WO2004032895A1

WO2004032895A1 - Use of detergents with a quotient from the haemolysis value and denaturing index of greater than or equal to 1 for achieving or increasing the selectivity of cleaning preparations

Info

Publication number: WO2004032895A1
Application number: PCT/EP2002/010819
Authority: WO
Inventors: Manfred Strassner; Stephan Ruppert; Andreas Schepky; Jens-Peter Vietzke; Harald Albrecht; Urte Maerker; Ralph Schimpf; Joachim Ennen; Claudius Rapp
Original assignee: Beiersdorf Ag
Priority date: 2002-09-26
Filing date: 2002-09-26
Publication date: 2004-04-22

Abstract

The invention relates to the use of one or several surface-active substances, selected from the group of detergents which have a quotient from haemolysis value and denaturing index of greater than or equal to 1, for achieving or increasing the selectivity of cosmetic or dermatological cleaning preparations.

Description

Beiersdorf Aktiengesellschaft

description

Use of surfactants with a quotient of hemolysis value and denaturation index of greater than or equal to 1 to achieve or increase the selectivity of cleaning preparations

The present invention relates to the use of surfactants with a quotient of hemolysis value and denaturation index of greater than or equal to 1 for achieving or increasing the selectivity of cosmetic or dermatological cleaning preparations.

When the skin is cleaned with the help of a simple water bath - without the addition of surfactants - the horny layer of the skin swells. The degree of this swelling depends on a. on the duration of the bath and its temperature. At the same time, water-soluble substances are washed off or washed out, e.g. B. water-soluble dirt components, but also the skin's own substances, which are responsible for the water retention capacity of the horny layer. Skin oils (surface and barrier lipids) are also dissolved and washed out to a certain extent by the skin's own surface-active substances.

While the removal of surface dirt and surface lipids, which originate primarily from the sebaceous glands and are largely responsible for the appearance of oily skin, is cosmetically desirable, washing out the barrier lipids can disrupt the function of the skin barrier, which is associated with a loss of moisture in the skin , This is accompanied by a temporary increase in transepidermal water loss (TEWL) and a temporary reduction in skin moisture. Especially in the case of products for cleaning the sensitive facial skin and here in particular in the case of products for oily skin, the most selective removal of surface dirt, make-up and skin sebum is for the consumer particularly important. On the other hand, the facial skin in particular needs particularly gentle cleaning.

In the case of healthy skin, the disorders caused by washing are generally limited in time, since the protective mechanisms of the skin can easily compensate for such slight disorders of the upper layers of the skin. But already in the case of non-pathological deviations from normal status - e.g. B. by environmental wear and tear or irritation, light damage, aging skin, etc. - the protective mechanism of the skin surface is disturbed. Under certain circumstances he may then no longer be able to fulfill his task on his own and must be regenerated by external measures. There has been no shortage of attempts to find suitable cleaning preparations for better or faster regeneration of the skin, which help the skin to maintain its natural balance.

Known agents for cleaning and simultaneous care of the skin are e.g. B. oil-containing cleaning preparations or cleaning preparations with different moisturizers or skin humidifiers, which are to re-grease or moisturize the skin during cleaning. For this purpose, the prior art knows, for example, oil bath preparations of various types and shower oils, cleaning creams and the like.

The main disadvantage of such preparations is that part of the barrier lipids is first removed and the skin is then regreased with the help of the added oil components. In addition, cleaning preparations of this type are washed off after use, so that only small amounts of the additives used remain on the skin.

It was therefore an object of the present invention to provide cosmetic or dermatological preparations which significantly improve the condition of the skin, in particular reduce the roughness of the skin and which are distinguished by a selectivity of the cleaning performance.

It was surprising and in no way foreseeable for the expert that the Use of one or more surface-active substances, selected from the group of surfactants, which have a quotient L / D from hemolysis value (L) and denaturation index (D) of greater than or equal to 1, in order to achieve or increase the selectivity of cosmetic or dermatological cleansing preparations - gene that would eliminate the disadvantages of the prior art.

Selective cleaning preparations in the sense of the present invention wash out significantly more surface or sebum lipids than barrier lipids. If the ratio of washed-out surface or sebum lipids to washed-out barrier lipids is determined, this is the case for preparations containing surfactants used according to the invention with a quotient L / D of greater than or equal to 1, preferably greater than or equal to 3, particularly preferably greater than or equal to 5 significantly greater than 1. The selectivity of a cleaning preparation can be increased according to the invention, for. B. in comparison to water. According to the present invention, products can be formulated which remove dirt and excess sebum with high selectivity and thereby protect the skin's own lipids, which are essential for preventing the skin from drying out.

The quotient L / D represents the ratio of the hemolysis value (L) to the denaturing index (D) and is determined by the standard RBC test.

The standard RBC test is used to estimate in vivo eye mucosal irritation potentials of surfactants and products containing surfactants. The process is based on the fact that surfactants interact strongly with cell membranes and proteins. Both effects are determined photometrically by analysis of the natural blood pigment oxyhemoglobin (Hb02). In contrast to other cell-based systems, the RBC test is able to differentiate between damage to the cell membrane (hemolysis) and protein denaturation (denaturation index). Fresh samples of calf blood are obtained directly from the slaughterhouse. The red blood cells are washed and centrifuged several times to separate the white blood cells and from all plasma residues. 1. Hemolysis: A defined aliquot of isolated calf erythrocytes is incubated with a series of increasing concentrations of the samples to be investigated containing wash-active substances (stock solution for raw materials 0.1% by weight active content of the wash-active substance in PBS) for 10 minutes with shaking at RT. PBS is a common standard phosphate buffer (pH 7.4) with the following composition:

Na ₂ HP0 ₄ ^* 2 H ₂ 0 3.95 g

KH ₂ P0 ₄ 0.76 g

NaCI 7.20 g

Glucose * 1 H ₂ 0 1, 80 g

Aqua dest. or "highly purified water" ad 1000 ml

The incubation period is ended by high speed, high speed centrifugation. After centrifugation, the supernatants obtained are analyzed photometrically for their content of released hemoglobin (Hb02) at 530nm. From this, the relative degree of hemolysis based on 100% hemolysis is calculated and the L value [μl / ml] (generally also referred to as the H50 value) is determined as a parameter from the concentration-response curve. This indicates the concentration of the test sample at which 50% of the hemoglobin is released.

2. Hb02 denaturation index:

A defined aliquot of isolated calf erythrocytes is incubated with a fixed concentration of the test sample (for surfactants: 0.1% active content in PBS) for 10 minutes with shaking at room temperature and then centrifuged quickly. The change in spectral absorption at 575 nm and 540 nm is measured in comparison to the native Hb02. The denaturation index D [%] is calculated from the ratio of the absorption values to one another. Na lauryl sulfate (0.1% active content) serves as the 100% standard.

L / D quotient: The quotient represents the ratio of the parameters of hemolysis (L) and denaturation index (D) and is used to classify and characterize the test samples examined. The procedure is also recorded in the INVITTOX database for depositing animal experiment alternatives under Protocol No. 37 and is also described in the following references:

1. Kondo, T. (1976) Mechanisms of hemolysis by surface active agents. Adv. Colloid & Interface Sei., 6, 139-172 Kondo, T. & Tomizawa, M. (1968) Haemolysis by nonionic surface-active agents. J. Pharm. Sci., 57, 1246-1248.

2. Gloxhuber, Ch. (1974) Toxicological properties of surfaetants. Arch. Toxicol., 32, 245-270.

3. Pape, W.J.W., Pfannenbecker, U. & Hoppe, U. (1987) Validation of the red blood cell test as an in vitro assay for the rapid screening of irritation potential of surfaetants.

Molecular Toxicology, 1, 525-536.

4. Pape, W. & Hoppe, U. (1988) Second World Surfaetants Congress, Paris. Evaluation of acute irritation potentials of tensides using the in vitro alternative red blood cell test system. Proceedings, IV, 414-428. 5. Pape, W.J.W. (1990) In vitro methods for the assessment of local effects of cosmetics on skin and mueous membranes. Presented at: In-cosmetics 1990, Birmingham, UK.

6. Pape, W.J.W. & Hoppe, U. (1991) Standardization on an in vitro red blood cell test for evaluating the acute cytotoxic potential of tensides. Drug Research, 40 (l), 4, 498-502.

7. Pape, W.J.W. & Hoppe, U. (1991) In vitro methods for the assessment of primary local effects of topically applied preparations. Skin Pharmacology (in press).

The surfactant or surfactants to be used according to the invention are advantageously selected from the group of surfactants which have a quotient L / D from hemolysis value (L) and denaturation index (D) of greater than or equal to 3, particularly preferably greater than or equal to 5.

The surfactant or surfactants to be used according to the invention are particularly advantageously selected from the group sodium N-alkyllyl glutamates, sodium alkyl sarcosinates, sodium alkyl sulfosuccinates and sodium salts of the ethoxylated and carboxylated triglycerides. For the purposes of the present invention, particular preference is given to the use of one or more of the following surfactants: sodium cocoyl glutamate, sodium lauroyl sarcosinate, disodium lauryl polyglycol ether sufosuccinate, sodium PEG-7 olive oil carboxylate.

The total amount of one or more surfactants used according to the invention in the finished cosmetic or dermatological preparations is advantageously chosen in the range from 0.1 to 10.0% by weight, preferably 0.5 to 5.0% by weight, in each case based on the total weight of the preparations.

The cleaning compositions containing surfactants used according to the invention can be composed as usual and can be used for cosmetic and / or dermatological cleaning of the skin and / or hair and as a make-up removal product for decorative cosmetics.

For use, the compositions comprising surfactants used according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.

The cleaning preparations for the purposes of the present invention advantageously also contain one or more detergent surfactants from the following four groups A to D:

A. Anionic surfactants

Anionic surfactants to be used advantageously are acylamino acids (and their salts), such as 1. acylglutamates, for example sodium acylglutamate, di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,

2. acyl peptides, for example palmitoyl hydrolyzed milk protein, sodium cocoyl hydrolyzed soy protein and sodium / potassium cocoyl hydrolyzed collagen,

3. sarcosinates, for example myristoyl sarcosin, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,

4. taurates, for example sodium lauroyl taurate and sodium methyl cocoyl taurate,

Carboxylic acids and derivatives, such as 1. carboxylic acids, for example lauric acid, aluminum stearate, magnesium alkanolate and zinc undecylenate,

2. ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauramide carboxylate, 3. ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate,

Phosphoric acid esters and salts such as DEA-Oleth-10 phosphate and Dilureth-4 phosphate,

Sulfonic acids and salts such as

1. acyl isethionates, e.g. Sodium / ammonium cocoyl isethionate,

2. alkylarylsulfonates,

3. alkyl sulfonates, for example sodium cocosmonoglyceride sulfate, sodium C _12-1 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate,

4. Sulfosuccinates, for example dioctyl sodium sulfosuccinate, disodium laureth sulfosuccinate, disodium lauryl sulfosuccinate and disodium undecylenamido MEA sulfosuccinate

as well as sulfuric acid esters, such as

1. alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium and sodium _C12 pareth ι _3,

2. Alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate.

B. Cationic surfactants

Cationic surfactants to be used advantageously

1. alkylamines,

2. alkylimidazoles,

3. Ethoxylated amines and 4. Quaternary surfactants.

Quaternary surfactants contain at least one N atom that is covalently linked to 4 alkyl or aryl groups. Regardless of the pH value, this leads to a positive charge. Benzalkonium chloride, alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hydroxysultain are advantageous. C. Amphoteric surfactants

Amphoteric surfactants to be used advantageously

1. acyl / dialkyl ethylenediamine, for example sodium acyl amphoacetate, disodium acyl amphodipropionate, disodium alkyl amphodiacetate, sodium acylamphohydroxypropyl sulfonate, disodium acylamphodiacetate and sodium acylamphopropionate,

2. N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.

3. N-alkyl or N-alkenyl betaines with at least 12 carbon atoms, such as. B. lauryl amidopropyl betaine and oleyl amidopropyl betaine

D. Non-ionic surfactants

Nonionic surfactants to be used advantageously are I. alcohols,

2. alkanolamides, such as cocamides MEA / DEA / MIPA,

3. amine oxides, such as cocoamidopropylamine oxide,

4. esters which are formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols, 5. ethers, for example ethoxylated / propoxylated alcohols, ethoxylated / propoxylated esters, ethoxylated / propoxylated glycerol esters, ethoxylated / propoxylated cholesterols, ethoxylated / propoxylated Triglyceride esters, ethoxylated propoxylated lanolin, ethoxylated / propoxylated polysiloxanes, propoxylated POE ethers and alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside. 6. sucrose esters, ether

7 polyglycerol esters, diglycerol esters, monoglycerol esters 8. methyl glucose esters, esters of hydroxy acids

The cleaning preparations within the meaning of the present invention particularly advantageously contain one or more wash-active surfactants according to the invention from the group of surfactants which have an HLB value of more than 25, very particularly those which have an HLB value of more than 35. It is advantageous in the sense of the present invention if the content of one or more detergent surfactants in the cosmetic or dermatological cleaning preparation is in the range from 1.5 to 20% by weight, very particularly advantageously from 2.0 to 15% by weight. % is selected, based in each case on the total weight of the preparation.

The compositions within the meaning of the present invention further advantageously contain water and optionally the additives customary in cosmetics, e.g. B. preservatives, preservation aids, bactericides, perfumes, dyes, pigments that have a coloring effect, moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, fats, oils, waxes or other usual components of a cosmetic or dermatological formulation.

Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin, which is available, for example, from Lonza under the trade name Glydant ™), iodopropyl butyl carbamate (for example those under the trade names Glycacil) -L, Glycacil-S available from Lonza and / or Dekaben LMB from Jan Dekker), parabens (ie alkyl p-hydroxybenzoate, such as methyl, ethyl, propyl and / or butyl paraben), phenoxyethanol, Ethanol, benzoic acid and the like. According to the invention, the preservation system usually also advantageously comprises preservation aids, such as, for example, octoxyglycerol, glycine soya, etc.

For the purposes of the present invention, the water phase of the preparations can advantageously contain customary cosmetic auxiliaries, such as, for example, alcohols, in particular those having a low C number, preferably ethanol and / or isopropanol, diols or polyols having a low C number, and their ethers, preferably propylene glycol, Glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, mono ethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analog products, polymers, foam stabilizers, electrolytes, dihydroxyacetone and in particular one or more thickeners, which or which advantageous can be selected from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for. B. hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the Group of the so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, each individually or in combination. Moisturizers can also be used with preference.

Moisturizers are substances or mixtures of substances that give cosmetic or dermatological preparations the property of reducing the release of moisture from the horny layer (also known as trans-epidermal water loss (TEWL)) and / or hydrating the skin after application or distribution on the skin surface To influence the horny layer positively.

Advantageous moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccaride gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides. Particularly advantageous are, for example, hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registration number 178463-23-5 and z. B. under the name Fucogel®1000 from the company SOLABIA S.A. is available.

Particularly advantageous preparations are also obtained if antioxidants are used as additives or active ingredients. According to the invention, the preparations advantageously contain one or more antioxidants. All of the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as inexpensive, but nevertheless optional, antioxidants.

For the purposes of the present invention, water-soluble antioxidants, such as vitamins, e.g. B. ascorbic acid and its derivatives.

Preferred antioxidants are also vitamin E and its derivatives and vitamin A and its derivatives. The amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 0.1 to 10% by weight, based on the total weight the preparation.

If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation.

If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to add their respective concentrations in the range from 0.001 to 10% by weight, based on the total weight of the formulation choose.

It is particularly advantageous if the cosmetic preparations according to the present invention contain cosmetic or dermatological active ingredients, preferred active ingredients being antioxidants which can protect the skin and / or the hair from oxidative stress.

Further advantageous active substances in the sense of the present invention are natural active substances and / or their derivatives, such as. B. alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, camitin, camosin, natural and / or synthetic isoflavonoids, creatine, taurine and / or ß-alanine.

The following examples are intended to illustrate the present invention. The numerical values in the examples mean percentages by weight, based on the total weight of the respective preparations.

Examples:

formulation Examples

Claims

claims:

1. Use of one or more surface-active substances, selected from the group of surfactants, which have a. Quotient of hemolysis value and denaturation index of greater than or equal to 1, preferably greater than or equal to 3, particularly preferably greater than or equal to 5, in order to achieve or Increase the selectivity of cosmetic or dermatological cleaning preparations.

2. Use according to claim 1, characterized in that the concentration ten-sided is in the range of 0.1 to 10 wt .-%, based on the total weight of the

Formulation.

3. Use according to one of the preceding claims, characterized in that the total concentration of all cleaning-active substances including the surfactants according to the invention in the range of 1, 5 to 20 wt .-% based on the

Total weight of the formulation, in particular in the range from 2.0 to 15% by weight.

4. Use according to one of the preceding claims, characterized in that the surfactants are selected from the group of sodium N-alkylyl glutamates,

Sodium alkyl sarcosinate, sodium alkyl sulfosuccinate and sodium salts of the ethoxylated and carboxylated triglycerides, in particular sodium cocoyl glutamate, sodium lauroyl sarcosinate, disodium lauryl polyglycol ether sufosuecinate, sodium PEG-7 olive oil carboxylate.

5. Use according to one of the preceding claims, characterized in that the cleaning preparations contain cosurfactants selected from the group of alkyl ether sulfates and / or alkyl taurates.

6. Use according to any one of the preceding claims, characterized in that the cleaning preparations contain gel formers from the group of polyacrylates and / or acrylate copolymers and / or polysaccharides.

7. Use according to one of the preceding claims, characterized in that the cleaning preparations are used for face cleaning.

8. Use according to one of the preceding claims, characterized in that the cleaning preparations for cleaning greasy and / or impure

Skin / scalp are used.

9. Use according to one of the preceding claims, characterized in that the cleaning preparations contain further cosmetic auxiliaries, in particular skin moisturizers, oil components, dyes, pigments, preservatives and perfume.

10. Use according to one of the preceding claims, characterized in that the cleaning preparations are suitable for foaming with a pump foam, preferably a splash-proof pump foam.

11. Use according to one of the preceding claims, characterized in that the cleaning preparations are suitable for body cleaning.