EP2571912A1 - Polysiloxane block copolymers and the use thereof in cosmetic formulations - Google Patents

Abstract

The invention relates to special polyorganosiloxane block copolymers which can be obtained by radical polymerization, and to the use of the polyorganosiloxane block copolymers for producing cosmetic or pharmaceutical compositions or body care compositions.

Description

Polysiloxane block copolymers and their use in cosmetic formulations

The invention relates to polyorganosiloxane compounds (polysiloxane block copolymers), in particular those suitable for use in cosmetic formulations and personal care formulations. The invention further relates to the preparation of the polyorganosiloxane compounds by nitroxide-based controlled radical polymerization (hereinafter abbreviated to NMP ("Nitroxide Mediated Polymerization")) and compositions containing the

Polyorganosiloxane compounds, as well as their use in cosmetic and personal care applications.

Cosmetic and pharmaceutical compositions and personal care compositions, e.g. Hair styling sprays, hair conditioners, foams, gels and shampoos often contain resins, gums and adhesives to provide a variety of beneficial effects, such as hair conditioning. B. film-forming properties, thickening properties, tactile properties, such as improved grip and hair shaping

Properties to produce.

Polymers used in such formulations include, but are not limited to, organic or silicone-containing linear or grafted copolymers which may be composed of a variety of different monomers. The polymer blocks may be alternating, random, block-structured, branched or hyperbranched or homopolymer blocks. Grafted polymers are known as film-forming polymers in cosmetic formulations for the treatment of hair or skin. These grafted polymers typically comprise a polymeric backbone and one or more macromonomers grafted onto the backbone, allowing the physical and chemical properties, such as glass transition temperature and water solubility, to be independently set for the polymeric backbone and grafted macromonomers to be as desired To adjust the overall properties of the complete polymer.

The documents WO 95/01383 and WO 95/01384 disclose the use of water and alcohol soluble or dispersible grafted copolymers in hair and skin care compositions in which the copolymer has a backbone and one or more polymeric side chains prepared by the random copolymerization of monomer A and monomer B. Monomer A is selected to have a hydrophobic character and macromonomer B has a long hydrophilic portion. EP 0 412 704, EP 0 408 313 and EP 0 412 707 disclose the use of silicone grafted acrylate copolymers in

Hair care applications. US 4,988,506 describes the use of grafted polysiloxane copolymers in hair care applications.

WO 02/053111 describes the use of silicone polyether block copolymers with (AB) _n structures in aqueous, surface-active body cleansing compositions which have good cosmetic properties especially for the volume, the combability and the

Shine of hair.

Block copolymers have the advantage over grafted copolymers that the polymer construction can be better controlled. This is particularly important and important if you want to tailor polymers with areas that For example, alternating "hard" and "soft" segments in a polymer for hairspray applications provide improved hold and feel to specific physical and chemical properties.

US 5,468,477 discloses cosmetic compositions containing a vinyl-silicone grafted copolymer or a block copolymer characterized in that the copolymer contains a silicone segment and a vinyl polymer segment. The block or grafted copolymer is prepared by free radical polymerization of a mercapto-functionalized silicone which functions as a chain transfer agent with a vinylic monomer. Copolymers made by this method typically have low molecular weights and low silicone content due to the early chain termination reactions.

Intramolecular crosslinking reactions additionally lead to an uncontrolled polymer structure. Thus, polydisperse systems are obtained with a mixture of chain lengths and different molecular architectures.

An alternative approach for the synthesis of block copolymers is the use of organopolysiloxane macroinitiators. These are organopolysiloxanes containing groups that can form radicals. Such compounds are described in US 5,523,365. The use for the preparation of copolymers is disclosed in WO 98/48771 and US 6,074,628. A disadvantage of this method is the handling of dangerous, prone to explosive decomposition, organosiloxane macroinitiators, which must be used in significant amounts, otherwise the final product contains too few silicone units. Furthermore, the large-scale production of macroinitiators is extremely difficult and associated with a considerable amount of security. In addition, the reaction is inefficient, since large amounts of unreacted silicone oil by means of a time-consuming extraction must be separated. This process is very difficult upscalebar.

WO 00/71606 describes a process for the preparation of polysiloxane block copolymers in which an organopolysiloxane macroinitiator in an atom transfer radical polymerization (ATRP) with copper salts as a catalyst for the preparation of controlled architecture block copolymers is used. Their use in cosmetic and personal care compositions, especially in formulations for the treatment of hair, is described. However, the document does not disclose anything about the copper content of the polymers produced. In addition, the polymers produced are terminated with bromine atoms, which is disadvantageous for use in cosmetic formulations.

WO 2009/043629 relates to polysiloxane block copolymers of the formula A [LB (S) Q] _m , where A is a polysiloxane block, L is a divalent organic linker, B is a polymer block composed of free-radically polymerizable monomers, S is a sulfur atom and Q is a monovalent organic radical and m is an integer from 1 to 50, a process for their preparation and their use in cosmetics or personal care. The process disclosed in WO 2009/043629 for the preparation of polysiloxane block copolymers is characterized in that it comprises the steps of A) reacting an atom transfer radical initiator which is a polysiloxane macroinitiator of the formula A [LX] _{m which} is at least one organic compound A halogen atom X, wherein A is a polysiloxane block, L is a divalent organic radical and m is an integer from 1 to 50, with free-radically polymerizable monomers in the presence of a transition metal, such as copper, having catalyst in a Po 1 yme rizationss ehr i 11th and B) adding a compound Q-SH where Q is a monovalent organic radical to the polymerization mixture of step A). A disadvantage of this The method is that halogen-containing initiators and copper are used and that these must then be removed in an additional process step again.

In addition to the ATRP, other controlled radical polymerization methods can also be used to build up block copolymers, e.g. the nitroxide-controlled polymerization:

US 2008/0312377 discloses the preparation of a polydimethylsiloxane (PDMS) macroinitiator by the esterification of a single-OH-terminated PDMS with iBA-DEPN, iBA-DEPN having the structure (Formula I):

 (I) with SGI is DEPN, where DEPN is the abbreviation for N-tert-butyl-N- [1-diethylphosphono- (2, 2, -dimethylpropyl)] nitroxide (formula II):

(II)

US 2008/0312377 also discloses reacting the macroinitiator with methyl methacrylate to form an AB block copolymer. A disadvantage of this method is that very mild reaction conditions, which are technically only with great effort to produce, are used for esterification because iBA-DEPN decomposes at temperatures> 30 ° C. Furthermore, only simple

Monoalkoxyamine siloxanes obtainable from monofunctionalized siloxanes. Such simply functionalized siloxanes are very difficult and expensive to produce and continue to limit the type of silicones used very strong. In addition, US2008 / 0312377 does not disclose use of the described polymers in cosmetic formulations.

EP 1 464 648 discloses the preparation of alkoxyamines of the following general formula (III):

Wherein R = H or CH ₃ and M is a sequence of radically polymerizable vinylic monomers, n is an integer which may also be zero, X is greater than or equal to 1, and Z is a mono- or polyfunctional structural unit which may also be a silicone can. However, EP 1 464 648 does not disclose the nature of the silicone, nor is an example given.

The preparation of alkoxyamines of the above formula (III) takes place by linking alkoxyamines of the following formula (IV):

CH ₃ C (CH ₃ ) ₃ O

A-OC-C (M) _n ON CH P-OC ₂ H ₅

RC (CH ₃ ) ₃ OC ₂ H ₅ (IV) where A is an OH radical or TO radical where T = alkali metal such as Li, Na, K, NH ₄ or a chlorine atom where R = H or CH ₃ and M is a sequence of free-radically polymerizable vinylic monomers, n is an integer which may also be zero, with a mono- or polyfunctional structural unit Z to form an ester functionality.

EP 1 526 138 Bl discloses the preparation of polyalkoxyamines of the formula (V)

 (V) in which m is an integer of less than or equal to n and greater than or equal to 2, in which, preferably under a nitrogen atmosphere, at least one monoalkoxyamine of the formula (VI)

R1 C (CH _{3) 3}

RICON CH-C (CH ₃ ) ₃

C (0) OR ₂ P (0) (OEt) _{2 (vi)}

Where R ^{1 is} a linear or branched alkyl radical having 1 to 3 carbon atoms, R ^{2 is} a hydrogen atom, a linear or branched alkyl radical having 1 to 8 carbon atoms, a phenyl radical, an alkali metal such as Li, Na or K or an ammonium such as NH ₄ ^+, NBu ₄ ⁺ or NHBu ₃ ⁺ represents and preferably R ¹ is CH ₃ and R ² is H; optionally in the presence of one or more solvents, at a reaction temperature of preferably between 0 and 90 ° C with a polyunsaturated compound of formula (VII). -CH = CH ₂

- ¹ n

 (VI I;

Wherein Z is an aryl group or a formula ZI- [XC (O)] _n , wherein ZI is a polyfunctional structure derived, for example, from a polyol-type compound, X is an oxygen atom, a nitrogen atom having a carbon-containing group or also is a hydrogen atom, where X can also be a sulfur atom and n is a number greater than or equal to two. EP 1 526 138 B1 makes no statement as to whether Z or ZI can also be a siloxane-containing polyfunctional structure or about the use of the polymers described in cosmetic formulations.

US 2006/0142511 describes the use of alkoxyamines of the formula (VI) for the polymerization and copolymerization of any monomers having a carbon-carbon double bond which can be free-radically polymerized. For the case of R ¹ = CH ₃ and R ² = H in formula (VI) is one such alkoxyamine under the trade name Block Builder ^® MA from the company Arkema available. The polymerization is carried out under conventional conditions known to those skilled in the art. However, US 2006/0142511 does not disclose the use of polysiloxane-containing compounds in combination with alkoxyamines of the formula (VI).

The object of the present invention was therefore to provide a process for the preparation of polyorganosiloxane compounds, in particular polysiloxane block copolymers, which do not have one or more disadvantages of the prior art. Surprisingly, it has been found that this object can be achieved by reacting free-radically polymerizable monomers in a nitroxide-based controlled radical polymerization with Alkoxyaminen the Fromel (VI) to a terminated with a nitroxide "living" polymer and these polymers then in a radical addition be covalently bonded to an at least single vinylically unsaturated polysiloxane. The present invention therefore relates to polyorganosiloxane compounds of the formula (VIII)

in which

 A is a polysiloxane block,

 L is a divalent organic radical,

G = -O-, -S-, -CR ³ (OH) -CH (R ³ ) -O-, -NR ³ -, with R ³ independently of one another hydrogen or a monovalent substituted or unsubstituted, linear or branched 1 to 18 Containing carbon atoms,

R ^{1 is} identical or different and is a linear or branched alkyl radical having 1 to 3 carbon atoms, preferably CH ₃ , R ^{2 is} a hydrogen atom, a linear or branched alkyl radical having 1 to 8 carbon atoms, a phenyl radical, an alkali metal such as Li, Na or K or Ammonium such as NH ₄ ⁺ , NR ⁵ R ⁶ R ⁷ R ⁸⁺ with R ⁵ , R ⁶ R ⁷ and R ⁸ independently of one another denote H or C 1 -C ₄₀ -alkyl radical, and preferably R ^{2 represents} H,

SGI is a radical of formula (II),

T is a polymer block composed of radically polymerized monomers, and

m is an integer from 1 to 50,

their use as well as compositions comprising these polyorganosiloxane compounds.

Likewise provided by the present invention is a process for the preparation of inventive compounds

Polyorganosiloxane compounds, characterized in that it comprises the steps:

 A) reacting at least one free-radically polymerizable monomer M with at least one alkoxyamine of the formula (VI)

to give a nitroxide-terminated polymer (XV)

 , and

 B) Reaction of the polymer (XV) with an at least monounsaturated compound of the formula (XVI)

A [LGC (O) -CH = CH ₂ ] m (XVI) with R ¹ , R ² , A, L, G, T and m as defined above. The process according to the invention has opened up an efficient and economical way to tailored siloxane-containing block copolymers. A disadvantage of the prior art process is that either the raw materials are difficult to access or the siloxane content is variable only within limited limits, which prevents a wide applicability of these block copolymers, since the properties can not tailor made. In addition, in the block copolymers constructed by means of ATRP additional process steps for purification necessary.

With the method according to the invention, the siloxane content or the composition of the siloxane radical can be varied widely. The compounds of the invention can be widely used in the field of cosmetic and personal care formulations, especially in hair care.

The polysiloxane block copolymers of the invention, a process for their preparation and their use are described below by way of example, without the invention should be limited to these exemplary embodiments. Given below, ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their contents are intended to form part of the disclosure content of the present invention. If the following information is given as a percentage, this is by weight unless otherwise stated. If mean values are indicated below, these are, unless stated otherwise, by number average.

The polyorganosiloxane compounds of the formula (VIII) according to the invention

are characterized by the fact that

A is a polysiloxane block,

L is a divalent organic radical,

G = -O-, -S-, -, -CR ³ (OH) -CH (R ³ ) -O-, -NR ³ -, with R ³ independently of one another hydrogen or a monovalent substituted or unsubstituted, linear or branched 1 containing up to 18 carbon atoms,

R ^{1 is} identical or different and is a linear or branched alkyl radical having 1 to 3 carbon atoms, preferably CH ₃ , R ^{2 is} a hydrogen atom or a linear or branched alkyl radical having 1 to 8 carbon atoms, a phenyl radical, an alkali metal cation such as Li ⁺ , Na ⁺ or K ⁺ or an ammonium like NH ₄ ⁺ , NR ⁵ R ⁶ R ⁷ R ⁸⁺ with R ⁵ , R ⁶ R ⁷ and R ⁸ independently of one another are H or C 1 -C 40 -alkyl radical, preferably a hydrogen atom,

SGI is a radical of the formula (II)

T is a polymer block composed of radically polymerized monomers, and

m is an integer from 1 to 50, preferably from 2 to 10 and preferably 2, 3 or 4

Preferred polyorganosiloxane compounds are those in which R ¹ = methyl and / or R ² = hydrogen and / or G = oxygen. Especially preferred

Polyorganosiloxane compounds are those in which R ¹ = methyl and R ² = hydrogen and G = oxygen.

In the polyorganosiloxane compound according to the invention, the unit A is preferably a polysiloxane radical of the formula (IX)

is with

j is a number from 0 to 10, preferably <5 and particularly preferably 0,

k is a number from 1 to 500, preferably 1 to 250 and particularly preferably 1 to 100,

R ^{f is the} same or different radicals R ⁹ or a bond to the building block L, with the proviso that m radicals R ^{f are} a bond to the building block L,

R ^{9 is} substituted or unsubstituted alkyl radicals having 1 to 18 C atoms, preferably 1 to 6 C atoms, more preferably methyl or an aryl radical, preferably a phenyl radical.

It is known to those skilled in the art that due to their polymeric nature, polysiloxane compounds are in the form of a mixture having a distribution substantially governed by statistical law. The values for the indices j and k therefore represent average values. The radical L is preferably a radical - (O) _X- L'-, where L 'is attached to G and an unbranched or branched, substituted or unsubstituted organic radical having 1 to 60 carbon atoms, preferably 1 to 20 C atoms and more preferably 3 - 10 C atoms, and x = 0 or 1. The radical L 'may be interrupted by divalent radicals attached to carbon atoms on both sides, such as -O-, -C (O) O-, CONR ^p , NR ^P C (O), or -C (O ) -, wherein R ^{p is} a monovalent substituted or unsubstituted, linear or branched 1 to 18 carbon atoms containing radical. Particularly preferred polyorganosiloxane compounds are those in which L is a linear unbranched hydrocarbon radical having 3 to 10 C atoms, preferably a -CH ₂ -CH ₂ -CH ₂ - or - CH ₂ - (CH ₂ ) 4 -CH ₂ - radical. The radically polymerizable monomers for constituting the block T may be selected from any known ones free radical polymer monomers M. In the polyorganosiloxane compound according to the invention, the polymer block T is preferably composed of free-radically polymerized monomers M selected from substituted or unsubstituted (meth) acrylic acids and their derivatives and unsaturated hydrocarbons, in particular styrenes.

Preferably used monomers M include acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, n-butyl-1-yl-acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate,

Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, octyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl acrylate, isobutyl ethacrylate, t-butyl methacrylate, 2-ethylhexyl ethacrylate, decyl methacrylate, oleyl methacrylate, 2, 3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2

Hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate,

Glyceryl monoacrylate, glyceryl monomethacrylate,

Glyceryl monoethacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, ethacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, Ν, Ν-dimethylmethacrylamide, N-

Ethylacrylamide, N-iso-propylacrylamide, N-butylacrylamide, N-t-butylacrylamide, N, -di-n-butylacrylamide, N, N-

Diethylacrylamide, N-octylacrylamide, N-octadecylacrylamide, N, -diethylacrylamide, N-phenylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-dodecylmethacrylate 1, N, N-dimethylaminoethylacrylamide, quaternized N, -dimethylaminoethylacrylamide, N -

Dimethylaminoethyl-methacrylamide, quaternized N, N-

Dimethylaminoethylmethacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, quaternized N, N-dimethylaminoethyl acrylate, quaternized N, -dimethylaminoethyl methacrylate, 2-

Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-

Hydroxyethyl methacrylate, glyceryl acrylate, 2-

Methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxy, 1-y-t-y-y-y-y-1-a, 2-ethoxy-ethyl-acrylate, 2-

Ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, maleic acid, maleic acid monoesters, maleic acid diesters, maleic anhydride, maleic imide, fumaric acid, itaconic acid, itaconic monoesters, itaconic diesters, itaconic anhydride, Crotonic acid, angelic acid, diallyldimethylammonium chloride, vinylpyrrolidone, vinylimidazole, methyl vinyl ether, methyl vinyl ketone,

Vinylpyridine, vinylfuran, styrenesulfonate, allyl alcohol, allyl citrate, Al 1 yl t art r at, vinyl acetate, Vi ny 1 a 1 koho 1, vinylcaprolactam and mixtures thereof. Also suitable monomers M are hydrocarbons having at least one unsaturated carbon-carbon double bond, preferably selected from styrene, alpha-methylstyrene, t-butylstyrene, butadiene, isoprene, Cycl ohexadien, ethylene, propylene, 1-butene, 2-butene, isobutene, para -Methylstyrene and mixtures thereof.

In a very particularly preferred embodiment, the monomers M are mixtures of monomers which contain from 50 to 99% by weight, preferably 75 to 95% by weight, of (meth) acrylic acid or derivatives thereof, in particular monomers selected from the group Methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, N, N-

D imethylaminoethylacry lat, N, N-dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate or monomers according to formulas (XIII) where the index o is preferably greater than 0, preferably from 10 to 15 and R ^r = CH ₃ and R ^s = methyl are particularly preferred indices o and p is greater than 0, and mixtures thereof, and from 1 to 50% by weight, preferably 5 to 25% by weight of hydrocarbons having at least one unsaturated carbon-carbon double bond, preferably selected from styrene, alpha-methylstyrene, t-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, para-methylstyrene and mixtures thereof.

The unit T preferably has a number-average molecular weight of from 1000 g / mol to 200000 g / mol, preferably a number-average molecular weight of 4000 g / mol to 120000 g / mol and more preferably from 4000 g / mol to 75000 g / mol.

The building block T is particularly preferably a poly (meth) acrylate block, preferably with a number average

Molecular weight of 1000 g / mol to 200000 g / mol, preferably having a number average molecular weight of 4000 g / mol to 120000 g / mol and more preferably having a number average molecular weight of 4000 g / mol to 75000 g / mol. The polyorganosiloxane compounds according to the invention preferably have a number-average molecular weight of from 2000 g / mol to 1,000,000 g / mol, preferably from 5000 g / mol to 500,000 g / mol and very particularly preferably from 10,000 g / mol to 250,000 g / mol.

The polyorganosiloxane compounds of the invention can be prepared in various ways. The polyorganosiloxane compounds according to the invention are preferably obtainable by the process according to the invention described below.

The process according to the invention for the preparation of the polysiloxane block copolymers according to the invention is characterized in that it comprises the steps:

A) Reaction of a free-radically polymerizable monomer M with at least one alkoxyamine of the formula (VI) to give a nitroxide-terminated polymer (XV)

 , and

 B) Reaction of the polymer (XV) with an at least monounsaturated compound of the formula (XVI)

A [LGC (O) -CH = CH ₂ ] _m (XVI) with R ¹ , R ² , A, L, G, T and m as defined above. Step A)

Process step A) comprises the polymerization and / or copolymerization of at least one free-radically polymerizable monomer M with at least one alkoxyamine of the formula (VI) where R ^{1 is} a linear or branched alkyl radical having 1 to 3 carbon atoms, R ² a hydrogen atom, a linear or branched alkyl radical having 1 to 8 carbon atoms, a phenyl radical, an alkali metal such as Li, Na or K or an ammonium such as NH ₄ ⁺ , NR ⁵ R ⁶ R ⁷ R ⁸⁺ with R ⁵ , R ⁶ R ⁷ and R ⁸ independently = H or C ¹ -C 40 alkyl, and preferably R ^{2 is} H, wherein a nitroxide-terminated polymer of the formula (IX) is obtained.

Very particular preference is given to using an alkoxyamine of the formula (VI) where R ¹ = CH ₃ and R ² = H. Such alkoxyamine is marketed under the trade name Bloc Builder ^® MA from the company Arkema.

As free-radically polymerizable monomers M, ethylenically unsaturated monomers are preferably used in step A).

By "polymerizable" is meant monomers which are polymerizable as described in the present invention using nitroxide-based controlled radical polymerization Preferably, in the nitroxide-based controlled radical polymerization, the polymer chain length and polymer architecture may be controlled in a known manner can with respect to the polydispersity of

Molar mass distribution (ratio of weight average molecular weight to number average molecular weight) narrowly distributed polymers can be obtained.

By "ethylenically" unsaturated monomers is meant monomers having at least one polymerizable carbon-carbon double bond, which double bond may be mono-, di-, tri-or tetra-substituted, either single monomers or mixtures of monomers selected to meet the desired physical and chemical properties of the polysiloxane block copolymer. Preferred ethylenically unsaturated monomers M which can be used for the polymerization are those of the formula (XII) H (R ⁹ ) C =C (R ¹⁰ ) (C (O) G ') (XII) where R ⁹ and R ^{10 are} radicals may be independently selected from the group comprising hydrogen, unbranched or branched Ci to Ci ₀ alkyl, methoxy, ethoxy, 2- hydroxyethoxy, 2-methoxyethyl and 2-ethoxyethylreste. The radical G 'may be selected from the group comprising - hydroxy, -O (M) _{1 / v} , -OR ¹¹ , -NH ₂ , -NHR ¹¹ and -N (R ¹¹ ) (R ¹² ); where M is a counterion of valency v selected from the group of metal ions such as alkali metal ions, alkaline earth metal ions, ammonium ions, substituted ones

Ammonium ions such as, mono-, di-, tri- or tetraalkylammonium ions, and each radical R ¹¹ and R ^{12 may be} independently selected from the group consisting of hydrogen, Ci - C ₄₀ straight or branched alkyl chains, polyether radicals, polyetheramine optionally substituted with one or more substituents selected from the group consisting of hydroxy, amino, Ci - C ₃ alkoxy, Ci - C ₃ alkylamino and di (Ci - C ₃ alkyl) amino, z. N, -dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl. Representative non-limiting examples of monomers also include protected or unprotected acrylic acid and methacrylic acid, as well as salts and esters and amides of these acids.

The salts can be derived from any metal, ammonium or substituted ammonium counterion. The esters can be derived from C ₁ -C ₄₀ straight-chain, C ₃ -C ₄₀ branched alkyl chains or C ₃ -C ₄₀ carbocyclic alcohols, from polyfunctional alcohols containing from 2 to 8 carbon atoms and from 2 to 8 hydroxyl groups, from amino alcohols and from polyethylene glycols or

Polypropylene glycols or other polyether radicals as well hydroxyl-functionalized polyethers, (nonlimiting examples include ethylene glycol,

Propylene glycol, butyleneglycol, hexyleneglycol, glycerol and 1,2,6-hexanetriol), of aminoalcohols (nonlimiting examples include aminoethanol, dimethylaminoethanol, diethylaminoethanol and their quaternized products) or of ether alcohols, such as e.g. As methoxyethanol or ethoxyethanol. The amides may be unsubstituted, N-alkyl or N-alkylamino mono substituted or dis, Ν-dialkyl, or N, -dialkylamino disubstituted, wherein the alkyl or alkylamino groups are derived from Ci - C ₄₀ straight-chain or C ₃ -C ₄₀ branched , or C ₃ -C ₄₀ cyclic units. In addition, the alkylamino group may be quaternized.

Also usable monomers are protected or unprotected acrylic and / or methacrylic acids, their salts, esters and amides, wherein the second or third carbon position of the acrylic acids and / or methacrylic acids may be substituted independently of one another. The substituents may be selected from the group comprising C 1 -C ₄ -alkyl radicals, hydroxyl, -CN, and -COOH, for example methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid. The salts, esters and amides of these substituted aryl and methacrylic acids as described above can also be used.

Other useful monomers M include: vinyl and allyl esters of straight chain, 3- to 40-carbon atom containing, branched or 3-40 carbon carbocarboxylic acids containing pyridines substituted with at least one vinyl or allyl group (eg, vinylpyridine or allylpyridine), Hydrocarbons having at least one unsaturated carbon-carbon double bond (eg. Styrene, alpha-methylstyrene, t-butlystyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, para-methylstyrene) and mixtures thereof. Preferably used as free-radically polymerizable monomers M substituted or unsubstituted (meth) acrylic acid or derivatives thereof. Preferably used monomers M include acrylic acid, methacrylic acid, ethacrylic acid,

Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate,

Decyl acrylate, octyl acrylate, methyl methacrylate,

Ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate,

Decyl methacrylate, octyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl acrylate, isobutyl ethacrylate, tert-butyl methacrylate, 2-ethylhexyl ethacrylate, decyl methacrylate, octyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-

Dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-

Hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate,

Glyceryl monoacrylate, glyceryl monomethacrylate,

Glyceryl monoethacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, ethacrylamide, N-methylacrylamide, N, -dimethylacrylamide, N, -dimethylmethacrylamide, N-ethylacrylamide, N-iso-propylacrylamide, N-butylacrylamide, Nt-butylacrylamide, N, -di-n Butyl acrylamide, N, N-

Diethylacrylamide, N-octylarylamide, N-octadecylacrylamide, N, N-diethylacrylamide, N-phenylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-dodecylmethacrylamide, N, N-dimethylaminoethylacrylamide, quaternized N, N-

Dimethylaminoethylacrylamide, N-dimethylaminoethylmethacrylamide, quaternized N, N-dimethylaminoethylmethacrylamide, N, -dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, quaternized N, N-dimethylaminoethyl acrylate, quaternized N, N

Dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate,

Glyceryl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, maleic acid, the monoesters of maleic acid, the diesters of maleic acid, maleic anhydride, maleimides,

Fumaric acid, itaconic acid, the monoesters of itaconic acid, itaconic acid diesters, itaconic anhydride, crotonic acid, angelic acid, diallyldimethylammonium chloride, vinylpyrrolidones, vinylimidazole, methyl vinyl ether,

Methyl vinyl ketone, vinyl pyridine, vinyl furan, styrenesulfonate, allyl alcohol, allyl citrate, allyl tartrate, vinyl acetate, vinyl alcohol, vinyl caprolactam, monomer of formula (XIII)

 u (XIII) with D is a bivalent radical of the general formula (XIV)

- (C ₂ H _{4 O} ) _o (C ₃ H _{6 O} ) _p (C ₄ H _{8 O} ) _q (C ₁₂ H _{24 O} ) _r (C ₈ H ₈ O) _s -

(XIV) where o, p, q, r, and s are independently integers from 0-100, with the proviso that the sum of o + p + q + r + s ^ 1, and if more than one of the indices o, p, q, r and s> 0, the general formula (XIV) represents a random oligomer, a block oligomer or a gradient oligomer, with R ^r independently of one another H or alkyl

R ^s is H, alkyl, preferably C 1 to C ₃ alkyl, preferably methyl

and mixtures of the monomers listed above. Particular preference is given to monomers selected from the group comprising methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl, Butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate,

Decyl acrylate, octyl acrylate, methyl methacrylate,

Ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate,

Decyl methacrylate, octyl methacrylate, N-octylacrylamide, 2-methoxyethyl 1-acrylate, 2-hydroxyethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate or monomers of formulas (XIII) where the index o is preferably greater than 0 , preferably from 10 to 15, and R ^r = CH ₃ and R ^s = methyl, and mixtures thereof.

Very particular preference is given to monomers selected from the group comprising methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, N, N-

Dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate or monomers according to formulas (XIII) where the index o is preferably greater than 0, preferably from 10 to 15 and R ^r = CH ₃ and R ^s = methyl. Particularly preferred are the indices o and p greater than 0, and mixtures thereof, used.

In a very particularly preferred embodiment, mixtures of monomers are used which contain from 50 to 99% by weight, preferably 75 to 95% by weight, of (meth) acrylic acid or derivatives thereof, in particular monomers selected from the group comprising methyl acrylate, Methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, N, N-

Dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate or monomers according to formulas (XIII) where the index o is preferably greater than 0, preferably from 10 to 15 and R ^r = CH ₃ and R ^s = methyl. Particularly preferred are the indices o and p greater than 0, and mixtures thereof, and from 1 to 50% by weight, preferably from 5 to 25% by weight of hydrocarbons having at least one unsaturated carbon-carbon double bond, preferably selected from styrene, alpha-methylstyrene, t-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, para-methylstyrene and mixtures thereof.

The polymerization in step A) can be carried out in bulk or in solution. The polymerization in step A) can be carried out as emulsion polymerization, miniemulsion or microemulsion polymerisation or suspension polymerization.

If a solvent or mixture of solvents is used in the process of the invention, preference is given to choosing from the group comprising water, alcohols, such as, for example, Ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert. Butanol, pentanol, hexanol, heptanol, octanol, C yc 1 xhe x ano 1, aromatic solvents, chlorinated and or fluorinated solvents, ethers, such. For example, tetrahydrofuran, 1,4-dioxane, organic esters such as butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone;

ether; Aliphatic, preferably pentane, hexane and further polar aprotic Lösemitten. The list is only exemplary and not exhaustive. The amount of solvent or solvent mixture is from 5 to 95% by weight, based on the amount of monomers M and alkoxyamine (VI) used, preferably from 10 to 75% by weight and very particularly preferably from 20 to 50% by weight. %. If the reaction in step A) is carried out in a solvent or a solvent mixture, then the solvent can be removed by distillation or by another method known to the person skilled in the art before process step B). The reaction after step A) can be carried out at atmospheric pressure, underpressure or overpressure, preferably at atmospheric pressure. The temperature in step A) of the process is preferably greater than or equal to 70 ° C. and particularly preferably greater than or equal to 80 ° C.

The reaction according to step A) is preferably carried out under a protective gas selected from the group comprising nitrogen, noble gases, C0 ₂ or gaseous hydrocarbons, such as methane, or mixtures thereof. Particularly preferred is the implementation under nitrogen as a protective gas.

Step B)

As the monounsaturated compound of the formula A [LGC (O) -CH = CH ₂ ] _m , it is possible to use all at least monounsaturated compounds which satisfy the formula A [LGC (O) -CH = CH ₂ ] _m . At least monounsaturated compounds of the formula A [LGC (O) -CH = CH ₂ ] _m can be synthesized, for example. B. be obtained by first a suitable vinylically unsaturated compound V with the / the reactive groups of a polysiloxane, for. B. is reacted in a nucleophilic substitution reaction.

In this reaction, the polysiloxane used is preferably a polysiloxane which has at least one functional group which has a 0, N or S atom and is suitable for nucleophilic attack on these atoms.

The polysiloxanes used for the preparation of at least monounsaturated polysiloxanes of the formula A [LGC (O) -CH = CH ₂ ] _m may be linear, branched or hyperbranched, provided they are functionalized with at least one group as described above. Preferably, polysiloxanes are used which are selected from polysiloxanes of the formula (IXa), With

b is a number from 0 to 10, preferably <5 and preferably 0, a is a number from 1 to 500, preferably 1 to 250 and preferably 1 to 100,

identical or different radicals R ^m or R ⁿ , with the proviso that at least one radical R ^{f is} a radical R ⁿ ,

_R m is alkyl having 1 to 18 C atoms, preferably 1 to 6 C atoms, or an aryl radical, preferably phenyl, where R ^{m may be} substituted or unsubstituted,

R is a radical of the general formula (X)

- (0) _x -L'-Y (X)

= Zero or one, preferably zero

 a divalent optionally branched substituted or unsubstituted hydrocarbon radical having 1 to 60 carbon atoms, preferably 1 to 20 carbon atoms and more preferably 3 to 10 carbon atoms, and

is selected from the group consisting of -OH, -SH, , -NH ₂ and -NHR ³ , where R ^{3 is} independently a monovalent substituted or unsubstituted, is a linear or branched radical containing 1 to 18 carbon atoms.

The divalent radical L 'may be interrupted by divalent radicals which are bonded to carbon atoms on both sides, for example -O-, -C (O) O-, CONR ⁴ , NR ⁴ C (O), or -C ( 0) -, wherein R ^{4 is} a monovalent substituted or unsubstituted, linear or branched 1 to 18 carbon atoms containing radical.

As the suitable vinyl unsaturated compound V, a compound containing at least one group C (O) X 'in which X' is a leaving group capable of undergoing nucleophilic attack by the O, N or S atom of the functional group of the Polysiloxane can be substituted and contains at least one vinylic double bond to which a nitroxide terminated polymer of formula (XV) can be added in a radical addition. Preferred suitable vinylic unsaturated compounds V are compounds of the formula (XVIII):

CH ₂ = CH-C (O) X '(XVIII) where X' is the leaving group. Preferably, the leaving group is a halogen atom (F, Cl, Br, or I) or an OH group. Most preferably, X 'is an OH group

Particular preference is given to using as suitable vinylic unsaturated compound for preparing at least monounsaturated polysiloxanes of the formula A [LGC (O) -CH = CH ₂ ] _m acrylic acid.

The nucleophilic substitution reaction between functional polysiloxane and suitable vinylic unsaturated compound can be carried out under the reaction conditions typical for such reactions, which are known in the art. The reaction of the at least monosaturated polysiloxane of the formula A [LGC (O) -CH = CH ₂ ] _m with the nitroxide-terminated polymer can take place without solvent or in the presence of one or a mixture of several solvents.

The solvent is preferably selected from the group comprising water, alcohols, e.g. Ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert. Butanol, pentanol, hexanol, heptanol, octanol, Cycl ohexano 1, aromatic solvents, chlorinated and or fluorinated solvents, ethers, such as. For example, tetrahydrofuran, 1,4-dioxane, organic esters such as butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone; ether; Aliphatic, preferably pentane, hexane and further polar aprotic Lösemitten. The list is only exemplary and not exhaustive.

The reaction after step B) can be carried out at atmospheric pressure, underpressure or overpressure, preferably at atmospheric pressure.

The reaction after step B) can be carried out in a temperature range from 0 ° C to 90 ° C, preferably from 0 ° C to 80 ° C, more preferably from 25 ° C to less than 80 ° C.

The molar ratio of nitroxide-terminated polymer (XV) and unsaturated polysiloxane of the formula A [LGC (O) -CH = CH ₂ ] _m is preferably from 1 to 1.5 m, preferably from m to 1, 25m.

The reaction after step B) is preferably selected from the group comprising nitrogen, noble gases, CO ₂ or gaseous hydrocarbons, such as, for example, under a protective gas Methane, or mixtures thereof. Particularly preferred is the implementation under nitrogen as a protective gas.

The polyorganosiloxane compounds of the formula (VIII) according to the invention can be used in many ways. In particular, the inventive

Polyorganosiloxane compounds of formula (VIII) can be used for the preparation of cosmetic or pharmaceutical compositions or of personal care compositions.

Compositions according to the invention comprise at least one polyorganosiloxane compound of the formula (VIII) according to the invention and at least one component other than this compound, eg. For example, a carrier suitable for cosmetic or pharmaceutical use under the body care compositions is suitable. The compositions of the invention may, for. Cosmetic or pharmaceutical compositions or personal care compositions.

The compositions according to the invention preferably contain from 0.01% by mass to 20% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 3% by mass of at least one organopolysiloxane compound according to formula (VIII) based on the total weight of the formulation.

The compositions of the invention may, for. As for the treatment of hair, as Kondi t ioniermi tel for hair treatment agents, used as a hair aftertreatment agent and to improve the hair structure. In particular, the compositions according to the invention can be used for the treatment of hair, in particular for use as a hair conditioner. However, the organopolysiloxane compounds according to the invention can also be used widely Areas of different types of products, such as Hair spray compositions, hair styling compositions, mousses, gels, lotions, sprays, shampoos, conditioners, hand and body lotions, facial moisturizers, sunscreen, anti-acne formulations, anti-aging formulations, topical analgesics, mascara and the like, the list being exemplary and not exhaustive, to be used. The vehicles and additional components needed to formulate such products vary with the type of product and can be readily selected by one skilled in the art. In the following, some possible carrier substances and additional components which may be contained in compositions according to the invention are described. Excipients:

 The compositions of the invention may, for. As a carrier or a mixture of different carriers, which are suitable for use in cosmetic or pharmaceutical compositions or in personal care compositions, in particular for use on

Hair. The content of carrier in the formulation is from 0.5% by weight to 99.5% by weight, preferably from 5.0% by weight to 99.5% by weight, particularly preferably 10.0 Weight% to 98% by weight

The term "suitable for use on hair" means that the wearer does not damage the hair, does not adversely affect the aesthetic appearance of the hair, or cause irritation to the underlying skin

Hair care compositions in the present invention include e.g. For example, those that are used in hair sprays, mousses, tonics, gels, shampoos, conditioners or rinses. The choice of suitable carrier depends on the block copolymer used and whether the formulated product should remain on the surface to which it has been applied (e.g. Hair spray, mousse, tonic or gel) or whether it is rinsed off again after application (eg shampoo, conditioner, rinses). The carriers used may comprise a wide range of compounds commonly used in compositions, especially hair care compositions. The carriers may comprise a solvent to dissolve or disperse the copolymer used, with water, C ₁ -C ₆ alcohols, alkyl acetates having alkyl groups comprising one to ten carbon atoms, and mixtures thereof being preferred. The carriers may contain a wide range of additional materials such as acetone, hydrocarbons (e.g., iso-butane, pentane, hexane, decane), halogenated hydrocarbons (such as freons), and volatile silicone derivatives such as cyclomethicone. When the formulation is a hair care composition such as a hair spray, tonic, gel or mousse, the preferred solvents include water, ethanol, volatile silicone derivatives and mixtures thereof. The solvents used in such mixtures may be miscible or immiscible with each other. Mousses and aerosol hair sprays may also contain any conventional propellant to apply the material as a foam (in the case of mousse) or as a fine, uniform spray (in the case of the aerosol hair spray). Examples of suitable blowing agents include materials from the group comprising trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethyl ether, propane, n-butane or isobutane or mixtures thereof. A low viscosity tonic or hairspray product may also contain an emulsifier. Examples of suitable emulsifiers include nonionic, cationic, anionic surfactants or mixtures thereof. When such an emulsifier is used, the composition contains the emulsifier in a concentration of 0.01% to 7.5%. The content of propellant can be adjusted as needed but is usually between 3% and 30% for mousse compositions and from 15% to 50% in aerosol hairsprays. Suitable containers for spraying are well known to those skilled in the art and include conventional non-aerosol pump sprays, ie "atomizers", aerosol containers or cans with propellant as described above, and also pump aerosol containers which use compressed air as the propellant.

If the hair care composition of the invention is a conditioner or conditioner, the carrier may contain a wide variety of conditioning compounds. If the hair care compositions are shampoos, the carrier may contain surfactants, suspending aids and thickeners.

The wearer may include various appearances, e.g. For example, the carrier may be an emulsion comprising e.g. As oil-in-water emulsions, water-in-oil emulsions, water-in-oil-in-water and oil-in-water-in-silicone emulsions. The viscosity of the emulsions can range from 100 cps to 200,000 cps. These emulsions can also be sprayed using either mechanical pumping containers or pressurized aerosol containers with the usual propellants. The carriers can also be applied in the form of mousse. Other suitable topical carriers include non-aqueous liquid solvents such as oils, alcohols and silicones (e.g., mineral oil, ethanol, isopropanol, dimethicones, cyclomethicones and the like), water-based liquid monophase solvents (e.g.

Water / alcohol solvent systems) and thickened variants of these non-aqueous solutions and water-based liquid single-phase solvents (eg where the viscosity of the solvent has been increased to a solid or semi-solid by the addition of suitable gums, waxes, resins, polymers , Salts and similar substances). Additional components:

 A wide variety of additional components can be used in the compositions of the present invention, particularly in the cosmetic and personal care compositions of the present invention. An enumeration of possible components can, for. For example, DE 10 2008 001 786 are taken. Examples include but not limited to:

Sunscreen, such. B. 2-ethylhexyl-p-methoxy cinnamate, 2-ethyl-N, -dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, Homomenthylsalycilate, Octylsalicylate, 4, 4 '- methoxy-t-butyldibenzoylmethane,

4-isopropyldibenzoylmethane, 3-benzylidene camphor, 3- (4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof.

 Antidandruff agents such as bis (2-pyridylthio) zinc Ι, Ι'-dioxide, piroctone, selenium disulphide, sulfur,

Coal tar and similar.

 Conditioners for hair care compositions such as hydrocarbons, liquid silicones, and cationic materials. The hydrocarbons may be unbranched or branched and between 10 and 16

Carbon atoms, preferably between 12 and 16 carbon atoms. Examples of suitable hydrocarbons are decane, dodecane, tetradecane, tridecane and mixtures thereof. Examples of conditioning agents containing silicone include, but are not limited to, cyclic or linear polydimethylsiloxanes, phenyl and alkylphenyl silicones, and silicone polyols. Cationic conditioning agents useful in the compositions include quaternary, even silicone-containing, ammonium salts or the salts of fatty acid amines. Surfactants for hair shampoos and conditioning compositions. For a shampoo, the content of surfactants is preferably from 10% to 30% and more preferably from 12% to 25% of the composition. For conditioners, the preferred level of surfactants is from about 0.2% to about 3%. The surfactants useful in the compositions include anionic, nonionic, zwitterionic, cationic and amphoteric surfactants.

Polymeric thickeners with carboxylic acid groups. These crosslinked or uncrosslinked polymers contain one or more derivatives of acrylic acid, substituted acrylic acid, salts and esters of these acrylic acids and substituted acrylic acids, in the case of crosslinked polymers, the crosslinking agent containing two or more carbon-carbon double bonds. Examples of polymeric thickeners are those selected from the group consisting of carbomers, acrylates / Cio-C ₃₀ alkyl acrylates crosslinked copolymers, and mixtures thereof. Compositions of the present invention may contain from 0.025% to 1%, preferably from 0.05% to 0.75%, and more preferably from 0.10% to 0.50% of the polymeric thickeners having carboxylic acid groups.

 Emulsifiers for emulsifying a wide variety of excipients described in composition in this invention. Suitable emulsifier types include polyethylene glycol 20 sorbitan monolaurate (polysorbate 20), polyethylene glycol 5 soybean sterol, steareth-20, ceteareth-20, PPG-2 methylglucose ether distearate, ceteth-10, polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, polysorbate 60, glyceryl stearate , PEG-100 stearate and mixtures thereof. The emulsifiers may be used singly or as a mixture of two or more emulsifiers. The cosmetic or

Personal care composition may have an emulsifier content from 0.15 to 10%, preferably from 1% to 7%, and more preferably from 1% to 5%.

 Vitamins and derivatives thereof (e.g., ascorbic acid, vitamin E, tocopherol acetate, retinoic acid, retinol, retinoids and the like)

 Cationic polymers (e.g., cationic guar derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chlorides, available under the trade name Jaguar C from Rhone-Poulenc)

 Preservatives, antioxidants, chelating and complexing agents, pearlescing agents, esthetic components such as perfume, perfumes, dyes, pigments, hair nutrients, and essential oils.

 Additives which are obvious to the person skilled in the art, but are not listed here.

In the examples given below, the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.

The preparation of polydimethylsiloxane diacrylates is known in the art and to those skilled in the art. The preparation of such compounds is e.g. described in DE 38 10 140. For preparing a polydimethylsiloxane diacrylate of formula (XV) with e.g. n = 30 is proceeded analogously to Example 1 from DE 38 10 140. In this case, one mole of a SiH-containing polydimethylsiloxane in Example 1 of DE 38th

10 140 listed average formula with D = 30 used. To obtain the polydimethylsiloxane diacrylates with n = 70 or 130, corresponding SiH-group-containing siloxanes are used. In a modification of Example 1, however, 2 moles of 1-hexenol are reacted instead of 2 moles of allyl alcohol. The hydroxy-functional Polydimethylsiloxane is then further reacted analogously to the description in Example 1 with 2 mol of acrylic acid and worked up as described. Example 1:

In one with stirrer, thermometer, Rü ckf 1 uss cow 1 er, nitrogen inlet tube and dropping funnel multi-neck bottom flask was placed a mixture of 100 g of methyl isobutyl ketone, 80 g of butyl acrylate and 6.5 g Dimethylaminoethylmetharcylat under N ₂ atmosphere and carefully degassed with nitrogen. The mixture was heated to 50 ° C and then 7.9 g Block Builder ^® MA were added rapidly and heated to 115 ° C. The mixture was then allowed to react with stirring for 4 h at 115 ° C. By means of ¹ H-NMR analysis, a monomer conversion of> 85% was determined.

Subsequently, 43 g of a polydimethylsiloxane diacrylate of the formula (XVII)

added with n = 30 and the mixture stirred at 115 ° C for a further 5h. Subsequently, the solvent was distilled off under reduced pressure and at a temperature <80 ° C. The residue is the desired P o 1 y s i 1 o x anha 1 t i ge block copolymer.

Example 2:

A mixture of 50 g of methyl isobutyl ketone, 15 g of butyl acrylate and 2.7 g of dimethylaminoethyl methacrylate was initially introduced into a multi-necked flask equipped with stirrer, thermometer, backflow tube, nitrogen inlet tube and dropping funnel under N ₂ atmosphere and carefully degassed with nitrogen. The mixture was warmed to 50 ° C and then 7.1 g Block Builder ^® MA were added rapidly and heated to 115 ° C. The mixture was then allowed to react with stirring for 3 h at 115 ° C. By means of ¹ H-NMR analysis, a monomeric turnover of> 85% was determined.

Subsequently, 102 g of a polydimethylsiloxane diacrylate of the formula (XVII) with n = 130 were added and the mixture was stirred at 115 ° C. for a further 5 h. Subsequently, the solvent was distilled off under reduced pressure and at a temperature <80 ° C. The residue is the desired polysiloxane-containing block copolymer.

Example 3:

In a multi-necked flask equipped with stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel, under N ₂ atmosphere, a mixture of 100 g of methyl isobutyl ketone, 90 g

Methoxypolyethylene glycol 500 methacrylate (MPEG 500 MA, Acting of Evonik Röhm GmbH), 1.8 g of styrene presented and the mixture after careful degassing to 50 ° C heated. Subsequently, 3.2 g Block Builder ^® MA were added and the mixture heated quickly to 80 ° C and stirred at this temperature for 2h. Subsequently, a carefully degassed mixture of 12.4 g

Dimethylaminoethylmethacrylat and 0.9 g of styrene was added dropwise and heated at 80 ° C for a further 3h.

Subsequently, 11.6 g of a polydimethylsiloxane diacrylate of the formula (XVII) with n = 30 were added and the mixture was stirred at 80 ° C. for a further 10 h. Subsequently, the solvent was distilled off under reduced pressure and at a temperature <80 ° C. The residue is the desired polysiloxane-containing block copolymer.

Example 4: In a multi-necked flask equipped with stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel, under N ₂ atmosphere, a mixture of 30 g of methyl isobutyl ketone, 95.8 g of methoxypolyethylene glycol 500 methacrylate (MPEG 500 MA, Actahme, Evonik Röhm GmbH), 13.2 submitted Dimethylaminoethylmetharcylat and 12.0 g of styrene and degassed carefully with nitrogen. The mixture was heated to 50 ° C and then 1.01 g Block Builder ^® MA were added rapidly and heated to 80 ° C. The mixture was then allowed to react with stirring for 5 h at 80 ° C. By means of ¹ H-NMR analysis, a monomer conversion of> 85% was determined. Subsequently, 6.2 g of a polydimethylsiloxane diacrylate of the formula (XVII) with n = 30 were added and the mixture was stirred at 80 ^° C. for a further 9 hours. Subsequently, the solvent was distilled off under reduced pressure and at a temperature <80 ° C. The residue is the desired polysiloxane-containing block copolymer.

Example 5:

A mixture of 30 g of methyl isobutyl ketone, 65 g of methoxypolyethyleneglycol 500 methacrylate (MPEG 500 MA, supplied by Evonik Röhm GmbH) under a N ₂ atmosphere was placed in a multi-necked flask equipped with stirrer, thermometer, backflow tube, nitrogen inlet tube and dropping funnel. Introduced 1.3 g of styrene and the mixture after careful degassing to 50 ° C heated. Subsequently, were added 2 g 6 Bloc Builder ^® MA added and the mixture heated quickly to 80 ° C and stirred at this temperature for 2h. Subsequently, a carefully degassed mixture of 8.9 g of dimethylaminoethyl methacrylate and 0.6 g of styrene was added dropwise and heated at 80 ° C for a further 4h. Subsequently, 38.7 g of a P o 1 ydime thy1 si 1 oxan diacrylate of the formula (XVII) were added with n = 70 and the mixture was stirred at 80 ° C for a further 11h. Subsequently, the solvent was distilled off under reduced pressure and at a temperature <80 ° C. The residue is the desired polysiloxane-containing block copolymer.

Example 6: Applications as hair conditioner

For the applications-related assessment, hair tresses are used for sensory tests are damaged beforehand standardized manner by a permanent wave treatment ^¬ and a bleaching treatment. For this purpose, hairdressing customary products are used. The test procedure, the base materials used and the details of the evaluation criteria are described in DE 103 27 871.

Test formulation:

 The polysiloxane copolymers were tested in a simple hair rinse having the composition given in Table 1.

Table 1: Composition of the test formulations

The TEGINACID ^® C and TEGO Alkanol 16 products are available from Evonik Goldschmidt GmbH The term "conditioner" refers to the polyorganosiloxane compounds according to the invention described in Examples 1 to 5. Standardized treatment of previously damaged strands of hair with conditioning samples:

The hair tresses previously damaged as described above were treated with the conditioning rinse described above as follows:

The hair strands were wetted under running, warm water. The excess water was gently squeezed out by hand, then the rinse was applied and gently incorporated into the hair (1 ml / strand of hair (2 g)). After a residence time of 1 min, the hair was rinsed for 1 min.

Before the sensory evaluation, the hair was dried in air at 50% humidity and 25 ° C for at least 12 hours. The formulation of the test formulation is deliberately simple in order to avoid affecting the test results by (normally present) formulation ingredients. Formulations according to the invention may contain, in addition to the ingredients mentioned and / or instead of the ingredients mentioned, further ingredients. especially the

Combination with other ingredients can lead to a synergistic improvement of the conditioning effect. Such ingredients are described above. assessment criteria

Sensory scores were scored on scores ranging from 1 to 5, with 1 being the worst and 5 being the best scores. The individual test criteria each receive their own rating. The test criteria are: Detangling, wet combability, wet grip, dry combability, dry grip, shine, volume.

The results of the testing of the conditioning properties of the polysiloxane block copolymers are given in Table 2. The control sample contained no polysiloxane block copolymer of the invention.

In the sensor test, the polysiloxane block copolymers have hair conditioning properties. They are significantly better than the control without conditioner control.

Table 2: Conditioning properties of the polysiloxane block copolymers

 Cond. = Conditioner according to example

 K = control (placebo)

Example 7: Formulation as a hair spray:

The polysiloxane block copolymer of Example 1 was incorporated into a formulation for a non-aerosol hair spray with 80% by mass of volatile organic compounds (so-called 80% VOC non-aerosol hairspray) according to the composition listed in Table 3.

Table 3: Formulation of an 80% VOC Non-Aerosol Hairspray Component proportion in% by weight

RESYN 28-2930 Polymer 5

 AMP-95 0.49

 Polysiloxane block copolymer 4,5

from Example 1

 ABIL B 8843 0.2

 Deionized water 13, 81

 SD Alcohol 40 80

RESYN 28-293 Polymer: (INCI name: VA / Crotonates / Vinyl Neodecanoate Copolymer) is a product of National Starch.

AMP-95: (INCI name: Aminomethyl Propanol) is a product of ANGUS Chemical Company.

 ABIL B 8843: (INCI name: PEG-14 Dimethicone) is a product of Goldschmidt GmbH.

SD Alcohol 40: Ethanol.

The formulation of Table 3, when applied as a hair spray, showed improved flexibility of the treated hair and produced a noticeably improved feel than a formulation containing no polysiloxane block copolymer of the invention.

Example 8: Formulation as a hair styling gel:

 The polysiloxane block copolymer of Example 1 was incorporated into a formulation for a hair styling gel according to the composition listed in Table 4.

Table 4: Formulation of a hair styling gel:

Component proportion in wt .-%

 AMP-95 0.8

 Polysiloxane block copolymer 2

from Example 1 Deionized water 86, 4

 SD Alcohol 40 10

 Carbopol ETD 2020 0.8

AMP-95: (INCI name: Aminomethyl Propanol) is a product of Angus.

 Carbopol ETD 2020: (INCI Name: Acrylic C 10-30 Alkyl Acrylate Crosspolymer) is a product of Noveon.

The formulation from Table 4 forms a gel with a pudding-like consistency which, when applied as a styling gel, leads to sufficient stability in the hair, while at the same time providing flexibility and a comfortable grip.

Claims

Claims:

1. polyorganosiloxane compound of the formula (VIII):

in which

 A is an m-linked polyorganosiloxane radical,

 L is a divalent organic radical,

G = -O-, -S-, -CR ³ (OH) -CH (R ³ ) -O-, -NR ³ -, with R ³ independently of one another hydrogen or a monovalent substituted or unsubstituted, linear or branched 1 to 18

Carbon atoms containing organic radical,

R ^{1 is the} same or different than a linear or branched one

Alkyl radical having 1 to 3 carbon atoms, preferably

CH ₃ ,

R ^{2 is} a hydrogen atom or a linear or branched alkyl radical having 1 to 8 carbon atoms, a phenyl radical, an alkali metal cation such as Li ⁺ , Na ⁺ or K ⁺ or an ammonium such as NH ₄ ⁺ , NR ⁵ R ⁶ R ⁷ R ⁸⁺ with R ⁵ , R ⁶ R ⁷ and R ⁸ independently of one another are H or C ¹ -C ₄₀ -alkyl, and R ^{2 is} preferably H,

 l (II),

(II) is

 T is a polymer block composed of free-radically polymerized monomers,

m is an integer from 1 to 50. Polyorganosiloxane compound according to claim 1, characterized in that R ¹ = methyl and / or R ² = hydrogen and / or G = oxygen. 3. polyorganosiloxane compound according to claim 1 or 2, characterized in that R ¹ = methyl and R ² = hydrogen and G = oxygen.

4. Polyorganosiloxanverbindung according to at least one of the preceding claims, characterized in that L is a radical - (0) _X- L'-, wherein L 'is attached to G and an unbranched or branched, substituted or unsubstituted organic radical having 1 to 60 carbon atoms and x = 0 or 1.

5. polyorganosiloxane compound according to claim 4, characterized in that L is a linear unbranched hydrocarbon radical having 3 to 10 carbon atoms.

6. Polyorganosiloxanverbindung according to at least one of the preceding claims, characterized in that the unit A is a polysiloxane radical of the formula (IX)

is with

 j is a number from 0 to 10,

 k is a number from 1 to 500,

R is the same or different radicals R ⁹ or a bond to the building block L, with the proviso that m radicals R ^{f are} a bond to the building block L,

 R 'substituted or unsubstituted alkyl radicals having 1 to 18 carbon atoms.

Polyorganosiloxanverbmdung according to at least one of the preceding claims, characterized in that T is a polymer block composed of radically polymerized monomers selected from substituted or unsubstituted (meth) acrylic acids and derivatives thereof and optionally unsaturated hydrocarbons, in particular styrenes. V e rv e n c e m e n t i o n c e m e n ts

Polyorganosiloxane compound according to at least one of claims 1 to 7, characterized in that it comprises the steps

 A) reacting at least one free-radically polymerizable monomer M with at least one

Alkoxyamine of the formula (VI) to give a nitroxide-terminated polymer (XV)

 , and

 B) Reaction of the polymer (XV) with a monounsaturated compound of the formula (XVI)

A [LGC (O) -CH = CH ₂ ] m (XVI) with R ¹ , R ² , A, L, G, T and m as defined in claims 1 to 7.

9. The method according to claim 8, characterized in that as monomers M those of the formula (XII)

H (R ⁹ C = C (R ¹⁰ ) (C (O) G ') (XII) can be used, where radicals R ⁹ and R ¹⁰ can be selected independently of one another from the group consisting of hydrogen, unbranched or branched C C 1 -C 4 -alkyl radicals, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl and 2-ethoxyethyl radicals and the radical G 'is selected from the group consisting of -hydroxy, 0 (M) i _v , -OR ¹¹ , - NH ₂ , -NHR ¹¹ and -N (R ¹¹ ) (R ¹² ), where M is a valence counter-ion v selected from the group of metal ions, such as alkali metal ions,

Alkaline earth metal ions, ammonium ions, substituted ones

Ammonium ions such as, mono-, di-, tri- or tetraalkylammonium ions, and each radical R ¹¹ and R ^{12 may be} independently selected from the group consisting of hydrogen, straight or branched Ci- to C ₄₀ - alkyl radicals, polyether radicals, polyetheramine radicals, each optionally substituted with one or more substituents selected from the group consisting of hydroxy, amino, Ci to C ₃ alkoxy, Ci to C ₃ alkylamino and di (Ci to C ₃ alkyl) amino.

A method according to claim 8 or 9, characterized in that step A) is carried out at a temperature of greater than or equal to 80 ° C.

11. The method according to any one of claims 8 to 10, characterized in that step B) is carried out at a temperature of 25 ° C to less than 80 ° C.

12. Use of a compound of formula (XV) as defined in claim 8 as a macroinitiator for the preparation of polyorganosiloxane compounds of the formula (VIII). 13. Use of a compound according to at least one of

Claims 1 to 7 for the preparation of cosmetic or pharmaceutical compositions or of

Personal care compositions.

14. Composition comprising at least one compound according to at least one of claims 1 to 7 and also at least one component other than this compound.