CA2139495A1 - Hair treatment preparation - Google Patents

Abstract

The use of water-based hair treatment preparations containing a combination of cellulose-based cationic polymers with zwitterionic polymers produces a very significant improvement in wet combability and a shift in dry combability into an optimal range for style retention.

Description

- - ~139~9~

H 470 PCT / 28.05.1993 ~air treatment preparations This invention relates to hair treatment prepara-tions containing a special combination of polymers.
The washing and care of hair is an important part of personal hygiene. Both the washing of hair with shampoos and the decorative finishing of hair styles, for example by coloring or permanent waving, are meas-ures which affect the natural structure and properties of hair. For example, the wet and dry combability of hair, its hold and its body can be adversely affected or the number of split ends can be increased by such measures.
Accordingly, it has long been standard practice to subject the hair to a special aftertreatment. To this end, the hair is treated, normally by rinsing, with special active substances, for example quaternary ammonium salts or special polymers. ComhAhility, hold and body are improved and the number of split ends are reduced by this treatment, depending on the formulation of the preparation used.
Additions of cationic polymers to hair treatment preparations generally lead to an improvement in wet and dry combability. Additions of amphoteric or zwitterion-ic polymers produce significant improvements in wet romh~hility but generally have little effect on dry combability.
Other positive effects can often be obtained by combining several active substances from different classes. Thus, it is known from DE-A1-30 44 738, for example, that hair treatment preparations can be pro-vided with a mixture of amphoteric and cationic poly-mers.
Whereas the improvement in wet combability, i.e.

2139~9~

a reduction in wet combing work, is desirable in every case, the circumstances regarding dry combability are more complicated. Low combing work values characterize an improvement in ro~h~hility. However, if combing work is overly reduced, the hair loses body and hold so that, in extreme cases, certain styles can no longer be created. Accordingly, a certain increase in dry combing work may be entirely desirable, above all in the case of relatively intricate styles, in order to improve style retention.
It has now surprisingly been found that prepara-tions cont~ining a combination of zwitterionic polymers and certain cationic polymers produce a surprisingly good improvement in the properties of hair.
Accordingly, the present invention relates to water-based hair treatment preparations cont~;ning a combination of cationic and zwitterionic polymers in addition to typical cosmetic constituents, characterized in that the cationic polymers are cellulose derivatives and do not contain any imidazolinium groups.
The cationic polymers suitable for use in accord-ance with the invention are cellulose derivatives.
One class of these cellulose derivatives are the substances obtained by modification of a cellulose base with cationic groups.
Examples of cellulose bases are cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and methyl hydroxypropyl cellu-lose.
Typical cationic groups are groups containing quaternary nitrogen or phosphorus atoms. Groups con-taining quaternary nitrogen atoms are preferred. The quaternary nitrogen atoms may contain four different constituents or partly the same substituents and may also be part of a ring system. Preferred substituents 2139~9~

are alkyl groups containing 1 to 4 carbon atoms, aryl groups, alkylaryl groups, cycloalkyl groups, alkoxyalkyl groups and alkoxyaryl ~LUU~s. Trialkyl ammonium groups, particularly trimethyl ammonium groups, are particularly preferred. The cationic groups may be attached to the cellulose base either directly or by intermediate groups. Preferred polymers are those in which the cationic groups are attached to the cellulose base by alkyl chains or alkoxyalkyl groups. Preferred counter-ions to the cationic groups are halide groups, par-ticularly chloride groups, and methosulfate groups.
Examples of such compounds are the compounds described in US-PS 3,472,840 which are commercially available under the name of Polymer J~.
Another class of cationic cellulose derivatives are compounds made up of cationic and nonionic units.
The cationic units may be synthesized similarly to the cationic cellulose derivatives mentioned above.
The cationic units may also be compounds which contain at least one polymerizable group in addition to at least one cationic group. The polymerizable group is preferably a vinyl group. The cationic ~lOU~S are pref-erably the ammonium groups mentioned above. Cationic units such as these are, for example, diallyl dimethyl ammonium chloride, methacrylamidopropyl trimethyl ammonium chloride, dimethyl aminomethacrylate quater-nized with diethyl sulfate and dimethyl aminoethyl methacrylate quaternized with diethyl sulfate.
Nonionic units are, for example, cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cel-lulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, vinyl pyrrolidone, vinyl acetate, acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate. Hydroxyethyl cellulose is a preferred nonionic unit.

2139~9S

Examples of such copolymers are the compounds obtainable under the name of Celquat.
Cationic polymers, which are copolymers of at least ane cationic unit and at least one nonionic unit, are preferred for the purposes of the present invention.
Copolymers in which the nonionic unit is hydroxyethyl cellulose are particularly preferred.
Celquat~L 200, a copolymer of hydroxyethyl cellulose and diallyl dimethyl ammonium chloride, is a particularly preferred cationic polymer.
"Zwitterionic polymers" are polymers which contain quaternary ammonium groups and -COO~ or -S03-groups in the molecule.
Examples of zwitterionic polymers suitable for use in accordance with the invention are the compounds mentioned in GB-A-2,104,091, in EP-A 47 714, in EP-A-283 817 and in DE-A-28 17 369.
Zwitterionic polymers consisting essentially of the following monomers are particularly preferred:
(~) monomers containing quaternary ammonium groups corresponding to general formula (I):

Rl-CH=CR2-Co-x-(cnH2n)-N(+)R3R4R5 A(-) (I) in which Rl and R2 independently of one another represent hydrogen or a methyl group and R3, R4 and R5 independently of one another represent C~
alkyl groups, X is an NH group or an oxygen atom, n is an integer of 2 to 5 and A( ~ is the anion of an organic or inorganic acid and (B) monomeric carboxylic acids corresponding to general formula (II):

2139~9S

R6-C~=CR7-CooH (II) in which R6 and R7 independently of one another are hydrogen or methyl groups.

According to the invention, these compounds may be used both directly and also in salt form, i.e. after neutralization of the polymers, for example with an alkali metal hydroxide. Particulars of the production of these polymers can be found in DE-A-39 29 973.
Polymers based on monomers (~), in which R3, R4 and R5 are methyl groups, X is an NH group and A~) is a halide, methoxysulfate or ethoxysulfate ion, are most particularly preferred. Acrylamidopropyl trimethyl ammonium chloride is a particularly preferred monomer (~). Acrylic acid or an alkali metal salt of acrylic acid, more particularly the sodium salt, is preferably used as the monomer (~) for the polymers mentioned above.
Other preferred zwitterionic polymers are those in which the number of monomers (~) is greater than the number of monomers (B). Ratios of the (~) to (B) monomers of greater than 1.5 are particularly preferred.
Both cationic and zwitterionic polymers are preferably present in the preparations according to the invention in quantities of 0.01 to 10% by weight, based on the preparation as a whole. Quantities of 0.01 to 5%
by weight are particularly preferred.
Preparations containing the cationic polymers and zwitterionic polymers in quantity ratios of S:l to 1:1 have proved to be particularly effective.
It has also been found that particularly good results are obtained in accordance with the invention if the preparations according to the invention also contain a surfactant. The surfactant may be an anionic, cation-~139495 ic, ampholytic, zwitterionic or nonionic surfactant.
Examples of cationic surfactants suitable for use in the hair treatment preparations according to the invention are, in particular, quaternary ammonium compounds, preferably ammonium halides, especially chloride and bromides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl amm~nium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride.
Other cationic surfactants suitable for use in accord-ance with the invention are quaternized protein hydroly-zates.
Also suitable for the purposes of the invention are silicone oils, such as for example the commercially available products Q2-7224 (a stabilized trimethyl silyl amodimethicone; a product of Dow Corning), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (General Electric), SLM-55067 (Wacker) and ABIL~-Quat 3270 and 3272 (Th. Goldschmidt; diquaternary polydimeth-yl siloxanes, Quaternium-80).
Apart from a favourable conditioning effect, alkyl amidoamines, particularly fatty acid amidoamines, such as the stearyl amidopropyl dimethyl amine commer-cially available as TEGO AMIDE~ S 18, are distinguished in particular by their ready biodegradability.
So-called esterquats, such as the dialkyl ammoni-um methosulfates and methyl hydroxyalkyl dialkoyloxy-alkyl ammonium methosulfates marketed under the name STEPANTEX~, are also readily biodegradable.
One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commer - 2139~9S

cial product GLUCQUAT~ of which the CTFA name is Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride.
Particularly preferred cationic surfactants are alkylamidoamines, quaternary ester compounds and quater-nary sugar derivatives.
Anionic surfactants suitable for the preparationsaccording to the invention are any of the anionic sur-factants which are suitable for use on the human body.
They are characterized by a water-solubilizing anionic group, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group containing approximately 10 to 22 carbon atoms. Glycol or polygly-col ether groups, ester, ether and amide groups and also hydroxyl groups may also be present in the molecule.
The following are examples of suitable anionic surfac-tants in the form of the sodium, potassium and ammonium salts and also the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group:
- linear fatty acids containing 10 to 22 carbon atoms (soaps), - ether carboxylic acids corresponding to the formula R-0-(CH2-CH20)~-CH2-COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x = 0 or 1 to 16, - acyl sarcosides containing 10 to 18 carbon atoms in the acyl group, - acyl taurides containing 10 to 18 carbon atoms in the acyl group, - acyl isethionates containing 10 to 18 carbon atoms in the acyl group, - sulfosuccinic acid mono- and dialkyl esters con-taining 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl 213949~

esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, - linear alkane sulfonates containing 12 to 18 carbon atoms, - linear alpha-olefin sulfonates containing 12 to 18 carbon atoms, - alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms, - alkyl sulfates and alkyl polyglycol ether sul-fates corresponding to the formula R-O(CH2-CH20)~-OSO3H, in which R is a preferably linear alkyl group containing 10 to 18 carbon atoms and x = O
or 1 to 12, - mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, - sulfated hydroxyalkyl polyethylene and/or hy-droxyalkyl propylene glycol ethers according to DE-A-37 23 354, - sulfonates of unsaturated fatty acids containing 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 which are adducts of approximately 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms.
Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and also sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters con-taining 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups.

Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one -COO~ or -SO3() group in the molecule. Particularly suitable zwitterionic surfac-tants are the so-called betaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacyl aminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and coco-acyl aminoethyl hydroxyethyl carboxymethyl glycinate.
A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name of Cocamidopro-pyl Betaine.
Ampholytic surfactants are surface-active com-pounds which, in addition to a CB_18 alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO3H group and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyl iminodipropionic acids, N-hydroxyethyl-N-alkyl amidopro-pyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acids all containing approximately 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfac-tants are N-cocoalkyl aminopropionate, cocoacyl amino-ethyl aminopropionate and C12-1B acyl sarcosine.
Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of compounds such as these are - adducts of 2 to 30 mol ethylene oxide and/or 0 to 5 mol propylene oxide with linear fatty alcohols containing 8 to 22 carbon atoms, with fatty acids containing 12 to 22 carbon atoms and with alkyl-phenols containing 8 to 15 carbon atoms in the alkyl group, - Clz22 fatty acid monoesters and diesters of adducts of 1 to 30 mol ethylene oxide with glycerol, - C~22 alkyl mono- and oligoglycosides and ethoxy-lated analogs thereof and - adducts of 5 to 60 mol ethylene oxide with castor oil and hydrogenated castor oil.

The compounds containing alkyl groups used as surfactants may be individual substances. However, it is generally preferred to produce the compounds in question from native vegetable or animal raw materials so that mixtures of compounds differing in their chain length according to the particular raw material used are obtained.
The surfactants which are adducts of ethylene and/or propylene oxide with fatty alcohols or deriva-tives of such adducts may be both products having a "normal-range" homolog distribution and also products having a "narrow-range" homolog distribution. "Normal-range" products are mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow-range products are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxr ides or alcoholates are used as catalysts. It may bebe preferable to use narrow-range products.

2139~95 The quantity of surfactants which may be present in the preparations according to the invention is dependent upon the particular type of surfactant and the purpose for which the preparation is intended.
Hair aftertreatment preparations preferably con-tain cationic and/or nonionic surfactants, more particu-larly in quantities of 0.1 to 10% by weight, based on the preparation as a whole. Quantities of 0.1 to 3% by weight are particularly preferred.
Hair tonics also preferably contain cationic and/or nonionic surfactants, more particularly in quan-tities of 0.1 to 10~ by weight, based on the preparation as a whole. Quantities of 0.1 to 5% by weight are particularly preferred.
Shampoos preferably contain anionic surfactants, if desired in combination with ampholytic and/or non-ionic surfactants, more particularly in quantities of 1 to 50% by weight, based on the preparation as a whole.
Quantities of 3 to 20% by weight are particularly preferred.
The preparations according to the invention pref-erably have pH values of 2.5 to 7 and, more particular-ly, in the range from 3 to 6.
Shampoos, hair aftertreatment preparations and hair tonics are preferred preparations according to the invention. Neverthelessj the preparations may also be permanent wave preparations, dyes, blow-wave prepara-tions and other typical hair treatment preparations.
The preparations may be formulated as aqueous or aqueous/alcoholic solutions, creams, lotions, gels, emulsions and other typical cosmetic preparations.
The preparations may contain any other known constituents according to the type of hair treatment preparation and the particular formulation.
The constituents in question are:

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- nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes, - anionic polymers such as, for example, polyacry-lic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrroli-done/vinyl acrylate copolymers, vinyl acetate/
butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers, acrylic acid/ethyl acrylate/N-tert.butyl acryl-amide terpolymers, - other cationic polymers such as, for example, quaternized cellulose ethers, polysiloxanes containing quaternary groups, acrylamide/dimethyl diallyl ammonium chloride copolymers and dimethyl aminomethacrylate/vinyl pyrrolidone copolymers quaternized with diethyl sulfate, - thickeners, such as agar agar, guar gum, algin-ates and xantham gum, - structurants, such as glucose and maleic acid, - hair-conditioning compounds, such as phospho-lipids, for example soya lecithin, egg lecithin, cephalins, and also silicone oils, - protein hydrolyzates, more particularly elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolyzates, condensation products thereof with fatty acids and quaternized protein hydrolyzates, - perfume oils, dimethyl isosorbide and cyclodex-trins, - solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, ~139995 ~ .

- dyes, - antidandruff agents, such as Piroctone Olamine and Zinc Omadine-, - other substances for pH adjustment, - active substances, such as panthenol, allantoin, pyrrolidone carboxylic acids, plant extracts and vitamins, - light stabilizers, - consistency regulators, such as sugar esters, polyol esters or polyol alkyl ethers, - fats and waxes, such as spermaceti, beeswax, montan wax, paraffins and fatty alcohols, - fatty acid alkanolamides, - complexing agents, such as EDTA, NTA and phos-phonic acids, - swelling and penetration agents, such as glycer-ol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, - opacifiers, such as latex, - pearlescers, such as ethylene glycol monostearate and distearate, - propellents, such as propane/butane mixtures, N2O, dimethyl ether, CO2 and air and - antioxidants, - substantive dyes, - so-called coupler and developer components as oxidation dye precursors, - reducing agents such as, for example, thioglycol-ic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid and ~-mercaptoethane-sulfonic acid, - oxidizing agents, such as hydrogen peroxide, potassium bromate and sodium bromate.
The present invention also relates to a process ,2139g95 for treating hair using a preparation according to the invention.
In a preferred embodiment of the process accord-ing to the invention, preparations containing the combination of active ingredients according to the invention are applied to the hair and, after a certain contact time, generally between a few seconds and about 20 minutes, are rinsed off from the hair either with water or with a preparation largely containing water.
The following Examples are intended to illustrate the invention.

E x a m p l e s I. Determination of wet combability Test methods Wet combability was determined by two different methods. Method 1 is based on the objective determina-tion of wet combing work while method 2 is based on the subjective assessment of examiners.

Method 1:
The combability tests were carried out by the method according to J. 8OC. Cosm. Chem. 1973 ~24) 782.
Combing work was studied on brown hair (Alkinco #6634, tress length 12 cm, tress weight 1 g). The hair used was lightly predamaged (cold-waved or bleached) hair which the average consumer would be expected to have. After the zero measurement, the tresses were soaked with 100 ml of the formulation to be tested.
After a contact time of 5 minutes, the tresses were rinsed out for 1 minute in running water (1 l/min., 38C). To determine wet combing work, the tresses were then remeasured.

~.

Method 2:
Hair tresses weighing approximately 2 g (obtained from the Kerling company) were predamaged by permanent wave treatment and by "medium bleaching" (treatment of the hair for 30 minutes with a 6% H2O2 solution adjusted with ammonia to a pH value of 9.4). The tresses were then washed twice with an aqueous solution of TEXAPON~
N 25 (sodium lauryl ether sulfate) adjusted to an active substance content of 12%. The tresses were then treated for 2 minutes with 0.5 g of the solution to be tested.
Finally, they were rinsed with water at 30C.

Results The composition of the test mixtures and the results of the combability tests are set out in Table 1.
The combing work values determined by method 1 are all based on the value of the zero measurement. The scores for the subjective assessment by method 2 ranged from 1 = very good through 2 = good, 3 = satisfactory and 4 =
adequate to 5 = unsatisfactory.

Table 1 (quantitie~ in part~ by weight) Component / mixture C1 C2 I1 C3 C4 CELQUAT~L 200~ 0.1 - 0.05 - 0.05 Acrylamidopropyl methyl ammonium chloride/acrylic acid copolymer, neutralized with sodium hydroxide (Polymer Pl acc. to DE 39 29 973) - 0.1 0.05 - -AMPHOMER~ ~' - - - 0.1 0.05 Water <------- and 100 ------->
Wet combing work - Method 1 [%] 64 46 43 85 72 - Method 2 2-3 2-3 1-2 3-4 3 Hydroxyethyl cellulose/diallyl dimethyl ammonium chloride (95~ active substance; CTFA name: Poly-quaternium-4) (DELFT NATIONAL) ~' Methyl methacrylate/tert.butyl aminoethyl meth-S acrylate/2-hydroxypropyl methacrylate/N-(1,1,3,3-tetramethylbutyl)-acrylamide copolymer II. Determination of curl retention Method A 15 cm long tress (Kerling; tress weight 2 g) was treated for 2 minutes with 0. 5 g of the mixture to be tested. The tress was then rinsed and wound around a glass tube with an external diameter of 2.0 cm, fixed and dried. A measure of the stability of the curl obtained after withdrawal of the glass tube is the so-called curl retention value (CR value) which is defined as ((l-1~)/(1-lo)) * 100%, where 1 is the length of the hair tress (lS cm), lo is the length of the curl immedi-ately after drying and 1~ is the length of the curl after hanging for x hours in a drying cabinet under constant conditions (25C/60% relative air humidity).

Results:
The results of the curl retention tests are set out in Table 2.

Table 2 Measured value / mixture Cl C2 Il C3 C4 CR values after - 6 hours [%] 81.4 82.6 86.5 88.4 82.9 - 8 hours [%] 79.8 80.7 83.7 86.2 81.3 The values for the treatment with pure water were 213~49~
. .

83.2 (after 6 hours) and 79.9 (after 8 hours).

III. Applic~tion Examples S The quantities in the following Examples are %
by weight.

1) Hair rinse STENOL016l82 3.0 CUTINA~9GMS2 0 . 5 EUMULGIN~B 14 O. 4 EUMULGIN~B 25 0.8 EUTANoL~G5 1.0 Acylamidopropyl methyl ammonium chloride/acrylic acid copolymer, neutral-ized with sodium hydroxide (polymer P1 acc. to DE 39 29 973) 0.2 CELQUAT~L200 1.0 GAFQUAT~755-N5 2.5 Water ad 100

2 Cl6/ Cl8 fatty alcohol (HENKEL)

3 Glycerol monostearate (CTFA name: Glyceryl Stearate) (HENKEL)

4 Cetostearyl alcohol containing approx. 12 mol EO
(CTFA name: Ceteareth-12) (HENKEL) Cetostearyl alcohol containing approx. 20 mol EO
(CTFA name: Ceteareth-20) (HENKEL) 6 Condensation product of saturated liquid fatty alcohols, primarily decyl alcohol, prepared by the Guerbet reaction (CTFA name: Octyldodecanol) (HENKEL) 7 Vinyl pyrrolidone/dimethylaminoethyl methacrylate copolymer quaternized with diethyl sulfate (19%
active substance in water) (GAF) 2139~9~

2) Hair rinse STANOL01618 1.8 TEGOAMID~S 18~ 1.6 1,2-Propylene glycol 1.0 Citric acid 0.6 CELQUAT0L 200 1.0 Polymer P1 acc. to DE 39 29 973 0.2 Perfume oil, water ad 100 o 8 N,N-dimethyl-N'-stearoyl-1,3-diaminopropane (CTFA
name: Stearamidopropyl Dimethylamine (GOLDSCHMIDT) 3) Hair rinse STENOL~1618 1.8 STEPANTEX~VS 909 1.8 1,2-Propylene glycol 0.7 Citric acid 0.2 CELQUAT~L 200 1.2 Polymer Pl acc. to DE 39 29 973 0.3 Perfume oil, dye, water ad 100 9 N-methyl-N-(2-hydroxyethyl)-N,N-di-(tallowacyloxy-ethyl)-ammonium methosulfate (90% active substance in isopropanol) (STEPAN) 4) Hair rinse STENOL~1618 2.5 EUMULGIN~B 1 1.0 EUMULGIN~B 2 1.0 EUTANOL~G 0.5 POLAWAX~GP 200ll 0.75 ABIL~QUAT 3270l2 0.5 DOW CORNING~929-Emulsionl3 2.6 Polymer JR0400l4 0.6 Polymer Pl acc. to DE 39 29 973 0.4 2139~95 . .

Citric acid 0.02 Water ad 100 ~ Ester of saturated long-chain fatty alcohols and fatty acids, primarily palmitic acid cetyl ester (CTFA name: Cetyl Palmitate) (HENKEL) Stearyl alcohol/polyethylene glycol stearate mix-ture (CTFA name: Stearyl Alcohol (and) PEG
Stearate) (CRODA) 0 12 Diquaternary polymethyl siloxane (CTFA name: Qua-ternium 80) (GOLDSCHMIDT) 3 Aminofunctional polydimethyl siloxane (35% active substance) (DOW CORNING) 14 Quaternized hydroxyethyl cellulose (CTFA name:
Polyquaternium-10) (UNION CARBIDE)

5) Hair rinse REWOQUAT~W 750015 1 . 1 LANETTE~0l6 3.0 EUMULGIN~B 1 0.8 EUMULGIN~B 2 1.6 CUTINA~GMS 0.5 EUTANOL~G 1.0 Polymer JR~40014 1.0 Polymer Pl acc. to DE 39 29 973 0.4 Water ad 100 5 1-Methyl-2-nortallowalkyl-3-tallow fatty acid amidoethyl imidazolinium methosulfate (approx. 75%
active substance) (REWO) 16 Mixture of higher saturated fatty alcohols, pri-marily cetyl and stearyl alcohol (CTFA name:
Cetearyl Alcohol (HENKEL) 17 Quaternized hydroxyethyl cellulose (CTFA name:
Polyquaternium-10) (UNION CARBIDE) 213999~

6) 8h~mpoo TEXAPON~N 25~ 43.0 DEHYToN'DKI9 10 . O
PLANTAREN0-12002 4.0 S EUPERLAN~PK 300021 1.6 ARQUAD~316n 0.5 CELQUAT~L 200 1.2 Polymer P1 acc. to DE 39 29 973 0.2 GLUCAMATE~DOE 12023 0.5 Sodium chloride 0.2 Water ad 100 18 Sodium lauryl ether sulfate (approx. 28% active substance; CTFA name: Sodium Laureth Sulfate) (HENKEL) ~9 Fatty acid amide derivative, betaine structure, corresponding to the formula R-CONH(CH2)3N+(CH3)2-CH2COO- (approx. 30% active substance; CTFA name:
Cocoamidopropyl Betaine) (HENKEL) 20 C12-C16 alkyl glucoside, degree of oligomerization 1.4 (approx. 50% active substance; CTFA name:
Lauryl Polyglycoside (HENKEL) 21 Liquid dispersion of pearlescing substances and amphosurfactant (approx. 62% active substance;
CTFA name: Glycol Distearate (and) Glycerin (and) Laureth-4 (and) Cocoamidopropyl Betaine) (HENKEL) 22 Tri-C16-alkyl methyl ammonium chloride (AKZO) 23 Ethoxylated methyl glucoside dioleate (CTFA name:
PEG-120 Methyl Glucose Dioleate) (AMERCHOL)

7) 8hampoo TEXAPON~N 70~ 21.0 PLANTAREN~-1200 8.0 GENAMIN~DSAC~ 1.2 CUTINA~EGMS26 0.6 ~1~9495 Polymer JR04Ool4 0.8 Polymer Pl acc. to DE 39 29 973 O.3 ANTIL0141 liquid~ 1.3 Sodium chloride 0.2 Water ad lOO

Sodium lauryl ether sulfate (approx. 72% active substance (~:NK~) ~ Dimethyl distearyl ammonium chloride (HOECHST) 26 Ethylene glycol monostearate (approx. 25-35% mono-ester, 60-70% diester; CTFA name: Glycol Stearate) (HE~KEL) n Polyoxyethylene propylene glycol dioleate (40%
active substance; CTFA Name: Propylene Glycol (and) PEG-55 Propylene Glycol Oleate) (GOLDSCHMIDT)

8) 8h~mpoo TEXAPON0K 14 S28 50.0 DEHYTON0K lO.O
AKYPO~RLM lOO NV29 4.5 CUTINA0AGS~ 2.0 D-Panthenol 0.5 Glucose l.O
Salicylic acid 0.4 Sodium chloride O.5 Polymer P1 acc. to DE 39 29 9730.6 CELQUAT0L 200 0.6 Water ad lOO
28 Sodium lauryl myristyl ether sulfate (approx. 28%
active substance; CTFA name: Sodium Myreth Sul-fate) (~NK~I) 29 C12-14 fatty alcohol+lO ethylene oxide acetic acid sodium salt (22% active substance; CTFA name:

2139~9S

.

Sodium Laureth-ll Carboxylate) (CHEM-Y) 30 Ethylene glycol stearate (approx. 5-15% monoester, 85-95g6 diester; CTFA name: Glycol Distearate) (HENKEL)

9) 8h~mpoo TEXAPON~9K 14 S 25.0 TEXAPONDSB 32~ 7-5 EUCARoL~TA32 12.0 AKYPO~RLM 100 NV 9.0 DEHYTONI9AB 3033 8.3 Sodium chloride 0.5 Polymer Pl acc. to DE 39 29 973 0.6 Polymer JR'19400l4 2.0 Water ad100 3~ Sulfosuccinic acid semiester based on an alkyl polyglycol ether, di-Na salt (approx. 40% active substance; CTFA name: Disodium Laureth Sulfosuc-cinate) (HENKEL) 32 Lauryl alcohol+7 ethylene oxide tartrate sodium salt (approx. 25% active substance; CTFA name:
Sodium Laureth-7 Tartrate) (AUSICHEM) 25 33 Fatty amine derivative, betaine structure (approx.
30% active substance; CTFA name: Coco-Betaine) (HENKEL) 34 Tallow alcohol+60 ethylene oxide myristyl ether (CTFA name: Talloweth-60 Myristyl Glycol) (AKZO)

10) Tonic pack (removable by rinsing) EUMULGIN~B 1 0-5 EUMULGIN~B 2 0.5 CUTINA0CP 1.0 ~139495 EU'rANOl~G 1.5 CARBoPoL~98035 0.004 DOW COkhlNG~929 Emulsion 2.9 Polymer P1 acc. to DE 39 29 973 0.3 CEI.QUAT~L200 2.0 Triethanolamine o.og Water ad 100 3~ Polyacrylic acid (GOODRICH)

11) To~ia paclc ~r~a~n~n~ on th- ~air) CELQUAT~L 200 0.6 1WISKOL~K3036 0.2 D-Panthenol O.5 DEHYQUART~SP7 1.0 NUT~T~
NATROSO1'~'250 HR39 1.1 Polymer Pl acc. to DE 39 29 973 o.5 Water ad 100 36 Polyvinyl pyrrolidone (95% actiYe substance; CTFA
name: PVP) (BASF) 3~ Aqueous solution of hydroxyethyl alkylammonium phosphate (approx. 50% active substance; CTFA
name: Quaternium-52) (n~;NK~;L) 3~ Collagen hydrolyzate (approx. 39% active subs-tance; CTFA name: Hydrolyzed Collagen) (HENKEL) 39 Hydroxyethyl cellulose (AQUALON) 30 12) D~eing cre~
C12,1~ Fatty alcohol 1.2 k ~ 0 4 . O
~IN~B 2 0.8 ~;ull~A~ RD 164 2.0 Sodium sulfite 0.5 :

213949~

L(+) Ascorbic acid 0.5 Ammonium sulfate 0.5 1,2-Propylene glycol 1.2 p-Aminophenol 0.35 p-Tolylene diamine 0.85 2-Methyl resorcinol 0.14 6-Methyl-m-aminophenol 0.42 Polymer Pl acc. to DE 39 29 973 0.5 CELQUAT0L 200 4.0 Ammonia 1.5 Water ad 100 Fatty acid mono/diglyceride emulsifier mixture (CTFA name: Tallow Glycerides (and) Glyceryl Stearate (and) Potassium Stearate) (HENKEL) 13) Developer dispersion for dyeing creAm 12) TEXAPON0N 25 2.1 Hydrogen peroxide (50~) 12.0 TURPINAl0SL4l 1.7 LATEKoLL0D42 12.0 Polymer P1 acc. to DE 39 29 973 0.1 Polymer JR0 400 0.1 Water ad 100 41 1-Hydroxyethane-l,l-diphosphonic acid (60% active substance; CTFA name: Etidronic Acid) (HENKEL) 44 Acrylate/methacrylic acid copolymer (25% active substance) (BASF) The dyeing cream had a pH value of 10Ø It gave the hair a strong red tint.

14) Tinting shampoo TEXAPON~N 70 14.0 DEHYTON~K 10.0 AKYPO~RLM 45 NV43 14.7 PLANTAREN~-1200 4.0 CREMOPHOR~RH 4046 0.8 Dye C.I. 12 719 0.02 Dye C.I. 12 251 0.02 Dye C.I. 12 250 0.04 Dye C.I. 56 059 0.03 PHB ester 0.25 CELQUAT~L200 0.8 Polymer Pl acc. to DE 39 29 973 0.2 Perfume oil q.s.
Water ad 100 5 43 Lauryl alcohol+4.5 ethylene oxide acetic acid sodium salt (20.4% active substance) (CHEM-Y) 44 Castor oil, hydrogenated + 45 ethylene oxide (CTFA
name: PEG-40 Hydrogenated Castor Oil) (BASF) When the hair was washed with this tinting shampoo, it was left bright light blond in color.

15) Permanent wave cream Wave cream PLANTAREN~-80045 5.0 Thioglycoltc acid 8.0 TURPINAL~SL 0.5 Ammonia (25%) 7.3 Ammonium carbonate 3.0 Cetostearyl alcohol 5.0 Guerbet alcohol 4.0 CELQUAT~L200 1.2 Polymer P1 acc. to DE 39 29 973 0.1 Perfume oil q.s.
Water ad 100 ,, . . ~139~9s C8-C~0 alkyl glucoside, degree of oligomerization 1.6 (approx. 60~ active substance) (HENKEL) Fixinq solution PLANTAREN~-800 5.0 Hydrogenated castor oil 2.0 Potassium bromate 3.5 Nitrilotriacetic acid 0.3 Citric acid 0.2 Polymer Pl acc. to DE 39 29 973 0.2 Polymer JR~ 400 1.0 Perfume oil q.S-Water ad 100

Claims (12)

New Claim 1

1. A water-based preparation for the treatment of hair containing a combination of cationic and zwitterionic polymers in addition to typical cosmetic components, characterized in that the cationic polymers are cellulose derivatives and do not contain any imidazolinium groups and the zwitterionic polymers are essentially composed of .alpha.) monomers containing quaternary ammonium groups corre-sponding to general formula (I):

R1-CH=CRZ-CO-Z-(CnH2n)-N(+)R3R4R5 A(-) (I) in which R1 and R2 independently of one another represent hydrogen or a methyl group and R3, R4 and R5 independently of one another represent alkyl groups containing 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer of 2 to 5 and A(-) is the anion of an organic or inorganic acid and .beta.) monomeric carboxylic acids corresponding to general formula (II):

R6 CH=CR7-COOH (II) in which R6 and R7 independently of one another represent hydrogen or methyl groups, or alkali metal, alkaline earth metal, aluminium or ammonium salts of these acids.

2. A preparation as claimed in claim 1, charac-terized in that the cationic polymer is a copolymer of at least one cationic unit and at least one nonionic unit.

3. A preparation as claimed in claim 2, charac-terized in that the nonionic unit is hydroxyethyl cellulose.

4. A preparation as claimed in any of claims 1 to 3, characterized in that the zwitterionic polymers consist essentially of (.alpha.) monomers containing quaternary ammoniun groups corresponding to general formula (I):
R1-CH=CR2-CO-x-(CnH2n)-N(?)R3R4R5 A(-) (I) in which R1 and R2 independently of one another represent hydrogen or a methyl group and R3, R4 and R5 independently of onc another represent C1-4 alkyl groups, X is an NH group or an oxygen atom, n is an integer of 2 to 5 and A(-) is the anion of an organic or inorganic acid and (.beta.) mononeric carboxylic acids corresponding to general formula (II):
R6-CH=CR1-COOH (II) in which R6 and R7 independently of one another are hydrogen or methyl groups, or alkali metal, alkaline earth metal, aluminium or ammonium salts of these acids.

5. A preparation as claimed in claim 4, charac-terized in that the monomer (.alpha.) is acrylamidopropyl trimethyl ammonium chloride while while the monomer (.beta.) is acrylic acid or an alkali metal salt, particularly the sodium salt, of acrylic acid.

6. A preparation as claimed in claim 4 or 5, characterized in that the number of monomers (.alpha.) in the zwitterionic polymer is greater than the number of monomers (.beta.).

7. A preparation as cliamed in any of claims 1 to 6, characterized in that it contains - 0.01 to 10% by weight ans more particularly 0.01 to 5% by weight zwitterionic polymers and - 0.01 to 10% by weight and more particulary 0.01 to 5% by weight cationic polymers, based on the preparation as a whole.

8. A preparation as claimed in any of claims 1 to 7, characterized in that it also contains a surfactant.

9. A preparation as claimed in claim 8, character-ized in that the surfactant is a cationic and/or non-ionic surfactant.

10. A preparation as claimed in any of claims 1 to 9, characterized in that the preparation has a pH value of 2.5 to 7 and, more particularly, in the range from 3.0 to 6Ø

11. A process for treating hair, characterized in that a preparation as claimed in any of claims 1 to 10 is applied to the hair.

12. A process as claimed in claim 11, characterized in that the hair is subsequently rinsed with water or with a preparation largely containing water.