DE102005015632A1 - Use of polyisobutene-containing copolymers in light stabilizers - Google Patents

Abstract

The present invention relates to the use of copolymers obtainable by copolymerization of at least one ethylenically unsaturated dicarboxylic 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 cosmetic or dermatological sunscreens with a sun protection factor (SPF) of at least 4.

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 kosmetischen oder dermatologischen Lichtschutzmitteln mit einem Lichtschutzfaktor (LSF) von wenigstens 4.

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 -alkene, in cosmetic or dermatological light stabilizers with a sun protection factor (SPF) of at least 4.

Farther the present invention relates to cosmetic compositions, selected from the group of cosmetic and dermatological sunscreens with a sun protection factor (SPF) of at least 4, comprising Copolymer a), optionally mixed with an oligomer b, as described above.

Under Cosmetic or dermatological sunscreens are included of this invention cosmetic or dermatological compositions understood, the at least one, preferably several UV filter substances contain.

Of the Term UV filter substance is known in the art and designated Substances or compositions that are cosmetic or dermatological Added funds for the purpose be to filter UV rays to protect the skin from certain Protect the effects of this radiation. In the narrower sense This also refers to compounds that have light with wavelengths in the Absorb UV area. Depending on the absorption spectrum, UV-A, Distinguished UV-B and UV-C filters. In general, UV filters are used fulfillment of spectral and formulation requirements as combinations used. Also pigments and micropigments (titanium dioxide, zinc oxide), the predominantly used for the aforementioned purpose are to be called UV filters.

cosmetic or dermatological compositions with a sun protection factor (LSF) of less than 4, as determined by the COLIPA method not the subject of this invention.

Compositions according to the invention can Of course also at the same time for be suitable for cosmetic and dermatological purposes. The term "cosmetic or dermatological light stabilizers "therefore also includes such compositions, the same time both cosmetic and dermatological purposes fulfill.

The The present invention relates to sunscreen compositions having an SPF of at least 4, in particular cosmetic or dermatological Light stabilizers containing at least one UV filter substance.

The cosmetic and / or dermatological sunscreen compositions of this invention serve the cosmetic and / or dermatological Sunscreen, further for the treatment and care of the skin and / or hair and as a make-up product in decorative cosmetics. To counting for example, sun creams, lotions, milks, oils, balms, gels, lip care and lipsticks, masking creams and sticks, Moisturizers, Lotions, Emulsions, Facial, Body and Body Hand creams, hair treatments and conditioners, Hair fixatives, styling gels, hair sprays, deodorant or eye wrinkle creams, Tropicals, Sunblock, Aftersun preparations. All preparations contain at least one UV filter substance.

The Ultraviolet radiation of sunlight can sometimes be harmful Effect on the skin. In addition to the acute injury (sunburn) occur Long-term damage like an elevated one Risk of developing skin cancer, excessive exposure to light from the UVB range (wavelength: 280-320 nm). Excessive influence the UVB and UVA radiation (wavelength: 320-400 nm) leads beyond to a weakening the elastic and collagen fibers of the connective tissue. This leads to numerous phototoxic and photoallergic reactions and has a premature Skin aging results. To protect the skin were therefore a number developed by sunscreen filter substances used in cosmetic Compositions can be used. These UVA and UVB filters are in most industrialized countries in the form of positive lists such as Annex 7 of the Cosmetics Regulation summarized.

Around estimate the effectiveness of the sunscreen filters for the skin can, In the 50s, the sun protection factor (LSF or LF) or Sun protection factor (SF, sun protection factor SPF) from Schulze introduced.

When UV light protection filters serve both inorganic pigments and the like Example titanium dioxide as well as organic compounds, mostly aromatic Substances with a pronounced π-electron system.

Sunscreens is available in different embodiments. Particularly popular are waterproof products, in which the filter substances on contact of the skin and / or the hair with water not immediately be washed off. This washes off by the presence of others Substances in the sunscreen reduced or suppressed. From The advantage is the formulation of the UV light protection filter in hydrophobic Application forms such as oils, emulsions, lipogels, Fat / wax-based pastes and / or incorporation of hydrophobic additions such as silicone derivatives or alkylated polyvinylpyrrolidone.

• a) Verwendung hydrophober Anwendungsformen wie Ölen, Emulsionen, Lipogelen, Pasten auf Fett/Wachsbasis oder
• b) Einarbeitung hydrophober Zusätze wie Silikonderivate oder alkyliertem Polyvinylpyrrolidon.

Cosmetic or dermatological light stabilizers should have the desired protective effect after the application to the target surface, for example the skin, during or after contacting the surface with, for example, water. Such water-repellent or water-resistant sunscreens are often referred to as "waterproof." The production of such products is made possible by

• a) Use of hydrophobic application forms such as oils, emulsions, lipogels, pastes based on fat / wax or
• b) incorporation of hydrophobic additives such as silicone derivatives or alkylated polyvinylpyrrolidone.

Of the Disadvantage of a large number of these products is that these products frequently feel greasy, no pleasant feeling on the skin convey and are sticky, so that for example sand extensively on the Skin sticks.

The object of the present invention was to provide cosmetic or dermatological light stabilizers which do not have these disadvantages, ie during and after the application pleasant skin feel, high resistance to water, good protective film properties against other Noxen with low and preferably no stickiness.

solution

• 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 kosmetischen Zusammensetzungen ausgewählt aus der Gruppe der kosmetischen oder dermatologischen Lichtschutzmittel mit einem Lichtschutzfaktor (LSF) von wenigstens 4.The above object has been solved 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 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 -alkene is available,

in cosmetic compositions selected from the group of cosmetic or dermatological sunscreens having a sun protection factor (SPF) of at least 4.

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 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 where 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 VIII

Phosphat-, phosphonat-, sulfat-, und sulfonathaltige Comonomere wie beispielsweise [2-{(Meth)acryloyloxy}-ethyl]-phosphat, 2-(Meth)acrylamido-2-methyl-1-propansulfonsäure;
α-Olefine, linear oder verzweigt, mit 18 bis 40 Kohlenstoffatomen, bevorzugt mit bis 24 Kohlenstoffatomen, beispielsweise 1-Oktadecen, 1-Eicosen, α-C₂₂H₄₄, α-C₂₄H₄₈ und Gemische der vorstehend genannten α-Olefine.The 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 ) -, - (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 1:10 to 100: 1, preferably from 1: 2 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.

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.

cosmetic or dermatological light stabilizers

The The present invention relates to cosmetic compositions selected from the group of cosmetic and dermatological sunscreens containing the aforementioned components a) and optionally b).

Under Cosmetic or dermatological sunscreens are used in the context of this invention cosmetic or dermatological compositions understood, the at least one, preferably several UV filter substance contain. Cosmetic or dermatological sunscreens of this invention have a sun protection factor (SPF) of at least 4 (determined by the COLIPA method, see below).

Sun oils are usually mixtures of various oils with one or more sunscreen filters and perfume oils. The oil components are selected according to different cosmetic properties. Oils that give good fat and soft feel, such as mineral oils (eg, paraffin oils) and fatty acid triglycerides (eg, peanut oil, sesame oil, avocado oil, medium chain triglycerides) are mixed with oils that enhance dispersibility and absorption of sun oils improve the skin, reduce the stickiness and make the oil film for air and water vapor (sweat) permeable. These include branched-chain fatty acid esters (eg, isopropyl palmitate) and silicone oils (eg, dimethylsilicone). When using oils based on unsaturated fatty acids antioxidants, eg. E-tocopherol is added to prevent rancidity. Sun oils as anhydrous formulations usually contain no preservatives. Sunmilk and creams are made as oil-in-water (O / W) emulsions and as water-in-oil (W / O) emulsions. Depending on the type of emulsion, the properties of the preparations are very different: O / W emulsions are easily distributed on the skin, they are usually absorbed quickly and are almost always readily washable with water. W / O emulsions are harder to rub in, they make the skin stronger and thus look a bit stickier, but on the other hand they better protect the skin from drying out. W / O emulsions are mostly waterproof. In the case of O / W emulsions, the emulsion base, the selection of suitable light stabilizers and, if appropriate, the use of auxiliaries (eg polymers) determine the degree of water resistance. The bases of liquid and cream-like O / W emulsions are similar in composition to other emulsions customary in skin care. Sunmilk should sufficiently grease the skin dried up by sun, water and wind. They must not be sticky, as this is particularly uncomfortable in the heat and in contact with sand.

The Sunscreens are usually based on a carrier that at least one oil phase contains. However, compositions based on water are also possible. Accordingly, oils, oil-in-water and water-in-oil emulsions, creams and pastes, lip balm sticks or fat free gels.

When Emulsions come i.a. also O / W macroemulsions, O / W microemulsions or O / W / O emulsions having surface-coated in dispersed form Titanium dioxide particles in question, wherein the emulsions by phase inversion technology, according to DE-A-197 26 121 available are.

Usual cosmetic Excipients, as additives can be considered are e.g. (Co) emulsifiers, fats and waxes, stabilizers, thickeners, biogenic agents, film formers, fragrances, dyes, pearlescing agents, Preservatives, pigments, electrolytes (e.g., magnesium sulfate) and pH regulators.

When Stabilizers can Metal salts of fatty acids such as. Magnesium, aluminum and / or Zinc stearate can be used.

Under Biogenic agents are, for example, plant extracts, protein hydrolysates and vitamin complexes.

common Film formers are, for example, hydrocolloids such as chitosan, microcrystalline Chitosan or quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, Polymers of the acrylic acid series, quaternary Cellulose derivatives and the like Links.

SPF (SPF) and COLIPA method

SPF (SPF)

The determination of the sun protection factor (SPF) - also abbreviated to SPF (Sun Protection Factor) - takes place in Europe according to the COLIPA standard of the European Cosmetic, Toiletry and Perfumery Association. It describes the protection of sunscreen products against UVB rays. These are major causes of sunburn. In addition, they have immunosuppressive and cell-damaging effects that lead to chronic stress on the onset of skin cancer (basalioma, spinalioma). Various UV filters or UV filter systems / combinations are used to achieve optimum protection performance. If one determines the minimum erythema dose (MED), that is, the amount of UVB radiation that induces a redness (erythema) that is just recognizable, the LSF results according to the following formula:

The test procedure begins with the determination of the individual UV sensitivity of the subjects by the irradiation of unprotected skin areas on the back. Irradiation sources are solar simulators, usually equipped with xenon lamps: they provide a sun-like radiation in their spectrum, but of higher intensity and thus shorter irradiation times possible. About 20 hours after the irradiation with different intensity, the MED _{u will} be visually evaluated for erythema in six skin determined areas.

to actual LSF determination will again test areas on the back of the subject for the to be applied Sunscreens marked. Each of these product areas will have an adjacent control area faced with untreated skin.

The intensity of irradiation is determined according to the sensitivity of the skin and the expected sun protection factor. After about 20 hours, MED _u and MED _{g are} visually determined. The resulting sun protection factors indicate the mean extension of the individual time to onset of erythema achieved by the application of the sunscreen preparation.

The COLIPA method is the one known in the art since 1997 throughout Europe valid Method for determining the sun protection factor (UVB protection) of sunscreen products. The test procedure is standardized and standardized: the irradiation spectrum and the output of the for the exam provided solar simulator are defined exactly. In addition are the order quantity and the type of product application specified. The test method is independent of the skin type and age of the test persons. With these precise specifications the COLIPA method can according to appropriate statistics with only ten subjects passed the exam be carried out by sunscreen products. The COLIPA method is a process that produces reproducible results with high reliability supplies.

UV filters

The Compositions of the invention contain oil-soluble and / or water-soluble UVA and / or UVB filters.

Advantageous The sunscreen compositions contain substances that UV radiation in the UVB range and substances that absorb UV radiation in the UVA range, wherein the total amount of filter substances e.g. 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1 to 15 wt .-%, based on the total weight of the compositions to cosmetic compositions to disposal to put the skin in front of the whole area of the ultraviolet Protect radiation.

Of the biggest part the sunscreen in protecting the human epidermis serving cosmetic or dermatological compositions from compounds that absorb UV light in the UV-B range. For example is the proportion of the invention to be used UV-A absorber 10 to 90 wt .-%, preferably 20 to 50 wt .-% relative on the total amount of UV-B and UV-A absorbing substances.

• – Benzimidazolsulfonsäure-Derivate wie z.B. 2-Phenylbenzimidazol-5-sulfonsäure und deren Salze
• – Benzotriazol-Derivate wie z.B. 2,2'-Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol)
• – 4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2-ethylhexyl)ester, 4-(Di-methy1amino)benzoesäureamylester;
• – Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethylhexyl)ester;
• – Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester, 4-Methoxyzimtsäureisopentylester;
• – Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methyl benzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon;
• – Methylidencampherderivate, vorzugsweise 4-Methylbenzylidencampher, Benzyl idencampher;
• – Triazinderivate, vorzugsweise 4,4',4''-(1,3,5-Triazin-2,4,6-triylimino)-tris-benzoesäure-tris-(2-ethylhexylester) [INCI: Diethylhexyl Butamido Triazine, UVA-Sorb^® HEB (Sigma 3V)] und 2,4,6-Tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-I,3,5-triazin [INCI: Octyl Triazone, UVINUL^®T 150 (BASF)].

The UVB filters may be oil-soluble or water-soluble. Advantageous UVB filter substances are, for example:

• - Benzimidazolsulfonsäure derivatives such as 2-phenylbenzimidazole-5-sulfonic acid and salts thereof
• Benzotriazole derivatives such as 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol)
• 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 4- (dimethylamino) benzoic acid amyl ester;
• Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzalmalonate;
• Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• - Methylidencampherderivate, preferably 4-Methylbenzylidencampher, benzyl idencampher;
• Triazine derivatives, preferably 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triylimino) tris-benzoic acid tris- (2-ethylhexyl ester) [INCI: Diethylhexyl butamido triazines, UVA -Sorb ^® HEB (3V Sigma)], and 2,4,6-tris [anilino (p-carbo-2'-ethyl-1'-hexyloxy)] - I, 3,5-triazine [INCI: octyl Triazone , UVINUL ^® T 150 (BASF)].

• – Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäure,2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäure und deren Salze.

Advantageously used water-soluble UVB filter substances are, for example:

• - Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and salts thereof.

• – 1,4-Phenylendimethincamphersulfonsäurederivate wie z.B. 3,3'-(1,4-phenylendimethin)-bis-(7,7-dimethyl-2-oxobicyclo[2.2.1]-heptan-1-methamsulfonsäure und ihre Salze
• – 1,3,5-Triazinderivate wie 2,4-Bis{[(2-ethylhexyloxy)-2-hydroxy)-phenyl}-6-(4-methoxyphenyl)-I,3,5)-triazin (z.B. Tinosorb^®S (Ciba))
• – Dibenzoylmethanderivate, vorzugsweise 4-Isopropyldibenzoylmethan, 4-(tert.-Butyl)-4'-methoxydibenzoylmethan
• – Benzoxazol-Derivate, beispielsweise das 2,4-Bis-[4-[5-(1,1-dimethylpropyl)benzoxazol-2-yl]phenylimino]-6-[(2-ethylexyl)imino]-1,3,5-triazin (CAS Nr. 288254-16-0, Uvasorb^®K2A (3V Sigma))
• – Hydroxybenzophenone, beispielsweise der 2-(4'-Diethylamino-2'-hydoxybenzoyl)benzoesäurehexylester (auch: Aminobenzophenon) (Uvinul^®A Plus (BASF))

Advantageously to be used UVA filters are, for example:

• 1,4-phenylenedimethine camphorsulfonic acid derivatives such as 3,3 '- (1,4-phenylenedimethine) bis- (7,7-dimethyl-2-oxobicyclo [2.2.1] heptane-1-methamsulfonic acid and its salts
• - 1,3,5-triazine derivatives such as 2,4-bis {[(2-ethylhexyloxy) -2-hydroxy) -phenyl} -6- (4-methoxyphenyl) -I, 3,5) -triazine (Tinosorb eg ^® S (Ciba))
• - Dibenzoylmethanderivate, preferably 4-Isopropyldibenzoylmethan, 4- (tert-butyl) -4'-methoxydibenzoylmethane
• Benzoxazole derivatives, for example the 2,4-bis [4- [5- (1,1-dimethylpropyl) benzoxazol-2-yl] phenylimino] -6 - [(2-ethyllexyl) imino] -1,3, 5-triazine (CAS no. 288254-16-0, Uvasorb K2A ^® (3V Sigma))
• - Hydroxybenzophenones, for example the 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoate (also: aminobenzophenone) (Uvinul A Plus ^® (BASF))

Furthermore, according to the invention, it may be advantageous to provide compositions with further UVA and / or UVB filters, for example certain salicylic acid derivatives such as 4-isopropylbenzyl salicylate, 2-ethylhexyl salicylate, octyl salicylate, homomenthyl salicylate. The total amount of salicylic acid derivatives in the cosmetic or dermatological compositions is advantageously selected from the range of 0.1-15.0, preferably 0.3-10.0, weight percent, based on the total weight of the compositions. A weiterr according to the invention to be used advantageously sunscreen is ethylhexyl-2-cyano-3,3-diphenylacrylate (octocrylene, Uvinul ^® N 539 (BASF)).

The following table summarizes some photoprotective filters suitable for use in the compositions of the invention:
For example, UV protection filters are:

Also polymeric or polymer-bound filter substances can be used according to the invention become.

Metal oxides such as titanium dioxide or zinc oxide are widely used in sunscreens. Their effect is based essentially on reflection, scattering and absorption of harmful UV radiation and depends essentially on the primary particle size of the metal oxides. The cosmetic or dermatological compositions according to the invention may advantageously also comprise inorganic pigments based on metal oxides and / or other sparingly soluble or insoluble metal compounds selected from the group consisting of the oxides of zinc (ZnO), iron (eg Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (eg MnO), aluminum (Al ₂ O ₃ ), cerium (eg Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides. Particular preference is given to pigments based on ZnO.

The inorganic pigments can in coated form, i. that she treated superficially are. This surface treatment may be, for example, that the pigments by itself known manner, as described in DE-A-33 14 742, with a thin hydrophobic Layer are provided.

to Use in the compositions according to the invention suitable light stabilizers are those described in EP-A 1 084 696 in paragraphs To [0053] mentioned compounds, to which reference is made in full at this point is taken. For the use according to the invention suitable are all UV photoprotective filters listed in Appendix 7 (to § 3b) of the German cosmetics regulation under "ultraviolet filter for cosmetic Means "called are.

The enumeration said UV light screening filter, which in the compositions of the invention can be used is not exhaustive.

antioxidants

UV radiation can lead to photochemical reactions, with the photochemical reaction products interfering with skin metabolism. Predominantly, such photochemical reaction products are free-radical compounds, for example hydroxy radicals. Also undefined radical As a result of their high reactivity, photoproducts which form in the skin itself may show uncontrolled sequelae. But singlet oxygen, a non-radical excited state of the oxygen molecule can occur under UV irradiation, as short-lived epoxides. In order to prevent these reactions, antioxidants and / or radical scavengers may additionally be incorporated into the cosmetic or dermatological formulations.

One additional Content of antioxidants is generally preferred. According to the invention as antioxidants all for used cosmetically and / or dermatologically acceptable antioxidants become.

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, homocysteinsulfoximine, buthionine sulfones, Pe nta-, 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 benzene resin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid, nordihydroguiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its 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 d The inventively suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these drugs mentioned.

The Amount of the aforementioned antioxidants (one or more compounds) in the emulsions 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.

Oils, fats and waxes

The compositions according to the invention preferably contain oils, fats and / or waxes. Ingredients of the oil and / or fat phase of the compositions of the invention are advantageously selected from the group of lecithins and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12 to 18 C. -atoms. For example, the fatty acid triglycerides may be advantageously selected from the group of synthetic, semi-synthetic and natural oils such as 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 , Other polar oil components can be selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 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 having a chain length of 3 to 30 carbon atoms. Such ester oils can then be advantageous ge 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, such as jojoba oil.

Further can one or more oil components chosen favorably are 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 paraffin oil, squalane and squalene advantageous 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. Erfindungsgemäß vorteilhaft werden der oder die Guerbet-Alkohole gewählt aus der Gruppe, wobei
R₁ = Propyl, Butyl, Pentyl, Hexyl, Heptyl oder Octyl und
R₂ = Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl oder Tetradecyl.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.

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

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

where the silicon atoms may be substituted by 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. 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 (Octamethylcyclotetrasiloxane), 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.

However, it is also advantageous to choose silicone oils of a similar constitution to the compounds described above, whose organic side chains are derivatized, for example polyethoxylated and / or poly are propoxylated. These include, for example polysiloxane polyalkyl-polyether copolymers such as cetyl dimethicone copolyol. Advantageously, cyclomethicone (octamethylcyclotetrasiloxane) is used as the silicone oil to be used according to the invention.

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 acid 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 Oi1, 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 incorporated herein by reference.

Other ingredients

The Compositions according to the invention except the aforementioned substances optionally in cosmetics or Dermatology usual Ingredients, for example perfume, dyes, antimicrobial Substances, moisturizing Agents, complexing and sequestering agents, pearlescent agents, plant extracts, Vitamins, Active Ingredients, Preservatives, Bactericides, Pigments, the one coloring Have surfactants, thickeners, softening, moisturizing and / or moisturizing substances, or other common ingredients 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.

solvent

If the cosmetic or dermatological composition for the purposes of the present invention is a solution or emulsion or dispersion, the solvents used may be:
Water or aqueous solutions; Oils, such as triglycerides of capric or caprylic acid, but preferably castor oil; Fats, waxes and other natural and synthetic fatty substances, preferably esters of fatty acids with lower C-number alcohols, for example with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with lower C-number alkanoic acids or with fatty acids;
Alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products.

Especially Mixtures of the abovementioned solvents are used. at alcoholic solvents Water can be another ingredient.

surfactants

• – 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,
• – Carbonsäuren und Derivate, wie beispielsweise Laurinsäure, Aluminiumstearat, Magnesiumalkanolat und Zinkundecylenat, Ester-Carbonsäuren, beispielsweise Calciumstearoyllactylat, Laureth-6 Citrat und Natrium PEG-4 Lauramidcarboxylat,
• – 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 und Alkylpolyglycoside wie Laurylglucosid, Decylglycosid und Cocoglycosid.

The compositions of the invention may contain surfactants. Such surfactants are, for example:

• 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,
• Carboxylic acids and derivatives, such as, for example, lauric acid, aluminum stearate, magnesium alkoxide and zinc undecylenate, ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauramide carboxylate,
• 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 and alkyl polyglycosides, such as lauryl glucoside, decyl glycoside and cocoglycoside.

Polysorbate

Further can Polysorbates are 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.

conditioners

In a preferred embodiment In accordance with the invention, the compositions also contain conditioning agents.

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

Table 1: Advantageously used conditioners

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.

powder raw materials

One Addition of powder raw materials can generally be advantageous. Especially the use of talc is preferred.

ethoxylated Glycerol fatty acid ester

The Compositions of the invention optionally contain ethoxylated oils selected from the group of ethoxylated Glycerol fatty acid ester, especially preferred are 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 Esters, PEG-6 caprylic acid / capric acid glycerides, PEG-10 Olive Oil Glycerides, PEG-13 Sonnenblumenölglyceride, PEG-7 hydrogenated castor oil, Hydrogenated palm kernel oil glyceride PEG-6 Esters, PEG-20 corn oil glycerides, 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 palm kernel oil glycerides, PEG-35 castor oil, 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. Low ethoxylated glycerol fatty acid esters (3-12 ethylene oxide units) usually serve as reclaimers to improve the skin feel after drying, glycerol fatty acid ester with a degree of ethoxylation from about 30-50 serve as a solubilizer for nonpolar Substances such as perfume oils. Highly ethoxylated Glycerol fatty acid ester are used as thickeners. All these substances are common, that they are on the skin when used in dilution with Water a special skin feeling produce.

drugs

It has been found that a variety of active ingredients with different solubilities can be incorporated homogeneously into the compositions according to the invention. The substantivity of the active ingredients on the skin and hair is higher from the described composition than from conventional surfactant-containing cleansing formulations. According to the invention, the active ingredients (one or more compounds) can be advantageously selected from the group consisting of acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, for. B. hydrocortisone-17-valerate, vitamins of the Bund 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 Toco pheryl acetate, vitamin C and its derivatives such as ascorbyl glucoside but also niacinamide, panthenol, bisabolol, polydocanol, unsaturated fatty acids such as the essential fatty acids (commonly referred to 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 products of plant and animal origin, e.g. B. evening primrose oil, borage oil or currant seed oil, fish oils, cod liver oil but also ceramides and ceramide-like compounds, frankincense extract, green tea extract, water extract, licorice extract, witch hazel, antidandruff active ingredients (eg, selenium disulfide, zinc pyrithione, piroctone, olamine, climbazole, octopirox, polydocanol and their combinatines) complexing agents such as 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 skin aging as well as for the treatment and prophylaxis of harmful Effects of ultraviolet radiation on the skin 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 Content of catechins or trakte from plants or parts of plants, which have a content of 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, (-) - gallocatechin, (+) - epicatechin, (-) - epicatechin, (-) - epicatechin Gallate, (-) - epigallocatechin, (-) - epigallocatechin gallate.

Also, flavone and its derivatives (often collectively called "flavones") are advantageous active ingredients in the sense of the present invention and are characterized by the following basic structure (substitution positions indicated):

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

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.In nature, flavones usually occur in glycosidated form. According to the invention, the flavonoids are preferably selected from the group of substances of the general formula

where Z ₁ to Z ₇ , independently of one another, are selected from the group consisting of H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and can have 1 to 18 C atoms, and Gly is chosen from the group of mono- and oligoglycoside radicals.

wobei Z₁ bis Z₆ 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 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

wherein Z ₁ to Z _{6 are} independently selected from the group H, OH, alkoxy and hydroxy xy-, wherein the alkoxy or hydroxyalkoxy groups may be branched and unbranched and have 1 to 18 carbon atoms, and wherein Gly is selected from the group of mono- and Oligoglycosidreste.

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 individually or together represent 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. Particularly advantageous in the sense of the present invention is, the or the flavone glycosides too choose from the group α-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-mentioned and other active substances which can be used in the compositions according to the invention are described in US Pat DE 103 18 526 A1 on pages 12 to 17, to which reference is made in its entirety.

preservative

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 if, as preservatives, iodopropyl butyl carbamates, Parabens (methyl, ethyl, propyl and / or butylparaben) and / or Phenoxyethanol be used.

According to the invention or the 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.

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 Ricinusöl und/oder gehärtetes 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 C_6/22-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-PEG-alkylphosphate 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 Kohlenstoffatomen, Methylglycose und Polyolen, vorzugsweise Glycerin oder Polyglycerin sowie
• (13) Polyalkylenglykole.

In a preferred embodiment, the compositions according to the invention additionally contain emulsifiers. Suitable (co) emulsifiers are preferably known W / O emulsifiers and, in addition, also O / W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides. Typical examples of fats are glycerides; Beeswax, paraffin wax or microwaxes, optionally in combination with hydrophilic waxes, may be mentioned as waxes. Examples of suitable emulsifiers include 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 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 (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside) as well as polyglucosides (eg cellulose);
• (9) mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates 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 compositions. 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 respect to the glycoside ester, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of 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, cocoacylaminoethylaminopropionate and C ₁₂ to C ₁₈ acylsarcosine.

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 cosmetic compositions 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, hydro xycitronellal, lilial and bourgeonate, among the ketones, for example, the ionones, cc-isomethyl ions and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terioneol, the hydrocarbons include mainly 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, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene ^® Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin, clary 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 used alone or in mixtures ,

dyes

When Dyes can the for used for cosmetic purposes suitable and approved substances as described, for example, in the publication "Cosmetic Colorants" of the Dye Commission the Deutsche Forschungsgemeinschaft, published by Verlag Verlag Chemie, Weinheim, 1984, are compiled. These dyes are commonly in concentration of 0.001 to 0.1 wt .-%, based on the total Mixture, used.

pigments

In a preferred embodiment contain the compositions of the invention at least one pigment.

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 (Ferric Ferro-Cyanide, C177510), 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 one embodiment, the composition according to the invention contains from 0.01 to 10, particularly preferably from 0.05 to 5,% by weight of at least one particulate substance. Suitable substances are, for example, substances which are solid at room temperature (25 ° C) and in the form of particles. Suitable examples are silica, silicates, aluminates, clays, mica, salts, in particular inorganic metal salts, metal oxides, for example 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.

pearlizing

When Pearlescing agents 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.

thickener

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)).

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

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.

antimicrobial medium

Farther can 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'-hexamethylene-bis [5- (4-chlorophenyl) -biguanide) and TTC (3,4,4'-trichlorocarbanilide). quaternary Ammonium compounds are also suitable in principle. Also numerous fragrances have antimicrobial properties. Also a big Number of 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.

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

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), acrylamidocopolymers (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 Compositions of 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 suitable polymers for the compositions according to the invention are copolymers containing carboxylic acid groups. These are polyelectrolytes with a larger number of anionically dissociable groups in the main chain and / or a side chain. They are capable of using 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 e.g. by radical polymerization α, β-ethylenic unsaturated Monomers available. In this case, monomers m1) are used which at least one free radical polymerizable, α, β-ethylenic unsaturated Double bond and at least one anionogenic and / or anionic Group per molecule contain.

suitable Containing carboxylic acid groups Polymers are also carboxylic acid group-containing Polyurethanes.

Preferably the monomers are selected under 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 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 previously referred to as components of the copolymer A) compounds a) to d) with the proviso the mole fraction of anionogenic and anionic groups containing the Carboxylic acid group-containing Polymer polymerized contains; 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.

worin
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 Hetero atom-haltige Gruppen, die ausgewählt sind unter O, S und NH unterbrochen sein können.Furthermore, the polymers containing carboxylic acid groups preferably contain in copolymerized form at least one monomer m2) which is selected from compounds of the general formula (VI)

wherein
R ^{1 is} hydrogen or C ₁ -C ₈ -alkyl,
Y ^{1 is} O, NH or NR ³ , and
R ² and R ³ independently of one another are C ₁ -C ₃₀ -alkyl or C ₅ -C ₈ -cycloalkyl, where 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-mclissinyl (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 l 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 l 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 the formula VIIk, preference is given to an integer from 1 to 500, in particular from 3 to 250. Before Igt stands for 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 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 optionally 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 / Octylacrylamid- copolymer), Amphomer ^® 28-4910 (Nationa l 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), and ^® 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-acrylate copolymer), Resyn XP ^® (National Starch; acrylates / octylacrylamide copolymer) Fixomer ^® A-30 (Ondeo Nalco, polymethacrylic acid (and) acrylamidomethylpropanesulfonic acid), 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 aryl (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.

dosage forms the compositions of the invention

The Sunscreen preparations according to the invention can be used in liquid, pasty or solid form, for example as water-in-oil creams, oil-in-water creams and lotions, aerosol creams, gels, oils, grease sticks, powders, sprays or alcoholic-watery Lotions etc ..

Used according to the invention Gels usually contain Low C-number alcohols, e.g. Ethanol, isopropanol, 1,2-propanediol, Glycerol and water or an above-mentioned oil in the presence a thickening agent, preferably in oily-alcoholic gels Silica or an aluminum silicate, in aqueous-alcoholic or alcoholic Gels is preferably a polyacrylate.

firm Pins contain e.g. natural or synthetic waxes, fatty alcohols or fatty acid esters. Lip balm sticks and stick formulations are preferred Körperdesodorierung used.

Usual basic materials, which for the use as cosmetic sticks in the sense of the present Are suitable, are liquid oils (eg. Paraffin oils, castor oil, Isopropyl myristate), semi-solid constituents (eg petrolatum, lanolin), solid components (eg beeswax, ceresin and microcrystalline Waxes or ozokerite) and high-melting waxes (eg carnauba wax, Candelilla).

When Propellant for from aerosol containers sprayable Cosmetic and / or dermatological compositions in the sense the present invention are the usual known volatile, liquefied propellant, For example, hydrocarbons (propane, butane, isobutane) suitable, which can be used alone or mixed with each other. Also Compressed air is advantageous to use.

Of course, the expert knows that there are nontoxic propellants, which are basically for the realization of the present invention in the form of aerosol preparations However, because of harmful effects on the environment or other accompanying circumstances should be waived, especially fluorocarbons and Chlorofluorocarbons (CFCs).

cosmetic Compositions according to the present invention may also as gels, in addition to an effective content of the active ingredient according to the invention and usually used solvents, preferably water, organic thickeners, z. Gum arabic, Xanthan gum, sodium alginate, cellulose derivatives, preferably methylcellulose, Hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, Hydroxypropylmethylcellulose or inorganic thickening agents, z. As aluminum silicates such as bentonites, or a mixture of polyethylene glycol and polyethylene glycol stearate or distearate, contain. The thickener is present in the gel e.g. in a crowd between 0.1 and 30% by weight, preferably between 0.5 and 15% by weight.

Of the Total content of auxiliaries and additives can 1 to 80, preferably 6 to 40 wt .-% and the non-aqueous Proportion ("active substance") 20 to 80, preferably 30 to 70 wt .-% - related on the means - amount. The preparation of the agents can be carried out in a manner known per se, i. for example, by hot, Cold, hot-hot / cold or PIT emulsification respectively. This is a purely mechanical process, a chemical reaction does not take place.

The Invention is illustrated by examples.

1. Synthesis Code for copolymerization and partial esterification

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 Method

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.

Sonnenschutzgelcremes:

O / W sun protection formulation:

Sunscreen Hydrodispersions:

W / O sunscreen formulations

Solid-stabilized emulsions:

Sunscreen sticks

PIT sunscreen emulsions:

Claims (11)

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 alkanes, in cosmetic or dermatological light stabilizers with a sun protection factor (SPF) of at least 4. 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 is} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, R ¹⁰ , R ¹¹ independently of one another are 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 from 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. Cosmetic or dermatological sunscreen with a sun protection factor (SPF) of at least 4, comprising Copolymer a), optionally mixed with an oligomer b), as in any of the claims 1 to 9 defined. Cosmetic composition according to claim 10, comprising at least one oil and / or Fat component.