US20120207694A1

US20120207694A1 - Agent for treating keratin-containing fibers, containing a non-ionic starch modified by propylene oxide and an anionic polymer

Info

Publication number: US20120207694A1
Application number: US13/453,291
Authority: US
Inventors: Burkhard Mueller; Pamela KAFTAN; Rolf Bayersdoerfer; Matthains Schweinsberg; Rolf Roenisch; Mathias Schriefers; Carine Dogan; Thorsten Knapp; Miriam Reineking
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2009-10-22
Filing date: 2012-04-23
Publication date: 2012-08-16
Also published as: US20120328532A1; EP2490659B1; EP2490653A2; US20120213724A1; EP2490659A1; EP2490656B1; EP2490657A1; WO2011048178A1; WO2011048172A3; WO2011048175A1; WO2011048177A1; US8603447B2; EP2490653B1; US20120207692A1; EP2490656A1; WO2011048176A1; EP2490658A1; US20120207693A1; WO2011048172A2; EP2490657B1

Abstract

An agent for treating keratin-containing fibers, in particular human hair, containing, in a cosmetically acceptable carrier, (a) at least one nonionic starch modified by means of propylene oxides, and (b) at least one anionic film-forming and/or anionic setting polymer, encompassing at least one structural unit of formula (I) and at least one structural unit of formula (II), in which R⁸, R⁹, R¹⁰, R¹¹, and A³are as defined in claim 1; use of the agents for the temporary deformation of hair and for hair care, in particular as an aerosol hair spray or

Description

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of International Application No. PCT/EP2010/065855 filed 21 Oct. 2010, which claims priority to German Patent Application Nos. 10 2009 045 925.1 and 10 2009 045 933.2, both filed 22 Oct. 2009, each of which are incorporated herein by reference.
The present invention relates to agents for hair treatment containing a combination of at least one nonionic starch modified using propylene oxide, and at least one specific anionic film-forming and/or anionic setting polymer; use of those agents for temporary deformation and/or care of keratin-containing fibers; and to aerosol hair sprays/foams based on those agents.
“Keratin-containing fibers” includes all animal hairs such as wool, horsehair, angora hair, furs, feathers, and products or textiles fabricated therefrom. Keratinic fibers are, however, preferably human hair.
Hair treatment agents that provide permanent or temporary shaping of the hair play an important role in cosmetics. Temporary shaping actions that are intended to yield good hold without impairing the hair's healthy appearance such as its shine can be achieved, for example, using hair sprays, hair waxes, hair gels, hair foams, blow-dry waves, etc.
Corresponding agents for temporary shaping usually contain synthetic polymers as a shaping component. Preparations containing a dissolved or dispersed polymer can be applied onto hair using propellant gases or a pump mechanism. Hair gels and hair waxes in particular, however, are generally not applied directly onto the hair but rather distributed in the hair by a comb or the hands.
An important property of an agent for temporary deformation of keratinic fibers, hereinafter also called a “styling agent,” is to impart the strongest possible hold to the treated fibers in the shape generated. If the keratinic fibers involved are human hairs, terms also used are a strong “hairstyle hold” or a high “degree of hold” of the styling agent. Hairstyle hold is determined substantially by the nature and quantity of the synthetic polymer used, although additional ingredients of the styling agent can also have an influence.
In addition to a high degree of hold, styling agents must also meet a large number of further requirements. These can be subdivided roughly into properties on the hair; properties of the particular formulation (e.g., properties of the foam, gel, or sprayed aerosol); and properties relating to the handling of the styling agent, with properties on the hair being of particular importance. These include moisture resistance, low tack, and a balanced conditioning effect. Further, if possible, a styling agent should be universally usable for all types of hair.
A number of synthetic polymers utilized in styling agents have already been developed in order to meet various requirements. The polymers can be subdivided into cationic, anionic, nonionic, and amphoteric film-forming and/or setting polymers. Ideally, upon application to the hair the polymers yield a polymer film that imparts a strong hold to the hairstyle while is sufficiently flexible so not to break under stress. If the polymer is too fragile, this results in the formation of “film plaques” (i.e., residues that detach as the hair moves and give the impression that the user of the styling agent has dandruff).
It is still difficult to develop styling agents having all desired properties in combination. This applies in particular to the combination of strong hold and simple, uniform application onto the keratin-containing fibers.
The present invention therefore provides an agent for temporary deformation and/or care of keratinic fibers that is notable for a high degree of hold or an excellent care-providing effect, and, in particular, has outstanding ease of handling during application onto the keratin-containing fibers.
It has now been found, surprisingly, that this can be achieved by combination of specific polymers. It has furthermore been possible in specific embodiments of the invention to provide, in addition to these outstanding properties, compositions without turbidity. Freedom from turbidity matters in particular in aerosol compositions, since solid suspended particles can clog the exit nozzle of the aerosol package. In turbid and low-viscosity compositions, a general risk of sedimentation additionally exists, which has a disadvantageous effect on shelf stability of the composition.
A first subject of the present invention is therefore an agent for treating keratin-containing fibers, particularly human hair, containing, in a cosmetically acceptable carrier,

- at least one nonionic starch modified with propylene oxide, and
- at least one anionic film-forming and/or anionic setting polymer having at least one structural unit of formula (I) and at least one structural unit of formula (II)

- wherein
- R¹and R²are, mutually independently, a hydrogen atom or a methyl group, with the provision that R¹and R²are not simultaneously a methyl group,
- R³is a hydrogen atom or a methyl group,
- R⁴is a carbamoyl group, a linear or branched (C₄to C₁₂) alkylaminocarbonyl group, a linear or branched (C₄to C₁₂) alkylaminoethylaminocarbonyl group, a linear or branched (C₄to C₁₂) alkylaminopropylaminocarbonyl group, a linear or branched (C₄to C₁₂) alkyloxycarbonyl group, a linear or branched (C₄to C₁₂) alkylaminoethyloxycarbonyl group, a linear or branched (C₄to C₁₂) alkylaminopropyloxycarbonyl group, or a linear or branched (C₂to C₁₂) acyloxy group, and
- A¹is a hydroxy group or an organic residue having at least one sulfonic acid group that bonds to the structural fragment via an oxygen atom or an NH group.

“Film-forming polymers” those polymers that, upon drying, leave behind a continuous film on the skin, hair, or nails. Film-formers of this kind can be used in a very wide variety of cosmetic products such as face masks, make-up, hair setting agents, hair sprays, hair gels, hair waxes, hair therapies, shampoos, or nail polishes. Those polymers having sufficient solubility in water, alcohol or in water/alcohol mixtures and present in the agent according to the invention in completely dissolved form are particularly preferred. Film-forming polymers can be of synthetic or natural origin.
“Film-forming polymers” are also according to the present invention those polymers that, when applied in a 0.01- to 20-wt % aqueous, alcoholic, or aqueous alcoholic solution, are capable of depositing a transparent polymer film on the hair.
Setting polymers contribute to hold and/or buildup of hair volume and hair fullness of the overall hairstyle. These polymers are at the same time also film-forming polymers and are therefore generally typical substances for shape-imparting hair-treatment agents such as hair setting agents, hair foams, hair waxes, and hair sprays. It is certainly possible for film formation to be localized, and for only a few fibers to be connected to one another.
The “curl retention” test is often used as a test method for the setting effect of a polymer.
In accordance with the above formula and all subsequent formulae, a chemical bond having the symbol “*” is a free valence of the corresponding structural fragment.
Properties of the agent according to the present invention prove to be particularly advantageous when it is packaged as an aerosol spray, aerosol foam, pump spray, or pump foam. This preferred form of packaging is described below in detail.
Starch is a reserve carbohydrate that is stored by many plants in the form of large starch grains (granules), usually 1 to 200 μm in size, in various parts of the plant, for example, in tubers or roots, cereal seeds, fruits and in the pith. Nonionic starch modified with propylene oxide that can be used according to the invention can be obtained from the starch of potatoes, corn, rice, peas, acorns, chestnuts, barley, wheat, bananas, sago, millet, sorghum, oats, barley, rye, beans, yams, arrowroot or cassava. Particularly pronounced effects according to the invention are achieved with nonionic tapioca starch modified with propylene oxide, nonionic potato starch modified with propylene oxide, or with mixtures of these two starches. Very particularly preferably, the agent contains at least one nonionic potato starch modified with propylene oxide.
Starch belongs to the homoglycan family and is a polycondensation product of D-glucose. Starch is made up of three structurally different polymers of d-glucopyranose, namely amylose, amylopectin, and an intermediate fraction. Higher plants contain 0 to 45 wt % amylose, based on dry substance.
The intermediate fraction, also referred to as “anomalous amylopectin,” is structurally intermediate between amylose and amylopectin. The quantitative indications defined in the context of this Application for amylopectin include the intermediate fraction.
It is preferred if the nonionic starch modified with propylene oxide has an amylose content of 25 wt % or less, particularly 20 wt % or less, based on weight of the modified starch. It has become apparent that starch having 17 to 22 wt % amylose and 78 to 83 wt % amylopectin is particularly suitable for achieving the effect according to the present invention.
Amylose is made up of predominantly linear α-1,4-glycosidically linked d-glucose, M_r50,000 to 150,000. The resulting chains form double helices in the starch.
Amylopectin also contains, besides the α-1,4 links described for amylose, α-1,6 bonds (in a quantity from 4 to 6%) as branching points. The average spacing between the branching points is equal to approximately 12 to 17 glucose units. The molar mass of 10⁷to 7*10⁸corresponds to approx. 10⁵glucose units, making amylopectin one of the largest biopolymers. Branching points are distributed over the molecule in such a way that a bundle structure with relatively short side chains develops. Each double helix is formed by two of these side chains. As a result of the many branching points, amylopectin is relatively easily soluble in water.
“Nonionic starch modified with propylene oxide” according to the invention is a reaction product of a starch with propylene oxide. A reaction product of this kind inicudes at least one structural unit of formula (PS)
wherein at least one of R, R′, or R″ is a group of the formula
wherein n is greater than or equal to zero, and at most two of R, R′, and R″ is a hydrogen atom. Nonionic starches modified with propylene oxide are provided, for example, by reacting a natural starch with propylene oxide. Before modification with propylene oxide, the starch can be exposed to a variety of physical or chemical processes such as heat treatment, shear, a thermal, acid-hydrolytic, oxidizing, or enzymatic cleavage, etc.
It is preferred if the nonionic starch modified with propylene oxide is not present in the agent according to the present invention as individual starch grains (granules). Accordingly, the starch grains are disintegrated, for example, by heat or shear and the corresponding polysaccharide molecules are released from the composite material. The released polysaccharide molecules are modified with propylene oxide after or before release.
In a preferred embodiment, nonionic starch modified with propylene oxide is gelatinized. When an aqueous suspension of starch is heated or compressed, a tangential swelling of the bodies is then observed at a critical temperature or pressure, with loss of birefringence, a change in X-ray structure, and an abrupt rise in the viscosity of the solution. This phenomenon is called “gelatinization.”
Nonionic starches according to the present invention modified with propylene oxide are present in the agent in a molecular weight distribution. Preferred nonionic starches modified with propylene oxide have an average molecular weight form 50 to 2500 kDa (weight average). Molecular weight distribution was determined experimentally by gel filtration chromatography against dextran. The weight average is an average molecular weight that takes into account the total weight of the molecules of various molecular weights, and not simply the number of molecules.
For statistical calculation of the weight average, firstly the “weight break” is defined:
w _i=(N _i M _i)/[Σ(N _i M _i].
This indicates the weight proportion, in the sample, of macromolecules that are made up of i segments (e.g., monomer modules) of mass M_iand that occur N_itimes in the sample. The weight average of the molecular weight M_w=Σw_iM_iis thus given by
M _w=[Σ(N _i M ² _i)]/[Σ(N _i M _i)].
Particularly preferred agents preferably contain nonionic starches modified with propylene oxide having an average molecular weight (weight average) from 100 to 2000 kDa, particularly 500 to 1800 kDa, very preferably from 700 to 1000 kDa.
In order to adjust the molecular weight, the starch is subjected to mechanical and/or chemical treatment before or after modification with propylene oxide. To elevate the molecular weight, the starch can be crosslinked. Crosslinking of the nonionic starch modified with propylene oxide exists when the linear or branched polysaccharide macromolecules of the starch are linked covalently with a crosslinking agent, forming a three-dimensional, insoluble, and still swellable polymeric network. Natural starch is generally considered uncrosslinked, and, if crosslinking were desirable, requires artificial crosslinking by synthesis chemistry. Artificial crosslinking of this kind can be carried out using crosslinking agents. (Nonionic) starches (modified with propylene oxide) that do not exhibit such crosslinking are uncrosslinked.
Crosslinking occurs, for example, using the crosslinking agent epichlorohydrin. Here, a mixture (42-wt % in water) of starch modified with propylene oxide is produced, into which the desired amount of epichlorohydrin is stirred at room temperature. Once the target viscosity is reached after a stirring time of 1 to 5 hours with viscosity monitoring, the crosslinked starch is isolated using ordinary methods.
It is particularly preferred, however, if the agents contain at least one uncrosslinked nonionic starch modified with propylene oxide.
To achieve a lower molecular weight from 100 to 400 kDa, the starches are preferably exposed to mechanical cleavage, enzymatic cleavage (particularly using α-amylase, β-amylase, glucoamylase, or debranching enzymes), acid-hydrolytic cleavage (particularly using hydrochloric acid, sulfuric acid, or phosphoric acid), thermal cleavage, or reaction with oxidizing agents (e.g., periodate, hypochlorite, chromic acid, permanganate, nitrogen dioxide, hydrogen peroxide, or organic percarboxylic acid, preferably with hydrogen peroxide). Kneaders, extruders, stator/rotor machines, and/or agitators are suitable for mechanical cleavage of the starch.
Oxidative cleavage using hydrogen peroxide is preferred. Here, for example, the nonionic starch modified with propylene oxide is added to water, heated to 50 to 70° C., hydrogen peroxide is added, and stirring occurs at 70 to 85° C. for 2 to 5 hours.
Propylene oxide content of the starch affects the fine-tuning of the hairstyle hold and hairstyle flexibility, as well as stability of the cosmetic agents. The parameters can be further optimized if the nonionic starch modified with propylene oxide has, based on weight of the modified starch, a propylene oxide content preferably from 1 to 20 wt %, more preferably from 4 to 12 wt %, very preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0 wt %. Propylene oxide content can be determined, for example, by carrying out a Hodges cleavage using the method according to DIN EN 13268.
Those cosmetic agents wherein the nonionic starch modified with propylene oxide has, in a 43-wt % aqueous solution, a preferred viscosity from 150 to 1,500,000 mPa·s (Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm) are outstandingly suitable for purposes of the invention. Particularly suitable starches modified with propylene oxide have viscosities from 10,000 to 200,000 mPa·s, particularly preferably from 25,000 to 180,000 mPa·s (measured under the conditions recited above).
Nonionic starch modified using propylene oxide that is particularly preferred according to the present invention is uncrosslinked, has an average molecular weight (weight average) from 100 to 2000 kDa, particularly 500 to 1800 kDa, very preferably from 700 to 1000 kDa, and has a propylene oxide content, based on weight of the modified starch, from 1 to 20 wt %, particularly from 4 to 12 wt %, very preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0 wt %. This is preferably a tapioca starch or potato starch, particularly potato starch.
Nonionic potato starch modified with propylene oxide that is very particularly preferred is uncrosslinked, has an average molecular weight (weight average) from 100 to 2000 kDa, particularly 500 to 1800 kDa, very preferably from 700 to 1000 kDa, and has a propylene oxide content, based on weight of the modified potato starch, from 4 to 12 wt %, very preferably a propylene oxide content from 9.5 to 10.5 wt % or from 4.0 to 6.0 wt %.
It is preferred if the cosmetic agent contains the nonionic starch modified with propylene oxide in an amount from 0.1 wt % to 10 wt %, more preferably from 0.2 wt % to 5.0 wt %, very preferably from 1.0 to 3.0 wt %, based on weight of the agent.
In addition, the agent according to the present invention can contain at least one anionic film-forming and/or anionic setting polymer. An “anionic” polymer according to the present invention is a polymer having, in a protic solvent under standard conditions, structural units having anionic groups that must be compensated for by counterions to maintain electroneutrality, and has no structural units having permanently cationic groups. “Anionic groups” include carboxyl groups and sulfonic-acid groups.
Anionic film-forming and/or anionic setting polymers (b) are present in the agent preferably in an amount from 0.1 wt % to 20.0 wt %, more preferably from 0.2 wt % to 15.0 wt %, very preferably from 0.5 wt % to 10.0 wt %, based on weight of the agent of the present invention.
Preferably, the anionic film-forming and/or anionic setting polymer (b) has at least one structural unit of formula (I) chosen from at least one structural unit of formulas (I-1) to (I-5)
It is particularly preferred if polymer (b) additionally contains, besides the structural units of formula (I) and (II), at least one structural unit of formula (III)
wherein

R¹⁵is a hydrogen atom or a methyl group,
R¹⁶is a (C₁to C₄) alkyl group (particularly a methyl group or an ethyl group).

Copolymers of methacrylic acid and ethyl acrylate and tert-butyl acrylate are preferably suitable, for example.
It is particularly preferred according to the present invention if the anionic film-forming and/or anionic setting polymer (b) has at least one structural unit of formula (II) chosen from at least one structural unit of formulae (II-1) to (II-15)
wherein

X³is an oxygen atom or a NH group,
R⁵is a (C₂to C₁₂) acyl group (particularly acetyl or neodecanoyl).

Preferably, X³according to formulae (II-5) to (II-12) is an oxygen atom.
In a first preferred embodiment of the invention, the agent has at least one anionic film-forming and/or anionic setting polymer (b) having at least one structural unit of formula (I-1), at least one structural unit of (II-3), and at least one structural unit of formula (II-16) (chosen particularly from formulae (II-5) to (II-12) with the provision that X³is an oxygen atom),
wherein

X³is an oxygen atom or an NH group,
R⁶is a hydrogen atom or a methyl group, and
R⁷is an alkyl group having 4 carbon atoms (particularly n-butyl, sec-butyl, isobutyl, or tert-butyl).

It is in turn particularly preferred if polymer (b) additionally contains, besides the above structural units of formula (I-1), (II-3), and (II-16), at least one structural unit of formula (III)
wherein

R⁸is a hydrogen atom or a methyl group,
R⁹is a (C₁to C₄) alkyl group (particularly a methyl group or an ethyl group).

Preferred polymers (b) of this kind are chosen from:

- copolymers of acrylic acid, (C₁to C₄) alkyl acrylates, C₄alkylaminoethyl methacrylate, and C₈alkyl acrylamide.

An example of a polymer (b) usable particularly preferably in this embodiment is the polymer obtainable under the trade name Amphomer® 028-4910 from the National Starch Company, having the INCI name Octylacrylamide/Acrylates/Butyla minoethylmethacrylate Copolymer.
Those agents having, in a cosmetically acceptable carrier,

- at least one uncrosslinked nonionic starch modified by means of propylene oxide, in particular having an average molecular weight (weight average) from 50 to 2500 kDa, and
- at least one anionic film-forming and/or anionic setting polymer having at least one structural unit of formula (I-1), at least one structural unit of formula (II-3), and at least one structural element of formula (II-16),

- wherein
- X³is an oxygen atom or an NH group (particularly an oxygen atom),
- R⁶is a hydrogen atom or a methyl group (particularly a methyl group), and
- R⁷is an alkyl group having 4 carbon atoms (particularly n-butyl, sec-butyl, isobutyl, or tert-butyl),
  are considered, in particular, to be very particularly preferred in this embodiment.

It is in turn particularly preferred in this context if polymer (b) additionally contains, besides the structural units of formula (I-1), (II-3), and (II-16), at least one structural unit of formula (III)
wherein

It is particularly preferred in this context if, for all embodiments of this first embodiment, the structural unit of formula (I-1) is present in entirely or partly neutralized fashion. At least one alkanolamine is preferably used for neutralization. Alkanolamines usable as an alkalizing agent according to the present invention are preferably chosen from primary amines having a C₂-C₆alkyl basic structure carrying at least one hydroxyl group. Particularly preferred alkanolamines are chosen from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol. Alkanolamines very particularly preferred according to the present invention are chosen from: 2-aminoethan-1-ol, 2-amino-2-methylpropan-1-ol, and 2-amino-2-methylpropane-1,3-diol.
In a second embodiment, those agents having as an anionic film-forming and/or anionic setting polymer (b) at least one polymer having at least one structural unit of formula (I-3) and at least one structural unit of formula (II-13)
are considered preferred according to the present invention.
Preferred polymers (b) of this kind are chosen from at least one polymer from

- copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide,
- copolymers of 2-acrylamido-2-methylpropanesulfonic acid, acrylamide, and acrylic acid.

Polymers of this kind are marketed, for example, in an inverse isohexadecane emulsion by the Seppic company under the commercial name Sepigel® 305 (INCI name: Polyacrylamide, C13-14 Isoparaffin, Laureth-7) or Simulgel® 600 (INCI name: Acrylamide/Acryloyldimethyltaurate Copolymer, Isohexadecane, Polysorbate-80).
An agent particularly preferred according to the present invention contains, as polymer (b), a copolymer (b1).
These copolymers (b1) can be described by the general formula
wherein m, n, and o each vary depending on the molar mass of the polymer and are not intended to signify that these are block copolymers. Structural units can instead be present in statistically distributed fashion in the molecule.
Particularly preferred agents according to the present invention are those wherein copolymer (b1) has a molar mass from 50 to 500 kDa, preferably from 100 to 450 kDa, more preferably from 150 to 400 kDa, and particularly from 200 to 300 kDa.
Copolymers of acrylamide with methacrylic acid and acryloyldimethyl taurate are obtainable, for example, under the commercial name Acudyne® SCP (Rohm & Haas).
Those agents in particular having, in a cosmetically acceptable carrier,

- at least one uncrosslinked nonionic starch modified by means of propylene oxide, in particular having an average molecular weight (weight average) from 50 to 2500 kDa, and
- at least one anionic film-forming and/or anionic setting polymer having at least one structural unit of formula (I-3) and at least one structural element of formula (II-13)

are very particularly preferred in the context of this embodiment.
In a third embodiment, those agents having as an anionic film-forming and/or anionic setting polymer (b) at least one polymer containing at least one structural unit of formula (I-5) and at least one structural unit of formula (II-15)
wherein R⁵is a (C₂to C₁₂) acyl group (particularly acetyl or neodecanoyl), are preferred according to the present invention.
Particularly preferred polymers (b) of this kind are chosen from at least one polymer of

- copolymers of vinyl acetate and crotonic acid,
- copolymers of vinyl propionate and crotonic acid,
- copolymers of vinyl neodecanoate, vinyl acetate, and crotonic acid.

Such copolymers are available, for example, from the Clariant company under the commercial name Aristoflex A 60 (INCI name: VA/Crotonates Copolymer) in an isopropanol-water mixture (60 wt % active substance), from the BASF company under the commercial name Luviset CA 66 (vinyl acetate/crotonic acid copolymer 90:10, INCI name: VA/Crotonates Copolymer), From the National Starch company under the commercial name Resyn 28-2942 resp. Resyn 28-2930 (INCI name: VA/CrotonatesNinyl Neodecanoate Copolymer).
Those agents in particular having, in a cosmetically acceptable carrier,

- at least one uncrosslinked nonionic starch modified with propylene oxide, in particular having an average molecular weight (weight average) from 50 to 2500 kDa, and
- at least one anionic film-forming and/or anionic setting polymer (b) having at least one structural unit of formula (I-5) and at least one structural unit of formula (II-15)

wherein R⁵is a (C₂to C₁₂) acyl group (particularly acetyl or neodecanoyl), are very particularly preferred in the context of this embodiment.
In the context of these embodiments, the preferred embodiments recited above of the amphiphilic cationic polymer (a) are suitable as preferred (see above).
Similarly, all preferred quantitative amounts recited above with regard to polymer components (a) and (b) of the agent according to the present invention are also considered preferred, mutatis mutandis, for these embodiments.
It is particularly preferred if, for all embodiments of this third embodiment, the structural unit of formula (I-5) is present in entirely or partly neutralized fashion. At least one alkanolamine is preferably used for neutralization. Alkanolamines usable as an alkalizing agent according to the present invention are preferably chosen from primary amines having a C₂-C₆alkyl basic structure having at least one hydroxyl group. Particularly preferred alkanolamines are chosen from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-arninobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol. Alkanolamines very particularly preferred according to the present invention are chosen from: 2-aminoethan-1-ol, 2-amino-2-methylpropan-1-ol, and 2-amino-2-methylpropane-1,3-diol.
To intensify the effect, agents according to the present invention preferably additionally contain at least one surfactant, with nonionic, anionic, cationic, and ampholytic surfactants being suitable in principle. The group of ampholytic or also amphoteric surfactants includes zwitterionic surfactants and ampholytes. The surfactants can, according to the present invention, already have an emulsifying effect.
Additional surfactants are present in the agent preferably in an amount from 0.01 wt % to 5 wt %, more preferably from 0.05 wt % to 0.5 wt %, based on weight of the agent.
It is particularly preferred if agents according to the present invention additionally contain at least one nonionic surfactant.
Nonionic surfactants contain as a hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group, or a combination of a polyol and polyglycol ether group. Such compounds include:

- addition products of 2 to 100 mol ethylene oxide and/or 1 to 5 mol propylene oxide with linear and branched fatty alcohols having 8 to 30 carbon atoms, with fatty acids having 8 to 30 carbon atoms, and with alkylphenols having 8 to 15 carbon atoms in the alkyl group,
- addition products, end-capped with a methyl or C₂to C₆alkyl residue, of 2 to 50 mol ethylene oxide and/or 1 to 5 mol propylene oxide with linear and branched fatty alcohols having 8 to 30 carbon atoms, with fatty acids having 8 to 30 carbon atoms, and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as, for example, the grades obtainable under the marketing designations Dehydol® LS, Dehydol® LT (Cognis),
- C₁₂to C₃₀fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide with glycerol,
- addition products of 5 to 60 mol ethylene oxide with castor oil and hardened castor oil,
- polyol fatty acid esters such as, for example, the commercial product Hydagen® HSP (Cognis), or Sovermol® grades (Cognis),
- alkoxylated triglycerides,
- alkoxylated fatty acid alkyl esters of formula (E4-I)

R¹CO—(OCH₂CHR²)_wOR³ (E4-I),

- in which R¹CO denotes a linear or branched, saturated and/or unsaturated acyl residue having 6 to 22 carbon atoms, R²denotes hydrogen or methyl, R³denotes linear or branched alkyl residues having 1 to 4 carbon atoms, and w denotes numbers from 1 to 20,
- amine oxides,
- hydroxy mixed ethers such as those described, for example, in German Application 19738866,
- sorbitan fatty acid esters and addition products of ethylene oxide with sorbitan fatty acid esters, for example the polysorbates,
- sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,
- addition products of ethylene oxide with fatty acid alkanolamides and fatty amines,
- sugar surfactants of the alkyl and alkenyl oligoglycoside types, in accordance with formula (E4-I I)

R⁴O-[G]_p (E4-II),

- wherein R⁴is an alkyl or alkenyl residue having 4 to 22 carbon atoms, G is a sugar residue having 5 or 6 carbon atoms, and p is a number from 1 to 10. They can be obtained according to relevant methods of preparative organic chemistry.

Alkylene oxide addition products with saturated linear fatty alcohols and fatty acids, having in each case 2 to 100 mol ethylene oxide per mol of fatty alcohol or fatty acid, are very particularly preferred nonionic surfactants. Preparations having outstanding properties are likewise obtained when they contain, as nonionic surfactants, C₁₂to C₃₀fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide with glycerol and/or addition products of 5 to 60 mol ethylene oxide with castor oil and hardened castor oil.
Very particularly preferably, agents according to the present invention contain as a surfactant at least one addition product of 15 to 100 mol ethylene oxide, particularly 15 to 50 mol ethylene oxide, with a linear or branched (particularly linear) fatty alcohol having 8 to 22 carbon atoms, This refers very particularly preferably to ceteareth-15, ceteareth-25, or ceteareth-50, marketed as Eumulgin® CS 15 (COGNIS), Cremophor A25 (BASF SE), or Eumulgin® CS 50 (COGNIS).
All anionic surface-active substances suitable for use on the human body are, in principle, appropriate as anionic surfactants. These are characterized by an anionic group imparting water solubility, for example, a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group having approximately 8 to 30 carbon atoms. Glycol ether or polyglycol ether groups, ester, ether, and amide groups, and hydroxyl groups can additionally be present in the molecule. Examples of suitable anionic surfactants are, in the form of the sodium, potassium, and ammonium and mono-, di, and trialkanolammonium salts having 2 to 4 carbon atoms in the alkanol group:

- linear and branched fatty acids having 8 to 30 carbon atoms (soaps);
- ethercarboxylic acids of the formula R—O—(CH₂—CH₂O)_x—CH₂—COOH, in which R is a linear alkyl group having 8 to 30 carbon atoms and x=0 or is 1 to 16;
- acyl sarcosides having 8 to 24 carbon atoms in the acyl group;
- acyl taurides having 8 to 24 carbon atoms in the acyl group;
- acyl isethionates having 8 to 24 carbon atoms in the acyl group;
- sulfosuccinic acid mono- and dialkyl esters having 8 to 24 carbon atoms in the alkyl group, and sulfosuccinic acid monoalkylpolyoxyethyl esters having 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups;
- linear alkanesulfonates having 8 to 24 carbon atoms;
- linear alpha-olefinsulfonates having 8 to 24 carbon atoms;
- alpha-sulfo fatty acid methyl esters of fatty acids having 8 to 30 carbon atoms;
- alkyl sulfates and alkyl polyglycol ether sulfates of the formula R—O—(CH₂—CH₂—O)_x—OSO₃H, in which R is a preferably linear alkyl group having 8 to 30 carbon atoms and x=0 or is 1 to 12;
- mixtures of surface-active hydroxysulfonates;
- sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropylene glycol ethers;
- sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds;
- esters of tartaric acid and citric acid with alcohols, representing addition products of approximately 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols having 8 to 22 carbon atoms;
- sulfated fatty acid alkylene glycol esters of formula (E1-II)

R⁷CO(AlkO)_nSO₃M (E1-II)

- wherein R⁷CO is a linear or branched, aliphatic, saturated and/or unsaturated acyl residue having 6 to 22 carbon atoms, Alk denotes CH₂CH₂, CHCH₃CH₂, and/or CH₂CHCH₃, n denotes numbers from 0.5 to 5, and M denotes a cation, as described in German Application 197 36 906;
- amide ether carboxylic acids;
- condensation products of C₈to C₃₀fatty alcohols with protein hydrolysates and/or amino acids and derivatives thereof, known to one skilled in the art as protein fatty acid condensates, such as the Lamepon® grades, Gluadin® grades, Hostapon® KCG, or the Amisoft® grades.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates, and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group, and sulfosuccinic acid monoalkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, monoglycerol disulfates, alkyl and alkenyl ether phosphates, as well as protein fatty acid condensates.
Cationic surfactants of the quaternary ammonium compound, esterquat, and amidoamine types are furthermore usable according to the present invention. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, and trialkylmethylammonium chlorides. Long alkyl chains of these surfactants preferably have 10 to carbon atoms, for example, as in cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride. Further preferred cationic surfactants are the imidazolium compounds known by the INCI names Quaternium-27 and Quaternium-83.
“Zwitterionic surfactants” refers to those surface-active compounds having in the molecule at least one quaternary ammonium group and at least one —COO⁽⁻⁾or SO³⁽⁻⁾group. Particularly suitable zwitterionic surfactants are betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example, cocalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example, cocacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, each having 8 to 18 carbon atoms in the alkyl or acyl group, as well as cocacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.
“Ampholytes” are those surface-active compounds having in the molecule, in addition to a C₈to C₂₄alkyl or acyl group, at least one free amino group and at least one —COOH or —SO₃H group, and are capable of forming internal salts. Examples of suitable ampholytes 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, having in each case approximately 8 to carbon atoms in the alkyl group. Particularly preferred ampholytes are N-cocalkylaminopropionate, cocacylaminoethylaminopropionate, and C₁₂to C₁₅acyl sarcosine.
Agents according to the present invention contain the ingredients or active substances in a cosmetically acceptable carrier.
Preferred cosmetically acceptable carriers are aqueous, alcoholic, or aqueous alcoholic media having by preference at least 10 wt % water, based on the entire agent. The alcohols contained can be, in particular, lower alcohols having 1 to 4 carbon atoms usually used for cosmetic purposes, for example, ethanol and isopropanol. Preferably, at least one (C₁to C₄) monoalkyl alcohol is used in the agents according to the present invention, particularly in an amount from 1 to 50 wt %, in particular from 5 to 30 wt %. This is in turn particularly preferred for packaging as a pump foam or aerosol foam.
Organic solvents or a mixture of solvents having a boiling point below 400° C. can be present as additional co-solvents in an amount from 0.1 to 15 wt %, preferably from 1 to 10 wt % based on entire agent. Unbranched or branched hydrocarbons such as pentane, hexane, isopentane, and cyclic hydrocarbons such as cyclopentane and cyclohexane, are particularly suitable as additional co-solvents. Further particularly preferred water-soluble solvents are glycerol, ethylene glycol, and propylene glycol, in an amount of up to 30 wt % based on entire agent.
The addition in particular of glycerol and/or propylene glycol and/or polyethylene glycol and/or polypropylene glycol increases the flexibility of the polymer film formed when the agent according to the present invention is used. If a flexible hold is desired, the agents therefore preferably contain 0.01 to 30 wt % glycerol and/or propylene glycol and/or polyethylene glycol and/or polypropylene glycol, based on entire agent.
The agents preferably have a pH from 2 to 11. Particularly preferably, the pH range is from 2 to 8. Reference to pH here, for purposes of this document, is to the pH at 25° C. unless otherwise noted.
Agents according to the present invention can furthermore contain adjuvants and additives usually added to conventional styling agents.
Additional care-providing substances can be recited in particular as suitable adjuvants and additives.
Silicone oil and/or a silicone gum can be used, for example, as a care-providing substance.
Silicone oils or silicone gums suitable according to the present invention include dialkyl- and alkylarylsiloxanes, for example, dimethylpolysiloxane and methylphenylsiloxane, as well as alkoxylated, quaternized, or anionic derivatives thereof. Cyclic and linear polydialkylsiloxanes, alkoxylated and/or aminated derivatives thereof, dihydroxypolydimethylsiloxanes, and polyphenylalkylsiloxanes are preferred.
Silicone oils produce a very wide variety of effects. For example, they simultaneously influence dry and wet combability, the feel of dry and wet hair, and shine. The skilled artisan understands the term “silicone oils” to mean several structures of organosilicon compounds. They are understood firstly as the dimethiconols. The following commercial products are recited as examples of such products: Botanisil NU-150M (Botanigenics), Dow Corning 1-1254 Fluid, Dow Corning 2-9023 Fluid, Dow Corning 2-9026 Fluid, Ultrapure Dimethiconol (Ultra Chemical), Unisil SF-R (Universal Preserve), X-21-5619 (Shin-Etsu Chemical Co.), Abil OSW 5 (Degussa Care Specialties), ACC DL-9430 Emulsion (Taylor Chemical Company), AEC Dimethiconol & Sodium Dodecylbenzenesulfonate (A & E Connock (Perfumery & Cosmetics) Ltd.), B C Dimethiconol Emulsion 95 (Basildon Chemical Company, Ltd.), Cosmetic Fluid 1401, Cosmetic Fluid 1403, Cosmetic Fluid 1501, Cosmetic Fluid 1401 DC (all the aforesaid Chemsil Silicones, Inc.), Dow Corning 1401 Fluid, Dow Corning 1403 Fluid, Dow Corning 1501 Fluid, Dow Corning 1784 HVF Emulsion, Dow Corning 9546 Silicone Elastomer Blend (all the aforesaid Dow Corning Corporation), Dub Gel SI 1400 (Stearinerie Dubois Fils), HVM 4852 Emulsion (Crompton Corporation), Jeesilc 6056 (Jeen International Corporation), Lubrasil, Lubrasil DS (both Guardian Laboratories), Nonychosine E, Nonychosine V (both Exsymol), SanSurf Petrolatum-25, Satin Finish (both Collaborative Laboratories, Inc.), Silatex-D30 (Cosmetic Ingredient Resources), Silsoft 148, Silsoft E-50, Silsoft E-623 (all the aforesaid Crompton Corporation), SM555, SM2725, SM2765, SM2785 (all the aforesaid GE Silicones), Taylor T-SiI CD-1, Taylor TME-4050E (all Taylor Chemical Company), TH V 148 (Crompton Corporation), Tixogel CYD-1429 (Sud-Chemie Performance Additives), Wacker-Belsil CM 1000, Wacker-Belsil CM 3092, Wacker-Belsil CM 5040, Wacker-Belsil DM 3096, Wacker-Belsil DM 3112 VP, Wacker-Belsil DM 8005 VP, Wacker-Belsil DM 60081 VP (all the aforesaid Wacker-Chemie GmbH).
Dimethicones constitute the second group of silicones that can be present according to the present invention. They can be both linear and branched, and also cyclic or cyclic and branched.
Dimethicone copolyols (S3) are a further group of suitable silicones. Corresponding dimethicone copolyols are commercially obtainable and are marketed, for example, by the Dow Corning company under the designation Dow Corning® 5330 Fluid.
The teaching of the present invention also includes the fact that the dimethiconols, dimethicones, and/or dimethicone copolymers can already be present as an emulsion. The corresponding emulsion of the dimethiconols, dimethicones, and/or dimethicone copolyols can be manufactured both after manufacture of the corresponding dimethiconols, dimethicones, and/or dimethicone copolyols, from them and using usual emulsification methods known to the skilled artisan. For this purpose cationic, anionic, nonionic, or zwitterionic surfactants and emulsifiers can be used, as auxiliaries, as adjuvants for manufacture of the corresponding emulsions. Emulsions of the dimethiconols, dimethicones, and/or dimethicone copolyols can also be manufactured directly by way of an emulsion polymerization method. Such methods, too, are very familiar to the skilled artisan.
If dimethiconols, dimethicones, and/or dimethicone copolyols are used as an emulsion, the droplet size of the emulsified particles is then, according to the present invention, from 0.01 to 10,000 μm, preferably 0.01 to 100 μm, particularly preferably 0.01 to 20 μm, and very preferably 0.01 to 10 μm. Particle size is determined using the light-scattering method.
If branched dimethiconols, dimethicones, and/or dimethicone copolyols are used, this means that the branching is greater than a random branching that occurs randomly as a result of contaminants in the respective monomers. “Branched” dimethiconols, dimethicones, and/or dimethicone copolyols therefore, for purposes of the present invention, mean that the degree of branching is greater than 0.01%. A degree of branching greater than 0.1% is preferred, and very particularly preferably it is greater than 0.5%. The degree of branching is determined from the ratio of unbranched monomers to the branching monomers (i.e., to the quantity of tri- and tetrafunctional siloxanes). Both low-branching and high-branching dimethiconols, dimethicones, and/or dimethicone copolyols can be very preferred according to the present invention.
Particularly preferred silicones are aminofunctional silicones, in particular the silicones grouped under the INCI name Amodimethicones. It is therefore preferred if the agents according to the present invention additionally contain at least one aminofunctional silicone. These are silicones having at least one optionally substituted amino group. These silicones are referred to according to the INCI declaration as Amodimethicones, and are obtainable, for example, in the form of an emulsion, as a commercial product Dow Corning® 939 or as a commercial product Dow Corning® 949, mixed with a cationic and a nonionic surfactant.
Those aminofunctional silicones having an amine number above 0.25 meq/g, preferably above 0.3 meq/g, and particularly preferably above 0.4 meq/g are used by preference. The amine number here is the milliequivalent of amine per gram of the aminofunctional silicone. It can be ascertained by titration, and can also be indicated with the “mg KOH/g” unit.
The agents contain silicones preferably in amounts from 0.01 wt % to 15 wt %, particularly preferably from 0.05 to 2 wt %, based on total agent.
The agent can contain a care-providing substance of a different compound class, for example, at least one protein hydrolysate and/or a derivative thereof.
Protein hydrolysates are product mixtures obtained by acid-, base-, or enzyme-catalyzed breakdown of proteins. The term “protein hydrolysates” also means total hydrolysates as well as individual amino acids and derivatives thereof, as well as mixtures of different amino acids. The molecular weight of protein hydrolysates usable according to the present invention is from 75 (the molecular weight of glycine) to 200,000; the molecular weight is equal to preferably 75 to 50,000 Dalton, and very particularly preferably to 75 to 20,000 Dalton.
According to the present invention, protein hydrolysates of vegetable, animal, marine or synthetic origin can be used.
Animal protein hydrolysates include protein hydrolysates of elastin, collagen, keratin, silk, and milk protein, which can also be present in the form of salts. Such products are marketed, for example, under the trademarks Dehylan® (Cognis), Promois® (Interorgana), Collapuron® (Cognis), Nutrilan® (Cognis), Gelita-Sol® (Deutsche Gelatine Fabriken Stoess & Co), Lexein® (Inolex), Sericin (Pentapharm), and Kerasol® (Croda).
Protein hydrolysates are present in agents according to the present invention, for example, in concentrations from 0.01 wt % to 20 wt %, preferably from 0.05 wt % to 15 wt %, and very preferably in amounts from 0.05 wt % to 5 wt %, based on the entire application preparation.
The agent can further contain at least one vitamin, provitamin, vitamin precursor, and/or derivative thereof as a care-providing substance.
Those vitamins, provitamins, and vitamin precursors that are usually assigned to groups A, B, C, E, F, and H are preferred.
The group of substances referred to as “vitamin A” includes retinol (vitamin A₁) as well as 3,4-didehydroretinol (vitamin A₂). β-Carotene is the provitamin of retinol. Vitamin A components that are appropriate according to the present invention are, for example, vitamin A acid and its esters, vitamin A aldehyde, and vitamin A alcohol, as well as esters thereof such as the palmitate and acetate. The agents contain the vitamin A component preferably in quantities from 0.05 to 1 wt % based on the entire application preparation.
Members of the vitamin B group or the vitamin B complex are, among others, vitamin B₁(thiamine), vitamin B₂(riboflavin), vitamin B₃(nicotinic acid and/or nicotinic acid amide (niacinamide)), vitamin B₅(pantothenic acid, panthenol, and pantolactone), vitamin B₆(pyroxidine as well as pyridoxamine and pyridoxal), vitamin C (ascorbic acid), vitamin E (tocopherols, in particular α-tocopherol), vitamin F (linoleic acid and/or linolenic acid), vitamin H.
Agents according to the present invention preferably contain vitamins, provitamins, and vitamin precursors from groups A, B, C, E and H. Panthenol, pantolactone, pyridoxine and its derivatives, as well as nicotinic acid amide and biotin, are particularly preferred.
D-panthenol is very particularly preferably used as a care-providing substance, optionally in combination with at least one of the silicone derivatives recited above.
Like the addition of glycerol and/or propylene glycol, the addition of panthenol also increases the flexibility of the polymer film formed upon utilization of the agent according to the present invention. If a particularly flexible hold is desired, the agents can thus contain panthenol instead of or in addition to glycerol and/or propylene glycol. In a preferred embodiment the agents contain panthenol, preferably in an amount from 0.05 to 10 wt %, particularly preferably 0.1 to 5 wt %, based on the entire agent.
Agents according to the present invention can further contain at least one plant extract as a care-providing substance.
These extracts are usually produced by extraction of the entire plant. In individual cases, however, it may also be preferred to produce the extracts exclusively from blossoms and/or leaves of the plant.
Especially preferred extracts according to the present invention are from green tea, oak bark, nettle, hamamelis, hops, henna, chamomile, burdock root, horsetail, hawthorn, linden blossoms, almond, aloe vera, pine needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lemon, wheat, kiwi fruit, melon, orange, grapefruit, salvia, rosemary, birch, mallow, lady's-smock, wild thyme, yarrow, thyme, lemon balm, restharrow, coltsfoot, hibiscus, meristem, ginseng, and ginger root.
It may furthermore be preferred to use mixtures of several, particularly two different plant extracts in the agents according to the present invention.
Mono- or oligosaccharides can also be used as a care-providing substance in agents according to the present invention.
Both monosaccharides and oligosaccharides, for example, raw sugar, milk sugar, and raffinose, can be used. Use of monosaccharides is preferred. Among the monosaccharides, those compounds having 5 or 6 carbon atoms are preferred.
Suitable pentoses and hexoses include ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fucose and fructose. Arabinose, glucose, galactose and fructose are carbohydrates that are preferably used. It is very particularly preferred to use glucose, which is suitable both in the D-(+) or L-(−) configuration or as a racemate. Derivatives of these pentoses and hexoses, such as the corresponding -onic and -uronic acids (sugar acids), sugar alcohols, and glycosides, can also be used according to the present invention. Preferred sugar acids are gluconic acid, glucuronic acid, saccharic acid, mannosaccharic acid, and mucic acid. Preferred sugar alcohols are sorbitol, mannitol, and dulcitol. Preferred glycosides are the methylglucosides. Because the mono- or oligosaccharides that are used are usually obtained from natural raw materials such as starch, as a rule they exhibit the configurations corresponding to those raw materials (e.g., D-glucose, D-fructose and D-galactose).
Mono- or oligosaccharides are present in agents according to the present invention preferably in an amount from 0.1 to 8 wt %, more preferably from 1 to 5 wt %, based on the entire application preparation.
The agent can furthermore contain at least one lipid as a care-providing substance.
Lipids suitable according to the present invention are phospholipids, for example, soy lecithin, egg lecithin, and kephalins, as well as the substances known by the INCI names Linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate, and Stearamidopropyl PG-Dimonium Chloride Phosphate. These are marketed, for example, by the Mona company under the commercial designations Phospholipid EFA®, Phospholipid PTC®, and Phospholipid SV®. Agents according to the present invention contain the lipids preferably in amounts from 0.01 to 10 wt %, particularly 0.1 to 5 wt %, based on the entire application preparation.
Oily substances are also suitable as a care-providing substance.
Included among the natural and synthetic cosmetic oily substances are, for example:

- Vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach-kernel oil, and the liquid components of coconut oil. Also suitable, however, are other triglyceride oils such as the liquid components of beef tallow, as well as synthetic triglyceride oils.
- Liquid paraffin oils, isoparaffin oils, and synthetic hydrocarbons, as well as di-n-alkyl ethers having a total of between 12 and 36 carbon atoms, in particular 12 to 24 carbon atoms, for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether, and n-hexyl-n-undecyl ether, as well as di-tert-butyl ether, diisopentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether, and 2-methylpentyl-n-octyl ether. The compounds 1,3-di-(2-ethylhexyl)cyclohexane (Cetiol® S) and di-n-octyl ether (Cetiol® OE), available as commercial products, can be preferred.
- Ester oils. “Ester oils” are the esters of C₆to C₃₀fatty acids with C₂to C₃₀fatty alcohols. Monoesters of fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Particularly preferred according to the present invention are isopropyl myristate (Rilanit® IPM), isononanoic acid C16-18 alkyl ester (Cetiol® SN), 2-ethylhexyl palmitate (Cegesoft® 24), stearic acid 2-ethylhexyl ester (Cetiol® 868), cetyl oleate, glycerol tricaprylate, coconut fatty alcohol caprinate/caprylate (Cetiol® LC), n-butyl stearate, oleyl erucate (Cetiol® J 600), isopropyl palmitate (Rilanit® IPP), oley oleate (Cetiol®), lauric acid hexyl ester (Cetiol® A), di-n-butyl adipate (Cetiol® B), myristyl myristate (Cetiol® MM), cetearyl isononanoate (Cetiol® SN), oleic acid decyl ester (Cetiol® V).
- Dicarboxylic acid esters such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, di-(2-ethylhexyl)succinate, and diisotridecyl acelaate, as well as diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di-(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate, neopentyl glycol dicaprylate.
- Symmetrical, asymmetrical, or cyclic esters of carbonic acid with fatty alcohols, described for example in German Application 197 56 454, glycerol carbonate, or dicaprylyl carbonate (Cetiol® CC).
- Fatty acid triesters of saturated and/or unsaturated linear and/or branched fatty acids with glycerol.
- Fatty acid partial glycerides include monoglycerides, diglycerides, and industrial mixtures thereof. When industrial products are used, small quantities of triglycerides may still be present for manufacturing-related reasons. Partial glycerides preferably conform to formula (D4-I):

- wherein R¹, R²and R³are, mutually independently, hydrogen or a linear or branched, saturated and/or unsaturated acyl residue having 6 to 22, preferably 12 to 18, carbon atoms, with the provision that at least one of these groups is an acyl residue and at least one of these groups is hydrogen. The sum (m+n+q) is 0 or a number from 1 to 100, preferably 0 or 5 to 25. Preferably R¹is an acyl residue and R²and R³are hydrogen, and the sum (m+n+q) is 0. Typical examples are mono- and/or diglycerides based on hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, as well as industrial mixtures thereof. Oleic acid monoglycerides are preferably used.

The amount of natural and synthetic cosmetic oily substances used in agents according to the present invention is usually from 0.1 to 30 wt % based on the entire application preparation, preferably 0.1 to 20 wt %, and in particular 0.1 to 15 wt %.
Although each of the aforesaid care-providing substances already yields a satisfactory result of itself, all embodiments wherein the agent contains multiple care-providing substances, including from different groups, are also included within the scope of the present invention.
Addition of a UV filter allows both the preparations themselves, and the treated fibers, to be protected from damaging influences of UV radiation. At least one UV filter is therefore preferably added to cosmetic agents according to the present invention. Suitable UV filters are not subject to any general restrictions in terms of their structure and their physical properties. Instead, all UV filters usable in the cosmetics sector, whose absorption maximum lies in the UVA (315 to 400 nm) UVB (280 to 315 nm), or UVC (<280 nm) regions, are suitable. UV filters having an absorption maximum in the UVB region, particularly from approximately 280 to approximately 300 nm, are particularly preferred.
Preferred UV filters are chosen from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoles, and o-aminobenzoic acid esters.
Examples of usable UV filters are 4-aminobenzoic acid, N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl)aniline methylsulfate, 3,3,5-trimethylcyclohexyl salicylate (Homosalate), 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium, and triethanolamine salts thereof, 3,3′-(1,4-phenylenedimethylene)-bis(7,7-dimethyl-2-oxo-bicyclo-[2.2.1]hept-1-yl-methanesulfonic acid) and salts thereof, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione, α-(2-oxoborn-3-yl idene)toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul® P 25), 4-dimethylaminobenzoic acid 2-ethylhexyl ester, salicylic acid 2-ethylhexyl ester, 4-methoxycinnamic acid isopentyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the sodium salt thereof (Benzophenone-4; Uvinul® MS 40; Uvasorb® S 5), 3-(4′-methylbenzylidene) D,L-camphor, 3-benzylidene camphor (3-Benzylidene Camphor), 4-isopropylbenzylsalicylate, 2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxi)-1,3,5-triazine, 3-imidazol-4-ylacrylic acid and ethyl esters thereof, polymers of N4(2 and 4)-[2-oxoborn-3-yl idenemethyl]benzyl}acrylamide, 2,4-dihydroxybenzophenone, 1,1′-diphenylacrylonitrilic acid 2-ethylhexyl ester, o-aminobenzoic acid menthyl ester, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5-sodiumsulfonate, and 2-cyano-3,3-diphenylacrylic acid 2′-ethylhexyl ester. 2-Hydroxy-4-methoxy-benzophenone-5-sulfonic acid and the sodium salt thereof, and/or ethoxylated 4-aminobenozic acid ethyl ester, are preferred.
The UV filters are present usually in amounts from 0.01 to 5 wt %, based on the entire application preparation. Quantities from 0.1 to 2.5 wt % are preferred.
In a particular embodiment, the cosmetic agent contains one or more substantive dyes. This allows the keratinic fibers treated upon use of the agent to be not only temporarily structured, but at the same time also dyed. This can be desirable, for example, particularly when only a temporary coloration with conspicuous “fashion” colors is desired, which can be removed again from the keratinic fibers simply by washing.
Substantive dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, or indophenols. Preferred substantive dyes are the compounds known by the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57:1, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(β-hydroxyethyl)amino-2-nitrobenzene, 3-nitro-4-(βhydroxyethyl)aminophenol, 2-(2′-hydroxyethyl)amino-4,6-dinitrophenol, 1-(2′-hydroxyethyl)amino-4-methyl-2-nitrobenzene, 1-amino-4-(2′-hydroxyethyl)amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2′-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and salts thereof, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid, and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. It is preferred to use cationic substantive dyes. Particularly preferred in this context are

- cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2, and Basic Violet 14;
- aromatic systems that are substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16, and Basic Brown 17; and
- substantive dyes that contain a heterocycle which comprises at least one quaternary nitrogen atom, such as those recited in EP-A2-998 908 in claims 6 to 11.

The dyes also known by the designations Basic Yellow 87, Basic Orange 31, and Basic Red 51 are very particularly preferred cationic substantive dyes of group (c). The cationic substantive dyes marketed under the trademark Arianor® are likewise very particularly preferred cationic substantive dyes according to the present invention.
Agents according to the present invention in this embodiment contain the substantive dyes preferably in an amount from 0.001 to 20 wt %, based on total agent.
It is preferred that the agents according to the present invention be free of oxidizing dye precursor products. Oxidizing dye precursor products are divided into developer components and coupler components. The developer components form the actual dyes with one another under the influence of oxidizing agents or atmospheric oxygen, or by coupling with one or more coupler components.
Agents according to the present invention can be formulated in any form usual for styling agents, for example, as solutions that can be applied onto the hair as a hair lotion or as a pump or aerosol spray, in the form of creams, emulsions, waxes, gels, or also surfactant-containing foaming solutions or other preparations suitable for application to the hair.
Hair creams and hair gels generally contain structuring agents and/or thickening polymers which serve to impart the desired consistency to the products. Structuring agents and/or thickening polymers are typically used in an amount from 0.1 to 10 wt %, based on total product. Quantities from 0.5 to 5 wt %, in particular 0.5 to 3 wt %, are preferred.
Agents according to the present invention are preferably packaged as a pump spray, aerosol spray, pump foam, or aerosol foam.
Here, agents according to the present invention are packaged in a delivery apparatus representing either a pressurized-gas container additionally filled with a propellant (“aerosol container”) or a non-aerosol container.
Pressurized-gas containers from which a product is distributed through a valve as a result of the internal gas pressure of the container are referred to as “aerosol containers.” A “non-aerosol container” is, conversely, a vessel under standard pressure from which a product is distributed by mechanical action by way of a pump system.
Agents according to the present invention are packaged particularly preferably as an aerosol hair foam or aerosol hair spray. The agent therefore preferably additionally contains at least one propellant.
Suitable propellants according to the present invention include N₂O, dimethyl ether, CO₂, air, alkanes having 3 to 5 carbon atoms such as propane, n-butane, isobutane, n-pentane, and isopentane, and mixtures thereof. Dimethyl ether, propane, n-butane, isobutane, and mixtures thereof are preferred.
According to a preferred embodiment, the alkanes, mixtures of the alkanes, or mixtures of the alkanes with dimethyl ether are used as the only propellant. The invention also expressly includes, however, concurrent use of chlorofluorocarbon propellants, particularly fluorocarbons.
For a given spray apparatus, the size of the aerosol droplets or foam bubbles and the respective size distribution can be adjusted by way of the quantitative ratio between the propellant and the other constituents of the preparations.
The amount of propellant used varies as a function of the specific composition of the agent, the packaging used, and the desired type of product (e.g., hair spray or hair foam). When conventional spray apparatuses are used, aerosol foam products contain propellant preferably in amounts from 1 to 35 wt %, based on total product. Quantities from 2 to 30 wt %, particularly 3 to 15 wt %, are particularly preferred. Aerosol sprays generally contain larger quantities of propellant. As such, the propellant is used preferably in an amount from 30 to 98 wt %, based on total product. Quantities from 40 to 95 wt %, particularly 50 to 95 wt %, are particularly preferred.
Aerosol products can be manufactured in usual fashion. All ingredients of the particular agent except for the propellant are introduced into a suitable pressure-tight container. The latter is then sealed with a valve. Lastly, the desired quantity of propellant is introduced using conventional techniques.
Isopentane is preferably suitable as a propellant for foaming gel-type agents in a two-chamber aerosol container, wherein propellant is incorporated into the agents according to the present invention and is packaged in the first chamber of the two-chamber aerosol container. Packaged in the second chamber of the two-chamber aerosol container is at least one further propellant different from isopentane that builds up in the two-chamber aerosol container a higher pressure than the isopentane. The propellants of the second chamber are preferably chosen from N₂O, dimethyl ether, CO₂, air, alkanes having 3 or 4 carbon atoms (such as propane, n-butane, isobutane), and mixtures thereof.
A preferred embodiment of the agent according to the present invention is aerosol hair foams or aerosol hair sprays containing the agent according to the present invention described previously, and at least one propellant.
Preferred agents according to the present invention and propellants of the aerosol hair foam or aerosol hair spray, as well as the respective quantities of propellant, correspond to the statements already made above.
A second subject of the invention is use of the agents according to the present invention for temporary deformation of hair and/or for hair care.
The agents according to the present invention, and products that contain these agents, in particular aerosol hair foams or aerosol hair sprays, are notable in particular for imparting a very strong, durable hairstyle hold to the treated hair, even though the hair remains flexible. If the agent is packaged as hair foam, a stable, fine-pored, and creamy foam forms, which can be distributed onto the hair evenly and without dripping.
A third subject of the invention is a method for treating keratin-containing fibers, particularly human hair, wherein, using a delivery apparatus, an agent in accordance with the first subject of the invention is foamed into a foam and the resulting foam is applied onto the keratin-containing fibers.
It is preferred that a shape is imparted to the keratin-containing fibers, and that the shape is fixed in place by the agent of the first subject of the invention.
The discharge apparatuses recited earlier (see above) are considered preferred according to the present invention.
A fourth subject of the invention is a method for treating keratin-containing fibers, particularly human hair, wherein, using a delivery apparatus, an agent according to the first subject of the invention is applied as a spray onto the keratin-containing fibers.
It is preferred according to the present invention that a shape is imparted to the keratin-containing fibers, and that the shape is fixed in place by the agent of the first subject of the invention.
The discharge apparatuses recited earlier (see above) are considered preferred according to the present invention.
The Examples that follow are intended to explain the subject matter of the present invention without in any way limiting it.

EXAMPLES

Unless otherwise noted, the quantitative indications below are understood as percentages by weight.
The following formulations were produced by mixing the raw materials indicated:


Raw materials	A	B	C	D

Amphomer¹	2.0	—	3.0	4.0
2-Amino-2-methylpropan-1-ol	0.4	0.2	0.5	0.7
HPS 1²	3.0	2.0	4.0	—
HPS 2³	—	—	—	4.0
Luvimer ® 36 D⁴	—	1.0	—	—
PEG-40 Hydrogenated Castor Oil	0.1	0.2	0.2	0.1

	Water	to 100

	¹(100% active substance) INCI name: Octylacrylamide/Acrylates/Butylaminoethylmethacrylate Copolymer (National Starch)
	²Nonionic potato starch modified with propylene oxide (propylene oxide content: 10.0 wt %; viscosity: 64,000 mPa · s; weight average: 900 kDa)
	³Nonionic tapioca starch modified with propylene oxide (propylene oxide content: 10.0 wt %; viscosity: 55,000 mPa · s; weight average: 800 kDa)
	⁴Copolymer of tert-butyl acrylate, ethyl acrylate, methacrylic acid (36 wt % active substance in water; INCI name: Acrylates Copolymer) (BASF SE)

All the formulations produced, after use on the hair, an outstandingly flexible hairstyle hold. The hair received very good care.

Claims

1. Agent for treating keratin-containing fibers comprising, in a cosmetically acceptable carrier:

at least one nonionic starch modified with propylene oxide, and

at least one anionic film-forming and/or anionic setting polymer having at least one structural unit of formula (I) and at least one structural unit of formula (II),

wherein

R¹and R²are, mutually independently, a hydrogen atom or a methyl group, with the provision that R¹and R²are not simultaneously a methyl group,

R³is a hydrogen atom or a methyl group,

R⁴is a carbamoyl group, a linear or branched (C₄to C₁₂) alkylaminocarbonyl group, a linear or branched (C₄to C₁₂) alkylaminoethylaminocarbonyl group, a linear or branched (C₄to C₁₂) alkylaminopropylaminocarbonyl group, a linear or branched (C₄to C₁₂) alkyloxycarbonyl group, a linear or branched (C₄to C₁₂) alkylaminoethyloxycarbonyl group, a linear or branched (C₄to C₁₂) alkylaminopropyloxycarbonyl group, a linear or branched (C₂to C₁₂) acyloxy group, and

A¹is a hydroxy group or an organic residue having at least one sulfonic acid group that bonds to the structural fragment via an oxygen atom or an NH group.

2. Agent according to claim 1, wherein the modified nonionic starch is a modified nonionic tapioca starch, a modified nonionic potato starch or mixtures thereof.

3. Agent according to claim 1, wherein the modified nonionic starch is present in an amount from 0.1 wt % to 10 wt %, based on the weight of the agent.

4. Agent according to claim 1, wherein the modified nonionic starch has, in a 43-wt % aqueous solution, a viscosity from 150 to 1,500,000 mPa·s, based on Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm).

5. Agent according to claim 1, wherein the modified nonionic starch has an average molecular weight (weight average) from 50 to 2500 kDa.

6. Agent according to claim 1, wherein the modified nonionic starch has propylene oxide content from 1 to 20 wt %, based on the weight of the modified starch.

7. Agent according to claim 1, wherein the modified nonionic starch is at least an uncrosslinked nonionic starch.

8. Agent according to claim 1, wherein the anionic film-forming and/or anionic setting polymer comprises at least one structural unit of formula (I) chosen from at least one structural unit of formulas (I-1) to (I-5)

9. Agent according to claim 1, wherein the anionic film-forming and/or anionic setting polymer comprises at least one structural unit of formula (II) chosen from at least one structural unit of formulas (II-1) to (II-15)

wherein

X³is an oxygen atom or a NH group,

R⁵is a (C₂to C₁₂) acyl group.

10. Agent according to claim 1, wherein the anionic film-forming and/or anionic setting polymer is chosen from at least one polymer from:

copolymers of acrylic acid, (C₁to C₄) alkyl acrylates, C₄alkylaminoethyl methacrylate, and C₈alkylacrylamide,

copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide,

copolymers of 2-acrylamido-2-methylpropanesulfonic acid, acrylamide, and acrylic acid,

copolymers of vinyl acetate and crotonic acid,

copolymers of vinyl propionate and crotonic acid,

copolymers of vinyl neodecanoate, vinyl acetate, and crotonic acid, and

copolymers of methacrylic acid and ethyl acrylate and tert-butyl acrylate.

11. Agent according to claim 1, wherein the anionic film-forming and/or anionic setting polymer is present in an amount from 0.1 wt % to 20.0 wt %, based on the weight of the agent.

12. Agent according to claim 1, wherein it is present in the form of an aerosol foam or aerosol spray.

13. Method for treating keratin-containing fibers comprising foaming an agent according to claim 1 into a foam using a delivery apparatus, and applying the resulting foam onto the keratin-containing fibers.

14. Method for treating keratin-containing fibers comprising applying as a spray with the use of a delivery apparatus an agent according to claim 1 onto the keratin-containing fibers.