DE102005015633A1 - Use of polysobutene-containing copolymers in shampoos and hair care products - Google Patents

Abstract

The present invention relates to the use of copolymers obtainable by copolymerization of at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms and at least one oligomer of branched or unbranched C¶3¶-C¶10¶ alkene in which at least one oligomer has an average molecular weight M n ¶ in the range of 300 to 5000 g / mol, preferably up to 1200 g / mol, or obtainable by oligomerization of at least 3 equivalents of C¶3¶ C¶10¶ alkene is, in shampoos and hair products.

Description

• a) Copolymerisaten, erhältlich durch Copolymerisation von (A) mindestens einem ethylenisch ungesättigten Dicarbonsäureanhydrid, abgeleitet von mindestens einer Dicarbonsäure mit 4 bis 8 C-Atomen, (B) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n im Bereich von 300 bis 5000 g/mol, bevorzugt bis zu 1200 g/mol aufweist oder durch Oligomerisierung von mindestens 3 Äquivalenten C₃-C₁₀-Alken erhältlich ist, (C) optional mindestens einem α-Olefin mit bis zu 24, bevorzugt mit bis zu 16 C-Atomen, (D) optional mindestens einem weiteren von (A), (B) und (C) verschiedenen ethylenisch ungesättigten Comonomer, gegebenenfalls Umsetzung mit (E) mindestens einer Verbindung der allgemeinen Formel Ia, Ib, Ic oder Id
  
  wobei A¹ C₂-C₂₀-Alkylen, gleich oder verschieden, R¹ C₁-C₃₀-Alkyl, linear oder verzweigt, Phenyl oder Wasserstoff, n eine ganze Zahl von 1 bis 200, gegebenenfalls anschließendem Kontaktieren mit Wasser, gegebenenfalls gemischt mit
• b) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n im Bereich von 300 bis 5000 g/mol, bevorzugt bis 1200 g/mol aufweist oder durch Oligomerisierung von mindestens 3 Äquivalenten C₃-C₁₀-Alken erhältlich ist, in Shampoos und Haarpflegemitteln.

The present invention relates to the use of

• a) Copolymers obtainable by copolymerization of (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms, (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alkene, wherein at least an oligomer having an average molecular weight M _n in the range from 300 to 5000 g / mol, preferably up to 1200 g / mol, or obtainable by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ -alkene, (C) optionally at least one α- Olefin having up to 24, preferably having up to 16 C atoms, (D) optionally at least one further of ethylenically unsaturated comonomer other than (A), (B) and (C), optionally reacting with (E) at least one compound of the general Formula Ia, Ib, Ic or Id
  
  wherein A ¹ C ₂ -C ₂₀ alkylene, identical or different, R ¹ C ₁ -C ₃₀ alkyl, linear or branched, phenyl or hydrogen, n is an integer from 1 to 200, optionally followed by contacting with water, optionally mixed With
• b) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alken, wherein at least one oligomer has an average molecular weight M _n in the range of 300 to 5000 g / mol, preferably up to 1200 g / mol or by oligomerization of at least 3 equivalents C ₃ -C ₁₀ alkane is available in shampoos and hair care products.

Farther The present invention relates to shampoos and hair care products containing the aforementioned components a) and optionally b).

The Invention therefore relates to compositions for cleaning and / or Care of the hair.

Farther relates to the invention hair care compositions containing the aforementioned Components a) and optionally b), wherein the hair care product selected is from the group consisting of pretreatment agents, hair conditioners, Hair conditioners, hair balms, leave-on hair treatments, rinse-off hair treatments, Hair tonics, Pomades, Hairdressing creams, Hairdressing lotions, Hairdressing gels, Lace fluids, Hot oil treatments and foam treatments.

other Bathing, showering or washing preparations are not the subject of this invention. Also cosmetic or dermatological Compositions with a sun protection factor (SPF) of at least 4, determined by the COLIPA method, are not the subject of this Invention.

Hair care products serve primarily dry and wet combability, the feeling of touch, the Gloss and improve the appearance of the hair as well as the To give hair antistatic properties.

One Shampoo should foam and cleanse the hair well, mild and well tolerated as well as practical and pleasant It must also be used for the care of the hair or in the handling contribute to the elimination of hair and scalp problems. These additional Effects and of course The cleaning effect has become characteristic of a modern shampoo.

From Shampoos will have sufficient cleansing power if not too strong Degreasing effect and at the same time adequate mildness expected. Important is that the cleaning power and the others you want Surfactant properties in both soft and hard water given are. Shampoos need good skin and mucous membrane compatible be and may therefore among the usual Application conditions have no aggressive effect. A good Cleaning performance does not have to be linked to heavy foaming. Nevertheless, foam quantity and quality of the shampoos during washing important criteria for the consumer that must be met by the shampoos.

The viscosity of shampoos must be so high that it still flows out of the bottle fast enough and on the hair is good and easy to disperse.

on the other hand It should not be so thin liquid be that it runs out of the hand and from the head. Cleaning and foaming power, skin compatibility, Thickenability and hydrolytic stability of the individual ingredients of shampoos are highly dependent on pH. The ones used in shampoos Ingredients are said to be neutral in properties and weak acidic pH range (pH 5-7) develop optimally, but also outside this pH range show no significant performance losses. The selected ingredients the shampoos need chemically stable and compatible with all other formulation ingredients, so that z. B. no impairments or segregations take place.

Hair products, which includes most shampoos are on a specific hair quality or tuned to a specific hair or scalp problem. For this be additional special auxiliaries needed. This includes the group of conditioning agents. Conditioners are auxiliaries, which pull on the hair and also after the rinsing process remain on the hair. They lead to improve combability, Handle and shine of the hair. For certain hair types (fine hair) or overdose can However, the conditioning also to an undesirable Weighting of the hair lead. From a formulation This means that when using conditioners always on a balanced balance between conditioning performance and hair weight reduction must be respected. Furthermore, when using conditioning agents also pay attention to the regular use of the product not to a steadily growing amount of conditioning agents leads to the hair (Build-up effect). Difficulties are often the provision of products with a complex property profile. Such complex Property profiles often require the use of many different ingredients in a preparation, what again the danger of an incompatibility across from one or more of these ingredients to the consumer.

The Object of the present invention was the aforementioned defects of the prior art to eliminate or at least reduce.

It there is a need for well-tolerated shampoos and hair care products, at the same time good sensory properties to the hair, like elasticity, give a pleasant grip and volume without a good one conditioning and cleansing effect of an unsatisfactory greasy and / or sticky appearance of the treated therewith Hair is accompanied.

It should shampoos and hair products with the aforementioned properties on the basis of as few as possible Be developed starting materials, since funds from the state of Technology the variety of necessary components partly to skin irritations, allergic reactions or other intolerances. Especially also in the field of children's and baby shampoos and hair care products there is a need for compositions with one as possible low number of different ingredients.

Solution of the task

• a) Copolymerisaten, erhältlich durch Copolymerisation von (A) mindestens einem ethylenisch ungesättigten Dicarbonsäureanhydrid, abgeleitet von mindestens einer Dicarbonsäure mit 4 bis 8 C-Atomen, (B) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n im Bereich von 300 bis 5000 g/mol, bevorzugt bis zu 1200 g/mol aufweist oder durch Oligomerisierung von mindestens 3 Äquivalenten C₃-C₁₀-Alken erhältlich ist, (C) optional mindestens einem α-Olefin mit bis zu 24, bevorzugt mit bis zu 16 C-Atomen, (D) optional mindestens einem weiteren von (A), (B) und (C) verschiedenen ethylenisch ungesättigten Comonomer, gegebenenfalls Umsetzung (E) mindestens einer Verbindung der allgemeinen Formel Ia, Ib, Ic oder Id
  
  wobei A¹ C₂-C₂₀-Alkylen, gleich oder verschieden, R¹ C₁-C₃₀-Alkyl, linear oder verzweigt, Phenyl oder Wasserstoff, n eine ganze Zahl von 1 bis 200, gegebenenfalls anschließendem Kontaktieren mit Wasser, gegebenenfalls gemischt mit
• b) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n im Bereich von 300 bis 5000 g/mol, bevorzugt bis 1200 g/mol aufweist oder durch Oligomerisierung von mindestens 3 Äquivalenten C₃-C₁₀-Alken erhältlich ist, in Shampoos und Haarpflegemitteln.

The above objects are achieved by the use of

• a) Copolymers obtainable by copolymerization of (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one Dicarboxylic acid having 4 to 8 carbon atoms, (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkene, wherein at least one oligomer has an average molecular weight M _n in the range of 300 to 5000 g / mol, preferably up to 1200 g / mol or obtainable by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ -alkene, (C) optionally at least one α-olefin having up to 24, preferably having up to 16 C atoms, (D) optionally at least one further ethylenically unsaturated comonomer other than (A), (B) and (C), if appropriate reaction (E) of at least one compound of the general formula Ia, Ib, Ic or Id
  
  wherein A ¹ C ₂ -C ₂₀ alkylene, identical or different, R ¹ C ₁ -C ₃₀ alkyl, linear or branched, phenyl or hydrogen, n is an integer from 1 to 200, optionally followed by contacting with water, optionally mixed With
• b) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alken, wherein at least one oligomer has an average molecular weight M _n in the range of 300 to 5000 g / mol, preferably up to 1200 g / mol or by oligomerization of at least 3 equivalents C ₃ -C ₁₀ alkane is available in shampoos and hair care products.

A preferred embodiment The invention relates to shampoos which simultaneously have conditioning properties exhibit. Another preferred embodiment of the invention are Shampoos that also have firming properties.

copolymer a) is in the compositions of the invention in an amount of 0.1 to 15% by weight, preferably 1 to 10, especially preferably 2 to 6 wt .-%, based on the weight of the composition contain. If the copolymer is mixed with oligomer b) in the composition before, that is the weight ratio of oligomer b) to copolymer a) in one embodiment of the invention preferably from 1:10 to 3: 1, more preferably from 1: 5 to 2: 1 and most preferably from 1: 2 to 1.5: 1.

Copolymer a)

• (A) mindestens einem ethylenisch ungesättigten Dicarbonsäureanhydrid, abgeleitet von mindestens einer Dicarbonsäure mit 4 bis 8 C-Atomen, beispielsweise Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid, Methylenmalonsäureanydrid, bevorzugt Itaconsäureanhydrid und Maleinsäureanhydrid und ganz besonders bevorzugt Maleinsäureanhydrid;
• (B) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n im Bereich von 300 bis 5000 g/mol, bevorzugt bis zu 1200 g/mol aufweist oder durch Oligomerisierung von mindestens 3 Äquivalenten C₃-C₁₀-Alken erhältlich ist,
• (C) optional mindestens einem α-Olefin mit bis zu 24, bevorzugt mit bis zu 16 C-Atomen,
• (D) optional mindestens einem weiteren von (A), (B) und (C) verschiedenen ethylenisch ungesättigten Comonomer, gegebenenfalls Umsetzung mit
• (E) mindestens einer Verbindung der allgemeinen Formel Ia, Ib, Ic oder Id
  
  wobei A¹ C₂-C₂₀-Alkylen, gleich oder verschieden, R¹ C₁-C₃₀-Alkyl, linear oder verzweigt, Phenyl oder Wasserstoff, n eine ganze Zahl von 1 bis 200, wobei die Carboxylgruppen des Copolymerisats a) zumindest partiell verestert oder amidiert sein können, und gegebenenfalls anschließendem Kontaktieren mit Wasser.

Copolymer a) is obtainable by preferably free-radical copolymerization of

• (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms, for example maleic anhydride, itaconic anhydride, citraconic anhydride, methylenemalonic anhydride, preferably itaconic anhydride and maleic anhydride and most preferably maleic anhydride;
• (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkene, wherein at least one oligomer has an average molecular weight M _n in the range of 300 to 5000 g / mol, preferably up to 1200 g / mol, or by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ -alkene is available,
• (C) optionally at least one α-olefin having up to 24, preferably having up to 16 C atoms,
• (D) optionally at least one further ethylenically unsaturated comonomer other than (A), (B) and (C), if appropriate, reaction with
• (E) at least one compound of general formula Ia, Ib, Ic or Id
  
  where A ^{1 is} C ₂ -C ₂₀ -alkylene, identical or different, R ¹ C ₁ -C ₃₀ -alkyl, linear or branched, phenyl or hydrogen, n is an integer from 1 to 200, where the carboxyl groups of the copolymer a) at least may be partially esterified or amidated, and optionally subsequent contact with water.

Oligomers (B) or b)

Suitable oligomers (B) and b) are oligomers of propylene or unbranched or preferably branched C ₄ -C ₁₀ -olefins, where at least one oligomer has an average molecular weight M _n in the range from 300 to 5000 g / mol, preferably up to 1200 g / mol or is obtainable by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ alkanes.

exemplary are oligomers of propylene, isobutene, 1-pentene, 2-methylbutene-1, 1-hexene, 2-methylpentene-1, 2-methylhexene-1, 2,4-dimethyl-1-hexene, diisobutene (mixture of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene), 2-ethyl-pentene-1,2-ethylhexene-1 and 2-propylhepten-1, 1-octene, 1-decene and 1-dodecene, especially preferred are oligomers of isobutene, diisobutene and 1-dodecene.

The Oligomers (B) and b) have an ethylenically unsaturated group in the form of a vinyl, vinylidene or alkylvinylidene group may be present.

Co-oligomers of the abovementioned olefins with one another or with up to 20 wt .-%, based on (B) or b), vinylaromatics such as styrene and α-methylstyrene, C ₁ -C ₄ -alkylstyrene such as 2-, 3 - And 4-methylstyrene and 4-tert-butylstyrene are suitable.

Particularly preferred oligomers (B) or b) are oligopropylenes and oligoisobutenes having an average molecular weight M _{n of} up to 1200 g / mol, preferably in the range from 300 to 1000 g / mol, more preferably of at least 400 g / mol, very particularly preferably of at least 500 g / mol, for example as determined by gel permeation chromatography (GPC).

In one embodiment of the present invention, oligomers (B) and / or b) have a polydispersity M _w / M _n in the range from 1.1 to 10, preferably up to 5 and particularly preferably from 1.5 to 1.8.

In one embodiment of the present invention, oligomers (B) and b) have a bimodal molecular weight distribution with a maximum of M _n in the range of 500 to 1200 g / mol and a local maximum of M _n in the range of 2000 to 5000 g / mol ,

oligomer (B) may be the same or different from oligomer (b). In a embodiment In the present invention, oligomer (B) and oligomer (b) are the same.

Oligomers of C ₄ olefins are preferably suitable as oligomer b). In one embodiment of the invention, the oligomers b) are hydrogenated oligomers of C ₄ olefins. Also particularly preferred as oligomers b) are, optionally hydrogenated, oligomers of 3, 4, 5, 6, 7 or 8 C ₄ -olefin molecules.

Comonomer (C)

As comonomer (C) used α-olefins having up to 16 carbon atoms are selected from propylene, 1-butene, Isobutene, 1-pentene, 4-methylbut-1-ene, 1-hexene, diisobutene (mixture of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene), 1-heptene , 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene; particularly preferred are isobutene, diisobutene and 1-dodecene.

Preparation of copolymer a)

you can for the preparation of copolymer used in the invention a) (A), (B) and optionally (C) copolymerize with each other. It is also possible to prepare copolymer a) (A), (B) according to the invention. and optionally (C) copolymerize with each other and optionally with (E) react or (A), (B) and optionally (C) and optionally copolymerize another comonomer (D) with each other, or one may (A) and (B) and optionally (C) and optionally another Copolymerize comonomer (D) with each other and optionally with (E) implement.

wobei die Variablen wie folgt definiert sind:
A¹ C₂-C₂₀-Alkylen, beispielsweise -(CH₂)₂-, -CH₂-CH(CH₃)-, -(CH₂)₃-, -CH₂-CH(C₂H₅)-, -(CH₂)₄-, -(CH₂)₅-, -(CH₂)₆-, vorzugsweise C₂-C₄-Alkylen; insbesondere -(CH₂)₂-, -CH₂-CH(CH₃)- und -CH₂-CH(C₂H₅)-;
R¹ Phenyl,
Wasserstoff
oder vorzugsweise C₁-C₃₀-Alkyl, linear oder verzweigt, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Dodecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, ganz besonders bevorzugt Methyl.
n eine ganze Zahl im Bereich von 1 bis 200, bevorzugt 4 bis 20.If it is desired to use a copolymer a) whose carboxyl groups are at least partially esterified or amidated, the compound (E) selected is at least one compound of the general formula Ia to Id, preferably Ia,

where the variables are defined as follows:
A ¹ C ₂ -C ₂₀ -alkylene, for example - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH ₂ -CH (C ₂ H ₅ ) - , - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, preferably C ₂ -C ₄ alkylene; in particular - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) - and -CH ₂ -CH (C ₂ H ₅ ) -;
R ^{1 is} phenyl,
hydrogen
or preferably C ₁ -C ₃₀ -alkyl, linear or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso -Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl , n-dodecyl, n-hexadecyl, n-octadecyl, n-eicosyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, very particularly preferably methyl.
n is an integer in the range of 1 to 200, preferably 4 to 20.

Of course, the groups A ¹ can only be different if n is a number greater than 1 or if different compounds of the general formula I a to I d are used.

• – Methylendgruppenverschlossene Polyethylenglykole der Formel HO-(CH₂CH₂O)m-CH₃ mit m = 1 bis 200, vorzugsweise 4 bis 100, besonders bevorzugt 4-50
• – Methylendgruppenverschlossene Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid mit einem Molekulargewicht M_n von 300 bis 5000 g/mol
• – Methylendgruppenverschlossene statistische Copolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid mit einem Molekulargewicht M_n von 300 bis 5000 g/mol
• – Alkoxylierte C₂- bis C₃₀-Alkohole, insbesondere Fettalkoholalkoxylate, Oxoalkoholalkoxylate oder Guerbet-Alkoholalkoxylate, wobei die Alkoxylierung mit Ethylenoxid, Propylenoxid und/oder Butylenoxid durchgeführt werden kann, Beispiele sind
• – C₁₃-C₁₅-Oxoalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten
• – C₁₃-Oxoalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₁₂C₁₄-Fettalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₁₀-Oxoalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₁₀-Guerbetalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₉-C₁₁-Oxoalkoholalkoxylate mit 2 bis 20 Ethylenoxideinheiten, 2 bis 20 Propylenoxideinheiten und/oder 1-5 Butylenoxideinheiten;
• – C₁₃-C₁₅-Oxoalkoholalkoxylate mit 2 bis 20 Ethylenoxideinheiten, 2 bis 20 Propylenoxideinheiten und/oder 1-5 Butylenoxideinheiten;
• – C₄-C₂₀-Alkoholethoxylate mit 2 bis 20 Ethylenoxideinheiten.

Particular examples of compounds of general formula Ia are

• - Methylendgruppenverschlossene polyethylene glycols of the formula HO- (CH ₂ CH ₂ O) m-CH ₃ with m = 1 to 200, preferably 4 to 100, particularly preferably 4-50
• - Methylendgruppenverschlossene block copolymers of ethylene oxide, propylene oxide and / or butylene oxide having a molecular weight M _n of 300 to 5000 g / mol
• - Methylendgruppenver closed statistical copolymers of ethylene oxide, propylene oxide and / or butylene oxide having a molecular weight M _n of 300 to 5000 g / mol
• - Alkoxylierte C ₂ - to C ₃₀ alcohols, in particular fatty alcohol alkoxylates, Oxoalkoholalkoxylate or Guerbet alcohol alkoxylates, wherein the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide, examples are
• - C ₁₃ -C ₁₅ -Oxoalkoholethoxylate with 3 to 30 ethylene oxide units
• C ₁₃ -oxo alcohol ethoxylates with 3 to 30 ethylene oxide units,
• C ₁₂ -C ₁₄ -fatty alcohol ethoxylates with 3 to 30 ethylene oxide units,
• C ₁₀ oxo alcohol ethoxylates with 3 to 30 ethylene oxide units,
• C ₁₀ -guerbet alcohol ethoxylates having from 3 to 30 ethylene oxide units,
• - C ₉ -C ₁₁ -Oxoalkoholalkoxylate with 2 to 20 ethylene oxide units, 2 to 20 propylene oxide units and / or 1-5 butylene oxide units;
• C ₁₃ -C ₁₅ oxo alcohol alkoxylates having from 2 to 20 ethylene oxide units, from 2 to 20 propylene oxide units and / or from 1 to 5 butylene oxide units;
• - C ₄ -C ₂₀ -alcohol ethoxylates with 2 to 20 ethylene oxide units.

Preferred examples of compounds of the formula Ib are methylene-end-capped polyethylene glycol amines of the formula H ₂ N- (CH ₂ CH ₂ O) m-CH ₃ with m = 1 to 200, preferably 4 to 100, particularly preferably 4 to 50.

If it is desired to react with compound Id, compound Ic can be reacted with alkylating agents such as, for example, halides or sulfates of the formula R ¹ -Y with Y selected from Cl, Br and I or (R ¹ ) ₂ SO ₄ . Depending on the use of the alkylating agent (s), compound Id is obtained with Y, SO ₄ ^2- or R ¹ -SO ₄ ^- as the counterion.

In one embodiment of the present invention, mixtures of different components (E), for example of the formula Ia, are used. In particular, it is possible to use those mixtures of compounds of the formula Ia in which, based in each case on the mixture, at least 95 mol%, preferably at least 98 mol%, up to a maximum of 99.8 mol% R ¹ for C ₁ -C ₃₀ Alkyl is and at least 0.2 mol% and at most 5 mol%, preferably at most 2 mol% of hydrogen.

In one embodiment of the present invention, for the preparation of the copolymer a) used according to the invention, the reaction mixture is contacted after the preferably free-radical copolymerization and, if appropriate, the reaction with (E) with water, where the water may also contain Brønsted acid or preferably Brønsted base. Examples of Brønsted acids are sulfuric acid, hydrochloric acid, tartaric acid and citric acid. Examples of Brønsted base are alkali metal hydroxide such as NaOH and KOH, alkali metal carbonate such as Na ₂ CO ₃ and K ₂ CO ₃ , alkali metal hydrogen carbonate such as NaHCO ₃ and KHCO ₃ , ammonia, amines such as trimethylamine, triethylamine, diethylamine, ethanolamine, N, N-diethanolamine, N, N, N-triethanolamine, N-methylethanolamine.

In another embodiment The present invention can be already during the preferably free radical Contact copolymerization with water.

Monomers (D)

Carbonsäureamide der Formel III,

nicht-cyclische Amide der allgemeinen Formel IV a und cyclische Amide der allgemeinen Formel IV b

C₁-C₂₀-Alkyl-vinylether wie Methyl-vinylether, Ethyl-vinylether, n-Propyl-vinylether, iso-Propyl-vinylether, n-Butyl-vinylether, iso-Butyl-vinylether, 2-Ethylhexyl-vinylether oder n-Octadecyl-vinylether;
N-Vinyl-derivate von stickstoffhaltigen aromatischen Verbindungen, bevorzugt N-Vinylimidazol, 2-Methyl-1-vinylimidazol, N-Vinyloxazolidon, N-Vinyltriazol, 2-Vinylpyridin, 4-Vinylpyridin, 4-Vinylpyridin-N-oxid, N-Vinylimidazolin, N-Vinyl-2-methylimidazolin,
α,β-ungesättigte Nitrile wie beispielsweise Acrylnitril, Methacrylnitril; alkoxylierte ungesättigte Ether der allgemeinen Formel V,

Ester und Amide der allgemeinen Formel VI,

ungesättigte Ester der allgemeinen Formel VII

vinylaromatische Verbindungen der allgemeinen Formel VIIIThe monomer or monomers (D) which can optionally be used to prepare copolymer (a) used according to the invention are different from (A), (B) and (C). Preferred monomers (D) are: C ₃ -C ₈ -carboxylic acids or carboxylic acid derivatives of the general formula II

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IV a and cyclic amides of the general formula IV b

C ₁ -C ₂₀ -alkyl-vinyl ethers such as methyl-vinyl ether, ethyl-vinyl ether, n-propyl-vinyl ether, iso-propyl-vinyl ether, n-butyl-vinyl ether, isobutyl-vinyl ether, 2-ethylhexyl-vinyl ether or n- octadecyl vinyl ether;
N-vinyl derivatives of nitrogen-containing aromatic compounds, preferably N-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 2-vinylpyridine, 4-vinylpyridine, 4-vinylpyridine-N-oxide, N-vinylimidazoline , N-vinyl-2-methylimidazoline,
α, β-unsaturated nitriles such as acrylonitrile, methacrylonitrile; alkoxylated unsaturated ethers of the general formula V,

Esters and amides of the general formula VI,

unsaturated esters of general formula VII

vinylaromatic compounds of the general formula VIII

Phosphate-, phosphonate-, sulphate- and sulphonate-containing comonomers such as [2- {(meth) acryloyloxy} -ethyl] -phosphate, 2- (meth) acrylamido-2-methyl-1-propanesulfonic acid;
α-olefins, linear or branched, having 18 to 40 carbon atoms, preferably having up to 24 carbon atoms, for example 1-octadecene, 1-eicosene, α-C ₂₂ H ₄₄ , α-C ₂₄ H ₄₈ and mixtures of the aforementioned α-olefins ,

The variables are defined as follows:
R ² , R ^{3 are} identical or different and selected from unbranched or branched C ₁ -C ₅ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert. Butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, more preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, iso-butyl, sec-butyl and tert -butyl;
and especially hydrogen;
R ^{4 is} identical or different and C ₁ -C ₂₂ -alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n -Pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-dodecyl, n-eicosyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
or more preferably hydrogen;
R ^{5 is} hydrogen or methyl,
x is an integer in the range of 2 to 6, preferably 3 to 5;
y is an integer selected from 0 or 1, preferably 1;
a is an integer in the range of 0 to 6, preferably in the range of 0 to 2;
R ⁶ , R ^{7 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert Butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl, preferably C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, all particularly preferably methyl;
X is oxygen or NR ⁴ ;
R ⁸ [A ³ -O] _n -R ⁴ ,
R ^{9 is} selected from unbranched or branched C ₁ -C ₂₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n- Decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl; preferably C ₁ -C ₁₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n -Tetradecyl,
and in particular hydrogen or methyl;
R ¹⁰ , R ¹¹ are each independently hydrogen, methyl or ethyl, preferably R ¹⁰ and R ^{11 are} each hydrogen;
R ^{12 is} methyl or ethyl;
k is an integer in the range from 0 to 2, preferably k = 0,
A ² , A ^{3 are} identical or different and C ₂ -C ₂₀ -alkylene, for example - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH ₂ -CH (C ₂ H ₅ ) -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, preferably C ₂ -C ₄ -alkylene; in particular - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) - and - (CH ₂ ) ₃ -;
A ⁴ C ₁ -C ₂₀ -alkylene, for example -CH ₂ -, -CH (CH ₃ )., -CH (C ₆ H ₅ ) -, -C (CH ₃ ) ₂ -, - (CH ₂ ) ₂ - , -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH ₂ -CH (C ₂ H ₅ ) -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, preferably C ₂ -C ₄ alkylene; in particular - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) - and - (CH ₂ ) ₃ -,
or especially a single bond.

The remaining variables are defined as above.

exemplary selected Compounds of the formula III are (meth) acrylamides, such as acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-undecylacrylamide or the corresponding methacrylamides.

exemplary selected Compounds of the formula IV a are N-vinylcarboxamides, such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide or N-vinyl-N-methylacetamide; exemplary selected Representative for Compounds of the formula IVb are N-vinylpyrrolidone, N-vinyl-4-piperidone and N-vinyl-ε-caprolactam.

exemplary selected Compounds of formula VI are (meth) acrylic esters and amides such as N, N-dialkylaminoalkyl (meth) acrylates or N, N-dialkylaminoalkyl (meth) acrylamides; Examples are N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethyl amino, N, N-diethylaminopropyl acrylate, N, N-diethylaminopropyl methacrylate, 2- (N, N-dimethylamino) ethylacrylamide, 2- (N, N-dimethylamino) ethyl methacrylamide, 2- (N, N -diethylamino) ethylacrylamide, 2- (N, N-diethylamino) ethylmethacrylamide, 3- (N, N-dimethylamino) propylacrylamide and 3- (N, N-dimethylamino) propylmethacrylamide.

exemplary selected Compounds of the formula VII are vinyl acetate, allyl acetate, vinyl propionate, Vinyl butyrate, vinyl 2-ethylhexanoate or vinyl laurate.

exemplary selected vinylaromatic compounds of the general formula VIII are α-methylstyrene, para-methylstyrene and especially styrene.

All is particularly preferably used as comonomer (D): acrylic acid, 1-octadecene, methacrylic acid, methyl acrylate, Methyl methacrylate, acrylamide, vinyl n-butyl ether, vinyl isobutyl ether, styrene, N-vinylformamide, N-vinylpyrrolidone, 1-vinylimidazole and 4-vinylpyridine.

The Copolymers a) can concerning (A), (B), optionally (C) and optionally (D) block copolymers, be alternating copolymers or random copolymers, wherein alternating copolymers are preferred.

In an embodiment The present invention relates to the anhydride groups of copolymer a) completely after the polymerization or partially hydrolyzed and optionally neutralized before.

In an embodiment The present invention relates to the anhydride groups of copolymer a) after the copolymerization as anhydride groups.

• (A) im Bereich von 5 bis 60 mol-%, bevorzugt 10 bis 55 mol-%,
• (B) im Bereich von 1 bis 95 mol-%, bevorzugt 5 bis 70 mol-%,
• (C) im Bereich von 0 bis 60 mol-%, bevorzugt 10 bis 55 mol-%,
• (D) 0 bis 70 mol-%, bevorzugt 1 bis 50 mol-%, jeweils bezogen auf Copolymerisat, wobei die Summe aus (A), (B), (C) und (D) 100 mol-% ergibt, und
• (A) im Bereich von 0 bis 50 mol-%, bevorzugt 1 bis 30 mol-%, besonders bevorzugt 2 bis 20 mol-%, bezogen auf alle Carboxylgruppen des Copolymerisats.

In one embodiment of the present invention, the molar ratios of copolymer used in accordance with the invention are

• (A) in the range of 5 to 60 mol%, preferably 10 to 55 mol%,
• (B) in the range of 1 to 95 mol%, preferably 5 to 70 mol%,
• (C) in the range of 0 to 60 mol%, preferably 10 to 55 mol%,
• (D) 0 to 70 mol%, preferably 1 to 50 mol%, in each case based on copolymer, wherein the sum of (A), (B), (C) and (D) gives 100 mol%, and
• (A) in the range of 0 to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 mol%, based on all carboxyl groups of the copolymer.

In an embodiment you choose a weight ratio from oligomer b) to copolymer a) in the range from 0.1: 1 to 100: 1, preferably from 0.5: 1 to 10: 1.

In another embodiment you choose a weight ratio from oligomer (b) to copolymer a) in the range from 1: 1 to 100: 1, preferably from 10: 1 to 50: 1.

The copolymers a) used according to the invention and also their mixtures with oligomer b) are described in the German patent applications with the file reference DE 10353557.8 . DE 10355402.5 and DE 10345094.7 , which is hereby incorporated by reference.

In one embodiment of the present invention, the copolymers a) of (A), (B) and optionally (C) and (D) used according to the invention have an average molecular weight M _w in the range from 1000 g / mol to 50,000 g / mol, preferably 1,500 g / mol to 25,000 g / mol, determined, for example, by gel permeation chromatography using dimethylacetamide as solvent and polymethyl methacrylate as standard.

Used according to the invention Copolymers a) of (A), (B) and optionally (C) and (D) and (E) can concerning (A), (B) and optionally (C) and (D) block copolymers, be alternating copolymers or random copolymers, wherein alternating copolymers are preferred.

The polydispersity M _w / M _n of copolymers of (A), (B) and optionally (C) and (D) and (E) used according to the invention as copolymer a) is generally in the range from 1.1 to 20, preferably from 2 to 10.

In an embodiment According to the invention, the present invention has been used as copolymer a) Copolymers of (A), (B) and optionally (C) and (D) and (E) Fikentscher K values in the range from 5 to 100, preferably 8 to 30 (measured according to H. Fikentscher at 25 ° C in cyclohexanone and a Polymer concentration of 2% by weight).

In an embodiment of the present invention used according to the invention Copolymers a) unpolymerized comonomer (B), for example in proportions of 1 to 50 wt .-%, based on the Total weight of copolymer a).

For the preparation of copolymers of (A), (B) and optionally (C) and (D) and (E) used according to the invention as copolymer a), the starting materials are (A), (B) and optionally (C) and (D ), which are preferably copolymerized with each other radically and optionally reacted with (E). The reaction with (E) may, if desired, be carried out before, during and after the copolymerization. While or before Preferably, after the copolymerization, it is possible to contact with water. But you can dispense with the contact with water for the production of copolymer used according to the invention a).

In a special embodiment of the present invention you first a radical copolymerization of (A), (B) and optionally (C) and (D), and then reacting with (E).

In another special embodiment The present invention is the radical copolymerization of (A), (B), and optionally (C) and (D) in the presence of the whole Amount or proportions of the compound (E) to be used.

In another special embodiment The present invention is first (A) and optionally (D) with (E) and then copolymerizes radically with (B) and optionally (C).

If a reaction of copolymer of (A), (B) and optionally (C) and (D) with (E) or a free-radical copolymerization in the presence of (E) is desired, then the total amount of (E) is calculated such that starting from a complete reaction of (E) and up to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 mol% (E), based on all carboxyl groups of the copolymer used. In the context of the present invention, the term "all carboxyl groups contained in the polymer" is understood as meaning those carboxyl groups of copolymerized comonomers (A) and optionally (D) which are present as anhydride, as C ₁ -C ₄ -alkyl ester or as carboxylic acid.

The free-radical copolymerization is advantageously started by initiators, for example peroxides or hydroperoxides. Suitable peroxides or hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permaleinate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-butyl peroxide. Chlorobenzoyl peroxide, Dicyclohexylperoxiddicarbonat, exemplified. The use of redox initiators is also suitable, for example combinations of hydrogen peroxide or sodium peroxodisulfate or one of the abovementioned peroxides with a reducing agent. Suitable reducing agents are, for example, ascorbic acid, tartaric acid, Fe (II) salts such as FeSO ₄ , sodium bisulfite, potassium bisulfite.

suitable Initiators are also Azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropion-amidine) dihydrochloride and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile).

in the Generally, initiator will be in amounts of from 0.1% to 20% by weight, preferably 0.2 to 15 wt .-%, calculated on the mass of all comonomers used.

you the copolymerization can be carried out in the presence or in the absence of solvents and precipitants carry out. As a solvent for the radical copolymerization come polar, compared to acid anhydride inert solvents considering such as e.g. Acetone, tetrahydrofuran and dioxane. Suitable precipitants For example, toluene, ortho-xylene, meta-xylene and aliphatic Hydrocarbons.

In a preferred embodiment you work without solvent or in the presence of only minor amounts of solvent, i. 0.1 to maximum 10 wt .-%, based on total weight of comonomers (A), (B) and optionally (C) and (D). As solvents are among the Conditions of copolymerization and esterification or Amide formation inert substances to understand, especially aliphatic and aromatic hydrocarbons such as cyclohexane, n-heptane, isododecane, benzene, Toluene, ethylbenzene, xylene as mixture of isomers, meta-xylene, ortho-xylene. If one works in the reaction with (E) without acidic catalyst or If one waives the implementation with (E), one can do the radical Copolymerization and optionally reaction with (E) also in solvents, chosen ketones such as acetone, methyl ethyl ketone, or cyclic ones or non-cyclic Ethern such as tetrahydrofuran or di-n-butyl ether perform.

The Copolymerization and optionally the reaction with (E) is preferably carried out with the exclusion of oxygen, for example in a nitrogen or argon atmosphere, preferably in a stream of nitrogen.

For the radical Copolymerization and, if appropriate, the reaction with (E) may be customary apparatuses be used, for. As autoclave and boiler.

The Order of addition of the comonomers can be different Make way.

In an embodiment put a mixture of (E) and (A) before and gives initiator and at the same time (B) and optionally (C) and (D). That's it preferably, (B) and optionally (C) and optionally (D) according to Add type of feed process.

In another embodiment put a mixture of (E) and (A) before and gives initiator and simultaneously (B) and optionally (C) and (D) in the manner of a feed process to, wherein initiator, (B) and optionally (C) and (D) respectively solved in (E) are.

In another embodiment if one introduces a mixture of (E) and (A) and gives initiator and (B), (C) and (D) in the manner of a feed process, wherein the feed rates of (B), (C) and (D) are chosen differently.

In another embodiment if one introduces a mixture of (E) and (A) and gives initiator and (B), (C) and (D) in the manner of a feed process, wherein the feed rates of (B), (C) and (D) are the same become.

In another embodiment one puts (A) and optionally (D) before and gives initiator and (B) and optionally (C) in the manner of a feed process and sets subsequently optionally with (E) um.

In another embodiment (A) and initiator, (B) and optionally (C) and (D) in the manner of a feed process and then sets, if appropriate with (E) um.

In another embodiment put (A) and (B) before and gives initiator and optionally (C) to Type of feed process and then optionally (E) around.

In another embodiment set (B), and optionally (C) and (D), and gives initiator and (A) in the manner of a feed process and then sets if necessary with (E) um.

In another embodiment put (B) and optionally (C) and give initiator, (A) and optionally (D) in the manner of a feed process and sets subsequently optionally with (E) um.

In another embodiment put (B) and optionally (D) and give initiator, (A) and optionally (C) in the manner of a feed process and sets subsequently optionally with (E) um.

In another embodiment one puts (A), (B) and optionally (C) and (E) and gives initiator and (D) in the manner of a feed process. (A), (B) and optionally (E) can also in a solvent be submitted.

In an embodiment one gives while the addition of (B), (C) and optionally (D) further initiator to.

In an embodiment one gives while the addition of (A) and optionally (D) further initiator.

In an embodiment is the temperature for the copolymerization of (A), (B) and optionally (C) and (D) in the range of 80 to 300 ° C, preferably 90 to 200 ° C.

Of the Pressure is for example in the range of 1 to 15 bar, preferably 1 to 10 bar.

It is possible to use regulators, for example C ₁ to C ₄ -aldehydes, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butylmercaptan, n-dodecylmercaptan. Polymerization regulators are generally used in amounts of from 0.1 to 10% by weight, based on the total weight of the comonomers used. Preference is given to working without the use of controllers.

It is possible during the copolymerization to add one or more polymerization inhibitors in small amounts, for example hydroquinone monomethyl ether. Polymerization inhibitor can be advantageously with (B) and optionally dosed (C) and (D). Suitable amounts of polymerization inhibitor are 0.01 to 1 wt .-%, preferably 0.05 to 0.5 wt .-%, calculated on the mass of all comonomers. The addition of polymerization inhibitor is particularly preferred when the copolymerization at temperatures above 80 ° C.

To Completion of the addition of (A), (B) and optionally (C) and (D), if appropriate (E) and, if appropriate, initiator, it is possible to react further to let.

The Duration of radical copolymerization is generally 1 to 12 Hours, preferably 2 to 9 hours, more preferably 3 to 6 Hours.

The Duration of the reaction with (E) can be 1 to 12 hours, preferably 2 to 9 hours, more preferably 3 to 6 hours.

Leading the preparation of (a) by reacting (A), (B) and optionally (C) and (D) copolymerized in the presence of the total amount of (E), so a reaction time of a total of 1 to 12 hours, is preferred 2 to 10 hours, more preferably 3 to 8.

you may be the reaction with (E) in the absence or even presence of catalysts, especially acid catalysts such as e.g. Sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, n-dodecylbenzenesulfonic acid, hydrochloric acid or acidic ion exchangers.

In Another variant of the method described leads you the reaction with (E) in the presence of an entrainer, with the optionally resulting in the reaction of water Azeotrope forms.

in the Generally governed under the conditions of the above Complete steps (E) or to some extent with the carboxyl groups of the anhydrides (A) and optionally the carboxyl groups from (D). In general less than 40 mol% remain as unreacted (E).

It is possible, by methods known per se such as extraction not reacted (E) obtainable by the preparation process according to the invention Separate copolymer.

In an embodiment one can point to the further step of separating unreacted (E) dispense with the copolymers produced. In this embodiment If one sets copolymers together with a certain percentage on unreacted (E) for the treatment of fibrous substrates one.

By the above-described copolymerization of (A), (B) and optionally (C) and (D) are obtained Copolymers. The resulting copolymers can be a cleaning subject to conventional methods, such as overturning or extractive removal of unreacted monomers. If a solvent or precipitant was used, so it is possible to remove this after completion of the copolymerization, for example by distilling off.

in the The scope of the present invention may be as described above contact prepared copolymer with water, calculated the amount of added water so that dispersion according to the invention gets which has a water content in the range from 30 to 99.5% by weight have on the total mass of aids.

In one embodiment, after the radical copolymerization and, if appropriate, the reaction with (E), water is added, it being still possible for the water to comprise Brønsted acid or preferably Brønsted base. Examples of Brønsted acids are sulfuric acid, hydrochloric acid, tartaric acid and citric acid. Examples of Brønsted base are alkali metal hydroxide such as NaOH and KOH, alkali metal carbonate such as Na ₂ CO ₃ and K ₂ CO ₃ , alkali metal hydrogen carbonate such as NaHCO ₃ and KHCO ₃ , ammonia, amines such as trimethylamine, triethylamine, diethylamine, ethanolamine, N, N-diethanolamine, N, N, N-triethanolamine, N-methylethanolamine. The concentration of Brønsted acid or preferably Brønsted base is generally from 1 to 20% by weight, based on the sum of water and Brønsted acid or water and Brønsted base.

It is already possible to add water during the free-radical copolymerization, but it is preferred to add water only toward the end of the free-radical copolymerization. If the free-radical copolymerization and the reaction with (E) has been carried out in the presence of solvent, it is preferred to first remove the solvent, for example by distilling off and only then with water taktieren.

By contacting with water, optionally Brønsted acid or prefers Brønsted base can contain the present in the copolymer carboxylic anhydride partially or completely be hydrolyzed.

To contacting with water, optionally Brønsted acid or prefers Brønsted base can be contained at temperatures in the range of 20 to 120 ° C, preferred React to 100 ° C let, for a period of 10 minutes to 48 hours.

In an embodiment the present invention is water, the water still Brønsted acid or prefers Brønsted base can contain at 50 to 100 ° C before and gives way in the manner of a feed process if necessary 50 to 120 ° C heated Copolymer to.

In a further embodiment the present invention sets copolymer at 50 to 120 ° C before and gives, if necessary, to 50 bis in the manner of a feed process 100 ° C heated water to, the water is still brønsted acid or prefers Brønsted base may contain.

In one embodiment of the present invention, a mixture of water, wherein the water may still contain Brønsted acid or preferably Brønsted base and nonionic surfactant, at 50 to 100 ° C before and gives in the manner of a feed optionally to 50 bis 120 ° C heated copolymer. Suitable nonionic surfactants are for example multiply, preferably 3 to 30 times alkoxylated C ₁₂ -C ₃₀ alkanols.

In a further embodiment, the copolymer is initially introduced at 50.degree. To 120.degree. C., and the mixture of water, optionally heated to 50.degree. To 100.degree. C., is added, the water also containing Brønsted acid or preferably Brønsted base and nonionic surfactant As a non-ionic surfactant is, for example, several times, preferably 3 to 30-fold alkoxylated C ₁₂ -C ₃₀ alkanol in question.

The The copolymers described above usually fall in the form of aqueous Dispersions or aqueous solutions or in bulk. aqueous Dispersions and solutions from the above-described copolymers are also subject matter of the present invention. From aqueous dispersions and solutions of the invention leave copolymers according to the invention isolate methods known per se to those skilled in the art, for example by evaporation of water or by spray drying.

Shampoos and Hair care products

The shampoos according to the invention containing copolymer a), optionally mixed with oligomer b) have washing activity without the addition of further surfactants.

In a preferred embodiment The invention contains the shampoos and hair care preparations according to the invention in addition to copolymer a), which is optionally mixed with oligomer b), at least one oil and / or fat phase.

In a preferred embodiment The invention contains the shampoos and hair care preparations according to the invention in addition to copolymer a), which is optionally mixed with oligomer b), further at least one surfactant.

In a preferred embodiment The invention contains the shampoos and hair care preparations according to the invention in addition to copolymer a), which is optionally mixed with oligomer b), at least one oil and / or fat phase and a Surfactant.

surfactants

When Surfactants can anionic, cationic, nonionic and / or amphoteric surfactants be used.

• – Acylglutamate, insbesondere Natriumacylglutamat
• – Sarcosinate, beispielsweise Myristoyl Sarcosin, TEA-Lauroyl Sarcosinat, Natriumlauroylsarcosinat und Natriumcocoylsarkosinat, Sulfonsäuren und deren Salze, wie
• – Acylisethionate, beispielsweise Natrium- oder Ammoniumcocoylisethionat
• – Sulfosuccinate, beispielsweise Dioctylnatriumsulfosuccinat, Dinatriumlaurethsulfosuccinat, Dinatriumlaurylsulfosuccinat und Dinatriumundecylenamido MEA-Sulfosuccinat, Dinatrium PEG-5 Laurylcitratsulfosuccinat und Derivate, sowie Schwefelsäureester, wie
• – Alkylethersulfat, beispielsweise Natrium-, Ammonium-, Magnesium-, MIPA-, TIPA-Laurethsulfat, Natriummyrethsulfat und Natrium C_12-3 Parethsulfat,
• – Alkylsulfate, beispielsweise Natrium-, Ammonium- und TEA-Laurylsulfat. Weitere vorteilhafte anionische Tenside sind
• – Taurate, beispielsweise Natriumlauroyltaurat und Natriummethylcocoyltaurat,
• – Ether-Carbonsäuren, beispielsweise Natriumlaureth-13 Carboxylat und Natrium PEG-6 Cocamide Carboxylat, Natrium PEG-7-Olivenöl-Carboxylat
• – Phosphorsäureester und Salze, wie beispielsweise DEA-Oleth-10 Phosphat und Dilaureth-4 Phosphat,
• – Alkylsulfonate, beispielsweise Natriumcocosmonoglyceridsulfat, Natrium C_12-14 Olefinsulfonat, Natriumlaurylsulfoacetat und Magnesium PEG-3 Cocamidsulfat,
• – Acylglutamate wie Di-TEA-palmitoylaspartat und Natrium Caprylic/Capric Glutamat,
• – Acylpeptide, beispielsweise Palmitoyl hydrolysiertes Milchprotein, Natrium Cocoyl hydrolysiertes Sojaprotein und Natrium-/Kalium Cocoyl hydrolysiertes Kollagen sowie Carbonsäuren und Derivate, wie
• – beispielsweise Laurinsäure, Aluminiumstearat, Magnesiumalkanolat und Zinkundecylenat, Ester-Carbonsäuren, beispielsweise Calciumstearoyllactylat, Laureth-6 Citrat und Natrium PEG-4 Lauramidcarboxylat
• – Alkylarylsulfonate.

Advantageous washing-active anionic surfactants for the purposes of the present invention are acylamino acids and their salts, such as

• - Acylglutamate, especially sodium acylglutamate
• Sarcosinates, for example myristoyl sarcosine, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate, sulfonic acids and their salts, such as
• Acyl isethionates, for example sodium or ammonium cocoyl isethionate
• Sulfosuccinates, for example dioctyl sodium sulphosuccinate, disodium laureth sulphosuccinate, disodium lauryl sulphosuccinate and disodium undecylenamido MEA sulphosuccinate, disodium PEG-5 lauryl citrate sulphosuccinate and derivatives, and sulfuric acid esters, such as
• Alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C _12-3 pareth sulfate,
• Alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate. Further advantageous anionic surfactants are
• Taurates, for example sodium lauroyl taurate and sodium methyl cocoyl taurate,
• Ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate, sodium PEG-7 olive oil carboxylate
• Phosphoric acid esters and salts such as DEA-oleth-10 phosphate and dilaureth-4 phosphate,
• Alkyl sulphonates, for example sodium coconut monoglyceride sulphate, sodium C _12-14 olefinsulphonate, sodium lauryl sulphoacetate and magnesium PEG-3 cocamide sulphate,
• Acylglutamates such as di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,
• Acyl peptides, for example palmitoyl hydrolyzed milk protein, sodium cocoyl-hydrolyzed soy protein and sodium / potassium cocoyl-hydrolyzed collagen, as well as carboxylic acids and derivatives, such as
• For example, lauric acid, aluminum stearate, magnesium alkoxide and Zinkundecylenat, ester carboxylic acids, for example, calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 Lauramidcarboxylat
• - Alkylarylsulfonates.

advantageous Washing-active cationic surfactants in the context of the present invention are quaternary surfactants. quaternary Surfactants contain at least one N atom containing 4 alkyl or aryl groups covalently linked. For example, alkylbetaine, Alkylamidopropylbetaine and Alkylamidopropylhydroxysultaine.

• – Alkylamine,
• – Alkylimidazole und
• – ethoxylierte Amine und insbesondere deren Salze.

Further advantageous cationic surfactants in the context of the present invention are further

• - alkylamines,
• - Alkylimidazoles and
• - ethoxylated amines and in particular their salts.

advantageous Washing-active amphoteric surfactants in the context of the present invention are acyl / dialkylethylenediamines, for example sodium acylamphoacetate, Disodium acylamphodipropionate, disodium alkylamphodiacetate, sodium acylamphohydroxypropylsulfonate, Disodium acylamphodiacetate, sodium acylamphopropionate, and N-coconut fatty acid amidoethyl-N-hydroxyethylglycinate Sodium salts.

Further advantageous amphoteric surfactants are N-alkyl amino acids, for example Aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.

• – Alkanolamide, wie Cocamide MEA/DEA/MIPA,
• – Ester, die durch Veresterung von Carbonsäuren mit Ethylenoxid, Glycerin, Sorbitan oder anderen Alkoholen entstehen,
• – Ether, beispielsweise ethoxylierte Alkohole, ethoxyliertes Lanolin, ethoxylierte Polysiloxane, propoxylierte POE Ether, Alkylpolyglycoside wie Laurylglucosid, Decylglycosid und Cocoglycosid, Glycoside mit einem HLB-Wert von wenigstens 20 (z.B. Belsil^®SPG 128V (Wacker)).

Advantageous washing-active nonionic surfactants in the context of the present invention are

• Alkanolamides, such as cocamide MEA / DEA / MIPA,
• Esters formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols,
• - ethers, for example ethoxylated alcohols, ethoxylated lanolin, ethoxylated polysiloxanes, propoxylated POE ethers, alkyl polyglycosides, such as lauryl glucoside, decyl glycoside and cocoglycoside, glycosides with an HLB value of at least 20 (eg, Belsil SPG ^® 128V (Wacker)).

Further advantageous nonionic surfactants are alcohols and amine oxides, like cocoamidopropylamine oxide.

preferred Shampoo Surfactants: Preferred anionic, amphoteric and nonionic Shampoo surfactants are described, for example, in "Kosmetik und Hygiene von Head to toe ", ed. W. Umbach, 3rd edition, Wiley-VCH, 2004, p.131-134 called what on this Place fully Reference is made.

Under The alkyl ether sulfates are especially sodium alkyl ether sulfates based on di- or tri-ethoxylated lauryl and myristyl alcohol prefers. They exceed the alkyl sulfates clearly with respect to Insensibility to water hardness, the thickening, the cold solubility and in particular skin and mucous membrane compatibility. You can also as sole washing raw materials for Shampoos can be used. Lauryl ether sulfate has better foam properties than myristyl ether sulfate but is inferior to this in mildness.

alkyl ether medium and especially higher ones are among the mildest surfactants ever, but show a poor foam and viscosity behavior. They are often in combination with alkyl ether sulfates and amphoteric surfactants in Shampoo used.

sulfosuccinic (Sulfosuccinates) are mild and but good foaming surfactants are because of their poor thickening preferred only together with other anionic and amphoteric surfactants and because of their low hydrolytic stability preferably used only in neutral or well-buffered products.

Amidopropylbetaines are virtually insignificant as sole washing raw materials, since you Foaming behavior and their thickening are only moderately pronounced. In contrast, show These surfactants have excellent skin and eye mucous membrane compatibility on. In combination with anionic surfactants their mildness can be synergistically improve. Preferred is the use of cocamidopropyl betaine.

Amphoacetates / amphodiacetates possess as amphoteric surfactants a very good skin and mucous membrane compatibility and can hair conditioning effect or the care effect of additives increase. she become similar like the betaines for optimizing alkyl ether sulfate formulations used. Most preferred are sodium cocoamphoacetate and Disodium.

Alkylpolyglykoside are nonionic washing raw materials. They are mild, have good universal properties, foam but weak. For this reason, they are preferred in combinations used with anionic surfactants.

sorbitan belong likewise to the nonionic washing raw materials. Because of their excellent Mild, they are preferably used for use in baby shampoos. As a weak foamer they are preferably used in combination with anionic surfactants.

It is advantageous, the one or more washing-active surfactants according to the invention to choose the group of surfactants which have an HLB value of more than 25, particularly advantageous are those which have an HLB value of more than 35.

It is advantageous according to the invention if one or more of these surfactants is in a concentration of 1 to 30% by weight, preferably at a concentration of 5 to 25% % By weight and most preferably in a concentration of 10 to 20% by weight, based in each case on the total weight of Composition is used.

Polysorbate

Further can Polysorbates according to the invention as wash-active agents advantageous be incorporated into the composition.

• – Polyoxyethylen(20)sorbitanmonolaurat (Tween 20, CAS-Nr. 9005-64-5)
• – Polyoxyethylen(4)sorbitanmonolaurat (Tween 21, CAS-Nr. 9005-64-5)
• – Polyoxyethylen(4)sorbitanmonostearat (Tween 61, CAS-Nr. 9005-67-8)
• – Polyoxyethylen(20)sorbitantristearat (Tween 65, CAS-Nr. 9005-71-4)
• – Polyoxyethylen(20)sorbitanmonooleat (Tween 80, CAS-Nr. 9005-65-6)
• – Polyoxyethylen(5)sorbitanmonooleat (Tween 81, CAS-Nr. 9005-65-5)
• – Polyoxyethylen(20)sorbitantrioleat (Tween 85, CAS-Nr. 9005-70-3).

In the context of the invention, advantageous polysorbates are the

• Polyoxyethylene (20) sorbitan monolaurate (Tween 20, CAS No. 9005-64-5)
• Polyoxyethylene (4) sorbitan monolaurate (Tween 21, CAS No. 9005-64-5)
• Polyoxyethylene (4) sorbitan monostearate (Tween 61, CAS No. 9005-67-8)
• Polyoxyethylene (20) sorbitan tristearate (Tween 65, CAS No. 9005-71-4)
• Polyoxyethylene (20) sorbitan monooleate (Tween 80, CAS No. 9005-65-6)
• Polyoxyethylene (5) sorbitan monooleate (Tween 81, CAS No. 9005-65-5)
• Polyoxyethylene (20) sorbitan trioleate (Tween 85, CAS No. 9005-70-3).

• – Polyoxyethylen(20)sorbitanmonopalmitat (Tween 40, CAS-Nr. 9005-66-7)
• – Polyoxyethylen(20)sorbitanmonostearat (Tween 60, CAS-Nr. 9005-67-8).

Particularly advantageous are in particular

• Polyoxyethylene (20) sorbitan monopalmitate (Tween 40, CAS No. 9005-66-7)
• Polyoxyethylene (20) sorbitan monostearate (Tween 60, CAS No. 9005-67-8).

These become advantageous according to the invention in a concentration of 0.1 to 5% by weight and in particular in a concentration of 1.5 to 2.5% by weight, based on the Total weight of the composition individually or as a mixture several Polysorbates used.

Hair care products

aim Hair care is the natural state of the newly regrown Hair over to obtain a long period of time and if possible in case of its loss restore. Radiant shine and a pleasant, smoother Handle are considered as features for natural, healthy hair.

When Hair care products are pretreated in the context of this invention, Hair conditioners (hair conditioners, Hair balm), hair treatments, whereby one differentiates between the cure products, which remain in the hair (leave-on) and those that are flushed out (rinse-off), hair lotions, Hairdressing products such as pomades, hairdressers, hairdressing lotions, Hair styling gels (hair gels, wet-look gels, glitter gels), top fluids, Hot oil treatments and foam treatments.

the Specialist known, usual Recipes of said hair care products are used in "cosmetics and Hygiene from head to toe ", ed. W. Umbach, 3rd edition, Wiley-VCH, 2004, chap. 9.2, p.247-264, to which reference is made in full at this point is taken. In addition to copolymer and optionally oligomer b) ingredients contained in hair care products are and hereinafter referred to and in part identical to those which also in the shampoos according to the invention may be included.

ever according to application the hair products as spray, foam, gel, gel spray, cream, lotion or wax are applied.

hairsprays include both aerosol sprays and pump sprays without propellant gas. hair foams include both aerosol foams as well as pump foams without propellant. Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components.

are in the hairsprays according to the invention and hair foams water-dispersible compounds used, they can be in the form of aqueous Microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm, are used. The solids content of these preparations usually lie here in a range of about 0.5 to 20 wt%. These microdispersions need in usually no emulsifiers or surfactants for their stabilization.

Hair styling means are no object of the present invention as hair fixatives, the not in the form of shampoos.

conditioners

The hair care compositions according to the invention and shampoo compositions in a preferred embodiment Conditioners.

According to the invention preferred Conditioning agents are, for example, all compounds which are used in the International Cosmetic Ingredient Dictionary and Handbook (Volume 4, publisher: R.C. Pepe, J.A. Wenninger, G.N. McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9th Edition, 2002) under Section 4 under the headings Hair Conditioning Agents, Humectants, Skin Conditioning Agents, Skin Conditioning Agents Emollient, Skin-Conditioning Agents-Humectant, Skin-Conditioning Agents-Miscellaneous, Skin-Conditioning Agents Occlusive and Skin Protectans are listed as well as all in the EP-A 934 956 (p.11-13) under "water soluble conditioning agent "and" oil soluble conditioning agent "listed compounds. Further advantageous conditioning substances, for example the compounds designated as polyquaternium according to INCI (in particular Polyquaternium-1 to Polyquaternium-56).

To The suitable conditioning agents include, for example, polymers quaternary Ammonium compounds, cationic cellulose derivatives, chitosan derivatives and polysaccharides.

According to the invention advantageous Conditioning agents can under the compounds shown in Table 1 below chosen become.

Table 1: Advantageously to be used for conditioning

Further according to the invention conditioners advantageous cellulose derivatives and quaternized guar gum derivatives, in particular guar hydroxypropylammonium chloride (for example, Jaguar Excel ^®, Jaguar ^® C 162 (Rhodia), CAS 65497-29-2, CAS 39421-75-5). Also, nonionic poly-N vinyl pyrrolidone / polyvinyl acetate copolymers (for example, Luviskol ^® VA 64 (BASF)), anionic acrylate copolymers (eg Luviflex ^® soft (BASF)), and / or amphoteric amide / acrylate / methacrylate copolymers (for example, Amphomer ^® (National Starch)) can According to the invention advantageously be used as a conditioner. Other possible conditioning agents are quaternized silicones.

thickener

For shampoos suitable thickeners are in "cosmetics and hygiene from head to toe ", ed. W. Umbach, 3rd edition, Wiley-VCH, 2004, p.235-236 called what on this Place fully Reference is made.

Consistency regulators enable the setting of the desired viscosity of shampoos. Thickeners which are formed by an enlargement of the surfactant micelles or by a swelling of the water phase viscostatic effect, come from chemically very different substance classes.

suitable Thickener for the compositions of the invention are crosslinked polyacrylic acids and their derivatives, polysaccharides such as xanthan gum, guar guar, agar-agar, Alginates or tyloses, cellulose derivatives, e.g. B. carboxymethylcellulose or hydroxycarboxymethylcellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, Fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and Polyvinylpyrrolidone.

Suitable thickeners are also polyacrylates such as Carbopol ^® (Noveon), Ultrez ^® (Noveon), Luvigel ^® EM (BASF), Capigel ^® 98 (Seppic), Synthalens ^® (Sigma), the Aculyn ^® brands from. Rohm and Haas as Aculyn ^® 22 (copolymer of acrylates and methacrylic acid with stearyl (20 EO units)) and Aculyn ^® 28 (copolymer of acrylates and methacrylic acid with behenyl (25 EO units)).

suitable Thickeners are also for example Aerosil types (hydrophilic Silicas), polyacrylamides, Polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, Esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, Fatty alcohol ethoxylates with restricted hornologist distribution or Alkyl oligoglucosides and electrolytes such as sodium chloride and ammonium chloride.

Particularly preferred thickening agents for the preparation of gels are ^® Ultrez 21, Aculyn ^® 28, Luvigel EM ^® and Capigel ^® 98th

Especially at higher Concentrated shampoo formulations can be used to regulate consistency it is also possible to add substances which reduce the viscosity of the formulation, such as As propylene glycol or glycerol. These substances influence the product features only a little.

preservative

As products with high water content shampoos must be reliably protected against contamination. The most important preservatives used for this purpose are urea condensates, p-hydroxybenzoic acid esters, the combination of phenoxyethanol with methyldibromoglutaronitrile and acid preservatives with benzoic acid, salicylic acid and sorbic acid.

Shampoo concentrates with high levels of surfactants or polyols and low water contents can also formulated preservative-free.

The compositions of the invention may advantageously contain one or more preservatives. Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde donors (such as, for example, DMDM hydantoin, which is commercially available for example under the trade name Glydant ^® (Lonza)), Iodopropylbutylcarbamate (eg Glycacil-L ^®, Glycacil-S ^® (Lonza) Dekaben ^® LMB (Jan Dekker)), parabens (p-hydroxybenzoic acid alkyl ester such as methyl, ethyl, propyl and / or butyl paraben), Dehydroacetic Acid (Euxyl ^® K 702 (Schulke & Mayr), phenoxyethanol, ethanol, benzoic acid. advantageously be Also called preservatives, such as octoxyglycerol, glycine, soy, etc. used.

The following table gives an overview of common preservatives:

Further advantageous in cosmetics are common preservatives or preservatives such as dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile), Phenoxyethanol, 3-iodo-2-propynyl butylcarbamate, 2-bromo-2-nitropropane-1,3-diol, Imidazolidinyl urea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, Benzalkonium chloride, benzyl alcohol, salicylic acid and salicylates.

It is particularly preferred when iodopropyl butylcarbamates as preservatives, Parabens (methyl, ethyl, propyl and / or butylparaben) and / or Phenoxyethanol be used.

complexing agents: Since the raw materials and also the shampoos themselves predominantly in steel equipment manufactured can, can the end products contain iron (ions) in trace amounts. To prevent that these impurities over Reactions with dyes and perfume oil ingredients adversely affect product quality complexing agents such as salts of ethylenediaminetetraacetic acid, the nitrilotriacetic acid, iminodisuccinic acid or phosphates added.

UV light protection filters: To those in the compositions of the invention contained ingredients such as dyes and perfume oils against changes stabilized by UV light, UV protection filters, such as B. benzophenone derivatives, be incorporated. Suitable for this are all cosmetically acceptable UV light protection filter.

The Compositions of the invention contain UV sunscreen filters in such an amount that the SPF (LSF, determined by the COLIPA method) of the compositions smaller than 4 is. Compositions with an SPF of at least 4 are not the subject of this invention.

Antioxidants: An additional content of antioxidants is generally preferred. Erfindungsge According to the invention, all antioxidants which are suitable or customary for cosmetic and / or dermatological applications can be used as antioxidants. Advantageously, the antioxidants are selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, γ-lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg Thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) as well as their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (eg buthionine sulfoximines, homocysteinesulfoximine, buthionine sulfones, pen ta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages (eg pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg. Citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, furfurylidene sorbitol and its derivatives Derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of Benzoeharzes, Rutinsäure and their derivatives, α-Glycosylrutin, Ferulasäure, Furfurylidenglucitol, Carnosin, Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, uric acid and their derivatives, Mannose and their derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and di e suitable derivatives according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of said active substances.

The Amount of the aforementioned antioxidants (one or more compounds) in the compositions preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20 Wt .-%, in particular 0.1 to 10 wt .-%, based on the total weight the composition.

Provided Vitamin E and / or derivatives thereof are the antioxidant (s), it is advantageous to use these in concentrations of 0.001 to 10% by weight, based on the total weight of the composition.

Provided Vitamin A, or vitamin A derivatives, or carotenes or their derivatives the antioxidant (s) is advantageous in these Concentrations of 0.001 to 10 wt .-%, based on the total weight of the composition.

Buffer: Ensure buffer the pH stability of the shampoo. Mostly Citrate, lactate and phosphate buffers are used.

Solubilizers: They are used to clear nourishing oils or perfume oils in solution to bring and also in the cold clear in solution to keep. The most common solubilizers are ethoxylated nonionic surfactants, eg. B. hydrogenated and ethoxylated Castor oils.

antimicrobial Medium: You can continue also antimicrobial agents are used. This generally includes all suitable preservatives with specific action against Gram-positive bacteria, e.g. Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether.), Chlorhexidine (1,1'-hexamethylenebis [5- (4-chlorophenyl) biguanide) and TTC (3,4,4'-trichlorocarbanilide). quaternary Ammonium compounds are in principle also suitable and will preferred for disinfectant soaps and washing lotions used. Also numerous Fragrances have antimicrobial properties. Also a large number essential oils or their characteristic ingredients such as e.g. Clove oil (eugenol), mint oil (Menthol) or thyme oil (Thymol), show a pronounced antimicrobial effectiveness.

The Antibacterial substances are usually in concentrations from about 0.1 to 0.3 wt .-% used.

dispersants: If in the shampoo insoluble Active ingredients, for. B. anti-dandruff agents or silicone oils, dispersed and to be kept in suspense in the long term, have dispersants and thickeners such. B. magnesium aluminum silicates, bentonites, Fatty acyl derivatives, polyvinylpyrrolidone or hydrocolloids, e.g. B. Xanthan gum or carbomers are used.

According to the invention are preservatives in a total concentration of at most 2, preferably at most 1.5 and more preferably at most 1% by weight, based on the total weight of the composition, contain.

Oils, fats and waxes

In addition to the optionally contained oligomer b) contain the inventive compositions prefers other oils, Fats or waxes.

One particular advantage of the present invention is that when used of copolymer a), which in a preferred embodiment mixed with oligomer b) is present, the required amount of other oils, fats or waxing may be significantly lower than usual, with the Application properties are at least as good or even better.

ingredients the oil and / or fatty phase of the composition according to the invention chosen favorably from the group of lecithins and fatty acid triglycerides, namely the triglycerol ester is more saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12 to 18 carbon atoms. The fatty acid triglycerides can for example, be selected advantageous from the group of synthetic, semisynthetic and natural oils, such as e.g. Olive oil, Sunflower oil, Soybean oil, Peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grapeseed oil, thistle oil, evening primrose oil, macadamia nut oil and the like more. Other polar oil components can to get voted from the group of saturated esters and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a ketene length. from 3 to 30 carbon atoms and from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 3 to 30 carbon atoms. Such ester oils can then chosen advantageous are from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, Isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, Isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate Dicaprylyl carbonate (Cetiol CC) and cocoglycerides (Myritol 331), Butylene glycol dicaprylate / dicaprate and dibutyl adipate as well as synthetic, semi-synthetic and natural Mixtures of such esters, e.g. Jojoba oil.

Further can one or more oil components are advantageously selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ether, the group of saturated or unsaturated, branched or unbranched alcohols.

Also any mixtures of such oil and wax components are advantageous in the sense of the present Use invention. It may also be advantageous if Waxes, for example cetyl palmitate, as the sole lipid component the oil phase use.

According to the invention advantageous becomes the oil component chosen from the group 2-ethylhexyl isostearate, octyldodecanol, Isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C12-15 alkyl benzoate, Caprylic capric triglyceride, Dicaprylyl.

According to the invention advantageous are mixtures of C12-15-alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C12-15 alkyl benzoate and isotridecyl isononanoate and mixtures from C12-15 alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

Particularly according to the invention are preferred as oils with one polarity from 5 to 50 mN / m fatty acid triglycerides, especially soybean oil and / or almond oil used.

From The hydrocarbons are advantageously paraffin oil, squalane, Squalene and in particular (optionally hydrogenated) polyisobutenes to be used in the sense of the present invention.

durch Oxidation eines Alkohols zu einem Aldehyd, durch Aldol-Kondensation des Aldehyds, Abspaltung von Wasser aus dem Aldol- und Hydrierung des Allylaldehyds. Guerbetalkohole sind selbst bei niederen Temperaturen flüssig und bewirken praktisch keine Hautreizungen. Vorteilhaft können sie als fettende, überfettende und auch rückfettend wirkende Bestandteile in kosmetischen Zusammensetzungen eingesetzt werden.Furthermore, the oil phase can be advantageously selected from the group of Guerbet alcohols. Guerbet alcohols are named after Marcel Guerbet, who first described their production. They arise according to the reaction equation

by oxidation of an alcohol to an aldehyde, by aldol condensation of the aldehyde, elimination of water from the aldol and hydrogenation of allyl aldehyde. Guerbet alcohols are fluid even at low temperatures and cause virtually no skin irritation. Advantageously, they can be used as greasing, overfatting and also moisturizing ingredients in cosmetic compositions.

aus. Dabei bedeuten R₁ und R₂ in der Regel unverzweigte Alkylreste.The use of Guerbet alcohols in cosmetics is known per se. Such species are usually characterized by the structure

out. R ₁ and R _{2 are} generally unbranched alkyl radicals.

Advantageously according to the invention, the Guerbet alcohol or alcohols are selected from the group, where
R ₁ = propyl, butyl, pentyl, hexyl, heptyl or octyl and
R ₂ = hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl.

According to the invention preferred Guerbet alcohols are (commercially available, for example as Isofol ^® 12 (Condea)) 2-butyloctanol and 2-hexyl decanol (for example commercially available as Isofol ^® 16 (Condea)).

Also mixtures of Guerbet alcohols are according to the invention may advantageously be used such as mixtures of 2-butyloctanol and 2-hexyl decanol (for example as Isofol ^® 14 (Condea) commercially available).

Also any mixtures of such oil and wax components are advantageous in the sense of the present Use invention.

Under Polydefins are the preferred substances for polyolefins. The Advantageously, the oil component furthermore have a content of cyclic or linear silicone oils or completely from such oils but it is preferred, except the silicone oil or the silicone oils an additional salary on other oil phase components to use.

Höhermolekulare Silicone oder Siliconöle sind in der Regel durch folgende allgemeine Formel definiert

wobei die Siliciumatome mit gleichen oder unterschiedlichen Alkylresten und/oder Arylresten substituiert sein können, welche hier verallgemeinernd durch die Reste R₁ bis R₄ dargestellt sind. Die Anzahl der unterschiedlichen Reste ist aber nicht notwendigerweise auf bis zu 4 beschränkt. m kann dabei Werte von 2 bis 200.000 annehmen. Erfindungsgemäß vorteilhaft einzusetzende cyclische Silicone sind in der Regel durch folgende allgemeine Formel definiert

wobei die Siliciumatome mit gleichen oder unterschiedlichen Alkylresten und/oder Arylresten substituiert werden können, welche hier verallgemeinernd durch die Reste R₁ bis R₄ dargestellt sind. Die Anzahl der unterschiedlichen Reste ist aber nicht notwendigerweise auf bis zu 4 beschränkt. n kann dabei Werte von 3/2 bis 20 annehmen. Gebrochene Werte für n berücksichtigen, daß ungeradzahlige Anzahlen von Siloxylgruppen im Zyklus vorhanden sein können.Low molecular weight silicones or silicone oils are generally defined by the following general formula

Higher molecular weight silicones or silicone oils are generally defined by the following general formula

wherein the silicon atoms are substituted with identical or different alkyl radicals and / or aryl radicals can, which are generalized here by the radicals R ₁ to R ₄ . However, the number of different residues is not necessarily limited to 4. m can assume values of 2 to 200,000. Cyclic silicones which are advantageously used in accordance with the invention are generally defined by the following general formula

wherein the silicon atoms can be substituted with identical or different alkyl radicals and / or aryl radicals, which are here generalized by the radicals R ₁ to R ₄ . However, the number of different residues is not necessarily limited to 4. n can assume values of 3/2 to 20. Broken values for n take into account that odd numbers of siloxyl groups may be present in the cycle.

Advantageous Phenyltrimethicone is chosen as the silicone oil. Also other silicone oils, for example Dimethicone, hexamethylcyclotrisiloxane, phenyldimethicone, cyclomethicone (e.g., decamethylcyclopentasiloxane), hexamethylcyclotrisiloxane, polydimethylsiloxane, Poly (methylphenylsiloxane), cetyl dimethicone, behenoxydimethicone advantageous to use in the context of the present invention. Advantageous are also mixtures of cyclomethicone and isotridecyl isononanoate, and those of cyclomethicone and 2-ethylhexyl isostearate.

It but is also beneficial, silicone oils similar constitution as the to select compounds referred to above, the organic side chains derivatized, for example polyethoxylated and / or polypropoxylated are. These include For example, polysiloxane polyalkyl polyether copolymers such as e.g. Cetyl dimethicone copolyol. Advantageously, cyclomethicone (octamethylcyclotetrasiloxane) as to be used according to the invention silicone oil used.

According to the invention advantageous fat and / or wax components to be used can be selected from the group of vegetable Waxes, animal waxes, mineral waxes and petrochemical waxes to get voted. For example, candelilla wax, carnauba wax, Japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, berry wax, ouricury wax, montan wax, jojoba wax, Shea butter, beeswax, shellac wax, spermaceti, lanolin (wool wax), Burdock fat, Ceresin, Ozokerite (earth wax), paraffin waxes and microwaxes.

Further advantageous fat and / or wax components are chemically modified waxes and synthetic waxes, such as Syncrowax HRC ^® (glyceryl tribehenate), and Syncrowax ^® AW 1 C (C _18-36 fatty acid) as well as Montanesterwachse, sasol waxes, hydrogenated jojoba waxes, synthetic or modified beeswaxes (z. B. dimethicone copolyol beeswax and / or C _30-50 alkyl beeswax), Cetyl Ricinoleate such as Tegosoft ^® CR, polyalkylene waxes, polyethylene glycol waxes, but also chemically modified fats such. Hydrogenated vegetable oils (for example hydrogenated castor oil and / or hydrogenated coconut fat glycerides), triglycerides such as hydrogenated soy glyceride, trihydroxystearin, fatty acids, fatty acid esters and glycol esters such as C _20-40 alkyl stearate, C _20-40 alkyl hydroxystearoyl stearate and / or glycol montanate. Also advantageous are certain organosilicon compounds which have similar physical properties to the fatty and / or wax components mentioned, such as, for example, stearoxytrimethylsilane. According to the invention, the fat and / or wax components can be used both individually and as a mixture in the compositions.

Also any mixtures of such oil and wax components are advantageous in the sense of the present Use invention.

Advantageously, the oil phase is selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, butylene glycol dicaprylate / dicaprate, 2-ethylhexyl cocoate, C _12-15 alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether. Particularly advantageous are mixtures of octyldodecanol, caprylic-capric triglyceride, dicaprylyl ether, dicaprylyl carbonate, cocoglycerides or mixtures of C _12-15 -alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C _12-15 alkyl benzoate and butylene glycol dicaprylate / dicaprate and mixtures of C _12-15 alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

From the hydrocarbons are paraffin oil, cycloparaffin, squalane, Squalene, hydrogenated polyisobutene or polydecene advantageous in the sense to use the present invention.

auszeichnen, wobei R' und R'' typischerweise unverzweigte aliphatische Reste mit 15 oder 17 Kohlenstoffatomen und bis zu 4 cis-Doppelbindungen darstellen.The oil component is also advantageously selected from the group of phospholipids. The phospholipids are phosphoric acid esters of acylated glycerols. Of the utmost importance among the phosphatidylcholines are, for example, the lecithins, which are distinguished by the general structure

characterized in that R 'and R''typically represent unbranched aliphatic radicals having 15 or 17 carbon atoms and up to 4 cis double bonds.

As according to the invention advantageous paraffin oil may according to the invention Mercury Weissoel Pharma 40 from Merkur Vaseline, Shell Ondina ^® 917, Shell Ondina ^® 927, Shell Oil 4222, Shell Ondina ^® 933 from Shell & DEA Oil, Pioneer ^® 6301 S, Pioneer ^® 2071 (Hansen & Rosenthal ) are used.

suitable cosmetically acceptable oil and fat components are in Karl-Heinz Schrader, basics and formulations of cosmetics, 2nd edition, publisher Hüthig, Heidelberg, pp. 319-355, which is hereby incorporated by reference Reference is made.

Of the Content of other oils, Greasing and waxing is at the most 50, preferably 30, more preferably at most 20% by weight, based on the total weight of the composition. The amount of oligomer b) falls not below the content of other further oils, fats and waxes.

The Compositions according to the invention except the aforementioned substances optionally in cosmetics or Dermatology usual Additives, for example perfume, dyes, antimicrobial Substances, moisturizing Agents, complexing and sequestering agents, pearlescent agents, Plant extracts, vitamins, active ingredients, preservatives, bactericides, Pigments that have a coloring effect have, thickeners, softening, moisturizing and / or moisturizing Substances, or other common ones Components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, organic acids for pH adjustment, Foam stabilizers, electrolytes, organic solvents or silicone derivatives.

Regarding said, known to those skilled in other ingredients for the compositions be on "cosmetics and hygiene from head to toe ", ed. W. Umbach, 3rd edition, Wiley-VCH, 2004, pp. 123-128, to which this Place fully Reference is made.

ethoxylated Glycerol fatty acid ester

The shampoos according to the invention and hair care products optionally contain ethoxylated oils selected from the group of ethoxylated glycerol fatty acid esters, especially preferred PEG-10 olive oil glycerides, PEG-11 avocado oil glycerides, PEG-11 cocoa butter glycerides, PEG-13 sunflower oil glycerides, PEG-15 glyceryl isostearate, PEG-9 coconut fatty acid glycerides, PEG-54 hydrogenated castor oil, PEG-7 hydrogenated castor oil, PEG-60 hydrogenated castor oil, jojoba oil Ethoxylate (PEG-26 Jojoba Fat Acids, PEG-26 Jojoba alcohol), glycereth-5 cocoate, PEG-9 coconut fatty acid glycerides, PEG-7 glyceryl cocoate, PEG-45 palm oil glycerides, PEG-35 castor oil, olive oil PEG-7 ester, PEG-6 caprylic acid / capric acid glycerides, PEG-10 olive oil glycerides, PEG-13 sunflower oil glycerides, PEG-7 hydrogenated castor oil, Hydrogenated palm kernel oil glyceride PEG-6 ester, PEG-20 Maisölglyceride, PEG-18 Glyceryl Olead Cocoate, PEG-40 Hydrogenated Castor Oil, PEG-40 castor oil, PEG-60 hydrogenated castor oil, PEG-60 corn oil glycerides, PEG-54 hydrogenated castor oil, PEG-45 Palmkernölglyceride, PEG-80 glyceryl cocoate, PEG-60 almond oil glycerides, PEG-60 "Evening Primrose" glycerides, PEG-200 Hydrogenated glyceryl palmitate, PEG-90 glyceryl isostearate.

preferred ethoxylated oils are PEG-7 glyceryl cocoate, PEG-9 coconut glycerides, PEG-40 hydrogenated castor oil, PEG-200 hydrogenated glyceryl palmitate.

ethoxylated Glycerol fatty acid ester be in watery Cleaning formulations used for various purposes. Glycerol fatty acid ester with a degree of ethoxylation of about 30-50 serve as solubilizers for nonpolar Substances such as perfume oils. Highly ethoxylated glycerol fatty acid esters are used as thickeners.

drugs

It It has been found that in the shampoos and hair products of the invention various active ingredients with different solubility work in homogeneously. The substantivity of the active ingredients on the hair is higher from the composition described than conventional surfactant-containing cleaning formulations.

According to the invention can Active ingredients (one or more compounds) are advantageously selected the group consisting of acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, e.g. B. hydrocortisone-17-valerate, vitamins of B and D series, especially vitamin B1, vitamin B12, vitamin D, vitamin A or its derivatives such as retinyl palmitate, vitamin E or its derivatives such as. Tocopheryl acetate, vitamin C and its derivatives such as e.g. Ascorbyl glucoside but also niacinamide, panthenol, bisabolol, polydocanol, unsaturated fatty acids, such as. the essential fatty acids (usually as vitamin F), in particular γ-linolenic acid, oleic acid, eicosapentaenoic acid, docosahexaenoic acid and their derivatives, chloramphenicol, caffeine, prostaglandins, thymol, Camphor, squalene, extracts or other plant and plant products animal origin, z. B. evening primrose oil, borage oil or currant seed oil, fish oils, cod liver oil but also ceramides and ceramide-like ones Compounds, Frankincense Extract, Green Tea Extract, Water Lilies Extract, Licorice extract, Hamamelis, anti-dandruff agents (e.g., selenium disulfide, zinc pyrithione, Piroctone, olamine, climbazole, octopirox, polydocanol and their combinatines), Complexing agents such as e.g. those from γ-oryzanol and calcium salts such as calcium panthotenate, calcium chloride, calcium acetate.

It is also to choose the active ingredients from the group of emollients advantageous, for example PurCellin, Eucerit ^® and Neocerit® ^®.

Especially Advantageously, the active substance (s) are further selected the group of NO synthase inhibitors, in particular when the compositions of the invention for the treatment and prophylaxis of the symptoms of intrinsic and / or extrinsic aging as well as for the treatment and prophylaxis of harmful Effects of ultraviolet radiation on the hair should serve. Preferred NO synthase inhibitor is nitroarginine.

Further Advantageously, the active substance (s) are selected from the group comprising Catechins and bile acid esters of catechins and watery or organic extracts of plants or parts of plants that have a Have catechins or bile acid esters of catechins, such as the leaves the plant family Theaceae, in particular the species Camellia sinensis (greener Tea). Particularly advantageous are their typical ingredients (e.g. Polyphenols or catechins, caffeine, vitamins, sugars, minerals, Amino acids, Lipids).

catechins represent a group of compounds known as hydrogenated flavones or anthocyanidins and derivatives of "catechol" (catechol, 3,3 ', 4', 5,7-flavanpentaol, 2- (3,4-dihydroxyphenyl) chroman-3,5,7-triol) represent. Also epicatechin ((2R, 3R) -3,3 ', 4', 5,7-flavanpentaol) is an advantageous active ingredient in the context of the present invention.

Advantageous are also herbal extracts containing catechins, in particular extracts of green tea, such as B. extracts from leaves the plants of the species Camellia spec., especially the teas Camellia sinenis, C. assamica, C. taliensis and C. inawadiensis, respectively and crosses of these with, for example, Camellia japonica.

preferred Active substances are also polyphenols or catechins from the group (-) - catechin, (+) - catechin, (-) - catechin gallate, (-) - gallocatechin gallate, (+) - epicatechin, (-) - epicatechin, (-) - epicatechin Gallate, (-) - epigallocatechin, (-) - epigallocatechin gallate.

Also, flavone and its derivatives (often collectively called "flavones") are beneficial agents in the art Meaning of the present invention. They are identified by the following basic structure (substitution positions specified):

Some the more important flavones, which are also preferably used in compositions of the invention can be are listed in Table 2 below.

Table 2: Flavones

In In nature, flavones usually occur in glycosidated form.

wobei Z₁ bis Z₇, unabhängig voneinander gewählt werden aus der Gruppe H, OH, Alkoxy- sowie Hydroxyalkoxy-, wobei die Alkoxy- bzw. Hydroxyalkoxygruppen verzweigt und unverzweigt sein und 1 bis 18 C-Atome aufweisen können, und wobei Gly gewählt wird aus der Gruppe der Mono- und Oligoglycosidreste.According to the invention, the flavonoids are preferably selected from the group of substances of the general formula

wherein Z ₁ to Z ₇ , are independently selected from the group H, OH, alkoxy and hydroxyalk oxy-, wherein the alkoxy or hydroxyalkoxy groups may be branched and unbranched and may have 1 to 18 carbon atoms, and wherein Gly is selected from the group of mono- and Oligoglycosidreste.

wobei Z₁ bis Z₆ unabhängig voneinander gewählt werden aus der Gruppe N, OH, Alkoxy- sowie Hydroxyalkoxy-, wobei die Alkoxy- bzw. Hydroxyalkoxygruppen verzweigt und unverzweigt sein und 1 bis 18 C-Atome auf weisen können, und wobei Gly gewählt wird aus der Gruppe der Mono- und Oligoglycosidreste.According to the invention, however, the flavonoids can also be chosen advantageously from the group of substances of the general formula

where Z ₁ to Z _{6 are} independently selected from the group consisting of N, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and can have 1 to 18 C atoms, and wherein Gly is selected from the group of mono- and oligoglycoside radicals.

wobei Z₁ bis Z₆ unabhängig voneinander wie vorgenannt und Gly₁, Gly₂ und Gly₃ unabhängig voneinander Monoglycosidreste oder Oligoglycosidreste darstellen. Gly₂ bzw. Gly₃ können auch einzeln oder gemeinsam Absättigungen durch Wasserstoffatome darstellen.Preferably, such structures can be selected from the group of substances of the general formula

where Z ₁ to Z ₆ independently of one another as mentioned above and Gly ₁ , Gly ₂ and Gly ₃ independently of one another are monoglycoside radicals or oligoglycoside radicals. Gly ₂ or Gly ₃ can also represent individually or jointly saturations by hydrogen atoms.

Preferably Gly ₁ , Gly ₂ and Gly _{3 are} independently selected from the group of Hexosylreste, in particular the Rhamnosylreste and Glucosylreste. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use.

It can also be advantageous according to the invention be to use Pentosylreste.

Advantageously, Z ₁ to Z _{5 are} independently selected from the group H, OH, methoxy, ethoxy and 2-hydroxyethoxy, and the flavone glycosides correspond to the general structural formula

wobei Gly₁, Gly₂ und Gly₃ unabhängig voneinander Monoglycosidreste oder Oligoglycosidreste darstellen. Gly₂ bzw. Gly₃ können auch einzeln oder gemeinsam Absättigungen durch Wasserstoffatome darstellen.Most preferably, the flavone glycosides are selected from the group represented by the following structure.

where Gly ₁ , Gly ₂ and Gly _{3 are} independently monoglycoside residues or oligoglycoside residues. Gly ₂ or Gly ₃ can also represent individually or jointly saturations by hydrogen atoms.

Preferably Gly ₁ , Gly ₂ and Gly _{3 are} independently selected from the group of Hexosylreste, in particular the Rhamnosylreste and Glucosylreste. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use.

It can also be advantageous according to the invention be to use Pentosylreste.

Especially advantageous in the context of the present invention, the or the Flavone glycosides to choose from the group a-glucosylrutin, α-glucosylmyricetin, α-glucosylisoquercitrin, α-glucosylisoquercetin and α-glucosylquercitrin.

Further advantageous active ingredients are sericoside, pyridoxol, vitamin K, biotin and flavorings.

In addition, the active compounds (one or more compounds) can also be chosen very advantageously from the group of hydrophilic active substances, in particular from the following group:
α-hydroxy acids such as lactic acid or salicylic acid or salts thereof such as Na lactate, Ca lactate, TEA lactate, urea, allantoin, serine, sorbitol, glycerol, milk proteins, panthenol, chitosan.

The List of active substances or combinations of active substances, which in the compositions of the invention can be used should of course not limiting. The active substances can be individual or in any Combinations are used together.

The Amount of such active ingredients (one or more compounds) in the Compositions according to the invention is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20 Wt .-%, in particular 1 to 10 wt .-%, based on the total weight the composition.

The above and other active ingredients verwen in the compositions of the invention can be in the DE 103 18 526 A1 on pages 12 to 17, to which reference is made in its entirety.

pearlescent

When Pearlescent waxes are, for example, suitable: alkylene glycol esters, special ethylene glycol disterate; Fatty acid alkanolamides, especially coconut fatty acid diethanoamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyfunctional, optionally hydroxysubstituted carboxylic acids with Fatty alcohols with 6 to 22 carbon atoms, especially long-chain Esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, Fatty ethers and fatty carbonates having a total of at least 24 carbon atoms, especially Lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic, Ring opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

The Compositions of the invention can furthermore glitter and / or other effect substances (for example color streaks) contain.

emulsifiers

• (1) Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe;
• (2) C12/18-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin;
• (3) Glycerinmono- und -diester und Sorbitanmono- und -diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte;
• (4) Alkylmono- und -oligoglycoside mit 8 bis 22 Kohlenstoffatomen im Alkylrest und deren ethoxylierte Analoga;
• (5) Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ölen, beispielsweise an Ricinusöl und/oder gehärtetem Ricinusöl;
• (6) Polyol- und insbesondere Polyglycerinester, wie z.B. Polyglycerinpolyricinoleat, Polyglycerinpoly-12-hydroxystearat oder Polyglycerindimerat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen;
• (7) Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• (8) Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C₆/₂₂-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipentaerythrit, Zuckeralkohole (z.B. Sorbit), Alkylglucoside (z.B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Polyglucoside (z.B. Cellulose);
• (9) Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEGalkylphosphate und deren Salze;
• (10) Wollwachsalkohole;
• (11) Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
• (12) Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE-PS 1165574 und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoff atomen, Methylglycose und Polyolen, vorzugsweise Glycerin oder Polyglycerin sowie
• (13) Polyalkylenglykole.

In a preferred embodiment, the shampoos and hair care compositions according to the invention additionally contain emulsifiers. Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

• (1) addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;
• (2) C12 / 18 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;
• (3) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;
• (4) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs;
• (5) addition products of 15 to 60 moles of ethylene oxide with oils, for example castor oil and / or hydrogenated castor oil;
• (6) polyol and especially polyglycerol esters such as polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds of several of these classes of substances;
• (7) addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• (8) partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) as well as polyglucosides (eg cellulose);
• (9) mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEGalkylphosphate and their salts;
• (10) wool wax alcohols;
• (11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• (12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methylglycose and polyols, preferably glycerol or polyglycerol and
• (13) Polyalkylene glycols.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are mixtures of homologs whose mean Alkoxylierungsgrad the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds. C ₁₂ to C ₁₈ fatty acid mono- and diesters of addition products of ethylene oxide with glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations. C ₈ to C ₁₈ alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycoside ester, it is true that both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol is attached, as well as oligomeric glycosides having a degree of oligomerization to preferably about 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

Farther can as emulsifiers zwitterionic surfactants are used. As zwitterionic Surfactants become such surface active Compounds referred to in the molecule at least one quaternary ammonium group and at least one carboxylate and / or sulfonate group. Particularly suitable zwitterionic surfactants are the so-called Betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example, the Kokosacylaminopropyldimethylammoniumglycinat, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines with in each case 8 to 18 C atoms in the alkyl or acyl group as well as cocoacylaminoethylhydroxyethylcarboxymethylglycinate.

Particularly preferred is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are to be understood as meaning those surface-active compounds which, apart from a C ₈ to C ₁₈ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH and / or -SO 3 H group and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C _{1 2} to C ₁₈ acyl sarcosine.

Next the ampholytic also includes quaternary emulsifiers, where those of the esterquat type, preferably methylquaternated Difatty acid triethanolamine ester salts, are particularly preferred.

perfume oils

Optionally, the shampoos and hair care compositions of the invention may contain perfume oils. As perfume oils, for example, mixtures of natural and synthetic fragrances may be mentioned. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Orange), Roots (Macis, Angelica, Celery, Cardamom, Costus, Iris, Calmus), Woods (Pine, Sandal, Guajac, Cedar, Rosewood), Herbs and Grasses (Tarragon, Lemongrass, Sage, Thyme), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, 4-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonate, to the ketones such as the ionones, cc-isomethyl ions and Methylcedrylketon to the alcohols Anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terioneol, the hydrocarbons mainly include the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene ^® Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclover-hexyl cinnamic aldehyde α tal, lavandin , muscatel sage oil, geranium oil bourbon, cyclohexyl salicylate, Vertofix ^® Coeur, Iso-e-Super ^®, Fixolide ^® NP, Evernyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat-damascone β alone or in mixtures used.

pigments

Possibly contain the shampoos of the invention and hair products continue to pigments.

The Pigments are present in the product mass in undissolved form and can in in an amount of from 0.01 to 25% by weight, more preferably from 5 to Be contained 15 wt .-%. The preferred particle size is 1 to 200 μm, in particular 3 to 150 μm, more preferably 10 to 100 microns. The pigments are practically insoluble colorants in the application medium and can be inorganic or organic. Also inorganic-organic mixed pigments are possible. Preference is given to inorganic pigments. The advantage of inorganic Pigments is their excellent light, weather and temperature resistance. The inorganic pigments can natural Origin, for example, made of chalk, ocher, umber, green earth, calcined Terra di Siena or graphite. The pigments can be white pigments such as. Titanium dioxide or zinc oxide to form black pigments, e.g. Iron oxide black, colored pigments such as e.g. Ultramarine or iron oxide red, luster pigments, metallic effect pigments, pearlescent pigments, as well as Fluorescent or Phosphoreszenzpigmente act, preferably at least one pigment is a colored, non-white pigment.

Suitable are metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulphurous silicates, metal sulphides, complex metal cyanides, Metal sulfates, chromates and molybdate and the metals themselves (bronze pigments). Titanium dioxide (CI 77891), black iron oxide are particularly suitable (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (C177289), iron blue (Fen-ic ferro-cyanide, CI7751 0), Carmine (Cochineal).

Particular preference is given to pearlescent and color pigments based on mica or mica which are coated with a metal oxide or a metal oxychloride such as titanium dioxide or bismuth oxychloride and optionally further coloring substances such as iron oxides, iron blue, ultramarines, carmines, etc., and the color is determined by varying the layer thickness can be. Such pigments are sold, for example under the trade names Rona ^®, Colorona ^®, Dichrona and Timiron ^{® ®} (Merck).

organic Pigments are, for example, the natural pigments sepia, cambogia, Bone charcoal, Kasseler brown, indigo, chlorophyll and other plant pigments. Synthetic organic pigments are, for example, azo pigments, Anthraquinoids, indigoids, dioxazine, quinacridone, phthalocyanine, Isoindolinone, Perylene and Perinone, Metal Complex, Alkali Blue and diketopyrrolopyrrole pigments.

In an embodiment contains the erfindungsmäße composition 0.01 to 10, more preferably from 0.05 to 5 wt .-% of at least a particulate Material. Suitable substances are e.g. Substances at room temperature (25 ° C) are and in the form of particles. Suitable are, for example, silica, Silicates, aluminates, clays, mica, salts, especially inorganic Metal salts, metal oxides, e.g. Titanium dioxide, minerals and polymer particles.

The Particles are in the means undissolved, preferably stably dispersed Form before and can after application to the surface of the application and evaporation of the solvent deposit in solid form.

preferred particulate Substances are silica (silica gel, silica) and metal salts, in particular inorganic metal salts, with silica being particularly preferred is. Metal salts are e.g. Alkali or alkaline earth halides such as Sodium chloride or potassium chloride; Alkali or alkaline earth sulfates such as sodium sulfate or magnesium sulfate.

polymers

The Compositions of the invention can continue additional Contain polymers.

Suitable polymers are, for example, cationic polymers having the INCI name Polyquaternium, eg copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^® FC, Luviquat ^® HM, Luviquat ^® MS, Luviquat ^® Care, Luviquat ^® Ultra Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate quaternized with diethyl sulfate (Luviquat ^® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat Hold ^®); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamido copolymers (Polyquaternium-7) and chitosan. Suitable cationic (quaternized) polymers are also Merquat ^® (polymer based on dimethyldiallylammonium chloride), Gafquat ^® (quaternary polymers are formed by reacting polyvinylpyrrolidone with quaternary ammonium compounds), Polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers based on plants, For example, guar polymers, such as the Jaguar ^® brands Fa. Rhodia.

Other suitable polymers are also neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate and / or stearyl (meth) acrylate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their Salts, cellulose derivatives, polyaspartic acid salts and derivatives. These included a Luviflex® ^® Swing (partially hydrolyzed copolymer of polyvinyl acetate and polyethylene glycol, Messrs. BASF) or Kollicoat ^® IR.

suitable Polymers are also those described in WO 03/092640, in particular as Examples 1 to 50 (Table 1, page 40 et seq.) and Examples 51 to 65 (Table 2, page 43) described (meth) Acrylsäureamidcopolymere, to the full extent at this point Reference is made.

Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinylcaprolactam, for example, Luviskol ^® Plus (BASF), or polyvinyl pyrrolidone and their copolymers, in particular with Vinylestern such as vinyl acetate, for example, Luviskol ^® VA 37 (BASF); Polyamides, for example based on itaconic acid and aliphatic diamines, as described, for example, in DE-A-43 33 238.

Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer ^® (National Starch) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers, as described for example in German patent applications DE 39 29 973 . DE 21 50 557 . DE 28 17 369 and DE 37 08 451 are disclosed. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are available under the name Amersette® ^® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon ^®).

Suitable polymers are also nonionic, siloxane-containing, water soluble or dispersible polymers, for example, polyether siloxanes, such as Tegopren ^® (Fa. Goldschmidt) or Belsil ^® (Fa. Wacker).

Also suitable are also biopolymers, i. Polymers made from naturally renewable Raw materials are obtained and built from natural monomer building blocks are, e.g. Cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.

Further preparations according to the invention contain at least one other water-soluble polymer, in particular Chitosans (poly (D-glucosamine)) of various molecular weights and / or chitosan derivatives.

Anionic polymers

Further for the preparations according to the invention suitable polymers are carboxylic acid group-containing Copolymers. These are polyelectrolytes with a larger number anionic dissociable groups in the main chain and / or a Side chain. You are capable with the copolymers A) to form polyelectrolyte complexes (symplexes).

In a preferred embodiment have the in the inventive compositions used polyelectrolyte complexes an excess of anionogenic / anionic Groups on.

The Polyelectrolyte complexes include in addition to at least one of the above mentioned copolymers A) also at least one acid group-containing polymer.

The Polyelectrolyte complexes preferably contain copolymers) A) and Containing acid groups Polymers in a weight ratio of about 50: 1 to 1:20, more preferably from 20: 1 to 1: 5.

Suitable carboxylic acid group-containing polymers are, for example, by free-radical polymerization α, β-ethylenically unsaturated monomers available. In this case, monomers m1) are used which contain at least one free-radically polymerizable, α, β-ethylenically unsaturated double bond and at least one anionogenic and / or anionic group per molecule.

suitable Containing carboxylic acid groups Polymers are also carboxylic acid group-containing Polyurethanes. Preferably, the monomers are selected below monoethylenically unsaturated Carboxylic acids, sulfonic acids, phosphonic acids and Mixtures thereof.

To the monomers m1) count monoethylenically unsaturated Mono- and dicarboxylic acids with 3 to 25 preferably 3 to 6 C atoms, which are also in the form of their Salts or anhydrides can be used. Examples of these are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic, citraconic, mesaconic, glutaconic, aconitic and fumaric acid. To the monomers count furthermore the half esters of monoethylenically unsaturated With dicarboxylic acids 4 to 10, preferably 4 to 6, C atoms, e.g. of maleic acid like Maleate. To the monomers count also monoethylenically unsaturated sulfonic acids and phosphonic acids, for example, vinylsulfonic acid, allylsulfonic acid, Sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and Allylphosphonic. To the monomers count also the salts of the abovementioned acids, in particular the sodium, Potassium and ammonium salts and the salts with the aforementioned ge called Amines. The monomers can used as such or as mixtures with one another. The stated proportions by weight are all based on the acid form.

Preferably the monomer m1) is selected under acrylic acid, methacrylic acid, Ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic, Citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and Mixtures thereof, particularly preferably acrylic acid, methacrylic acid and Mixtures thereof.

The aforementioned monomers m1) each used individually or in the form of any mixtures become.

in principle are suitable as comonomers for the preparation of the carboxylic acid group-containing Polymers the compounds previously mentioned as components of the copolymer A) a) to d) with the proviso, the mole fraction of anionogenic and anionic groups containing the Carboxylic acid group-containing Contains copolymerized polymer, is larger as the mole fraction of cationogenic and cationic groups.

In a preferred embodiment contain the carboxylic acid group-containing Polymers copolymerized at least one monomer which is selected among the aforementioned crosslinkers d). On suitable and preferred Crosslinker d) is referred to.

R¹ für Wasserstoff oder C₁-C₈-Alkyl steht,
Y¹ für O, NH oder NR³ steht, und
R² und R³ unabhängig voneinander für C₁-C₃₀-Alkyl oder C₅-C₈-Cycloalkyl stehen, wobei die Alkylgruppen durch bis zu vier nicht benachbarte Heteroatome oder Heteroatom-haltige Gruppen, die ausgewählt sind unter O, S und NH unterbrochen sein können.The carboxylic acid-group-containing polymers furthermore preferably contain, in copolymerized form, at least one monomer m2) which is selected from compounds of the general formula (VI) embedded image in which

R ^{1 is} hydrogen or C ₁ -C ₈ -alkyl,
Y ^{1 is} O, NH or NR ³ , and
R ² and R ^{3 are} independently C ₁ -C ₃₀ alkyl or C ₅ -C ₈ cycloalkyl, wherein the alkyl groups are substituted by up to four nonadjacent heteroatoms or heteroatom-containing groups selected from O, S and NH can be interrupted.

In the formula VI, R ¹ is preferably hydrogen or C ₁ -C ₄ -alkyl, in particular hydrogen, methyl or ethyl. R ² in the formula VI is preferably C ₁ -C ₈ -alkyl, preferably methyl, ethyl, n-butyl, isobutyl, tert-butyl or a group of the formula -CH ₂ -CH ₂ -NH-C (CH _{3 3} . If R ^{3 is} alkyl, then preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, isobutyl and tert-butyl.

suitable Monomers m2) are methyl (meth) acrylate, methyl ethacrylate, ethyl (meth) acrylate, Ethyl ethacrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, Tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, Palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, Arrachinyl (meth) acrylate, behenyl (meth) acrylate, lignocerenyl (meth) acrylate, Cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl (meth) acrylate, Linolyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate, Lauryl (meth) acrylate and mixtures thereof.

suitable Monomers m2) are furthermore acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, piperidinyl (meth) acrylamide and morpholinyl (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-arrachinyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-lignocerenyl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl (meth) acrylamide, N-palmitoleinyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide and N-lauryl (meth) acrylamide.

worin
die Reihenfolge der Alkylenoxideinheiten beliebig ist,
k und 1 unabhängig voneinander für eine ganze Zahl von 0 bis 1000 stehen, wobei die Summe aus k und l mindestens 5 beträgt,
R⁴ für Wasserstoff, C₁-C₃₀-Alkyl oder C₅-C₈-Cycloalkyl steht,
R⁵ für Wasserstoff oder C₁-C₈-Alkyl steht,
Y² für O oder NR⁶ steht, wobei R⁶ für Wasserstoff, C₁-C₃₀-Alkyl oder C₅-C₈-Cycloalkyl steht.Furthermore, the polymers containing carboxylic acid groups preferably contain, in copolymerized form, at least one monomer m3) which is selected from compounds of the general formula VII

wherein
the order of the alkylene oxide units is arbitrary,
k and 1 independently of one another represent an integer from 0 to 1000, the sum of k and l being at least 5,
R ^{4 is} hydrogen, C ₁ -C ₃₀ -alkyl or C ₅ -C ₈ -cycloalkyl,
R ^{5 is} hydrogen or C ₁ -C ₈ -alkyl,
Y ^{2 is} O or NR ⁶ , wherein R ^{6 is} hydrogen, C ₁ -C ₃₀ alkyl or C ₅ -C ₈ cycloalkyl.

In formula VII, k is preferably an integer from 1 to 500, in particular from 3 to 250. Preferably, l is an integer from 0 to 100. R ⁵ is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular for hydrogen, methyl or ethyl. In the formula VII, R ⁴ is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl , Preferably, Y ² in formula VII is O or NH.

Suitable polyether acrylates VII) are, for example, the polycondensation products of the abovementioned α, β-ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols. Suitable polyetherols can be readily prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule such as water or a short-chain alcohol R ⁴ -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates VII) can be used alone or in mixtures for the preparation of the polymers used according to the invention. Suitable polyether acrylates II) are also urethane (meth) acrylates with alkylene oxide groups. Such compounds are in the DE 198 38 851 (Component e2)), which is incorporated herein by reference.

Examples of anionic polymers which are preferred as carboxylic acid-containing polymers are, for example, homo- and copolymers of acrylic acid and methacrylic acid and salts thereof. These include crosslinked polymers of acrylic acid, such as those available under the INCI name Carbomer. Such crosslinked homopolymers of acrylic acid are available commercially for example under the name Carbopol ^® by the company Noveon. Also hydrophobically modified crosslinked polyacrylate polymers such as Carbopol ^® Ultrez 21 are preferably from Noveon.

Further examples of suitable anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes and polyureas. Particularly suitable polymers are copolymers of (meth) acrylic acid and polyether acrylates, wherein the polyether chain is terminated with a C ₈ -C ₃₀ -alkyl radical. These include, for example, acrylate / beheneth-25-methacrylate copolymers, which are available under the name Aculyn ^® from Rohm and Haas. Particularly suitable polymers are also copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example, Luvimer ^® 100P, Luvimer ^® Pro55), copolymers of ethyl acrylate and methacrylic acid (eg Luviumer ^® MAE), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid ( Ultrahold ^® 8, Ultrahold ^® Strong), copolymers of vinyl acetate, crotonic acid and, if appropriate further Vinylester (eg Luviset ^® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, for example carboxy, t-butyl acrylate, methacrylic acid (for example, Luviskol ^® VBM) , Copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as C ₄ -C ₃₀ alkyl esters of meth (acrylic acid), C ₄ -C ₃₀ alkyl vinyl esters, C ₄ -C ₃₀ alkyl vinyl ethers and hyaluronic acid. Examples of anionic polymers are also vinyl acetate / crotonic acid copolymers, as are, for example, under the names Resyn ^® (National Starch) and Gafset ^® (GAF), and vinyl pyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF) , Other suitable polymers are the commercially available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymer and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyester.

Furthermore, for example, the group of suitable anionic polymers comprises Balance ^® CR (National Starch; Acrylate Copolymer), Balance ^® 0/55 (National Starch; Acrylate Copolymer), Balance ^® 47 (National Starch; octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer), Aquaflex ^® FX 64 (ISP; isobutylene / ethylmaleimide / hydroxyethylmaleimide copolymer) Aquaflex ^® SF-40 (ISP / National Starch; VP / vinyl caprolactam / DMAPA acrylates copolymer), Alliance ^® LT-120 (ISP / Rohm &Haas; acrylate / C1-2 succinate / hydroxyacrylate copolymer), Aquarez ^® HS (Eastman, polyester-1), and ^® Diaformer Z-400 (Clariant; methacryloylethylbetaine / methacrylate copolymer), ^® Diaformer Z-711 (Clariant; methacryloylethyl N-oxide / methacrylate copolymer), Diaformer ^® Z-712 (Clariant; methacryloylethyl N-oxide / methacrylate copolymer), Omnirez ^® 2000 (ISP; monoethyl ester of poly (methyl vinyl ether / maleic acid in ethanol), Amphomer ^® HC (National Starch; acrylate / octylacrylamide copolymer ) Amphomer.RTM ^® 28-4910 (National Starch; octyl-acrylamide / acrylate / butylaminoethyl methacrylate copolymer), Advantage ^® HC 37 (ISP; Terpolymer of vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate), Advantage ^® LC55 and LC80 or LC A and LC E, Advantage ^® Plus (ISP; VA / Butyl Maleate / Isobornyl Acrylate Copolymer), Aculyne ^® 258 (Rohm &Haas; acrylate / Hydroxyesteracrylat copolymer ), Luviset ^® PUR (BASF, polyurethane-1), Luviflex ^® Silk (BASF), Eastman ^® AQ 48 (Eastman), Styleze ^® CC-10 (ISP, VP / DMAPA Acrylates copolymer), Styleze ^® 2000 (ISP; VP / Acrylates / lauryl Methacrylate copolymer), DynamX ^® (National Starch; Polyurethane-14 AMP-Acrylates copolymer), Resyn XP ^® (National Starch; Acrylates / octylacrylamide copolymer), Fixomer ^® A-30 (Ondeo Nalco, polymethacrylic acid (and) acrylamidomethylpropanesulfonic ), Fixate G-100 ^® (Noveon; AMP-Acrylates / allyl Methacrylate copolymer).

Suitable carboxylic acid group-containing polymers are also those in the US 3,405,084 described terpolymers of vinyl pyrrolidone, C ₁ -C ₁₀ alkyl cycloalkyl and A ryl (meth) acrylates and acrylic acid. Suitable polymers containing carboxylic acid groups are furthermore the terpolymers of vinylpyrrolidone, tert-butyl (meth) acrylate and (meth) acrylic acid described in EP-A-0 257 444 and EP-A-0 480 280. Suitable polymers containing carboxylic acid groups are furthermore the copolymers described in DE-A-42 23 066, which contain at least one (meth) acrylic ester, (meth) acrylic acid and also N-vinylpyrrolidone and / or N-vinylcaprolactam in copolymerized form. The disclosure of these documents is hereby incorporated by reference.

The Preparation of the aforementioned carboxylic acid group-containing polymers takes place by known methods, for example the solution, precipitation, Suspension or emulsion polymerization as before for the copolymers A).

suitable Carboxylic acid group-containing Polymers are also carboxylic acid group-containing Polyurethanes.

The EP-A-636361 discloses suitable block copolymers with polysiloxane blocks and Polyurethane / polyurea, the carboxylic acid and / or sulfonic acid groups exhibit. Suitable silicone-containing polyurethanes are also in the WO 97/25021 and EP-A-751 162.

suitable Polyurethanes are also described in DE-A-42 25 045, whereupon is hereby fully incorporated by reference.

The acid groups of the carboxylic acid group-containing polymers may be partially or completely neutralized. Then at least a part of the acid groups is present in deprotonated form, the counterions are preferably selected from alkali metal ions, such as Na ⁺ , K ⁺ , ammonium ions and their organic derivatives, etc.

Shampoo Types

At Shampoos are given according to hair quality or scalp problem additional Requirements made. The mode of action of the preferred shampoo types with the main additional Effects or main special objectives will be discussed below described.

According to the invention preferred are shampoos for example normal or fast greasy or damaged hair, antidandruff shampoos, Baby shampoos and 2-in-1 shampoos (Shampoo and conditioner in one).

shampoos for normal Hair: the hair wash is to hair and scalp of the skin fat formed in sebaceous glands, the from sweat glands waterborne inorganic salts, amino acids, urea and lactic acid, shed skin particles, environmental dirt, odors and possibly residues hair-cosmetic Get rid of treatments. Normal hair means short to shoulder-length hair, which only weakly damaged is. Accordingly, the proportion of Kondi tionierhilfsstoffen be optimized for this hair type.

shampoos for fast greasy hair: an elevated Fat production of the sebaceous glands the scalp is already leading 1-2 days after shampooing to a stringy, unsightly hairstyle. Oil- and waxy skin fat ingredients complain the hair and degrade the friction from hair to hair and thus reduce the hairstyle hold. The actual hair cosmetic problem with fast greasy hair is therefore the premature coincidence of voluminous hairstyles. To avoid this, One must prevent the hair surface from being weighted and too smooth and becomes supple. This is preferred by the surfactant base from well-cleansing and especially less substantive washing raw materials reached. additional Nursing agents that would add to skin fat, such as lipids or Also conditioning excipients, are used in shampoos for fast Greasy hair is not used or used with great care. Volume giving shampoos for fine Hair can be formulated comparably.

shampoos for dry, damaged (damaged) Hair. The structure of the hair gets through in the course of hair growth mechanical influences like combing, to brush and above all Toupieren (combing against the direction of growth), by the action of UV radiation or visible light and through cosmetic treatments, such as perms, bleaching or coloring changed. The cuticle of the hair points from root to tip an increasingly strained appearance; in extreme cases she completely at the top worn, and the hair tips are split (hair splitting). Damaged hair can basically no longer be attributed to the state of healthy hair growth. But it succeeds, this ideal condition in terms of grip, shine and combing by using shampoos according to the invention with, if appropriate high levels of nourishing substances (conditioners) very to get close.

A even better effect than with a shampoo with a hair care composition according to the invention for example in the form of a flushing or spa treatment after shampooing achieved.

2-in-1 according to the invention Shampoos are particularly strong nourishing shampoos, by which the conception as "shampoo and conditioner in one "the added benefit Care equivalent is placed next to the basic cleaning benefits. 2-in-1 compositions according to the invention contain increased Quantities of conditioning agents.

Anti-dandruff shampoos: Anti-dandruff shampoos according to the invention have the advantage over antidandruff hairs that they not only by appropriate agents against dandruff the Reduce formation of new visible dandruff and long-term Prevent application, but with the Haanväsche already abgeschilferte Remove dandruff. After rinsing the wash liquor remains However, only a small, but sufficient proportion of the active ingredients on scalp and hair back. There are several anti-dandruff agents that are useful in the shampoo compositions of the present invention can be incorporated such as Zinc pyrithione, ketoconazole, clotrimazole, climbazole or Piroctone Olamin. additionally these substances have a normalizing the Abschilferung effect on.

The Base of antidandruff shampoos largely corresponds to the formulation of shampoos for normal hair with good cleansing effect.

Baby shampoos: in a preferred embodiment The invention relates to the shampoo preparations according to the invention to baby shampoos. These are optimally skin and mucous membrane compatible. combinations from wash raw materials with very good skin compatibility form the basis these shampoos. additional Substances to further improve skin and mucous membrane compatibility and the care properties are advantageously added, such as z. As nonionic surfactants, protein hydrolysates and panthenol or Bisabolol. All necessary raw materials and auxiliary substances, such as preservatives, Perfume oils, dyes, etc., will be selected in terms of high compatibility and mildness.

shampoos for dry Scalp: in a further preferred embodiment of the invention acts it is the shampoo preparations according to the invention for shampoos for dry scalp. The primary The aim of these shampoos is to prevent dehydration of the scalp, because dry scalp can cause itching, redness and inflammation. As with the baby shampoos form combinations of washing raw materials with very good skin compatibility the base of these shampoos. additionally can if necessary, moisturizer and humectants, such as. As glycerol or urea used become. Because of the surprising rehydrating and humectant action of copolymer a), optionally is present mixed with oligomer b), is the addition of further Rückfettern and humectants are not mandatory, but can be more bring about beneficial effects.

The shampoo compositions according to the invention can also as shampoo concentrates with increased surfactant contents of 20-30% available. They are based on special washing raw material combinations and consistency regulators, which are the good dispersibility and the spontaneous Foaming power too ensure a small application amount. A special advantage is for example the possibility the fertility of 200 ml of shampoo with a 100 ml bottle too to reach.

administration

It is advantageous if the efindungsgemäße cosmetic compositions stored in a bottle or squeeze bottle and out of it be applied. As a result, bottles or squeeze bottles, which is a composition according to the invention contained, according to the invention.

The Invention is illustrated by examples.

All Reactions were - if not stated otherwise - under an atmosphere carried out by nitrogen.

The K values of the copolymers according to the invention were after H. Fikentscher, Cellulose Chemistry, Volume 13, 58-64 and 761-774 (1932) in cyclohexanone at 25 ° C and a polymer concentration determined by 2 wt .-%.

Preparation instructions for copolymer a)

206 g of polyisobutene having a molecular weight M _n of 550 g / mol and 185 g of diisobutene (mixture of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene in a molar ratio of 80:20 , determined by ¹ H-NMR spectroscopy) were placed in a 4-liter kettle and heated to 110 ° C in a gentle stream of nitrogen. After reaching the temperature of 110 ° C was within 5 hours 184 g of maleic anhydride in liquid form as a melt of about 70 ° C and within 5.5 hours 5.5 g Tert.-Butylperoctoat, dissolved in 25 g of diisobutene (mixture from 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene). Subsequently, one hour at 120 ° C was reheated. Thereafter, the temperature was raised to 160 ° C and distilled unreacted diisobutene.

The resulting reaction mixture was cooled to 90 ° C and simultaneously with 2400 g of water and 140 g of 50 wt .-% aqueous Sodium hydroxide added. Subsequently was 4 hours at 90 ° C touched and then cooled to room temperature. This gave copolymer a) in the form of an aqueous Dispersion having a pH of 6.5 and a water content of 80 wt .-% had. The K value was 14.7.

Mixing of copolymer a) and oligomer b)

Mixture 1:

A first mixture of copolymer a) with oligomer b) was prepared by mixing 90 g of polyisobutene (oligomer b)) having a molecular weight M _n of 550 g / mol with 10 g of the above-described dispersion of copolymer a) by stirring in a Beaker mixed.

Mix 2:

A second mixture of copolymer a) with oligomer b) was prepared by mixing 90 g of polyisobutene (oligomer b)) having a molecular weight M _n of 1000 g / mol with 10 g of the above-described dispersion of copolymer a) by stirring in one Beaker mixed.

you got so two for the use according to the invention suitable mixtures of copolymer a) and oligomer b).

Application examples:

With the above-described mixtures 1 and / or 2 are described below prepared compositions. The quantities are each in% by weight, unless otherwise stated.

The in the tables amount of mixture 1 and mixture is 2 in each case the amount of copolymer a), ie without other components. The corresponding amount of oligomer b) is not in the tables indicated, leaves but simply calculate from the compositions of the mixtures.

Examples A1-A5: Clear shampoos

Examples A6-A10: Clear conditioner shampoos

A11-A17 shampoos

A18-A20 conditioner shampoos with pearlescent

• pH adjusted to 6.0

A21-A23 Clear Conditioner Shampoos

• pH adjusted to 6.0

A24-A26 clear light shampoos with volume effect

• pH adjusted to 5.5

Claims (14)

Use of a) copolymers obtainable by copolymerization of (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms, (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alkene, wherein at least one oligomer has an average molecular weight M _n in the range from 300 to 5000 g / mol, preferably up to 1200 g / mol, or obtainable by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ -alkene, (C) optionally at least one α-olefin having up to 24, preferably having up to 16 carbon atoms, (D) optionally at least one other of ethylenically unsaturated comonomer other than (A), (B) and (C), optionally reacting with (E) at least one compound of the general formula Ia, Ib, Ic or Id

wherein A ¹ C ₂ -C ₂₀ alkylene, identical or different, R ¹ C ₁ -C ₃₀ alkyl, linear or branched, phenyl or hydrogen, n is an integer from 1 to 200, optionally followed by contacting with water, optionally mixed with b) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alken, wherein at least one oligomer has an average molecular weight M _n in the range of 300 to 5000 g / mol, preferably up to 1200 g / mol or by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ -alkene is available, in shampoos and hair products. Use according to claim 1, wherein oligomer (B) is a branched C ₄ -C ₁₀ olefin oligomer. Use according to one of claims 1 or 2, wherein oligomer (B) is polyisobutene. Use according to any one of claims 1 to 3, wherein the at least an ethylenically unsaturated dicarboxylic anhydride (A) maleic anhydride is. Use according to any one of claims 1 to 4, wherein the at least an α-olefin (C) selected is made of isobutene, diisobutene and 1-dodecene. Use according to one of claims 1 to 5, wherein the at least one further ethylenically unsaturated comonomer (D) is selected from ethylenically unsaturated C ₃ -C ₈ -carboxylic acids and carboxylic acid derivatives of the general formula II

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IV a or cyclic amides of the general formula IV b

C 1 -C 20 -alkyl vinyl ethers, N-vinyl derivatives of nitrogen-containing aromatic compounds, α, β-unsaturated nitriles, alkoxylated unsaturated ethers of the general formula V

Esters or amides of the general formula VI

unsaturated esters of the general formula VII

vinyl aromatic compounds of the formula VIII

Phosphorus, phosphonate, sulfate and sulfonate group-containing comonomers, α-olefins having 18 to 40 carbon atoms, wherein in the general formulas the variables are defined as follows: R ² , R ^{3 are} identical or different and selected from hydrogen, straight-chain or branched C ₁ -C ₅ -alkyl and COOR ⁴ , R ^{4 are} identical or different and selected from hydrogen or C ₁ -C ₂₂ -alkyl, branched or unbranched, R ^{5 is} hydrogen or methyl, x is an integer in the range from 2 to 6, y is an integer selected from 0 or 1, a is an integer in the range of 0 to 6, R ⁶ , R ^{7 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, X Oxygen or NR ⁴ R ⁸ [A ³ -O] _n -R ⁴ , R ^{9 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, R ¹⁰ , R ^{11 are} independently hydrogen, methyl or ethyl , R ^{12 is} selected from methyl and ethyl, k is an integer in the range of 0 to 2, A ² , A ³ C ₂ C ₂₀ alkylene A ⁴ C ₁ -C ₂₀ alkylene or a single bond and the other variables are as defined above. Use according to any one of claims 1 to 6, wherein the copolymer (a) available is by copolymerization of (A) in the range of 5 to 60 Mol% (A), (B) in the range of 1 to 95 mol% (B), (C) in the range of 0 to 60, preferably 10 to 55 mol% (C), (D) in the range of 0 to 70 mol%, in each case based on copolymer, wherein the sum of (A), (B), (C) and (D) gives 100 mol%, and Implementation with (E) in the range of 0 to 50 mol%, based on all carboxyl groups of the copolymer. Use according to any one of claims 1 to 7, wherein the weight ratio is oligomer b) to copolymer a) in the range from 0.1: 1 to 100: 1, preferably from 0.5: 1 to 10: 1. Use according to any one of claims 1 to 8, wherein oligomer (b) is polyisobutene. Shampoos and hair care products containing a copolymer a) optionally mixed with an oligomer b) as in one of claims 1 to 9 defined. Shampoos and hair-care preparations according to claim 10, containing further at least one oil and / or fat component. Shampoos and hair care preparations according to one of claims 10 or 11, further containing at least one surfactant. Shampoos and hair care preparations according to one of claims 10 to 12, further comprising at least one conditioning agent. Hair care product according to one of the claims to 10 to 13, wherein the hair care agent is selected from the group consisting from pretreatment agents, hair conditioners, hair conditioners, hair balms, leave-on hair treatments, rinse-often hair conditioners, Hair tonics, Pomades, Hairdressing creams, Hairdressing lotions, Hairdressing gels, Lace fluids, Hot oil treatments and foam treatments.