DE29910159U1 - Liquid detergent mixture - Google Patents

Description

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Liquid detergent mixture

The present invention relates to a liquid aqueous-based detergent mixture with optimal properties, in particular a body cleansing agent, preferably a hair shampoo, or also a manual dishwashing agent. Such agents usually contain at least one surface-active substance, in particular an anionic surfactant, and, in the case of shampoos, also a hair-conditioning polymer, preferably a cationic one.

Although these products have proven themselves, there is still a need to improve their effectiveness, particularly in terms of volume, shine, combability and the feel of the hair washed with them. In addition, a body cleanser is expected to have good foaming power, especially a high foam volume. Finally, such products should also be extremely mild, i.e. completely compatible with the skin and mucous membranes.

It has now been found that a detergent mixture is obtained which optimally meets these requirements if this mixture contains, on an aqueous basis, at least one anionic surfactant, at least one surface-active Cs-C ₂₂ -acylaminocarboxylic acid or its water-soluble salts, and 0.25 to 10% by weight of at least one glycerol mono-Ce-C-is fatty acid ester.

EP 521 965 B1 already discloses aqueous detergent preparations which contain 1 to 20% by weight of a condensation product of C ₁₂ -C ₂₂ fatty acids and amino acids, water-soluble oligo- and/or polypeptides or their water-soluble salts and 1 to 20% by weight of a C ₈ -C ₂₂ alkyl glycoside with a degree of polymerization of 1 to 10.

If necessary, 1 to 8 wt.% of an amphoteric or zwitterionic surfactant can be added to these compositions.
The acylaminocarboxylic acids are used instead of conventional anionic surfactants, the combination of which with alkyl glycosides and optionally amphoteric surfactants has long been known, for example from EP 70 074 B1.

With these known mixtures, the properties achievable with the compositions according to the invention, in particular mildness to the skin and improved foaming ability, cannot be achieved.

A further advantage of these compositions is the self-thickening effectiveness of this surfactant mixture, ie it is not necessary to add additional inorganic or organic thickeners to achieve the viscosity range of 1000 to 10,000 mPa*s at 20 ⁰ C, measured in a Brookfield viscometer, which is particularly preferred for shampoos.
The presence of such thickeners can cause stability problems because they can interfere with other ingredients. This is not the case with compositions based on the composition according to the invention.

Suitable anionic surfactants in the context of the invention are contained in an amount of at least 5 to about 40% by weight, preferably 10 to 25% by weight of the composition.

These are those of the sulfate, sulfonate, carboxylate and alkyl phosphate type, especially of course those which are usually used in shampoos, for example the well-known _CiO -Ci8-alkyl sulfates and in particular the corresponding ether sulfates, for example Ci2-Ci4-alkyl ether sulfate, lauryl ether sulfate, in particular with 1 to 4 ethylene oxide groups in the molecule, furthermore monoglyceride (ether) sulfates, fatty acid amide sulfates which are obtained by ethoxylation and subsequent sulfation of fatty acid alkanolamides,

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and their alkali salts as well as salts of long-chain mono- and dialkyl phosphates, which are mild, skin-compatible detergents.

Anionic surfactants which are also suitable within the scope of the invention are α-olefin sulfonates or their salts and in particular alkali salts of sulfosuccinic acid semiesters, for example the disodium salt of monooctyl sulfosuccinate and alkali salts of long-chain monoalkylethoxy sulfosuccinates.

Suitable carboxylate-type surfactants are alkyl polyether carboxylic acids and
whose salts have the formula

R - (C ₂ M ₄ O) _n - O - CH ₂ COOX,

wherein R is a Ce-C^o-alkyl group, preferably a Ci ₂ -C ₁₄ -alkyl group, η is a number from 1 to 20, preferably 2 to 17, and X is H or preferably a cation from the group sodium, potassium, magnesium and ammonium, which may optionally be hydroxyalkyl-substituted, and alkylamidopolyethercarboxylic acids of the general formula

R— C -N -CH ₂ - CH2 _- ( _{C2 H4} O) - CH ₂ — COOX

I

OH

wherein R and X have the meaning given above and η in particular stands for a number from 1 to 10, preferably 2.5 to 5.

Such products have been known and commercially available for some time, for example under the trade names "&Agr;&Kgr;&Ugr;&Rgr;&Ogr;®" and "AKYPO-SOFT®".

C ₈ -C ₂ o-acylisethionates can also be used, alone or in a mixture with other surfactants, as can sulfo fatty acids and their esters.

Mixtures of several anionic surfactants can also be used, for example a mixture of an a-olefin sulfonate and a sulfo-

fosuccinate, preferably in a ratio of 1:3 to 3:1, or an ether sulfate and a polyethercarboxylic acid or alkylamidoethercarboxylic acid.

An overview of the anionic surfactants used in liquid body cleansing products can be found in the monograph by K. Schrader, "Fundamentals and Recipes of Cosmetics", 2nd edition (1989, Hüthig Buchverlag), pp. 683 to 691.

The preferred range of amounts of anionic surfactants in the liquid personal cleansing agents according to the invention is between about 5 and about 30% by weight, in particular about 7.5 to about 25% by weight, particularly preferably about 10 to about 20% by weight, calculated on the total composition of the agent.

As a second component, the shampoos according to the invention contain at least one C ₈ -C 22 acylaminocarboxylic acid or its water-soluble salts, preferably in an amount of 0.5 to 10, in particular 1 to 7.5% by weight, calculated on the total composition.

N-lauroyl glutamate is particularly preferred, in particular as the sodium salt. Other suitable N-acylaminocarboxylic acids are, for example, N-lauroyl sarcosinate, N-C^-C^-acylaspartic acid, N-myristoyl sarcosinate, N-oleoyl sarcosinate, N-lauroyl methylalanine, N-lauroyl lysine and N-lauroyl aminopropyl glycine, preferably in the form of their water-soluble alkali or ammonium, in particular sodium, salts.

The third essential component of the detergent mixtures according to the invention is a glycerol mono-Cs-Cis fatty acid ester, preferably glyceryl laurate.

The use of these glycerol fatty acid esters in cosmetic products as thickeners and emulsion stabilizers is known. However, it was surprising and unforeseeable that they were used in the special detergent mixtures

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according to the invention have a foam-enhancing and anti-skin-irritation activity.

In addition to the glycerol mono- or glycerol monodilaurate preferred according to the invention, glycerol mono- or glycerol monodioleate, glycerol mono- or glycerol monodimyristate, glycerol mono- or monodistearate, glycerol monoisostearate, mixed esters such as glycerol mono- or monodicocoate, glycerol mono- or monodirinioleate, etc. can also be used.

The preferred amount is about 0.5 to 5, especially about 0.75 to about 2.5% by weight of the detergent mixture.

The compositions according to the invention can also contain non-ionic compounds. Such compounds are, for example,

RO-(R ¹ O) _n -Z _x ,

wherein R is an alkyl group having 8 to 18 carbon atoms, R ¹ is an ethylene or propylene group, Z is a saccharide residue having 5 to 6 carbon atoms, η is a number from 0 to 10, and x is a number between 1 and 5.
These alkyl polyglucosides have become known in particular as excellent skin-compatible foam-improving agents in liquid washing and body cleaning compositions and are preferably contained in an amount of about 1 to 15, in particular 2.5 to 10 wt.% of the total composition.
Other optional non-ionic surfactant components include long-chain fatty acid mono- and dialkanolamides, such as coconut fatty acid monoethanolamide and myristic fatty acid monoethanolamide, which can also be used as foam enhancers.

Other non-ionic surfactants that can also be used are, for example, the various sorbitan esters, such as polyethylene glycol sorbitan stearic acid esters, fatty acid

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polyglycol esters or mixed condensates of ethylene oxide and propylene oxide, such as those sold under the trade name "Pluronics".

Other surfactants that can be used additionally are amine oxides in an amount of about 0.25 to about 5, preferably about 0.5 to about 3.5 wt.%, calculated on the total composition of the agent.

Such amine oxides have long been part of the state of the art, for example C ₁₂ -C ₁₈ alkyldimethylamine oxides such as lauryldimethylamine oxide, C ₁₂ -C ₁₈ alkylamidopropyl or ethylamine oxides, C 12 -C 18 alkyldi(hydroxyethyl) or (hydroxypropyl)amine oxides, or also amine oxides with ethylene oxide and/or propylene oxide groups in the alkyl chain.

Such amine oxides are sold under the names "Ammonyx®", "Aromox®" or "Genaminox®".

Mixtures of anionic surfactants and alkylpolyglucosides and their use in liquid body cleansing agents are already known per se, for example from EP-A 70 074. The mixtures described therein are in principle also suitable within the scope of the present invention; as are the mixtures of sulfosuccinates and alkylpolyglucosides known from EP-A 358 216.

The compositions according to the invention can also contain amphoteric or zwitterionic surfactants as a further surfactant component in an amount of about 0.5 to about 10, preferably about 1 to about 5 wt.%, based on the total composition.

These include in particular the various known betaines such as fatty acid amidoalkylbetaines and sulfobetaines, for example laurylhydroxysulfobetaine; also long-chain alkylamino acids such as cocoaminoacetate, cocoamino-

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nopropionate and sodium cocoamphopropionate and acetate have proven to be suitable.

In particular, betaines can have the structure

_CH3

RN®-(CH ₂ )n-COOQ I
_CH3

CH ₂ -CH ₂ -OH I R- C- N-CH ₂ -CH ₂ -N©-CH ₂ COOe

11 I I

OH &eegr;

where R is a C ₈ -C ₁₈ alkyl group and η is 1 to 3,
Sulfobetaines of the structure

_CH3

R-NS- (CH ₂ J _n - S0 ₃ e

I _CH3

where R is a Cs-Cie alkyl group and η is 1 to 3,
and amidoalkylbetaines of the structure

_CH3
RCN- (CH ₂ ) _n - NS-CH ₂ - COO ¹

,Θ;

OH

where R is a Ce-Cie alkyl group and η is 1 to 3.

The weight ratio of anionic surfactant to C8- _C22 -acylaminocarboxylic acid(s) is preferably between 1:1 and 15:1, of _C8 -C22-acylaminocarboxylic acid(s) to nonionic surfactant between 1:3 and 3:1, and of _C8 - _C22 -acylaminocarboxylic acid(s) to amphoteric or zwitterionic surfactant between 1:3 and 3:1.

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The detergent mixtures according to the invention can also contain conditioning active ingredients such as protein hydrolysates and polypeptides, e.g. keratin hydrolysates, collagen hydrolysates of the "Nutrilan®" type or elastin hydrolysates and in particular also vegetable, optionally cationized protein hydrolysates, e.g. "Gluadin ^R ".

Other conditioning additives for shampoos are hair conditioning polymers. These can be non-ionic polymers, preferably alcohol- and/or water-soluble vinylpyrrolidone polymers such as a vinylpyrrolidone homopolymer or copolymer, in particular with vinyl acetate.

Suitable vinylpyrrolidone polymers are, for example, the products known under the trade name "Luviskol®", for example the homopolymers "Luviskol® K 30, K 60 and K 90" as well as the water- or alcohol-soluble copolymers of vinylpyrrolidone and vinyl acetate, which are sold by BASF AG under the trade name "Luviskol® VA 55 or VA 64".

Other suitable non-ionic polymers are vinylpyrrolidone/vinyl acetate/vinyl propionate copolymers such as "Luviskol® VAP 343", vinylpyrrolidone/(meth)acrylic acid ester copolymers and chitosan derivatives.

Their proportion in the compositions according to the invention, if present, is between about 0.05 and about 5, preferably 0.1 and 2.5, in particular about 0.15 to 1.5% by weight, based on the total composition of the agent.

Instead of or in addition to the non-ionic polymer, cationic and/or anionic and/or amphoteric polymers can also be used as hair conditioning polymers in the amounts mentioned.

Preferred hair conditioning cationic polymers are the well-known quaternary cellulose derivatives of the type "Polymer JR" as well as quaternized homo- and copolymers of dimethyldiallylammonium chloride, as sold under the trade name "Merquat®", quaternary vinylpyrrolidone copolymers,

in particular with dialkylaminoalkyl (meth)acrylates, as known under the name "Gafquat®", copolymers of vinylpyrrolidone and vinylimidazolinium methochloride, which are sold under the trade name "Luviquat®", polyamino-polyamide derivatives, for example copolymers of adipic acid-dimethylaminohydroxypropyldiethylenetriamine, as sold under the name "Cartaretine® F", and also bisquaternary long-chain ammonium compounds of the urea structure described in US Pat. No. 4,157,388, which are sold under the trade name "Mirapol® A 15".
In this context, reference is also made to the cationic polymers mentioned in DE-OSs 25 21 960, 28 11 010, 30 44 738 and 32 17 059 as well as the products described in EP-A 337 354 on pages 3 to 7. Mixtures of different cationic polymers can also be used.

The cationic polymers also include the quaternization products of graft polymers of organopolysiloxanes and polyethyloxazolines described in EP-A 524 612 and EP-A 640 643.

Examples of amphoteric polymers which are used alone or in a mixture with at least one other cationic, non-ionic or anionic polymer are, in particular, copolymers of N-octylacrylamide, (meth)acrylic acid and tert-butylaminoethyl methacrylate of the "Amphomer®" type; copolymers of methacryloylethyl betaine and alkyl methacrylates of the "Yukaformer®" type, e.g. the butyl methacrylate copolymer "Yukaformer® Am75"; copolymers of monomers containing carboxyl groups and sulfone groups, ζ. β. (Methacrylic acid and itaconic acid, with monomers containing basic groups, in particular amino groups, such as mono- or dialkylaminoalkyl(meth)acrylates or mono- or dialkylaminoalkyl(meth)acrylamides; copolymers of N-octylacrylamide, methyl methacrylate, hydroxypropyl methacrylate, N-tert-butylaminoethyl methacrylate and acrylic acid as well as the copolymers known from US-A 3,927,199.

Suitable anionic polymers are vinyl alkyl ether, especially methyl vinyl ether/maleic acid copolymers, which are produced by hydrolysis of vinyl ether/maleic anhydride copolymers and are sold under the trade name "Gantrez

I · β ·

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AN or ES". These polymers can also be partially esterified, for example "Gantrez® ES 225", the ethyl ester of an ethyl vinyl ether/maleic acid copolymer, or the butyl or isobutyl ester thereof.

Other suitable anionic polymers are in particular vinyl acetate/crotonic acid or vinyl acetate/vinyl neodecanoate/crotonic acid copolymers of the "Resyn®" type; sodium acrylate/vinyl alcohol copolymers of the "Hydagen® F" type, sodium polystyrene sulfonate, e.g. "Flexan® 130"; ethyl acrylate/acrylic acid/N-tert-butylacrylamide copolymers of the "Ultrahold®" type; vinylpyrrolidone/vinyl acetate/itaconic acid copolymers, acrylic acid/acrylamide copolymers or sodium salts thereof of the "Reten®" type; etc.

The detergent mixtures according to the invention can of course contain all substances commonly used, in particular in body and hair cleansing agents.

Examples of such substances include complexing agents, dyes, preservatives,
pH regulators, viscosity regulators such as inorganic salts, insofar as they are not already contained in the surfactant starting mixtures, fragrances, pearlescent agents, thickeners, humectants, vegetable and animal oils such as jojoba oil, etc.

A list of such additives can also be found in Schrader, I.e., on pp. 695 to 722.

Another preferred component is ethoxydiglycol, preferably in an amount of 0.1 to 5% by weight of the composition according to the invention.

Finally, known polysiloxanes can also be used as conditioning agents in the liquid hair shampoos according to the invention. The preferred proportion thereof is between about 0.5 and about 5, in particular 1 to 3% by weight of the total composition.

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*&Iacgr;&igr;

Both highly volatile and semi-volatile cyclic or linear polysiloxanes are suitable, for example the silicone oils known by the trivial names "dimethicone" or "phenyldimethicone" as well as "cyclomethicone".

Also suitable, for example, are the silicone derivatives described in EP-A 398 177, which are used there in combination with alkyl polyglucosides in liquid detergent compositions.

The compositions according to the invention can also contain dyes for the direct or oxidative coloration of hair, i.e. so-called tinting or coloring shampoos.

It has been shown that the addition of glycerin fatty acid esters also significantly increases the coloring properties, in particular the coloring intensity of such coloring or tinting shampoos.

The pH value of the compositions according to the invention is in the usual range between about 5 and 8.5; for special products it can also be set below 5.

The viscosity is in the usual range between about 1000 and about 10 000 mPa*s at 20 ⁰ C, preferably about 2,000 to about 6,000, in particular 2,500 to 5,000 mPa»s at 20 ⁰ C, measured according to Brookfield or Höppler at a

-1

Shear stress of 10 see .

The following examples serve to illustrate the invention. The products according to the invention are prepared by stirring the individual components together in water, although premixes of different components can also be used.

·

·

·

· · · * · · » · · · « · · · · · · • · · · · ·»« &Iacgr;2 example 1 Shampoo concentrate C^-Cu fatty alcohol ether sulfate 14.0 wt.% C ₈ -C ₁₂ alkyl glucoside (PD = 1.5) 1.0 Sodium lauroyl glutamate 2.0 Glyceryl laurate 1.0 Cationic polymer (polyquaternium-7) 0.2 Sodium benzoate 0.6, Sodium sorbate 0.3 Perfume 0.4 PEG-40 Hydrogenated Castor Oil 0.5 Benzophenone-3 0.1 pH6.0 Water to 100.0

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This shampoo was compared to a shampoo that did not contain glyceryl laurate.

The shampoo according to the invention showed significantly better foaming behavior in terms of foam volume, "creaminess" of the foam and uniformity of the foam (uniform pore size).

Furthermore, the addition of glyceryl laurate resulted in a skin irritation value reduced by approximately 65%.

In the half-side double-blind test on 10 subjects, a significantly improved wet and dry combability as well as an increased shine were also observed.

♦ ·

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Example 2 Shampoo for dry or damaged hair

Sodium lauroyl ether sulfate Sodium lauroyl sarcosinate Ci2-C ₁₄ alkyl glucoside (PD = 1.4) Lauroyl hydroxysultaine

Cationic conditioner (esterquat; tetranyl CO 40)

Perfume

Glyceryl laurate

Sodium Benzoate Benzophenone-3 Citric Acid

Water

8.0 wt.% 2.0 1.0 1.0 0.8 0.6 0.8 0.6 0.1

pH

6.0

to 100.0

A shampoo with very good foaming power and skin compatibility as well as hair conditioning properties compared to a shampoo without glyacryllaurate was obtained.

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Example 3 5.0 wt.% Shower room 3.5 Sodium lauroyl ether carboxylate (10 EO) 1.4 Disatrate lauryl ether sulfosuccinate 3.0 Decyl glucoside (P.D. ξ 1,4) 3.0 Sodium lauroyl glutamate 2.0 Cocoamide propyl betaine 0.2 Glyceryl cocoate 0.6 Cationic polymer (polyquaternium-16) 0.5 Sodium benzoate 0.5 Citric acid to 100.0 Perfume Water

Compared to a composition without glycerin esters, this shower gel produced a significantly higher foam volume and a creamy, fine-pored foam; the skin irritation ("irritation score") was reduced by about 2/3.

* ••t ···

• · · · φ »φ φ •#·♦ ··· 15 ·· «« i Example 4 Bubble bath concentrate Sodium lauroyl ether sulfate; 10.5 wt.% Sodium lauroyl ether sarcosinate 4.0 Sodium lauroyl glutamate 1.0 Ci2-Ci4-alkyl glucoside (P.D. = 1.4) 2.5 Cocodimethylamine oxide 1.5 Sodium cocamphoacetate 2.5 Glycerol monooleate 1.5 Preservatives 0.5 Citric acid 0.5 Lactic acid 0.1 Pyrrolidonecarboxylic acid 0.1 Glycolic acid 0.1 Malic acid 0.1 Perfume 0.5 Water to 100.0

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This product showed superior foaming behavior and a 62% reduction in skin irritation value compared to a glycerin monooleate-free product.

Claims (6)

1. Aqueous-based shampoo containing a) 5 to 40% by weight of at least one anionic surfactant of the sulfate, sulfonate, carboxylate and/or alkyl phosphate type, excluding C ₈ -C ₂₂ acylaminocarboxylic acids and their water-soluble salts; b) 0.5 to 10% by weight of at least one C ₈ -C ₂₂ acylaminocarboxylic acid or its water-soluble salts; and c) 0.25 to 10 wt.% of at least one glycerol mono-C ₁₀ -C ₁₈ fatty acid ester, each calculated on the total composition. 2. Detergent mixture according to claim 1, characterized in that it contains as component b) lauroyl glutamate and/or a salt thereof. 3. Detergent mixture according to claim 1 or 2, characterized in that it contains 1 to 7.5% by weight of component b), calculated on the total composition. 4. Detergent mixture according to one or more of claims 1 to 3, characterized in that it contains component c) in an amount of 0.5 to 5% by weight, calculated on the total composition. 5. Detergent mixture according to one or more of claims 1 to 4, characterized in that it contains glyceryl laurate as component c). 6. Detergent mixture according to one or more of claims 1 to 5, characterized in that the weight ratio of component a) to component b) is between 1:1 and 15:1.