CA2003517A1 - Surfactant mixtures combining cleaning effectiveness with gentleness to skin - Google Patents
Surfactant mixtures combining cleaning effectiveness with gentleness to skinInfo
- Publication number
- CA2003517A1 CA2003517A1 CA002003517A CA2003517A CA2003517A1 CA 2003517 A1 CA2003517 A1 CA 2003517A1 CA 002003517 A CA002003517 A CA 002003517A CA 2003517 A CA2003517 A CA 2003517A CA 2003517 A1 CA2003517 A1 CA 2003517A1
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- Prior art keywords
- composition
- component
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
Abstract
Abstract of the Disclosure Surface-active aqueous compositions containing fatty alcohol ether sulfates and at least one other anionic sur-factant from the group of fatty alcohol ether tartrates and fatty alcohol ether citrates, in which the fatty alcohol ether sulfates and the other anionic surfactants mentioned are present in a quantitative ratio of 70:30 to 1:99, and which also contain from 0.01 to 3% by weight of alkaline earth metal ions, based on the composition as a whole, are distinguished by high skin compatibility, high cleaning effectiveness, and good foaming.
Description
^` Z003517 PATEN~
Docket D 8313 8URFACTANT MIXTURE~ CONBINING CLEANING BFFECTIYBNB8~ ~ITH
Field of the Invention This invention relates to mixtures of surfactants, and to cosmetic and cleaning compositions containing them, which are exceptionally gentle to the skin and also have high effectiveness in cleaning.
Statement of Related Art To enhance their effectiveness, aqueous compositions intended for cleaning normally contain surface-active com-pounds. However, this increased cleaning effect is gener-ally accompanied by an increased stress on the skin. This is true in particul~r for the important class of anionic surfactants.
Although this increased stress on the skin is not a problem in many applications of compositions for cleaning, it should be avoided in the field of personal hygiene com-positions. This applies in particular to people having sensitive or already damaged skin, to small children, and to babies. However, gentleness to the skin is also impor~
tant for products which are intended for frequent appli-cation, are used for intimate hygiene, or come into contact with mucous membranes.
Accordingly, there is a need for personal hygiene com-positions which combine an adequate cleaning effect and satisfactory other properties with distinctly lower stress to the skin.
It is known,that products having improved compatibil-ity with the skin can be obtained by the use of magnesium cations for anionic surfactants, such as fatty alcohol sulfates and ether sulfates.
European patent applications 199 131 and 209 910 relate to esters of hydroxycarboxylic acids, such as for example citric acid and tartaric acid. Anionic surfactant ~0~3517 solutions having improved compatibility with the skin are obtained by partially replacing the usual anionic surfac-tants by such esters.
It is also known that ampholytic and nonionic surfac-tants often have improved skin compatibility, compared withanionic surfactants. For many applications, however, these classes of surfactants cannot be used as a substitute for anionic surfactants, because they do not match the proper-ties of the latter in crucial aspects, for example in their cleaning effectiveness. In addition, the foaming which consumers prefer in shampoos is not guaranteed in composi-tions in which ampholytic surfactants are exclusively or predominantly used.
It is known from an Article published in Arztliche Kosmetologie 13, 39 - 45 (1983) that, in some cases, the skin compatibility of mixtures of anionic and ampholytic surfactants is higher than that of pure anionic surfac-tants. Thus, the skin compatibility of surfactant solu-tions can be increased by the partial replacement of anionic surfactants by ampholytic surfactants, although disadvantages have to be accepted in regard to important properties, such as the cleaning effect and foaming.
Accordingly, it is an object of the present invention to provide detergents which are characterized by high cleaning power and foaming and by distinctly less stress to the skin.
Description of the Invention It has now surprisingly been found that certain com-binations of anionic surfactants which show comparatively high skin compatibility for anionic surfactants produce a synergistic increase in gentleness to the skin. According-ly, it is possible on the basis of these surfactant combi-nations to formulate detergents which combine the advant-ages of anionic surfactants, such as high cleaning power and hiqh foaming, with increased skin compatibility.
Accordingly, the present invention includes aqueous surface-active mixtures containing fatty alcohol ether 200~517 sulfate molecules and molecules of at least one other anionic surfactant selected from the group of fatty alcohol ether tartrates and fatty alcohol ether citrates, in which (a) the mixtures contain from 0.01 to 3% by weight of alkaline earth metal ions, based on the mixture as a whole, and (b) the fatty alcohol ether sulfates and the other anionic surfactants mentioned are present in a quantitative ratio by weight of from 70:30 to 1:99.
In the context of this invention, a fatty alcohol is defined as a compound containing at least one linear carbon chain that is at least six carbon atoms long and that has a hydroxyl substituent on at least one of the terminal car-bons in the chain. The fatty alcohol as a whole may be saturated or unsaturated and linear or branched and may contain other substituents than the required terminal hydroxyl group without falling outside the definition above. These fatty alcohols, on which the fatty alcohol ether sulfates used for the invention are based, may be pure compounds. However, it is usually preferred to use mixtures of various fatty alcohols obtained from natural raw materials, such as fats and oils. Either pure or mixed fatty alcohols can be obtained by methods well known in the art.
A mixture of fatty alcohol molecules to be used in making a fatty alcohol ether sulfate component for the invention is normally first condensed with ethylene oxide (Eoj and/or propylene oxide (P0). These fatty alcohols may be reacted with the alkylene oxides, for example under pressure and in the presence of catalysts, to form fatty alcohol alkoxylates. It is known to one skilled in the art that a mixture of residual quantities of free fatty alcohol and a number of homologous, oligomeric, adducts of 1,2,3, ..... n, n+1, n+2 .... etc. molecules of alkylene oxide per molecule of fatty alcohol, rather than a single adduct, is obtained in alkoxylation reactions such as, for example, the adduction of n moles of ethylene oxide onto 1 mole of fatty alcohol by the known ethoxylation process. The : . :
average degree of alkoxylation (n) is determined by the starting quantities of fatty alcohol and ethylene oxide.
The distribution curve of the homolog mixture generally shows a maximum in the range from n-3 to n+3. More information on these aspects can be found, for example, in the journal Soap/Cosmetics/Chemical Specialities, January 1988, page 34. For the purposes of this invention, the average degree of alkoxylation should be at least 0.7 The desired fatty alcohol ether sulfate molecules may obtained by reaction of fatty alcohol alkoxylates with, for example, sulfur trioxide and subsequent neutralization with alkali metal, alkaline earth metal, or ammonium or organo ammonium hydroxides. Neutralization with alkaline earth metal hydroxides is preferred, because alkaline earth metal cations are needed as part of the compositions of the invention. ;~
It is preferred to use fatty alcohol ether sulfates of which the linear or branched alkyl or alkenyl radicals con~
tain 8 to 22 C atoms. It is also preferred to use fatty alcohol ether sulfates which have an average degree of alkoxylation of 2 to 15 and more especially 3 to 10. The --use of ethoxylated products is particularly preferred. ~ -Fatty alcohol ether tartrates suitable for use in accordance with the invention are monoesters of tartaric ~ ~ -acid with alcohols which represent adducts of ethylene oxide and/or propylene oxide with fatty alcohols. These fatty alcohols may be saturated and/or unsaturated, linear and/or branched. Fatty alcohols containing 8 to 22 C atoms are preferred. Degrees of alkoxylation of 2 to 15 and more especially 3 to 10 are also preferred. So far as the sig-nificance of the~degreejof alkoxylation is concerned, ref-erence is made to the observations in the description of the fatty alcohol ether sulfates. The monoesterified tar-taric acid may be used both directly and also in the form of its salts obtainable by reaction of the non-esterified carboxyl group with corresponding bases. Preferred salts are the alkali metal, alkaline earth metal, and ammonium -` ` 2~51~
and organoammonium salts. Processes for the preparation of these compounds are described in European patent application 209 910.
Fatty alcohol ether citrates suitable for use in accordance with the invention are monoesters and/or di-esters of citric acid with alcohols which are at least predominantly adducts of ethylene oxide and/or propylene oxide with fatty alcohols. These fatty alcohols may be saturated and/or unsaturated, linear and/or branched. It is preferred to use C822 fatty alcohols. Degrees of alkoxylation of 2 to 15 and more especially 3 to 10 are also preferred. So far as the significance of the degree of alkoxylation is concerned, reference is again made to the observations in the description of the fatty alcohol ether sulfates. The mono- and/or di-esterified citric acid may be used both directly and in the form of its salts obtainable by reaction of the nonesterified carboxyl groups or group with corresponding bases. Preferred salts are the alkali metal, alkaline earth metal, and ammonium and organoammonium salts. Processes for the preparation of these compounds are described in European patent - application 199 131.
The ethoxylated compounds are preferred both for the fatty alcohol ether tartrate component and for the fatty alcohol ether citrate component.
Particularly high skin compatibility was observed in with mixtures containing the fatty alcohol ether sulfates and the other anionic surfactants mentioned in a quantitative ratio of 60:40 to 10:90.
Compositions containing a combination of fatty alcohol ether sulfates and fatty alcohol ether tartrates show par-ticularly favorable properties. A particularly preferred fatty alcohol ether tartrate is sodium (lauryl + 7 EO) tartrate.
Compositions containing 0.05 to 1% by weight and more especially 0.05 to 0.5% by weight of alkaline earth metal ions are particularly preferred for the purposes of the `" 21~ 5~7 invention. Particular preference is for magnesium ions.
The surface-active compositions preferably contain a total of 2 to 50% by weight, more preferably 5 to 30% by weight, of total anionic surfactants, including but not limited to the fatty alcohol ether sulfates, tartrates, and citrates described above.
In addition to the anionic surfactants, the composi-tions according to the invention may additionally contain 0.5 to 20% by weight and, more preferably, 1 to 10% by weight of ampholytic and/or zwitterionic surfactants.
Ampholytic surfactants are to be understood herein to be surfactants which, in addition to a C8l8 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO3H group in the molecule. Ampholytic surfactants are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyl-iminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl-aminopropionic acids, and alkylaminoacetic acids containingapproximately 8 to 18 C atoms in the alkyl group.
Zwitterionic surfactants are to be understood herein to be surfactants which contain at least one quaternary ammonium group and at least one -COO or -S03 group in the molecule. Particularly suitable zwitterionic surfactants ~ are the so-called betaines, such as (i) the N-alkyl-N,N-dimethyl ammonium glycinates, for example coconut oil alkyl dimethyl ammonium glycinate, (ii) N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example coconut oil acylaminopropyl dimethyl ammonium glycinate, (iii) 2-alkyl-3-carboxymethyl-3-hydroxy~ethyl imidazolines containing 8 to 18 C atoms in the alkyl or acyl group, and (iv) coconut oil acylaminoethyl hydroxyethyl carboxymethyl glycinate.
The compositions according to the invention show particularly high skin compatibility when they are formulated in such a way that they have a pH value in the vicinity of the neutral point. Accordingly, compositions ` Z~30:~517 having pH values in the range from 5.5 to 7.5 and more especially in the range from 6.5 to 7.5 are preferred.
The compositions according to the invention may be used in a variety of consumer products, such as hair-care compositions, shampoos, body-care lotions, shower bath, and baby-care products.
In addition to the described combination of surfac-tants, these products can contain such typical constituents as emulsifiers, oil components, fats and waxes, solubiliz-ers, thickeners, super-fatting agents, biogenic agents, film formers, fragrances, dyes, pearlescers, foam stabilizers, preservatives, and pH regulators.
Suitable emulsifiers are the substances typically used in cosmetic compositions such as, for example, fatty acid partial glycerides, fatty acid sorbitan partial esters and ethoxylates thereof, soaps, fatty alcohol sulfates, polyol fatty acid esters, fatty alcohol polyglycol ethers, lano-lin, wool wax alcohols, and alkyl phosphates.
Suitable oil components include such substances as paraffin oil, vegetable oils, fatty acid esters, perhydro-squalene (2,6,10,15,19,23-hexamethyltetracosane), and 2-octyl dodecanol, while suitable fats and waxes include, for example, spermaceti, beeswax, montan wax, paraffin, and cetostearyl alcohol.
Suitable solubilizers normally used include low molecular weight monohydric or polyhydric alcohols, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, 1,3-butylene glycol, and diethylene glycol.
Suitable super-fatting agents are such substances as polyethoxylated lanolin derivatives, lecithin derivatives, and fatty acid alkanolamides, the latter of which may also serve as foam stabilizers.
Suitable thickeners include, for example, (i) polysac-charides, particularly xanthan gum, guar gum, agar agar, alginates and tyloses, (ii) carboxymethyl cellulose and hydroxyethyl cellulose, (iii) relatively high molecular weight polyethylene glycol monoesters and diesters of fatty :''- ~'~. .~
200~
acids, tiv) polyacrylates, (v) polyvinyl alcohol, (vi) polyvinyl pyrrolidone, and (vi) electrolytes, such as sodi-um chloride and ammonium chloride, if desired in combina-tion with alkyl ether sulfates.
Suitable biogenic agents include vegetable extracts, protein degradation products, and vitamin complexes.
Suitable film formers include, for example, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose d~rivatives, and the like.
Suitable preservatives include any of the compounds listed as preservatives in the Appendix to the Kosmetik-verordnung (Cosmetics Act, Federal Republic of Germany).
Suitable pearlescers include, in particular, glycol distearic acid esters, such as ethylene glycol distearate, and also fatty acid monoglycol esters.
Suitable dyes include any of the substances suitable and permitted for cosmetic purposes which are listed, for example, in the publication Kosmetische Farbemittel of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, published by Verlag Chemie, Weinheim, 1984, These dyes are normally used in concentrations of from 0.001 to 0.1% by weight, based on the mixture as a whole.
Other optional components of the compositions according to the invention include fragrances and pH
regulators.
The compositions according to the invention are preferably used in products used for the washing, dyeing, waving or rinsing of hair. The mixtures according to the invention are particularly suitable for hair shampoos.
The following Examples are intended to illustrate the invention without limiting it in any way.
E x a m p l e s 1. BINARY MIXTURES CONTAINING AS SURFACTANTS ONLY THE TWO
ANIONIC TYPES REQUIRED FOR THE INVENTION
1.1. Skin compatibility tests 2(~ 517 .. ;,,. . :
,.. ..
The in vitro method developed by Zeidler and Reese, which is described in detail in the journal Arztliche Kos-metologie 13, 39-45 (1983), was used to determine the skin compatibility of the surfactant compositions.
The swelling of pig epidermis was used as a measure of the skin compatibility of the surfactant compositions. The epidermis required for this purpose was obtained immediate-ly after the slaughter of young pigs and was stored in deep frozen form.
To carry out the measurement, 1 centimeter ("cm") x 6 cm strips punched out from the epidermis were immersed for 30 minutes in the surfactant solutions containing 2 % by weight active ingredient; the solutions were kept at 39 C
and adjusted to pH 5. The weight of the swollen strips was then determined after brief rinsing and removal of the ad-hering water by gentle squeezing under defined conditions.
The strips were then dried over calcium chloride for 24 hours and reweighed. To eliminate influences attributable to specific properties of the particular animal or the point of removal, such as back or ~ide, of the test strip from the epidermis, a control measurement was carried out in each case. For this, an immediately adjacent epidermis . :. : .
strip was similarly treated with water instead of the -~
surfactant solution. Numerical values, denoted as "t" for 25the surfactant treatment and "w" for the treatment with water, were derived from the weight measurements according ~;~
to the following equation:
weight (swollen epidermis) - weight (dry epidermis) -t, w = . .
weight (dry epidermis) Finally, the standardized, relative changeiin swelling "Q" -~
is defined as : ~ , . .
t Q = ( ~ 100%
w Accordingly, the Q-value of water is by definition 0 %;
negative values of Q indicate swelling inhibiting ~ ~
9 ~;.
200~517 ,. ,:
properties.
The properties of compositions of a fatty alcohol ether sulfate surfactant mixture "T" with Eucarol TA were investigated. Eucarol~ TA is an aqueous solution of sodium (lauryl +7 EO) tartrate with 25% active ingredient, available from Raffineria Olli Lubrificanti S.p.A. ("ROL"), Milan, Italy. The surfactant mixture T was prepared as follows:
A mixture of 96 kilograms ("kg") of an adduct of 10 moles of ethylene oxide with each mole of C~z18 coconut oil fatty alcohol (54% by weight C12, 22% by weight C14, 10~ by weight Cl6, 12% by weight Cl8), 113 kg of an adduct of 2 moles of ethylene oxide with each mole of Cl2l4 coconut oil fatty alcohol (73% by weight Clz, 27% by weight Cl4), and 24.5 kg of an adduct of 2 moles of ethylene oxide with each mole of an oleyl/cetyl alcohol ~65% by weight Cl8, 30% by weight C16, 5% by weight C14, iodine value 50) was reacted with 74.4 kg of chlorosulfonic acid at a temperature of 10 to 20 C in a continuous reactor, to form sulfuric acid monoesters, and the reaction product was subsequently ;
neutralized with 55.5 kg of a 50% aqueous sodium hydroxide ~ ;
solution diluted with 660 kg water. The alkyl ether sulfate mixture obtained had an anionic surfactant content -~
of 0.592 mole/kg (as determined by two-phase titration by DGF-Einheitsmethode ~DGF Standard Method~ H-III-10). -~
An amount of 28.2 grams ("g") of MgSO4-7H2O (0.114 mole), 4.6 g of trisodium citrate, and 65 g of sodium -~
chloride (1.1 mole) were added to 880 g of this ether sulfate. The surfactant mixture T thus obtained had an anionic surfactant content of approximately 28% by weight, corresponding to approximately 0.59 moles~kg (calculated for an average molecular weight of the anionic surfactants of 475)- -~
Q values, as defined above, were measured for mixture T, Eucarol TA, and mixtures of these materials and are shown in Table 1.
1 0 ' Z00~517 _ Table 1 Weight ratio of the active ingredients, Surfactant mixture T: Eucarol~ TA O value 100 : 0 36 + 11 60 : 40 16 + 8 40 : 60 2 + 7 20 : 80 -8 + 6 0 : 100 36 + 9 1.2. Determination of foamina behavior The foaming behavior of the surfactant compositions was determined using a motorized foam generator in accordance with DIN ("German Industrial Standard") 53 902.
An amount of 340 milliliters ("ml") of surfactant solution, containing 2 % by weight of active ingredient in tap water from Dusseldorf-Holthausen having a hardness of 18 German hardness, was prepared for the test. The foam was generated at room temperature, using a perforated plate with holes 1 millimeter ("mm") in diameter, 10 total beats at a frequency of 50 beats/minute ("min"), and a lifting or beating stroke length of 13 centimeters ("cm"). The foam formed was very fine and thus generally corresponds to the foam formed during shampooing of the hair. The measure-ments were carried out in duplicate, with no fat, oil, orgrease added to the surfactant solution.
~ he foaming behavior of a known high-foaming mixture, containing 42% by weight of Texapon N 25 (= 12~ active ingredient), 10% by weight of Dehyton K (= 3% active ingredient),;l~ by weight of Comperlan ~S (= 1% a~tive ingredient), and 47% by weight water was determined for comparison. Texapon N 25 is an aqueous solution of sodium lauryl ether sulfate (about 28% active ingredient), available from Henkel KGaA, Dusseldorf, FRG; Dehyton K is an aqueous solution of a fatty acid amide derivative of , , ~ ,.
., ... -, 1 1 -: - , ., .:, ~ ~ .
-- 20~17 betaine structure corresponding to the formula:
R-CONH-(CHz)3-N (CH3)2-CH2 COO , with the CTFA name (i.e., the name in the CTFA Cosmetic Ingredient DirectorY published by the Cosmetic, Toiletry and Fragrance Association, Inc., Washington, DC) of Cocoamidopropyl Betaine (about 30% active ingredient, about 5% NaCl), available from Henkel KGaA, Dusseldorf, FRG;
ComperlanX LS is a mixture of coconut oil fatty acid diethanolamide (about 70~) and (lauryl + 2 ethylene oxide) alcohol (about 20%) with water, free amine, free fatty acid, and ester, available from Henkel KGaA, Dusseldorf, FRG.
This mixture was diluted with water, from the same source as that used to dilute the mixtures of Mixture T and Eucarol~ TA, to form a solution containing 2% by weight of active ingredients. The following foam volumes were measured: after 1 min, 240 ml: after 3 min, 210 ml; and `~ -~
after 5 min, 190 ml. ~ ~`
The measured foam volumes generated by the surfactant solutions according to the invention are shown in Table 2 ;~
in percent, based on the foam volume generated by the known high-foaming comparison substance described above.
.:
Table 2 Mixing ratio of the active ingredients Relative foam volume. %
surfactant Mixture T : Eucarol after after after 1 min 3 min 5 min 30100 : 0 87 95 95 ` ' 60 l 40 ` 71 71 79 40 : 60 88 90 95 ;~
20 : 80 83 81 84 0 : 100 88 90 84 ~
ZOO~S17 2. TERN~RY COMPOSITIONS CONTAINING AMPHOLYTIC AND/OR
ZWITTERIONIC SURFACTANTS IN ADDITION TO THE TWO
ANIONIC SURFACTANT TYPES REQUIRED FOR THE INVENTION
2.1. Skin swellin~ measurements The degree of skin swelling produced by aqueous compositions containing 1.6 % by weight active ingredient of a mixture of surfactant mixture T and Eucarol TA in a weight ratio of 20 : 80, based on the active ingredients, along with 0.4% by weight of active ingredient of various ampholytic and~or zwitterionic surfactants, was investigat-ed in the same manner as described in part 1 above for compositions without the zwitterionic and/or amphoteric surfactants. The results are shown in Table 3, which also ~ , repeats from Table 1, for ease of comparison, the value ~;
obtained for a mixture containing 2% by weight active ;-ingredient of the binary mixture of surfactant mixture T
and EucarolX TA without any other surfactants.
Table 3 Zwitterionic and/orO value Ampholytic Surfactant ~ -None -8 + 6 Dehyton AB 301 11 + 5 -~ `~
Dehyton G2 17 + 8 Dehytcn G-SF3 0 + 7 Dehyton C* 3 + 7 Notes for Table 3 1 Aqueous solution of a fatty amine derivative of betaine structure, CTFA name Coco-Betaine (about 30% active -ingredient, about 6% NaCl) available from Henkel KGaA, Dusseldorf, FRG. -2 Aqueous solution of N-hydroxyethyl-N-coconut oil alkyl-amidoethyl glycinate sodium salt, CTFA name: Cocoampho-diacetate (about 30% active ingredient, about 7% NaCl) available from Henkel KGaA, Dusseldorf, FRG.
2003~17 .
Docket D 8313 8URFACTANT MIXTURE~ CONBINING CLEANING BFFECTIYBNB8~ ~ITH
Field of the Invention This invention relates to mixtures of surfactants, and to cosmetic and cleaning compositions containing them, which are exceptionally gentle to the skin and also have high effectiveness in cleaning.
Statement of Related Art To enhance their effectiveness, aqueous compositions intended for cleaning normally contain surface-active com-pounds. However, this increased cleaning effect is gener-ally accompanied by an increased stress on the skin. This is true in particul~r for the important class of anionic surfactants.
Although this increased stress on the skin is not a problem in many applications of compositions for cleaning, it should be avoided in the field of personal hygiene com-positions. This applies in particular to people having sensitive or already damaged skin, to small children, and to babies. However, gentleness to the skin is also impor~
tant for products which are intended for frequent appli-cation, are used for intimate hygiene, or come into contact with mucous membranes.
Accordingly, there is a need for personal hygiene com-positions which combine an adequate cleaning effect and satisfactory other properties with distinctly lower stress to the skin.
It is known,that products having improved compatibil-ity with the skin can be obtained by the use of magnesium cations for anionic surfactants, such as fatty alcohol sulfates and ether sulfates.
European patent applications 199 131 and 209 910 relate to esters of hydroxycarboxylic acids, such as for example citric acid and tartaric acid. Anionic surfactant ~0~3517 solutions having improved compatibility with the skin are obtained by partially replacing the usual anionic surfac-tants by such esters.
It is also known that ampholytic and nonionic surfac-tants often have improved skin compatibility, compared withanionic surfactants. For many applications, however, these classes of surfactants cannot be used as a substitute for anionic surfactants, because they do not match the proper-ties of the latter in crucial aspects, for example in their cleaning effectiveness. In addition, the foaming which consumers prefer in shampoos is not guaranteed in composi-tions in which ampholytic surfactants are exclusively or predominantly used.
It is known from an Article published in Arztliche Kosmetologie 13, 39 - 45 (1983) that, in some cases, the skin compatibility of mixtures of anionic and ampholytic surfactants is higher than that of pure anionic surfac-tants. Thus, the skin compatibility of surfactant solu-tions can be increased by the partial replacement of anionic surfactants by ampholytic surfactants, although disadvantages have to be accepted in regard to important properties, such as the cleaning effect and foaming.
Accordingly, it is an object of the present invention to provide detergents which are characterized by high cleaning power and foaming and by distinctly less stress to the skin.
Description of the Invention It has now surprisingly been found that certain com-binations of anionic surfactants which show comparatively high skin compatibility for anionic surfactants produce a synergistic increase in gentleness to the skin. According-ly, it is possible on the basis of these surfactant combi-nations to formulate detergents which combine the advant-ages of anionic surfactants, such as high cleaning power and hiqh foaming, with increased skin compatibility.
Accordingly, the present invention includes aqueous surface-active mixtures containing fatty alcohol ether 200~517 sulfate molecules and molecules of at least one other anionic surfactant selected from the group of fatty alcohol ether tartrates and fatty alcohol ether citrates, in which (a) the mixtures contain from 0.01 to 3% by weight of alkaline earth metal ions, based on the mixture as a whole, and (b) the fatty alcohol ether sulfates and the other anionic surfactants mentioned are present in a quantitative ratio by weight of from 70:30 to 1:99.
In the context of this invention, a fatty alcohol is defined as a compound containing at least one linear carbon chain that is at least six carbon atoms long and that has a hydroxyl substituent on at least one of the terminal car-bons in the chain. The fatty alcohol as a whole may be saturated or unsaturated and linear or branched and may contain other substituents than the required terminal hydroxyl group without falling outside the definition above. These fatty alcohols, on which the fatty alcohol ether sulfates used for the invention are based, may be pure compounds. However, it is usually preferred to use mixtures of various fatty alcohols obtained from natural raw materials, such as fats and oils. Either pure or mixed fatty alcohols can be obtained by methods well known in the art.
A mixture of fatty alcohol molecules to be used in making a fatty alcohol ether sulfate component for the invention is normally first condensed with ethylene oxide (Eoj and/or propylene oxide (P0). These fatty alcohols may be reacted with the alkylene oxides, for example under pressure and in the presence of catalysts, to form fatty alcohol alkoxylates. It is known to one skilled in the art that a mixture of residual quantities of free fatty alcohol and a number of homologous, oligomeric, adducts of 1,2,3, ..... n, n+1, n+2 .... etc. molecules of alkylene oxide per molecule of fatty alcohol, rather than a single adduct, is obtained in alkoxylation reactions such as, for example, the adduction of n moles of ethylene oxide onto 1 mole of fatty alcohol by the known ethoxylation process. The : . :
average degree of alkoxylation (n) is determined by the starting quantities of fatty alcohol and ethylene oxide.
The distribution curve of the homolog mixture generally shows a maximum in the range from n-3 to n+3. More information on these aspects can be found, for example, in the journal Soap/Cosmetics/Chemical Specialities, January 1988, page 34. For the purposes of this invention, the average degree of alkoxylation should be at least 0.7 The desired fatty alcohol ether sulfate molecules may obtained by reaction of fatty alcohol alkoxylates with, for example, sulfur trioxide and subsequent neutralization with alkali metal, alkaline earth metal, or ammonium or organo ammonium hydroxides. Neutralization with alkaline earth metal hydroxides is preferred, because alkaline earth metal cations are needed as part of the compositions of the invention. ;~
It is preferred to use fatty alcohol ether sulfates of which the linear or branched alkyl or alkenyl radicals con~
tain 8 to 22 C atoms. It is also preferred to use fatty alcohol ether sulfates which have an average degree of alkoxylation of 2 to 15 and more especially 3 to 10. The --use of ethoxylated products is particularly preferred. ~ -Fatty alcohol ether tartrates suitable for use in accordance with the invention are monoesters of tartaric ~ ~ -acid with alcohols which represent adducts of ethylene oxide and/or propylene oxide with fatty alcohols. These fatty alcohols may be saturated and/or unsaturated, linear and/or branched. Fatty alcohols containing 8 to 22 C atoms are preferred. Degrees of alkoxylation of 2 to 15 and more especially 3 to 10 are also preferred. So far as the sig-nificance of the~degreejof alkoxylation is concerned, ref-erence is made to the observations in the description of the fatty alcohol ether sulfates. The monoesterified tar-taric acid may be used both directly and also in the form of its salts obtainable by reaction of the non-esterified carboxyl group with corresponding bases. Preferred salts are the alkali metal, alkaline earth metal, and ammonium -` ` 2~51~
and organoammonium salts. Processes for the preparation of these compounds are described in European patent application 209 910.
Fatty alcohol ether citrates suitable for use in accordance with the invention are monoesters and/or di-esters of citric acid with alcohols which are at least predominantly adducts of ethylene oxide and/or propylene oxide with fatty alcohols. These fatty alcohols may be saturated and/or unsaturated, linear and/or branched. It is preferred to use C822 fatty alcohols. Degrees of alkoxylation of 2 to 15 and more especially 3 to 10 are also preferred. So far as the significance of the degree of alkoxylation is concerned, reference is again made to the observations in the description of the fatty alcohol ether sulfates. The mono- and/or di-esterified citric acid may be used both directly and in the form of its salts obtainable by reaction of the nonesterified carboxyl groups or group with corresponding bases. Preferred salts are the alkali metal, alkaline earth metal, and ammonium and organoammonium salts. Processes for the preparation of these compounds are described in European patent - application 199 131.
The ethoxylated compounds are preferred both for the fatty alcohol ether tartrate component and for the fatty alcohol ether citrate component.
Particularly high skin compatibility was observed in with mixtures containing the fatty alcohol ether sulfates and the other anionic surfactants mentioned in a quantitative ratio of 60:40 to 10:90.
Compositions containing a combination of fatty alcohol ether sulfates and fatty alcohol ether tartrates show par-ticularly favorable properties. A particularly preferred fatty alcohol ether tartrate is sodium (lauryl + 7 EO) tartrate.
Compositions containing 0.05 to 1% by weight and more especially 0.05 to 0.5% by weight of alkaline earth metal ions are particularly preferred for the purposes of the `" 21~ 5~7 invention. Particular preference is for magnesium ions.
The surface-active compositions preferably contain a total of 2 to 50% by weight, more preferably 5 to 30% by weight, of total anionic surfactants, including but not limited to the fatty alcohol ether sulfates, tartrates, and citrates described above.
In addition to the anionic surfactants, the composi-tions according to the invention may additionally contain 0.5 to 20% by weight and, more preferably, 1 to 10% by weight of ampholytic and/or zwitterionic surfactants.
Ampholytic surfactants are to be understood herein to be surfactants which, in addition to a C8l8 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO3H group in the molecule. Ampholytic surfactants are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyl-iminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl-aminopropionic acids, and alkylaminoacetic acids containingapproximately 8 to 18 C atoms in the alkyl group.
Zwitterionic surfactants are to be understood herein to be surfactants which contain at least one quaternary ammonium group and at least one -COO or -S03 group in the molecule. Particularly suitable zwitterionic surfactants ~ are the so-called betaines, such as (i) the N-alkyl-N,N-dimethyl ammonium glycinates, for example coconut oil alkyl dimethyl ammonium glycinate, (ii) N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example coconut oil acylaminopropyl dimethyl ammonium glycinate, (iii) 2-alkyl-3-carboxymethyl-3-hydroxy~ethyl imidazolines containing 8 to 18 C atoms in the alkyl or acyl group, and (iv) coconut oil acylaminoethyl hydroxyethyl carboxymethyl glycinate.
The compositions according to the invention show particularly high skin compatibility when they are formulated in such a way that they have a pH value in the vicinity of the neutral point. Accordingly, compositions ` Z~30:~517 having pH values in the range from 5.5 to 7.5 and more especially in the range from 6.5 to 7.5 are preferred.
The compositions according to the invention may be used in a variety of consumer products, such as hair-care compositions, shampoos, body-care lotions, shower bath, and baby-care products.
In addition to the described combination of surfac-tants, these products can contain such typical constituents as emulsifiers, oil components, fats and waxes, solubiliz-ers, thickeners, super-fatting agents, biogenic agents, film formers, fragrances, dyes, pearlescers, foam stabilizers, preservatives, and pH regulators.
Suitable emulsifiers are the substances typically used in cosmetic compositions such as, for example, fatty acid partial glycerides, fatty acid sorbitan partial esters and ethoxylates thereof, soaps, fatty alcohol sulfates, polyol fatty acid esters, fatty alcohol polyglycol ethers, lano-lin, wool wax alcohols, and alkyl phosphates.
Suitable oil components include such substances as paraffin oil, vegetable oils, fatty acid esters, perhydro-squalene (2,6,10,15,19,23-hexamethyltetracosane), and 2-octyl dodecanol, while suitable fats and waxes include, for example, spermaceti, beeswax, montan wax, paraffin, and cetostearyl alcohol.
Suitable solubilizers normally used include low molecular weight monohydric or polyhydric alcohols, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, 1,3-butylene glycol, and diethylene glycol.
Suitable super-fatting agents are such substances as polyethoxylated lanolin derivatives, lecithin derivatives, and fatty acid alkanolamides, the latter of which may also serve as foam stabilizers.
Suitable thickeners include, for example, (i) polysac-charides, particularly xanthan gum, guar gum, agar agar, alginates and tyloses, (ii) carboxymethyl cellulose and hydroxyethyl cellulose, (iii) relatively high molecular weight polyethylene glycol monoesters and diesters of fatty :''- ~'~. .~
200~
acids, tiv) polyacrylates, (v) polyvinyl alcohol, (vi) polyvinyl pyrrolidone, and (vi) electrolytes, such as sodi-um chloride and ammonium chloride, if desired in combina-tion with alkyl ether sulfates.
Suitable biogenic agents include vegetable extracts, protein degradation products, and vitamin complexes.
Suitable film formers include, for example, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose d~rivatives, and the like.
Suitable preservatives include any of the compounds listed as preservatives in the Appendix to the Kosmetik-verordnung (Cosmetics Act, Federal Republic of Germany).
Suitable pearlescers include, in particular, glycol distearic acid esters, such as ethylene glycol distearate, and also fatty acid monoglycol esters.
Suitable dyes include any of the substances suitable and permitted for cosmetic purposes which are listed, for example, in the publication Kosmetische Farbemittel of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, published by Verlag Chemie, Weinheim, 1984, These dyes are normally used in concentrations of from 0.001 to 0.1% by weight, based on the mixture as a whole.
Other optional components of the compositions according to the invention include fragrances and pH
regulators.
The compositions according to the invention are preferably used in products used for the washing, dyeing, waving or rinsing of hair. The mixtures according to the invention are particularly suitable for hair shampoos.
The following Examples are intended to illustrate the invention without limiting it in any way.
E x a m p l e s 1. BINARY MIXTURES CONTAINING AS SURFACTANTS ONLY THE TWO
ANIONIC TYPES REQUIRED FOR THE INVENTION
1.1. Skin compatibility tests 2(~ 517 .. ;,,. . :
,.. ..
The in vitro method developed by Zeidler and Reese, which is described in detail in the journal Arztliche Kos-metologie 13, 39-45 (1983), was used to determine the skin compatibility of the surfactant compositions.
The swelling of pig epidermis was used as a measure of the skin compatibility of the surfactant compositions. The epidermis required for this purpose was obtained immediate-ly after the slaughter of young pigs and was stored in deep frozen form.
To carry out the measurement, 1 centimeter ("cm") x 6 cm strips punched out from the epidermis were immersed for 30 minutes in the surfactant solutions containing 2 % by weight active ingredient; the solutions were kept at 39 C
and adjusted to pH 5. The weight of the swollen strips was then determined after brief rinsing and removal of the ad-hering water by gentle squeezing under defined conditions.
The strips were then dried over calcium chloride for 24 hours and reweighed. To eliminate influences attributable to specific properties of the particular animal or the point of removal, such as back or ~ide, of the test strip from the epidermis, a control measurement was carried out in each case. For this, an immediately adjacent epidermis . :. : .
strip was similarly treated with water instead of the -~
surfactant solution. Numerical values, denoted as "t" for 25the surfactant treatment and "w" for the treatment with water, were derived from the weight measurements according ~;~
to the following equation:
weight (swollen epidermis) - weight (dry epidermis) -t, w = . .
weight (dry epidermis) Finally, the standardized, relative changeiin swelling "Q" -~
is defined as : ~ , . .
t Q = ( ~ 100%
w Accordingly, the Q-value of water is by definition 0 %;
negative values of Q indicate swelling inhibiting ~ ~
9 ~;.
200~517 ,. ,:
properties.
The properties of compositions of a fatty alcohol ether sulfate surfactant mixture "T" with Eucarol TA were investigated. Eucarol~ TA is an aqueous solution of sodium (lauryl +7 EO) tartrate with 25% active ingredient, available from Raffineria Olli Lubrificanti S.p.A. ("ROL"), Milan, Italy. The surfactant mixture T was prepared as follows:
A mixture of 96 kilograms ("kg") of an adduct of 10 moles of ethylene oxide with each mole of C~z18 coconut oil fatty alcohol (54% by weight C12, 22% by weight C14, 10~ by weight Cl6, 12% by weight Cl8), 113 kg of an adduct of 2 moles of ethylene oxide with each mole of Cl2l4 coconut oil fatty alcohol (73% by weight Clz, 27% by weight Cl4), and 24.5 kg of an adduct of 2 moles of ethylene oxide with each mole of an oleyl/cetyl alcohol ~65% by weight Cl8, 30% by weight C16, 5% by weight C14, iodine value 50) was reacted with 74.4 kg of chlorosulfonic acid at a temperature of 10 to 20 C in a continuous reactor, to form sulfuric acid monoesters, and the reaction product was subsequently ;
neutralized with 55.5 kg of a 50% aqueous sodium hydroxide ~ ;
solution diluted with 660 kg water. The alkyl ether sulfate mixture obtained had an anionic surfactant content -~
of 0.592 mole/kg (as determined by two-phase titration by DGF-Einheitsmethode ~DGF Standard Method~ H-III-10). -~
An amount of 28.2 grams ("g") of MgSO4-7H2O (0.114 mole), 4.6 g of trisodium citrate, and 65 g of sodium -~
chloride (1.1 mole) were added to 880 g of this ether sulfate. The surfactant mixture T thus obtained had an anionic surfactant content of approximately 28% by weight, corresponding to approximately 0.59 moles~kg (calculated for an average molecular weight of the anionic surfactants of 475)- -~
Q values, as defined above, were measured for mixture T, Eucarol TA, and mixtures of these materials and are shown in Table 1.
1 0 ' Z00~517 _ Table 1 Weight ratio of the active ingredients, Surfactant mixture T: Eucarol~ TA O value 100 : 0 36 + 11 60 : 40 16 + 8 40 : 60 2 + 7 20 : 80 -8 + 6 0 : 100 36 + 9 1.2. Determination of foamina behavior The foaming behavior of the surfactant compositions was determined using a motorized foam generator in accordance with DIN ("German Industrial Standard") 53 902.
An amount of 340 milliliters ("ml") of surfactant solution, containing 2 % by weight of active ingredient in tap water from Dusseldorf-Holthausen having a hardness of 18 German hardness, was prepared for the test. The foam was generated at room temperature, using a perforated plate with holes 1 millimeter ("mm") in diameter, 10 total beats at a frequency of 50 beats/minute ("min"), and a lifting or beating stroke length of 13 centimeters ("cm"). The foam formed was very fine and thus generally corresponds to the foam formed during shampooing of the hair. The measure-ments were carried out in duplicate, with no fat, oil, orgrease added to the surfactant solution.
~ he foaming behavior of a known high-foaming mixture, containing 42% by weight of Texapon N 25 (= 12~ active ingredient), 10% by weight of Dehyton K (= 3% active ingredient),;l~ by weight of Comperlan ~S (= 1% a~tive ingredient), and 47% by weight water was determined for comparison. Texapon N 25 is an aqueous solution of sodium lauryl ether sulfate (about 28% active ingredient), available from Henkel KGaA, Dusseldorf, FRG; Dehyton K is an aqueous solution of a fatty acid amide derivative of , , ~ ,.
., ... -, 1 1 -: - , ., .:, ~ ~ .
-- 20~17 betaine structure corresponding to the formula:
R-CONH-(CHz)3-N (CH3)2-CH2 COO , with the CTFA name (i.e., the name in the CTFA Cosmetic Ingredient DirectorY published by the Cosmetic, Toiletry and Fragrance Association, Inc., Washington, DC) of Cocoamidopropyl Betaine (about 30% active ingredient, about 5% NaCl), available from Henkel KGaA, Dusseldorf, FRG;
ComperlanX LS is a mixture of coconut oil fatty acid diethanolamide (about 70~) and (lauryl + 2 ethylene oxide) alcohol (about 20%) with water, free amine, free fatty acid, and ester, available from Henkel KGaA, Dusseldorf, FRG.
This mixture was diluted with water, from the same source as that used to dilute the mixtures of Mixture T and Eucarol~ TA, to form a solution containing 2% by weight of active ingredients. The following foam volumes were measured: after 1 min, 240 ml: after 3 min, 210 ml; and `~ -~
after 5 min, 190 ml. ~ ~`
The measured foam volumes generated by the surfactant solutions according to the invention are shown in Table 2 ;~
in percent, based on the foam volume generated by the known high-foaming comparison substance described above.
.:
Table 2 Mixing ratio of the active ingredients Relative foam volume. %
surfactant Mixture T : Eucarol after after after 1 min 3 min 5 min 30100 : 0 87 95 95 ` ' 60 l 40 ` 71 71 79 40 : 60 88 90 95 ;~
20 : 80 83 81 84 0 : 100 88 90 84 ~
ZOO~S17 2. TERN~RY COMPOSITIONS CONTAINING AMPHOLYTIC AND/OR
ZWITTERIONIC SURFACTANTS IN ADDITION TO THE TWO
ANIONIC SURFACTANT TYPES REQUIRED FOR THE INVENTION
2.1. Skin swellin~ measurements The degree of skin swelling produced by aqueous compositions containing 1.6 % by weight active ingredient of a mixture of surfactant mixture T and Eucarol TA in a weight ratio of 20 : 80, based on the active ingredients, along with 0.4% by weight of active ingredient of various ampholytic and~or zwitterionic surfactants, was investigat-ed in the same manner as described in part 1 above for compositions without the zwitterionic and/or amphoteric surfactants. The results are shown in Table 3, which also ~ , repeats from Table 1, for ease of comparison, the value ~;
obtained for a mixture containing 2% by weight active ;-ingredient of the binary mixture of surfactant mixture T
and EucarolX TA without any other surfactants.
Table 3 Zwitterionic and/orO value Ampholytic Surfactant ~ -None -8 + 6 Dehyton AB 301 11 + 5 -~ `~
Dehyton G2 17 + 8 Dehytcn G-SF3 0 + 7 Dehyton C* 3 + 7 Notes for Table 3 1 Aqueous solution of a fatty amine derivative of betaine structure, CTFA name Coco-Betaine (about 30% active -ingredient, about 6% NaCl) available from Henkel KGaA, Dusseldorf, FRG. -2 Aqueous solution of N-hydroxyethyl-N-coconut oil alkyl-amidoethyl glycinate sodium salt, CTFA name: Cocoampho-diacetate (about 30% active ingredient, about 7% NaCl) available from Henkel KGaA, Dusseldorf, FRG.
2003~17 .
3 Aqueous solution of N-hydroxyethyl-N-alkylamidoethyl propionate, CTFA name: Cocoamphodipropionate (about 40 active ingredient) available from Henkel KGaA, Dusseldorf, FRG.
4 Aqueous solution of a fatty amide derivative of betaine structure, CTFA name: Coco-Betaine (about 31% active ingredient, about 6.5% NaCl) available from Henkel KGaA, ;
Dusseldorf, FRG.
The Q values shown in Table 4 were measured in the investigation of analogous compositions containing the same concentrations of a mixture of surfactant mixture T and Eucarol TA in a weight ratio of 40 : 60, based on the active ingredients, with the same additional surfactants as above.
Table 4 Zwitterionic and/orO value ~-Ampholytic Surfactant None 2 + 7 Dehyton AB 30 -4 + 5 Dehyton~ G -3 + 4 Dehyton~ G-SF 1 + 7 Dehyton~ CB 6 + 4 Dehyton~ K 8 + 5 -~
':
2.2. Foaminq behavior The foaming behavior of these ternary surfactant mixtures was determined in the same way as for the binary mixtures. The aqueous mixtures contained 1.6% by weight of active ingredient o~ the binary composition surfactant~
T/Eucarol TA in the ratio shown below and 0.4% by weight -active ingredient of the third zwitterionic and/or ampho-lytic surfactant component. ~`~
The measured foam volumes of the surfactant solutions ;~ ;
according to the invention are shown in Table 5 in percent, based on the foam volume of the comparison substance. For ~' . ` ' 200~
comparison, the Table also shows the value obtained for a :;
mixture containing 2% by weight active ingredient of the binary composition of surfactant T and Eucarol TA, without any zwitterionic or ampholytic surfactant.
:
Table 5 Zwitterionic and/or Relative foam volumes, Percent Ampholytic Surfactant after after after 1 min 3 min 5 min a) Binary composition of surfactant T and Eucarol TA in a weight ratio ~ `~
of 40 : 60, based on active -~
ingredient None 88 90 95 Dehyton K 74 71 78 Dehyton AB 30 83 76 89 ~-Dehyton G 87 86 94 ~ :
Dehyton G-SF 88 90 95 Dehyton CB 61 62 67 b) Binary composition of surfactant T and Eucarol TA in a weight ratio of 20 : 80, based on active ingredients None 88 90 95 Dehyton~ K . 87 91 94 :-Dehyton AB 30 83 81 94 DehytonX G 74 76 83 Dehyton~ G-SF 83 86 89 DehytonX CB 100 100 94 - :~
2~0~17 ~
3. COMPLETE TOILETRY COMPOSITION EXAMPLES
3.1.Hiqh-foaminq mild sham~oo~
ComponentParts by weiaht EucarolX TA 28 . 8 Surfactant mixture T 17.1 Dehyton0 G-SF 9.7 Edenor~ KPK5 1.0 Comperlan KD6 1.0 -Sodium chloride2.0 ~-Waterbalance to 100 parts Notes for Example 3.1: ;~
Coconut oil/palm kernel oil fatty acid ~ 9.2 ethylene oxide available from Henkel KGaA, Dusseldorf, FRG.
6 Coconut oil fatty acid diethanolamide (about 90% active ingredient) Composition of the fatty acid:
about 56% lauric acid -about 21% myristic acid about 10% palmitic acid about 12% stearic and oleic acids 3.2 Clear colorless shampoo:
ComponentParts bY weiakt Eucarol TA 28.8 Surfactant mixture T 17.1 Dehyton G-SF 9.7 -Comperlan~ KD 1.0 Aminoxid WS 357 1.0 Antil 1418 1.0 ~;
Sodium chloride 1.0 ;
Waterbalance to 100 parts Notes for Example 3.2: ~ ~ -7 Aqueous solution of dimethyl coconut oil acylamidopropyl `~
amine oxide (about 35% active ingredient) (available from Th. Goldschmidt AG ("Goldschmidt"), Essen, FRG) .,"-,:
: . ,, .:
200~i17 , .
8 Aqueous solution of polyoxyethylene polypropylene glycol dioleate (about 40~ active ingredient) (available from Goldschmidt) 3.3. Conditioninq sham~oo:
Component Parts by weight EucarolX TA 28.8 Surfactant mixture T 17.1 Dehyton~ G-SF 9.7 Edenor~ KPK 1.0 Polymer JR~ 40091.0 Sodium chloride 1.0 Water balance to 100 parts Note for Example 3.3:
9 Hydroxyethyl cellulose, quaternized (available from Union Carbide) : .;
3.4.Colorless. clear mild. hi~h-foamin~ sham~oo with ; ~:
creamy foam Component Parts bv weight Eucarol TA 28.8 - :~
Surfactant mixture T 18.2 Dehyton CB 9.7 Alkyl glucoside10 3.3 Edenor~ KPX 1.0 Sodium chloride 0.5 Glucamate DOE-12011 0.5 Water balance to 100 parts Notes for Example 3.4:
10 R1o(ZjX with Z = glucose, x = an average of 1.4, and R1 _ n-alkyl(C1214), 60.8% active ingredient 1' Poly(120)ethylene glycol methyl glucose dioleate -~
(available from Amerchol, Edison, NJ, USA) 20035~7 3.5.Clear. mild. hiah-foaminq conditioninq shampoo Component Parts by weiaht Eucarol~ TA 28.8 Surfactant mixture T 18.2 Dehyton~ G-SF 7.5 Alkyl glucoside as in 3~4 3.3 Comperlan~ KD 1.0 Aminoxid WSX 35 1.0 Dehydol LS312 1.0 Sodium chloride 1.0 AntilX 141 1.0 Merquat~ 55012 1.5 Ethanol 2.0 Waterbalance to 100 parts -Notes for Exam~le 3.5:
(C1214 fatty alcohol + 3 EO), available from Henkel KGaA, Dusseldorf, FRG.
Dimethyl diallyl ammonium chloride/acrylamide copolymer, 0~ active inqredient in water, available from Merck.
'':' ~';,'."'' ' . ~ .: : , ~
':. `''' ' ~
18 -~
;
Dusseldorf, FRG.
The Q values shown in Table 4 were measured in the investigation of analogous compositions containing the same concentrations of a mixture of surfactant mixture T and Eucarol TA in a weight ratio of 40 : 60, based on the active ingredients, with the same additional surfactants as above.
Table 4 Zwitterionic and/orO value ~-Ampholytic Surfactant None 2 + 7 Dehyton AB 30 -4 + 5 Dehyton~ G -3 + 4 Dehyton~ G-SF 1 + 7 Dehyton~ CB 6 + 4 Dehyton~ K 8 + 5 -~
':
2.2. Foaminq behavior The foaming behavior of these ternary surfactant mixtures was determined in the same way as for the binary mixtures. The aqueous mixtures contained 1.6% by weight of active ingredient o~ the binary composition surfactant~
T/Eucarol TA in the ratio shown below and 0.4% by weight -active ingredient of the third zwitterionic and/or ampho-lytic surfactant component. ~`~
The measured foam volumes of the surfactant solutions ;~ ;
according to the invention are shown in Table 5 in percent, based on the foam volume of the comparison substance. For ~' . ` ' 200~
comparison, the Table also shows the value obtained for a :;
mixture containing 2% by weight active ingredient of the binary composition of surfactant T and Eucarol TA, without any zwitterionic or ampholytic surfactant.
:
Table 5 Zwitterionic and/or Relative foam volumes, Percent Ampholytic Surfactant after after after 1 min 3 min 5 min a) Binary composition of surfactant T and Eucarol TA in a weight ratio ~ `~
of 40 : 60, based on active -~
ingredient None 88 90 95 Dehyton K 74 71 78 Dehyton AB 30 83 76 89 ~-Dehyton G 87 86 94 ~ :
Dehyton G-SF 88 90 95 Dehyton CB 61 62 67 b) Binary composition of surfactant T and Eucarol TA in a weight ratio of 20 : 80, based on active ingredients None 88 90 95 Dehyton~ K . 87 91 94 :-Dehyton AB 30 83 81 94 DehytonX G 74 76 83 Dehyton~ G-SF 83 86 89 DehytonX CB 100 100 94 - :~
2~0~17 ~
3. COMPLETE TOILETRY COMPOSITION EXAMPLES
3.1.Hiqh-foaminq mild sham~oo~
ComponentParts by weiaht EucarolX TA 28 . 8 Surfactant mixture T 17.1 Dehyton0 G-SF 9.7 Edenor~ KPK5 1.0 Comperlan KD6 1.0 -Sodium chloride2.0 ~-Waterbalance to 100 parts Notes for Example 3.1: ;~
Coconut oil/palm kernel oil fatty acid ~ 9.2 ethylene oxide available from Henkel KGaA, Dusseldorf, FRG.
6 Coconut oil fatty acid diethanolamide (about 90% active ingredient) Composition of the fatty acid:
about 56% lauric acid -about 21% myristic acid about 10% palmitic acid about 12% stearic and oleic acids 3.2 Clear colorless shampoo:
ComponentParts bY weiakt Eucarol TA 28.8 Surfactant mixture T 17.1 Dehyton G-SF 9.7 -Comperlan~ KD 1.0 Aminoxid WS 357 1.0 Antil 1418 1.0 ~;
Sodium chloride 1.0 ;
Waterbalance to 100 parts Notes for Example 3.2: ~ ~ -7 Aqueous solution of dimethyl coconut oil acylamidopropyl `~
amine oxide (about 35% active ingredient) (available from Th. Goldschmidt AG ("Goldschmidt"), Essen, FRG) .,"-,:
: . ,, .:
200~i17 , .
8 Aqueous solution of polyoxyethylene polypropylene glycol dioleate (about 40~ active ingredient) (available from Goldschmidt) 3.3. Conditioninq sham~oo:
Component Parts by weight EucarolX TA 28.8 Surfactant mixture T 17.1 Dehyton~ G-SF 9.7 Edenor~ KPK 1.0 Polymer JR~ 40091.0 Sodium chloride 1.0 Water balance to 100 parts Note for Example 3.3:
9 Hydroxyethyl cellulose, quaternized (available from Union Carbide) : .;
3.4.Colorless. clear mild. hi~h-foamin~ sham~oo with ; ~:
creamy foam Component Parts bv weight Eucarol TA 28.8 - :~
Surfactant mixture T 18.2 Dehyton CB 9.7 Alkyl glucoside10 3.3 Edenor~ KPX 1.0 Sodium chloride 0.5 Glucamate DOE-12011 0.5 Water balance to 100 parts Notes for Example 3.4:
10 R1o(ZjX with Z = glucose, x = an average of 1.4, and R1 _ n-alkyl(C1214), 60.8% active ingredient 1' Poly(120)ethylene glycol methyl glucose dioleate -~
(available from Amerchol, Edison, NJ, USA) 20035~7 3.5.Clear. mild. hiah-foaminq conditioninq shampoo Component Parts by weiaht Eucarol~ TA 28.8 Surfactant mixture T 18.2 Dehyton~ G-SF 7.5 Alkyl glucoside as in 3~4 3.3 Comperlan~ KD 1.0 Aminoxid WSX 35 1.0 Dehydol LS312 1.0 Sodium chloride 1.0 AntilX 141 1.0 Merquat~ 55012 1.5 Ethanol 2.0 Waterbalance to 100 parts -Notes for Exam~le 3.5:
(C1214 fatty alcohol + 3 EO), available from Henkel KGaA, Dusseldorf, FRG.
Dimethyl diallyl ammonium chloride/acrylamide copolymer, 0~ active inqredient in water, available from Merck.
'':' ~';,'."'' ' . ~ .: : , ~
':. `''' ' ~
18 -~
;
Claims (85)
1. A surface-active aqueous composition, comprising:
(A) a fatty alcohol ether sulfate component of molecules selected from the group consisting of molecules corresponding to the general formula I:
R2-(OC?H2?)m-O-SO3- M+ (I), in which m represents zero or a positive integer, v represents either 2 or 3 and may be independ-ently selected for each of the m units in the formula, R2 represents a monovalent radical derived from a fatty alcohol by removing a terminal -OH group thereof, and M represents an alkali metal cation, an ammonium ion, or one half of an alkaline earth metal cation: the average value of m for the entire fatty alcohol ether sulfate component being at least 0.7; and (B) a partial ester component of molecules selected from the group consisting of molecules conforming to one of the general formulas II or III:
R3-OOC-CH(OH)-CH(OH)-COO-Q (II) (III), wherein R3 represents a group according to general formula IV:
R7-(OC?H2?)n- (IV), in which R7 represents a monovalent radical derived from a fatty alcohol by removing a terminal -OH group thereof, n is zero or a positive integer, and v is 2 or 3 and may be independently selected for each of the n units in the group; Q represents unionized hydrogen, a monovalent cation including a hydrogen cation, or a monovalent fraction of a multivalent cation;
and either (i) one of R4, R5, and R6 represents a group according to general formula IV and the other two of R4, R5, and R6 each represents a group as defined above for Q and may be the same or different, or (ii) one of R4, R5, and R6 represents a group as defined above for Q and the other two of R4, R5, and R6 each represents a group according to general formula IV and may be the same or different, the average value of n for all of the partial ester component being at least 0.7, with the weight ratio of component (A) to component (B) being from 70 : 30 to 1 : 99, said surface-active aqueous composition containing a total of from 0.01 to 3% by weight of alkaline earth metal cations, based on the composition as a whole.
(A) a fatty alcohol ether sulfate component of molecules selected from the group consisting of molecules corresponding to the general formula I:
R2-(OC?H2?)m-O-SO3- M+ (I), in which m represents zero or a positive integer, v represents either 2 or 3 and may be independ-ently selected for each of the m units in the formula, R2 represents a monovalent radical derived from a fatty alcohol by removing a terminal -OH group thereof, and M represents an alkali metal cation, an ammonium ion, or one half of an alkaline earth metal cation: the average value of m for the entire fatty alcohol ether sulfate component being at least 0.7; and (B) a partial ester component of molecules selected from the group consisting of molecules conforming to one of the general formulas II or III:
R3-OOC-CH(OH)-CH(OH)-COO-Q (II) (III), wherein R3 represents a group according to general formula IV:
R7-(OC?H2?)n- (IV), in which R7 represents a monovalent radical derived from a fatty alcohol by removing a terminal -OH group thereof, n is zero or a positive integer, and v is 2 or 3 and may be independently selected for each of the n units in the group; Q represents unionized hydrogen, a monovalent cation including a hydrogen cation, or a monovalent fraction of a multivalent cation;
and either (i) one of R4, R5, and R6 represents a group according to general formula IV and the other two of R4, R5, and R6 each represents a group as defined above for Q and may be the same or different, or (ii) one of R4, R5, and R6 represents a group as defined above for Q and the other two of R4, R5, and R6 each represents a group according to general formula IV and may be the same or different, the average value of n for all of the partial ester component being at least 0.7, with the weight ratio of component (A) to component (B) being from 70 : 30 to 1 : 99, said surface-active aqueous composition containing a total of from 0.01 to 3% by weight of alkaline earth metal cations, based on the composition as a whole.
2. A composition as claimed in claim 1, containing a total of from 0.05 to 1 % by weight of alkaline earth metal cations, based on the composition as a whole.
3. A composition as claimed in claim 2, containing a total of from 0.05 to 0.5 % by weight of alkaline earth metal cations, based on the composition as a whole.
4. A composition as claimed in claim 1, containing a total of from 0.05 to 1 % by weight of magnesium cations, based on the composition as a whole.
5. A composition as claimed in claim 4, containing a total of from 0.05 to 0.5 % by weight of magnesium cations, based on the composition as a whole.
6. A composition as claimed in claim 5, containing total anionic surfactants in an amount of from 2 to 50% by weight, based on the composition as a whole.
7. A composition as claimed in claim 4, containing total anionic surfactants in an amount of from 2 to 50% by weight, based on the composition as a whole.
8. A composition as claimed in claim 3, containing total anionic surfactants in an amount of from 2 to 50% by weight, based on the composition as a whole.
9. A composition as claimed in claim 2, containing total anionic surfactants in an amount of from 2 to 50% by weight, based on the composition as a whole.
10. A composition as claimed in claim 1, containing total anionic surfactants in an amount of from 2 to 50% by weight, based on the composition as a whole.
11. A composition as claimed in claim 10, containing total anionic surfactants in an amount of from 5 to 30% by weight, based on the composition as a whole.
12. A composition as claimed in claim 9, containing total anionic surfactants in an amount of from 5 to 30% by weight, based on the composition as a whole.
13. A composition as claimed in claim 8, containing total anionic surfactants in an amount of from 5 to 30% by weight, based on the composition as a whole.
14. A composition as claimed in claim 7, containing total anionic surfactants in an amount of from 5 to 30% by weight, based on the composition as a whole.
15. A composition as claimed in claim 6, containing total anionic surfactants in an amount of from 5 to 30% by weight, based on the composition as a whole.
16. A composition as claimed in claim 15, in which at least one of the average value of m for all the molecules of component (A) or the average value of n for all the molecules of component (B) is from 3 to 10.
17. A composition as claimed in claim 14, in which at least one of the average value of m for all the molecules of component (A) or the average value of n for all the molecules of component (B) is from 3 to 10.
\
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18. A composition as claimed in claim 13, in which at least one of the average value of m for all the molecules of component (A) or the average value of n for all the molecules of component (B) is from 3 to 10.
19. A composition as claimed in claim 12, in which at least one of the average value of m for all the molecules of component (A) or the average value of n for all the molecules of component (B) is from 3 to 10.
20. A composition as claimed in claim 11, in which at least one of the average value of m for all the molecules of component (A) or the average value of n for all the molecules of component (B) is from 3 to 10.
21. A composition as claimed in claim 1, in which at least one of the average value of m for all the molecules of component (A) or the average value of n for all the molecules of component (B) is from 2 to 15.
22. A composition as claimed in claim 21, in which component (A) is selected from molecules conforming to general formula I with an R2 group containing from 8 to 22 carbon atoms and component (B) is selected from molecules conforming to general formula II or III with R7 containing 8 to 22 carbon atoms.
23. A composition as claimed in claim 20, in which component (A) is selected from molecules conforming to general formula I with an R2 group containing from 8 to 22 carbon atoms and component (B) is selected from molecules conforming to general formula II or III with R7 containing 8 to 22 carbon atoms.
24. A composition as claimed in claim 19, in which component (A) is selected from molecules conforming to general formula I with an R2 group containing from 8 to 22 carbon atoms and component (B) is selected from molecules conforming to general formula II or III with R7 containing 8 to 22 carbon atoms.
25. A composition as claimed in claim 18, in which component (A) is selected from molecules conforming to general formula I with an R2 group containing from 8 to 22 carbon atoms and component (B) is selected from molecules conforming to general formula II or III with R7 containing 8 to 22 carbon atoms.
26. A composition as claimed in claim 17, in which component (A) is selected from molecules conforming to general formula I with an R2 group containing from 8 to 22 carbon atoms and component (B) is selected from molecules conforming to general formula II or III with R7 containing 8 to 22 carbon atoms.
27. A composition as claimed in claim 16, in which component (A) is selected from molecules conforming to general formula I with an R2 group containing from 8 to 22 carbon atoms and component (B) is selected from molecules conforming to general formula II or III with R7 containing 8 to 22 carbon atoms.
28. A composition as claimed in claim 1, in which component (A) is selected from molecules conforming to general formula I with an R2 group containing from 8 to 22 carbon atoms and component (B) is selected from molecules conforming to general formula II or III with R7 containing 8 to 22 carbon atoms.
29. A composition as claimed in claim 28, in which component (B) is selected from molecules conforming to general formula II only.
30. A composition as claimed in claim 27, in which component (B) is selected from molecules conforming to general formula II only.
31. A composition as claimed in claim 26, in which component (B) is selected from molecules conforming to general formula II only.
32. A composition as claimed in claim 25, in which component (B) is selected from molecules conforming to general formula II only.
33. A composition as claimed in claim 24, in which component (B) is selected from molecules conforming to general formula II only.
34. A composition as claimed in claim 23, in which component (B) is selected from molecules conforming to general formula II only.
35. A composition as claimed in claim 22, in which component (B) is selected from molecules conforming to general formula II only.
36. A composition as claimed in claim 21, in which component (B) is selected from molecules conforming to general formula II only.
37. A composition as claimed in claim 1, in which component (B) is selected from molecules conforming to general formula II only.
38. A composition according to claim 37, in which component (B) is selected from molecules conforming to general formula II with R7 representing lauryl and the average value of n for all the molecules in the component being 7.
39. A composition according to claim 36, in which component (B) is selected from molecules conforming to general formula II with R7 representing lauryl and the average value of n for all the molecules in the component being 7.
40. A composition according to claim 35, in which component (B) is selected from molecules conforming to general formula II with R7 representing lauryl and the average value of n for all the molecules in the component being 7.
41. A composition according to claim 34, in which component (B) is selected from molecules conforming to general formula II with R7 representing lauryl and the average value of n for all the molecules in the component being 7.
42. A composition according to claim 33, in which component (B) is selected from molecules conforming to general formula II with R7 representing lauryl and the average value of n for all the molecules in the component being 7.
43. A composition according to claim 32, in which component (B) is selected from molecules conforming to general formula II with R7 representing lauryl and the average value of n for all the molecules in the component being 7.
44. A composition according to claim 31, in which component (B) is selected from molecules conforming to general formula II with R7 representing lauryl and the average value of n for all the molecules in the component being 7.
45. A composition according to claim 30, in which component (B) is selected from molecules conforming to general formula II with R7 representing lauryl and the average value of n for all the molecules in the component being 7.
46. A composition according to claim 29, in which component (B) is selected from molecules conforming to general formula II with R7 representing lauryl and the average value of n for all the molecules in the component being 7.
47. A composition as claimed in claim 46, having a pH
value in the range from 5.5 to 7.5.
value in the range from 5.5 to 7.5.
48. A composition as claimed in claim 29, having a pH
value in the range from 5.5 to 7.5.
value in the range from 5.5 to 7.5.
49. A composition as claimed in claim 28, having a pH
value in the range from 5.5 to 7.5.
value in the range from 5.5 to 7.5.
50. A composition as claimed in claim 10, having a pH
value in the range from 5.5 to 7.5.
value in the range from 5.5 to 7.5.
51. A composition as claimed in claim 7, having a pH value in the range from 5.5 to 7.5.
52. A composition as claimed in claim 4, having a pH value in the range from 5.5 to 7.5.
53. A composition as claimed in claim 3, having a pH value in the range from 5.5 to 7.5.
54. A composition as claimed in claim 1, having a pH value in the range from 5.5 to 7.5.
55. A composition as claimed in claim 54, having a pH
value in the range from 6.5 to 7.5.
value in the range from 6.5 to 7.5.
56. A composition as claimed in claim 53, having a pH
value in the range from 6.5 to 7.5.
value in the range from 6.5 to 7.5.
57. A composition as claimed in claim 52, having a pH
value in the range from 6.5 to 7.5.
value in the range from 6.5 to 7.5.
58. A composition as claimed in claim 51, having a pH
value in the range from 6.5 to 7.5.
value in the range from 6.5 to 7.5.
59. A composition as claimed in claim 50, having a pH
value in the range from 6.5 to 7.5.
value in the range from 6.5 to 7.5.
60. A composition as claimed in claim 49, having a pH
value in the range from 6.5 to 7.5.
value in the range from 6.5 to 7.5.
61. A composition as claimed in claim 48, having a pH
value in the range from 6.5 to 7.5.
value in the range from 6.5 to 7.5.
62. A composition as claimed in claim 47, having a pH
value in the range from 6.5 to 7.5.
value in the range from 6.5 to 7.5.
63. A composition according to any of claims 60 - 62, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
64. A composition according to any of claims 57 - 59, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
65. A composition according to any of claims 54 - 56, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
66. A composition according to any of claims 51 - 53, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
67. A composition according to any of claims 48 - 50, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
68. A composition according to any of claims 45 - 47, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
69. A composition according to any of claims 42 - 44, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
70. A composition according to any of claims 39 - 41, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
71. A composition according to any of claims 36 - 38, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
72. A composition according to any of claims 33 - 35, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
73. A composition according to any of claims 30 - 32, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
74. A composition according to any of claims 27 - 29, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
75. A composition according to any of claims 24 - 26, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
76. A composition according to any of claims 21 - 23, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
77. A composition according to any of claims 18 - 20, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
78. A composition according to any of claims 15 - 17, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
79. A composition according to any of claims 12 - 14, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
80. A composition according to any of claims 9 - 11, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
81. A composition according to any of claims 6 - 8, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
82. A composition according to any of claims 3 - 5, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
83. A composition according to any of claims 1 - 2, additionally comprising from 0.5 to 20 % by weight of ampholytic and/or zwitterionic surfactants, based on the composition as a whole.
84. A composition as claimed in claim 1, effective as a shampoo.
85. A process for treating hair, comprising applying thereto a composition as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3839769.2 | 1988-11-25 | ||
| DE3839769A DE3839769A1 (en) | 1988-11-25 | 1988-11-25 | SURFACE ACTIVE BLENDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2003517A1 true CA2003517A1 (en) | 1990-05-25 |
Family
ID=6367850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002003517A Abandoned CA2003517A1 (en) | 1988-11-25 | 1989-11-21 | Surfactant mixtures combining cleaning effectiveness with gentleness to skin |
Country Status (6)
| Country | Link |
|---|---|
| EP (2) | EP0371339B1 (en) |
| AT (1) | ATE86095T1 (en) |
| CA (1) | CA2003517A1 (en) |
| DE (2) | DE3839769A1 (en) |
| ES (1) | ES2053920T3 (en) |
| WO (1) | WO1990006105A2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4122200A1 (en) * | 1991-07-04 | 1993-01-07 | Henkel Kgaa | AQUEOUS PREPARATIONS OF SURFACE-ACTIVE SUBSTANCES |
| DE4301994C1 (en) * | 1993-01-26 | 1994-08-25 | Wella Ag | Hair and body cleansers |
| ITMI981579A1 (en) * | 1998-07-10 | 2000-01-10 | Condea Augusta Spa | DETERGENT COMPOSITION WITH SOFTENING AND PROTECTIVE ACTION OF NATURAL FIBERS |
| DE19945577B4 (en) * | 1999-09-23 | 2004-08-12 | Cognis Deutschland Gmbh & Co. Kg | Cosmetic and / or pharmaceutical preparations and their use |
| DE19945578B4 (en) * | 1999-09-23 | 2004-08-19 | Cognis Deutschland Gmbh & Co. Kg | Cosmetic and / or pharmaceutical preparations and their use |
| DE10055303A1 (en) * | 2000-11-08 | 2002-05-23 | Cognis Deutschland Gmbh | Use of mixtures |
| DE102004035633A1 (en) * | 2004-07-22 | 2006-02-09 | Cognis Ip Management Gmbh | Conditioning surfactant preparation |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1201411B (en) * | 1985-03-26 | 1989-02-02 | Rol Raffineria Olii Lubrifican | TESNIOACTIVES DERIVED FROM CITRIC ACID |
| IT1187714B (en) * | 1985-07-26 | 1987-12-23 | Rol Raffineria Olii Lubrifican | BIOCARBOXYL HYDROXIACID DERIVATIVES |
| US4759875A (en) * | 1986-01-14 | 1988-07-26 | S. C. Johnson & Son, Inc. | Oxo-derived mild surfactant blends |
-
1988
- 1988-11-25 DE DE3839769A patent/DE3839769A1/en not_active Withdrawn
-
1989
- 1989-11-16 DE DE8989121215T patent/DE58903666D1/en not_active Expired - Fee Related
- 1989-11-16 EP EP89121215A patent/EP0371339B1/en not_active Expired - Lifetime
- 1989-11-16 AT AT89121215T patent/ATE86095T1/en not_active IP Right Cessation
- 1989-11-16 ES ES89121215T patent/ES2053920T3/en not_active Expired - Lifetime
- 1989-11-16 WO PCT/EP1989/001375 patent/WO1990006105A2/en not_active Application Discontinuation
- 1989-11-16 EP EP89912959A patent/EP0445159A1/en active Pending
- 1989-11-21 CA CA002003517A patent/CA2003517A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0445159A1 (en) | 1991-09-11 |
| EP0371339A3 (en) | 1990-08-01 |
| ES2053920T3 (en) | 1994-08-01 |
| WO1990006105A2 (en) | 1990-06-14 |
| EP0371339B1 (en) | 1993-03-03 |
| DE58903666D1 (en) | 1993-04-08 |
| WO1990006105A3 (en) | 1990-07-12 |
| EP0371339A2 (en) | 1990-06-06 |
| ATE86095T1 (en) | 1993-03-15 |
| DE3839769A1 (en) | 1990-05-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |