DE4316242A1 - Hair treatment products - Google Patents

Description

The invention relates to hair treatment agents with special bases contain neutralized polymers.

It is known to increase hair volume and bounce as well to support special hairstyle shapes as polymeric compounds Use film formers. These are either the usual treatment agents such as shampoos or conditioners as further active ingredients added, or in special products like hair sprays in a foundation formulated for optimal application.

Both neutralizable and non-neutralized can be used as film formers sizable polymers are used. The development is clear towards neutralizable connections. This is u. a. thereby greening det that, for example, hair setting and hair sprays in increasingly stronger Scope on an alcoholic or aqueous-alcoholic basis instead of z. B. Methylene chloride as a solvent and with lower alkanes or dimethyl ethers can be formulated as propellants instead of CFCs. By correspond appropriate choice of degree of neutralization and used for neutralization Base can neutralize both the properties of the polymers resulting film on the hair as well as the compatibility of the new Tralisbaren polymers with the ü for the selected application form components are improved.

Although there is already experience here, it is still common Problems with the solubility of the polymers at low temperatures as well with liability and washability of the resulting film. Using the usual neutralizing agents aminomethyl propanol and  Aminomethylpropanediol films appear immediately after use with the desired properties; through the subsequent evaporation this base or by diffusion into the hair takes the neutral sationsgrad of the films, so that z. B. the good washability, a Basic requirement for certain hair setting products, over time get lost.

It has now surprisingly been found that when using speci ellen amphoteric bases as neutralizing agents for certain polymers the polymer films formed on the hair are significantly improved.

The invention therefore relates to a hair treatment composition comprising in addition to conventional cosmetic components, anionic (A) and / or hermaphrodite ionic polymers (Z), the anionic groups of 50-100% by ampho tere bases (B) are neutralized, characterized in that

• a) the anionic polymers (A) are selected from
• - Homopolymers of acrylic acid or methacrylic acid and their salts and Derivatives obtained by cross-linking with polyfunctional agents will hold
• - Copolymers of acrylic acid or methacrylic acid with acrylic acid and / or Methacrylic acid esters and / or acrylamides and / or methacrylamides and / or vinyl pyrrolidone,
• Polyaldehydocarboxylic acids and their salts,
• Polyketocarboxylic acids and their salts,
• Polymers of crotonic acid and their copolymers with acrylic acid or methacrylic acid esters and amides,
• b) the zwitterionic polymers (Z) as cationic quaternary groups Contain ammonium groups of the type -N⁺R¹R²R³, where R¹, R² and R³ unab dependent on each other for alkyl groups with 1 to 4 carbon atoms or Hydroxyalkyl groups having 2 to 4 carbon atoms, and
• c) the amphoteric bases (B) at least 2 basic groups and at least contain an acidic group provided that the number of basi groups is greater than the number of acid groups.

French patent specification 2,350,834 has hair lacquers and lotions NEN, which ent both polymers and certain amino acids ent hold. The publication, however, gives no indication of the invention Medium.

The hair treated with the agents according to the invention shows a very natural, lasting bounce. Even in high humidity there is no reduction in hair volume and the hair does not become sticky. The polymer film adheres better to the hair when dry, while swelling slightly when wet; this allows the film to vary If desired, the type of formulation can be achieved by rinsing with pure water be removed. It arises primarily from aqueous-alcoholic formulation a highly elastic film that dries without sticking.

Examples of anionic polymers suitable according to the invention are:

• - Polyacrylic and polymethacrylic acids, their salts, their copolymers with Acrylic acid and methacrylic acid esters and amides and their derivatives, the can be obtained by cross-linking with polyfunctional agents. Connections of this type are for example under the names Carbopol® 934, Carbopol® 934P, Carbopol® 940, Carbopol® 950 Carbopol® 980 and Hostacerin® PN 73 available.
• - Polyoxycarboxylic acids, such as polyketo- and polyaldehydocarboxylic acids and de other salts, such as POC® HS 5060 and POC® AS5060.
• - Polymers and copolymers of crotonic acid with esters and amides of acrylic and methacrylic acid, such as
  • - Vinyl acetate / crotonic acid copolymers, which are commercially available, for example, under the names Resyn® and Gafset®, and
  • - Vinyl acetate / vinyl propionate / crotonic acid copolymers, which are available as Luviset® CA-66 and Luviset® CAP.
• - Vinylpyrrolidone / vinyl acrylate copolymers, available for example at the Luviflex® trademark. A preferred polymer is under Description Luviflex® VBM-35 available vinyl pyrrolidone / acrylate ter polymers.

Zwitterionic polymers suitable according to the invention contain both cationic as well as anionic groups, being called cationic groups contain quaternary ammonium groups of the type -N⁺R¹R²R³, in which R¹, R² and R³ independently of one another for alkyl groups with 1 to 4 carbon atoms or hydroxyalkyl groups having 2 to 4 carbon atoms.

Examples of anionic groups are carbon, sulfone and phos phosphoric acid groups in free form or in salt form. The carbon acid groups and their alkali, alkaline earth, aluminum and ammonium salts are preferred anionic groups.

The zwitterionic polymers used according to the invention can consist of Monomers can be built up that are both cationic and anionic Groups included. In this case, the polymers can consist of one tens of monomer types exist. However, it is also possible to use copolymers from the mentioned monomers and other nonionic monomers. Such nonionic monomers can have, for example, esters and amides Vinyl base, such as methyl acrylate, ethyl acrylate, methyl methacrylate, Ethyl methacrylate, hydroxypropyl methacrylate, acrylamide, vinyl pyrrolidone and Be ethanol. These copolymers preferably contain at least 20%, in particular at least 50%, of ionic monomers.

Zwitterionic polymers preferred in the context of the invention are made of at least 2 ionic monomers, one cationic and one anionic Monomer, built up. Cationic and anionic monomers can in a molar ratio of 1: 1. However, it is preferred to use a mono type, especially the cationic monomers, to be used in excess. As a rule, cationic and anionic monomers in a ratio of 95: 5 used up to 60: 40. The polymers can also be nonionic mono mers of the type mentioned above in amounts up to 50 mol%, in particular up to 20 mol%.

According to the invention, the zwitterionic polymers are preferably those in the DE-A-39 29 973 described zwitterionic polymers that are essentially composed of monomers with quaternary ammonium groups of the general formula (I),

R¹-CH = CR²-CO-Z- (C _n H _2n ) -N (⁺) R³R⁴R⁵ A (⁻) (I)

in which R¹ and R² independently represent hydrogen or a Methyl group and R³, R⁴ and R⁵ independently of one another for alkyl groups 1 to 4 carbon atoms, Z an NH group or an oxygen atom, n an integer from 2 to 5 and A (⁻) the anion of an organic or an organic acid and monomeric carboxylic acids of the general formula (II),

R⁶-CH = CR⁷-COOH (II)

in which R⁶ and R⁷ independently of one another are hydrogen or methyl groups are, or alkali, alkaline earth, aluminum or ammonium salts of these Acids.

The acrylamidopropyl trimethylammonium chloride is a very special one preferred monomer of formula (I).

Monomeric carboxylic acids of the general formula (II) are acrylic acid, meth acrylic acid, crotonic acid and 2-methyl-crotonic acid. Acrylic are preferred or methacrylic acid, especially acrylic acid. Preferably one The salts of these carboxylic acids are lithium, sodium, potassium, Magnesium, calcium and aluminum salt. Na is particularly preferred trium salt. The ammonium salts in which the ammonium ion one to three alkyl groups with 1-4 carbon atoms or Have hydroxyalkyl groups with 2-4 carbon atoms as substituents can. Salts with unsubstituted ammonium ions and triethanolammonium ions are preferred.

Regarding the production of these zwitterionic polymers is express Lich referred to the disclosure of DE-A-39 29 973.

Suitable zwitterionic polymers are also methacrylethylbetaine / Methacrylate copolymers sold under the name Amersette® are available as well as polysiloxane-polyorganobetaine copolymers.

As far as the anionic or zwitterionic polymers in salt form are set, it is the alkali, alkaline earth, ammonium or Mono-, di- or trialkanolammonium salts. The alkali metal salts, ins especially the sodium salts are preferred.  

The anionic or zwitterionic polymers are preferably 80 to 100% neutralized with amphoteric bases (B). The one in the specific case The person skilled in the art can achieve the desired degree of neutralization within the usual range Target concentration ranges for polymer and base.

The polymers mentioned are preferred in the agents according to the invention in Amounts of 0.5 to 10 wt .-%, based on the total agent. Amounts of 1 to 8% by weight are particularly preferred.

The amphoteric bases (B) which can be used according to the invention contain both acidic as well as basic groups. The condition is that the number of basic groups is greater than the number of acidic groups. More common the bases contain two to four basic groups; Bases with 2 or three basic groups are preferred. The number of acidic groups is usually 1 to 3, wherein bases with one or two acidic groups be are preferred.

The basic groups preferably contain a nitrogen atom. Amino, Imino- and heterocyclic nitrogen-containing groups are particularly be prefers. Basic groups which are preferred according to the invention are in for example amino, aminoalkyl, aminohydroxyalkyl such as aminohydroxyethyl and aminohydroxypropyl, aminocarboxyalkyl such as aminocarboxymethyl, Guanidyl, piperidyl and pyridinium groups. Amido groups as in for example, amidoacyl groups are also basic groups in the sense of Invention.

The amphoteric bases according to the invention can be used as acid groups for example contain carboxyl, sulfate and phosphate groups. Carboxyl Groups are preferred.

A preferred group of amphoteric bases are amino acids with several basic groups. Examples of such amino acids are lysine, arginine, Histidine, tryptophan and asparagine.

Another preferred group of amphoteric bases are the so-called betaines, ie peralkylated zwitterions of the formula R¹R²R³N⁺- (CH₂) _x -COO-. R¹ to R³ are, for example, alkyl, hydroxyalkyl, aminoalkyl and carboxyalkyl groups having 1 to 22 carbon atoms and two or three of these groups can also be a heterocyclic radical such as pyridinium or piperidinium, and x is one Number from 1 to 3. The carbon chains in these groups can be linear or branched, saturated or mono- or polyunsaturated. Furthermore, the chain lengths can be both uniform and represent mixtures such as those used in the processing of native raw materials, e.g. B. coconut oil occur. Finally, if desired, the chains can be alkoxylated, in particular ethoxylated or propoxylated, the mean degree of alkoxylation preferably being between 1 and 10. Examples of such betaines which can be used according to the invention are aminopropyl betaine, 2-N-pyridinium-5-aminocaproate and N-carboxymethyl-N-aminopropylpiperidinium betaine.

The agents according to the invention can be either one of the amphoteric mentioned Contain bases as well as mixtures of these bases. Furthermore, you can in addition to the bases according to the invention, the commonly used bases Bases are used to neutralize the polymers. Among these Bases known to those skilled in the art are 2-amino-2-methyl-1-propanol and 2-amino-2- methyl-1,3-propanediol preferred. The quantitative ratio of the fiction moderate bases (B) to these bases is preferably 10: 1 to 1: 2, in particular another 5: 1 to 1: 1.

The amphoteric bases are preferably in amounts of 0.05 to 2% by weight, also based on the total agent. Quantities from 0.2 to 1.0% by weight is particularly preferred.

The further components of the agent according to the invention are by Type of agent determined. For example, if it’s a shampoo, tensides are included as further main components.

All anionic surfactants are suitable for use on humans Body suitable anionic surfactants. These are ge characterized by a water-solubilizing, anionic group such as e.g. B. a carboxylate, sulfate, sulfonate or phosphate group and one lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, Molecule glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be included. Examples of suitable ones  Anionic surfactants are in the form of sodium, potassium and ammo nium and the mono-, di- and trialkanolammonium salts with 2 or 3 C- Atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH₂-CH₂O) _x -CH₂-COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 10,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Sulphosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the Alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• linear alkanesulfonates with 12 to 18 carbon atoms,
• linear alpha-olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH₂-CH₂O) _x -OSO₃H, in which R is a preferably linear alkyl group having 10 to 18 carbon atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 Double bonds according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide Represent fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulf fate and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, as well as sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfons mono-alkyl polyoxyethylsuccinate with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups.

Such surface-active compounds are called zwitterionic surfactants referred to, which in the molecule at least one quaternary ammonium group and  carry at least one -COO (⁻) - or -SO₃ (⁻) group. Particularly suitable zwitterionic surfactants are so-called betaines such as N-alkyl-N, N- dimethylammonium glycinate, for example cocoalkyl dimethylammo niumglycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, at for example the cocoacylaminopropyl dimethylammonium glycinate, and 2- Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each with 8 to 18 C- Atoms in the alkyl or acyl group as well as the cocoacylaminoethylhy droxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fat known under the CTFA name Cocamidopropyl Betaine acid amide derivative.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C₈-C₁₈ alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO₃H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

Non-ionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of poly ol and polyglycol ether group. Such connections are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles Propylene oxide on linear fatty alcohols with 8 to 22 carbon atoms, on fatty acid ren with 12 to 22 carbon atoms and alkylphenols with 8 to 15 carbon atoms in the alkyl group,
• - C₁₂-C₂₂ fatty acid monoesters and diesters of addition products from 1 to 30 moles of ethylene oxide to glycerol,
• - C₈-C₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues,
• - Glycerol mono- and diesters and sorbitan mono- and diesters of saturated ten and unsaturated C₈-C₂₂ fatty acids and their ethylene oxide plant products and  
• - Adducts of 5 to 60 moles of ethylene oxide with castor oil and ge hardened castor oil.

With the compounds with alkyl groups used as surfactants, it can are each a uniform substance. However, it is in the Re gel preferred in the manufacture of these substances from native vegetable or animal raw materials, so that you can mix substances with different alkyl chain lengths depending on the respective raw material receives.

In the case of surfactants, the addition products of ethylene and / or propylene oxide to fatty alcohols or derivatives of these adducts, can use products with a "normal" homolog distribution as well those with a narrow homolog distribution can be used. Under "Normal" homolog distribution, mixtures of homologs are ver stood, which one in the implementation of fatty alcohol and alkylene oxide under Use of alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Restricted In contrast, homolog distributions are obtained if, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earths talloxides, hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be to be preferred.

When formulating the agents according to the invention as hair rinses are white tere preferred components are cationic surfactants and cationic polymers.

Cationic surfactants can be used in the hair treatment according to the invention Finally, especially quaternary ammonium compounds such as alkyl trimethylammonium chloride, dialkyldimethylammonium chloride and trialkyl methylammonium chloride, e.g. B. cetyltrimethylammonium chloride, stearyltri methylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethyl ammonium chloride may be included. Examples of other suitable cationi surfactants are cetylpyridinium chloride and tallow alkyl tris (oligooxy alkyl) ammonium phosphate and quaternized protein hydrolyzates.  

Suitable cationic polymers usually contain a quaternary one Nitrogen atom, for example in the form of an ammonium group. Preferred Cationic polymers are for example

• quaternized cellulose ethers, polysiloxanes with quaternary groups,
• Dimethyldiallylammonium chloride polymers,
• Acrylamide-dimethyldiallylammonium chloride copolymers,
• - Dimethylaminoethyl methacrylate vinyl quaternized with diethyl sulfate pyrrolidone copolymers,
• Vinylpyrrolidone-methoimidazolinium chloride copolymers,
• - quaternized polyvinyl alcohol

as well as those under the designations

• - polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

The preparations according to the invention preferably contain the surface active compounds A in amounts of 0.5 to 30 wt .-%, based on the respective preparation.

The agents according to the invention are particularly preferred as hair fixings formulated medium. In this case, water and lower alcohols are like Ethanol and isopropanol main components of the agent. When formulated as Hair sprays come with blowing agents, e.g. B. dimethyl ether, lower alkanes such as Propane and butane, air, nitrogen, carbon dioxide and nitrous oxide added.

Further constituents of the agents according to the invention can be:

• - Nonionic polymers such as polysiloxanes, polyvinylpyr rolidone and vinyl pyrrolidone copolymers e.g. B. with vinyl acetate,
• Thickeners such as agar agar, guar gum, alginates and xanthan gum,
• Structurants such as glucose and maleic acid,
• - Protein hydrolyzates, especially elastin, collagen, keratin, milk Protein, soy protein and wheat protein hydrolyzates, their condensate on products with fatty acids and quaternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,  
• - Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,
• - dyes,
• - anti-dandruff agents such as Piroctone Olamine and Zink Omadine,
• - substances for adjusting the pH such as citric acid / sodium citrate buffer,
• - Active ingredients such as panthenol, allantoin, pyrrolidone carboxylic acids, plants extracts and vitamins,
• - light stabilizers,
• - consistency agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as walrus, beeswax, montan wax, paraffins and Fatty alcohols,
• - Superfatting agents such as polyethoxylated lanolin derivatives, lecithinderi vate and fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and pri mary, secondary and tertiary phosphates,
• Opacifiers (e.g. polymer dispersions),
• - Pearlescent agents such as ethylene glycol mono- and distearate and
• - antioxidants.

The invention also relates to a method for treating the hair, in which an agent according to claims 1 to 7 is used. Especially be A method is preferred in which the hair after the application of the agents according to the invention can no longer be rinsed.

Examples

The information in the following formulation examples is Ge important parts.

Claims (9)

1. Hair treatment composition containing, in addition to conventional cosmetic components, anionic (A) and / or zwitterionic polymers (Z), whose 50-100% of ionic groups are neutralized by amphoteric bases (B), characterized in that

• a) the anionic polymers (A) are selected from
• Homopolymers of acrylic acid or methacrylic acid and their salts and derivatives, which are obtained by crosslinking with polyfunctional agents,
• Copolymers of acrylic acid or methacrylic acid with acrylic acid and / or methacrylic acid esters and / or acrylamides and / or meth acrylamides and / or vinyl pyrrolidone,
• Polyaldehydocarboxylic acids and their salts,
• Polyketocarboxylic acids and their salts,
• Polymers of crotonic acid and their copolymers with acrylic acid or methacrylic acid esters and amides,
• b) the zwitterionic polymers (Z) contain quaternary ammonium groups of the type -N⁺R¹R²R³ as cationic groups, where R¹, R² and R³ are independently alkyl groups with 1 to 4 carbon atoms or hydroxyalkyl groups with 2 to 4 carbon atoms, and
• c) the amphoteric bases (B) contain at least 2 basic groups and at least one acidic group, provided that the number of basic groups is greater than the number of acidic groups.

2. Composition according to claim 1, characterized in that in the amphoteric Base the basic groups amino, imino or nitrogen-containing he terocyclic groups and the acidic groups are carboxylic acid groups. 3. Composition according to one of claims 1 or 2, characterized in that the amphoteric base (B) is an amino acid or a betaine.   4. Agent according to one of claims 1 to 3, characterized in that the polymers (A) and (Z) to 80-100% with amphoteric bases (B) neutra are listed. 5. Agent according to one of claims 1 to 4, characterized in that the polymers (A) and (Z) in amounts of 0.5 to 10 wt .-%, based on all the means are included. 6. Agent according to one of claims 1 to 5, characterized in that the amphoteric base (B) in amounts of 0.05 to 2% by weight, in particular from 0.1 to 1% by weight, based in each case on the total composition is. 7. Composition according to one of claims 1 to 6, characterized in that it is a hair fixative. 8. A method of treating the hair, characterized in that a Agent according to one of claims 1 to 7 is used. 9. The method according to claim 8, characterized in that the hair after the application of the agent no longer rinsed become.