, which comprises an aqueous dispersion of a pre-crosslinked organopolysiloxane. The active content of the organopolysiloxane in the cosmetic composition is 0.5%.

[0474] To prepare the cosmetic composition of comparative experiment VA1-DEO, the procedure of examples VA1 and VA2 was repeated, with the modification that the precrosslinked, non-inventive emulsion V1 was used instead of emulsions E1 and E2 (emulsions of non-precrosslinked organopolysiloxanes).

[0475] Preparation Instructions:

[0476] The initially charged water is heated to 75°C with stirring. 2.0 parts of hydroxyethylcellulose are added. When 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 biscitamide chloride are added. The mixture is stirred until 75°C is reached and the ingredients are in solution. The mixture is then cooled. During cooling, 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 emulsions for comparative experiments shown in Table 4 are added. The composition is homogenized for 15 minutes with stirring.

[0477] Table 4: Rinse-off Conditioner VA1-DEO

[0478]

[0479] The raw materials listed in Table 4 are available under the following trade names:

[0480] 1) Hydroxyethylcellulose: Natrosol 250HR, Ashland

[0481] 2) Cetyl alcohol: Cetyl alcohol, Merck KGaA

[0482] 3) Polysorbate 80: Tween TM 80, Croda GmbH

[0483] 4) Dicitamide chloride: KDMP, Clariant GmbH

[0484] 5) Stearyl alcohol: Stearyl alcohol Merck KGaA

[0485] 6) Citric acid: Citric acid, Sigma

[0486] 7) Tetrasodium EDTA: B powder, BASF Corporation

[0487] 8) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0488] Comparison of the rinse-off conditioners of Examples A1-a, A1-c, and A2-a of the present invention with Comparative Experiments VA1 and VA2

[0489] The examples and comparative experiments cited differ in that in the case of Examples A1-a, A1-c and A2-a, aqueous dispersions according to the invention of precrosslinked organopolysiloxanes were used, whereas comparative experiments VA1 and VA2 in each case used similar aqueous dispersions of corresponding non-precrosslinked organopolysiloxanes. The active content of organopolysiloxane in the cosmetic composition was 0.5%.

[0490] In direct comparison, the following examples / comparative experiments correspond to:

[0491] Example A1-a - Comparative Experiment VA1

[0492] Example A1-c - Comparative Experiment VA1

[0493] Example A2-a - Comparative Experiment VA2

[0494] Wet combing force after treatment of damaged hair with rinse-off conditioner and after multiple shampooing simulated by agitating the hair in aqueous surfactant solution (persistent effect)

[0495] Examples A1-a and A1-c - Comparative Experiment VA1

[0496] The use of the aqueous dispersions of the inventive precrosslinked organopolysiloxanes B1-a and B1-c in rinse-off conditioners (Examples A1-a and A1-c) leads to an improvement in the conditioning properties, as shown by a reduction in the combing forces in the wet state compared to the rinse-off conditioner not according to the invention from Example VA1 (comprising a dispersion of a non-precrosslinked organopolysiloxane E1). Another object of the rinse-off conditioners according to the invention is to retain the conditioning properties even after multiple shampooing of the hair. In this example, a shampooing process is simulated by stirring a hair strand treated with a rinse-off conditioner for 4 hours in a surfactant solution. The details of this treatment are described above under the test methods.

[0497] For the rinse-off conditioners of Examples A1-a, A1-c and VA1 in Table 5, the results of the determination of the combing force in the wet state are listed below.

[0498] Table 5: Rinse-off conditioners / Results for reduction of wet combing forces on damaged Caucasian hair after treatment with a rinse-off conditioner of the invention compared to a conditioner not of the invention and after simulating multiple shampooing by agitating the hair in an aqueous surfactant solution for four hours. All results refer to comparisons relative to untreated tresses.

[0499]

[0500] By treating with a rinse-off conditioner according to the invention comprising an aqueous emulsion of a precrosslinked organopolysiloxane B1-a (Example A1-a), a significant reduction in the measured wet combing force of the hair tresses (value of 84%) can be achieved. In particular, the high conditioning effect is maintained after stirring the treated hair in the surfactant solution, and this is reflected in a sustained reduction in the wet combing force of 39%. Similarly, treatment with a rinse-off conditioner according to the invention comprising an aqueous emulsion of a precrosslinked organopolysiloxane B1-c (Example A1-c) achieves a high measured reduction in the wet combing force of the hair tresses of 81%. After stirring the treated hair in the surfactant solution, the wet combing force is continuously reduced by 31%.

[0501] Hair treated with a rinse-off conditioner not according to the invention comprising emulsion E1 (Comparative Example VA1) exhibited a slightly reduced wet comb force reduction of 79%. However, the 21% wet comb force reduction after surfactant treatment was significantly lower than that of Examples A-1a and A-1c. Treatment of the hair in a surfactant solution represents a simulation of multiple shampooing and demonstrates that the rinse-off conditioners of the invention exhibit better wash fastness and that the conditioning properties are retained longer than when the hair is treated with a rinse-off conditioner not according to the invention.

[0502] Comparison of silicone deposition after treatment of damaged hair with rinse-off conditioners and after multiple shampooing simulated by agitating the hair in aqueous surfactant solution for 4 hours

[0503] Example A2-a - Comparative Experiment VA2

[0504] As a further criterion, the efficiency of silicone deposition on damaged hair after treatment with rinse-off conditioners was evaluated and, in addition, the amount of conditioning organopolysiloxane remaining on the hair surface after simulated shampooing by agitating the hair for 4 hours in a surfactant solution was studied. The results are summarized in Table 6. The determination of silicone deposition is described in the test methods above.

[0505] Table 6: Rinse Conditioner / Silicone Deposition

[0506]

[0507]

[0508] Table 6 shows that the deposition of silicone in Example A2-a according to the invention (even after shampooing) is more effective and more resistant to shampooing by comparison with comparative experiment VA2 not according to the invention.

[0509] Comparison of the rinse-off conditioner of Example A1-a of the present invention with the comparative experiment VA1-DEO

[0510] The examples and comparative experiments differ in that in the case of example A1-a, an aqueous dispersion according to the invention of a precrosslinked organopolysiloxane was used, whereas comparative experiment VA1-DEO used a similar aqueous dispersion not according to the invention of a corresponding precrosslinked organopolysiloxane. The active content of organopolysiloxane in the cosmetic composition was 0.5%.

[0511] Wet combing force after treatment of damaged hair with rinse-off conditioner and after multiple shampooing simulated by agitating the hair in aqueous surfactant solution (persistent effect)

[0512] Example A1-a - Comparative Experiment VA1-DEO

[0513] The use of the aqueous dispersion B1-a of the inventive precrosslinked organopolysiloxane in a rinse-off conditioner (Example A1-a) leads to an improvement in the conditioning properties, as shown by a reduction in the combing forces in the wet state compared to a non-inventive rinse-off conditioner comprising a dispersion of a precrosslinked organopolysiloxane from Example VA1-DEO (Comparative Experiment V1). A further object of the rinse-off conditioner of the invention is that the conditioning properties are retained even after multiple shampooings of the hair. In this example, a shampooing process is simulated by stirring a hair strand treated with a rinse-off conditioner for 4 hours in a surfactant solution. The details of this treatment are described above under the test methods.

[0514] The results of the determination of the combing force in the wet state for the rinse-off conditioners of Examples A1-a and VA1-DEO are listed below in Table 7.

[0515] Table 7: Rinse-off conditioners / Results for reduction of wet combing forces on damaged Caucasian hair after treatment with a rinse-off conditioner of the invention compared to a conditioner not of the invention and after simulating multiple shampooing by agitating the hair in an aqueous surfactant solution for four hours. All results refer to comparisons relative to untreated tresses.

[0516]

[0517] By treating with a rinse-off conditioner according to the invention comprising an aqueous emulsion of precrosslinked organopolysiloxane B1-a (Example A1-a), a significant reduction in the measured wet combing force of the hair tresses can be achieved (value of 84%). In particular, the high conditioning effect remains after stirring the treated hair in the surfactant solution, and this is reflected in a sustained reduction in the wet combing force of 39%. Hair treated with a rinse-off conditioner not according to the invention VA1-DEO comprising the emulsion from comparative example V1 exhibits a slightly reduced reduction in the wet combing force of 77%. However, the 20% reduction in the wet combing force after the surfactant treatment is significantly smaller than in Example A-1a. The treatment of the hair in the surfactant solution represents a simulation of multiple shampooing and demonstrates that the rinse-off conditioners according to the invention exhibit better wash fastness and that the conditioning properties are retained longer than in the case of treatment of the hair with a rinse-off conditioner not according to the invention.

[0518] Example A3-a

[0519] Cosmetic composition: Shampoo

[0520] The following examples represent cosmetic compositions A3-a of the present invention comprising emulsion B3. Comparative Example VA3 represents a cosmetic composition comprising dimethicone (dimethylpolysiloxane; DM 5102E, available from Wacker Chemie AG), with 60000 mm 2 The active content of the organopolysiloxane in the cosmetic composition is 1.3%.

[0521] The composition of the shampoo is summarized in Table 8.

[0522] Preparation Instructions:

[0523] An initial charge of 32.11 parts of water is heated to 50° C. with stirring. During this time, 0.20 parts of Guar Hydroxypropyltrimonium Chloride, 6.06 parts of Sodium Lauryl Sulfate, 29.90 parts of Sodium Laureth Sulfate, 0.05 parts of Citric Acid and 5.0 parts of Cocamidopropyl Betaine are added. The mixture is stirred until 50° C. is reached and the ingredients are in solution. The mixture is then cooled. A separate container is charged with 20.0 parts of water, 0.60 parts of Carbomer are added with stirring, and stirring is continued until a homogeneous mixture is obtained. 0.06 parts of Lactic Acid are then added. This mixture is added to the first mixture. At 40° C., 0.95 parts of Phenoxyethanol and Ethylhexylglycerin are added. Stirring is continued and 0.30 parts of C12-13 Alkyl Lactate, 2.91 parts of Emulsion B3 of the invention or 2.60 parts of a Dimethicone Emulsion not of the invention are added. DM 5102E, 0.40 parts of sodium hydroxide, and 0.66 parts of sodium chloride. The pH can be adjusted to the desired value of 6.5 by adding sodium hydroxide as required.

[0524] Table 8: Shampoo formula A3-a and VA3

[0525]

[0526] 1) Citric acid: Citric acid, Sigma

[0527] 2) Cocamidopropyl betaine: Genagen CAB 818 30%, Clariant

[0528] 3) Sodium Laureth Sulfate: LRO 26, 5%, Clariant

[0529] 3) Ethylene glycol distearate: PMS, Clariant GmbH

[0530] 4) Guar Hydroxypropyltrimonium Chloride: BF13, Ashland

[0531] 5) Sodium lauryl sulfate: Texapon K 12G, BASF

[0532] 6) Carbomer: Carbopol 980, Lubrizol

[0533] 7) Lactic acid: L-(+)lactic acid, 90%, Bernd Kraft GmbH

[0534] 8) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0535] 9) C12-13 Alkyl Lactate: Ceraphyl TM 41 Ester, Ashland

[0536] 10) DM 5102E, obtained from Wacker Chemie AG

[0537] 11) Sodium hydroxide: Sodium hydroxide, Sigma-Aldrich

[0538] 12) Sodium chloride: pure sodium chloride, Bernd Kraft GmbH

[0539] Comparison of the shampoo of Example A3-a of the present invention with that of comparative experiment VA3

[0540] The difference between the examples and the comparative experiments is that in the case of example A-3a, an aqueous dispersion of a pre-crosslinked organopolysiloxane was used. In comparative experiment VA3, a commercially available aqueous dimethylpolysiloxane emulsion was used. DM 5102E (Wacker Chemie AG), the emulsion comprises a 60 000 mm 2 / s viscosity of dimethicone (dimethyl polysiloxane) as an active conditioning ingredient. The active content of organopolysiloxane in the cosmetic composition is 1.3%.

[0541] The results of the cosmetic effects of the shampoos are summarized in Table 9.

[0542] Table 9: Shampoo / Results on reduction of wet combing force and improvement of softness on damaged hair after treatment with shampoo. All results were compared with untreated tresses.

[0543]

[0544] *) DM 5102E (dimethicone emulsion), available from Wacker Chemie AG

[0545] Compared to the shampoo of comparative experiment VA3 with the commercial dimethicone emulsion, the shampoo of example A-3a with the emulsion according to the invention shows a substantially higher reduction in the wet combing force and a significantly improved softness (according to the tensile test).

[0546] Embodiment A3-b:

[0547] Cosmetic composition - shampoo

[0548] The following examples represent cosmetic compositions comprising Emulsion B3.

[0549] The active content of the organopolysiloxane in the cosmetic composition is 1.0%.

[0550] The composition of the shampoo is summarized in Table 10.

[0551] Preparation Instructions:

[0552] 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. During heating, 0.20 parts of PEG-150 distearate are added at 50°C and 0.50 parts of ethylene glycol distearate are added at 65°C. The mixture is then cooled. When 35°C is reached, 0.90 parts of phenoxyethanol, 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.

[0553] Damaged hair treated with the shampoo according to Example A3-b was softer than the damaged untreated hair.

[0554] Table 10: Shampoo formulation A3-b (amounts in parts by weight)

[0555]

[0556]

[0557] 1) Guar Hydroxypropyltrimonium Chloride: 3196, Ashland.

[0558] 2) Sodium Laureth Sulfate: LRO 26, 5%, Clariant GmbH

[0559] 3) Ethylene glycol distearate: EGDS, The Hallstar Company

[0560] 4) PEG-120 Methyl Glucose Dioleate: GluclabateTM DOE 120 thickener, Lubrizol

[0561] 5) DM 5102E, obtained from Wacker Chemie AG

[0562] 6) Cocamidopropyl Betaine: CAB 30%, Clariant GmbH

[0563] 7) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0564] Embodiment A3-c:

[0565] Cosmetic composition - shampoo

[0566] The following examples represent cosmetic compositions comprising Emulsion B3.

[0567] The active content of the organopolysiloxane in the cosmetic composition is 1.0%.

[0568] The composition of the shampoo is summarized in Table 11.

[0569] Table 11: Shampoo formulation A3-c (amounts in parts by weight)

[0570]

[0571] 1) Polyquaternium-10: UCARE Polymer JR 400, Dow Chemical.

[0572] 2) Sodium Laureth Sulfate: LRO 26, 5%, Clariant GmbH

[0573] 3) PEG-150 Distearate: EO 33, BASF AG

[0574] 4) Cocamide MEA: Comperlan 100, BASF AG

[0575] 5) Cocamidopropyl Betaine: CAB 30%, Clariant GmbH

[0576] 7) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0577] Damaged hair treated with the shampoo according to Example A3-c was softer than the damaged untreated hair.

[0578] Examples A1-b and A2-b

[0579] Rinse-off Conditioner

[0580] The following examples represent cosmetic compositions A1-b and A2-b comprising emulsions B-1b and B2. The active content of organopolysiloxane in the cosmetic composition is 2.0%.

[0581] The compositions of the rinse-off conditioners are summarized in Table 12.

[0582] Preparation Instructions:

[0583] The initially charged water is heated to 75°C with stirring. 1.1 parts of hydroxyethylcellulose are added. When 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 biscitamide chloride are added. The mixture is stirred until 75°C is reached and the ingredients are in solution. The mixture is then cooled. During cooling, 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 of the example is added. The composition is homogenized for 15 minutes with stirring.

[0584] Table 12: Rinse-off Conditioners A1-b and A2-b

[0585]

[0586]

[0587] The starting materials listed in Table 12 are available under the following trade names:

[0588] 1) Hydroxyethylcellulose: Natrosol 250HR, Ashland

[0589] 2) Cetyl alcohol: Cetyl alcohol, Merck KGaA

[0590] 3) Polysorbate 80: Tween TM 80, Croda GmbH

[0591] 4) Dicitamide chloride: KDMP, Clariant GmbH

[0592] 5) Stearamidopropyl dimethylamine, Incromine TM SB, Croda GmbH

[0593] 6) Stearyl alcohol: Stearyl alcohol, Merck KGaA

[0594] 7) Citric acid: Citric acid, Sigma

[0595] 8) Tetrasodium EDTA: B powder, BASF Corporation

[0596] 9) Phenoxyethanol, Ethylhexylglycerin: Euxyl PE 9010, Schülke & Mayr

[0597] Damaged hair treated with the rinse-off conditioners from Examples A1-b and A2-b was softer than damaged untreated hair according to the panel test.

[0598] Example A4

[0599] Cosmetic composition: Nourishing setting spray

[0600] The following example represents a cosmetic composition A4 according to the invention comprising emulsion B1-a.

[0601] To prepare cosmetic composition A4, 9.3 g of emulsion B1-a were diluted with 90.7 g of water. The active content of organopolysiloxane in the cosmetic composition was 3.0%.

[0602] Comparative Example VA4

[0603] Cosmetic composition: Nourishing setting spray

[0604] Comparative experiment VA4 represents a cosmetic composition not according to the invention, comprising the aqueous dispersion V2 of a precrosslinked organopolysiloxane.

[0605] To prepare the cosmetic composition of comparative experiment VA4, the procedure of example A4 was repeated with the modification that precrosslinked non-inventive emulsion V2 was used. 8.7 g of emulsion V2 were diluted with 91.3 g of water. The active content of organopolysiloxane in the non-inventive cosmetic composition VA4 was 3.0%.

[0606] Comparison between the nourishing styling spray of Example A4 of the present invention and the comparative experiment VA4

[0607] To investigate the shaping properties of the nourishing styling spray on the hair, curls were created as described in the section "Curl Retention at High Humidity", sprayed with 0.2 g of the corresponding spray and the curl retention was measured.

[0608] Table 13: Nourishing Setting Spray / Curl Retention Results in High Humidity after 7h.

[0609]

[0610] The result is that the curled locks of hair treated with the styling spray according to the invention from Example A4 showed a curl retention of 73% after 7 h. The curled locks felt pleasantly soft and retained their shape even after combing. The curled locks could be combed without resistance. For the curled locks treated with the spray from comparative example VA4 not according to the invention, a curl retention of 30% was determined. The curl retention of these curled locks at high humidity is therefore significantly inferior to that of the curled locks treated with the spray from example A4 according to the invention.

Claims

1. An aqueous dispersion, preferably an aqueous emulsion, comprising a pre-crosslinked organopolysiloxane The pre-crosslinked organopolysiloxane comprises on average at least one structural unit having the general formula SiRO 2 / 2 -Y-SiRO 2 / 2 (I) and the following unit R 2 SiO 2 / 2 (II) Y represents a group having 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 - No. 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 represents a monovalent SiC-bonded hydrocarbon radical having 1 to 18 carbon atoms and which may contain one or more heteroatoms selected from the group of N, P, S, O and halogen, R 2 may be identical 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 identical 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 is preferably a hydrogen atom, R 4 may be identical or different and represent a divalent hydrocarbon radical having 1 to 6 carbon atoms, preferably an alkylene radical 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 from 1 to 500, preferably from 20 to 350, Z 1 Indicates -OH, H or -NHR 3 , Z 2 Indicates -OH, -H or -NHR 3 .

2. The aqueous dispersion according to claim 1, It is characterized in that The pre-crosslinked organopolysiloxane comprises The siloxane unit of the formula R 3-d (OR 1 )dSiO1 / 2 (III) R is defined in claim 1, R 1 may be identical or different and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms and which may be interrupted by one or more individual oxygen atoms, and d is 0 or 1.

3. The aqueous dispersion according to claim 1 or 2, It is characterized in that 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 R is defined in claim 1, x is 0 or 1, b is an integer from 0 or 1 to 500, preferably from 20 to 350, and R 2 The formula is -(CH 2 ) 3 -or-CH 2 -CH(CH 3 )-CH 2 -group.

4. A process for producing an aqueous dispersion, preferably an aqueous emulsion, of a pre-crosslinked organopolysiloxane, wherein An aqueous dispersion, preferably an aqueous emulsion (R 1 O) d A e R 3-d-e SiO(SiARO) p (SiR 2 O) q S i 3-d-e A e (OR 1 ) d (IV) A is an amino group having the general formula -R 2 -[NO 3 -R 4 -] x NR 3 2 R may be the same or different and represents a monovalent SiC-bonded hydrocarbon radical having 1 to 18 carbon atoms and which may contain one or more heteroatoms selected from the group of N, P, S, O and halogen, R 1 which may be identical or different and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms and which may be interrupted by one or more individual oxygen atoms, R 2 may be identical 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 identical 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 is preferably a hydrogen atom, R 4 may be identical or different and represent a divalent hydrocarbon radical having 1 to 6 carbon atoms, preferably an alkylene radical having 1 to 6 carbon atoms, d is 0 or 1, e is 0 or 1, p is an integer at least 1 and at most 1000, q is 0 or an integer from 1 to 2000, and x is 0, 1, 2, 3 or 4, preferably 0 or 1, React with the reactive ester (2) of the following formula: R 5 -ABOUT 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 -(V)NR 3 -OC-[C(Z 2 )(H)] k2 -[C(Z 1 )(H)] k1 -CO 2 -R 5 Among them, R 2 , R 3 and R 4 As defined above, R 5 may be identical or different and represent an O-bonded, saturated or unsaturated, linear or branched, monovalent hydrocarbyl group having 1 to 20 carbon atoms per group and which may contain one or more heteroatoms from the group of N, P, S, O and halogen, 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 from 1 to 500, preferably from 20 to 350, Z 1 Indicates -OH, -H or -NHR 3 ,and Z 2 Indicates -OH, -H or -NHR 3 .

5. The method according to claim 4, It is characterized in that A is an amino group of the formula -R 2 -[NH-CH 2 CH 2 -] x NH 2 in x is 0 or 1, and R 2 The formula is -(CH 2 ) 3 -or-CH 2 -CH(CH 3 )-CH 2 -group.

6. The method according to claim 4 or 5, It is characterized in that The reactive ester (2) is an organopolysiloxane terminated with oxalylamino-methyl ester and an organopolysiloxane terminated with oxalylamino-ethyl ester.

7. A pre-crosslinked organopolysiloxane comprising an average of at least one, preferably at least two, more preferably at least three structural units of the following general formula SiRO 2 / 2 -Y-SiRO 2 / 2 (I) and the following unit R 2 SiO 2 / 2 (II) Y represents a group having 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 - No. 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 defined in claim 1.

8. The pre-crosslinked organopolysiloxane according to claim 7, It is characterized in that It contains siloxane units of the formula R 3-d (OR 1 )dSiO1 / 2 (III) R is defined in claim 1, and d and R 1 As defined in claim 2.

9. A method for producing a pre-crosslinked organopolysiloxane, Features The aminoorganopolysiloxane of the 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) Reaction with a reactive ester of the formula: R 5 -ABOUT 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(V) (WITH 2 )(H)] k2 -[C(Z 1 )(H)] k1 -WHAT 2 -R 5 in 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 defined in claim 4, and optionally subsequently emulsifying the obtained pre-crosslinked organopolysiloxane in water.

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 produced according to claim 4, 5 or 6 or a pre-crosslinked organopolysiloxane according to claim 7 or 8 or produced according to claim 9.

11. The cosmetic composition according to claim 10, It is characterized in that These include conditioning agents.

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

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

14. The use according to claim 12 or 13, It is characterized in that The keratin fiber is hair.

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

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