EP1496844A1

EP1496844A1 - Cosmetic and dermatological washing active preparations containing one or more pregelatinized, cross-linked starch derivatives and one or more ethoxylated oils

Info

Publication number: EP1496844A1
Application number: EP03724946A
Authority: EP
Inventors: Stephan Ruppert
Original assignee: Beiersdorf AG
Current assignee: Beiersdorf AG
Priority date: 2002-04-11
Filing date: 2003-04-02
Publication date: 2005-01-19
Also published as: WO2003084486A1; DE10216506A1

Abstract

The invention relates to cosmetic and dermatological cleansing preparations containing: a) one or more pregelatinized, cross-linked starch derivatives, and; one or more ethoxylated oils.

Description

description

Cosmetic and dermatological detergent preparations containing one or more pregelatinized, crosslinked starch derivatives and one or more ethoxylated oils

The present invention relates to cosmetic cleaning agents. Such means are known per se. These are essentially surface-active substances or mixtures of substances that are offered to the consumer in various preparations.

The production of cosmetic cleaning agents has shown an increasing trend for years. This is mainly due to the increasing health awareness and hygiene needs of consumers.

Cleaning means the removal of (environmental) dirt and thus increases the psychological and physical well-being. Cleaning the surface of skin and hair is a very complex process that depends on many parameters. On the one hand, substances coming from outside, such as hydrocarbons or inorganic pigments from a wide variety of environments, as well as residues from cosmetics or undesired microorganisms, should be removed as completely as possible. On the other hand, the body's excretions such as sweat, sebum, skin and hair flakes can be washed off without deep intervention in the physiological balance.

The demands placed on the properties of cosmetic cleaning preparations have changed significantly in recent years. In the past, effects such as cleaning and foaming were the focus of consumer requests. At the moment, the ecological, economic and, in particular, dermatological properties of the products are paramount, although the foaming power continues to play a decisive role, for example as an indicator to remove residual amounts of surfactants after cleaning the skin and hair or to overdosage during use avoid. However, cosmetic products

PAWI / 2002/202-XL Wi03 products - in contrast to most technical cleaning agents - the skin and mucous membrane compatibility absolutely in the foreground; the products should be "mild".

Cosmetic or dermatological cleansing preparations are so-called "rinse off" preparations, which are rinsed off the skin after use. They are usually applied in the form of a foam with water to the parts of the body to be cleaned. All cosmetic or dermatological cleaning products are based on detergent surfactants. Surfactants are amphiphilic substances that can dissolve organic, non-polar substances in water. They are characterized by an ambivalent behavior towards water and lipids: the surfactant molecule contains at least one hydrophilic and one lipophilic group, which enable it to attach to the interface between these two classes of substances. In this way, surfactants ensure a reduction in the surface tension of the water, wetting of the skin, easier removal and removal of dirt, easy rinsing and - if desired - also for foam regulation. This provides the basis for removing dirt from lipid-containing soiling.

The hydrophilic parts of a surfactant molecule are mostly polar functional groups, for example -COO ^" , -OSO ₃ ^2" , -SO ₃ ^" , while the hydrophobic parts generally represent non-polar hydrocarbon residues. Surfactants are generally of type and charge of the hydrophilic part of the molecule. There are four groups:

Anionic surfactants,

Cationic surfactants,

• amphoteric surfactants and

• nonionic surfactants.

Anionic surfactants generally have carboxylate, sulfate or sulfonate groups as functional groups. In aqueous solution they form negatively charged organic ions in an acidic or neutral environment. Cationic surfactants are characterized almost exclusively by the presence of a quaternary ammonium group. In aqueous solution, they form positively charged organic ions in an acidic or neutral environment. Amphoteric surfactants contain both anionic and cationic groups and therefore behave like anionic or cationic surfactants in aqueous solution depending on the pH. They are positive in a strongly acidic environment and negative in an alkaline environment. dung. In the neutral pH range, however, they are zwitterionic, as the following example should illustrate:

RNH ₂ ⁺ CH ₂ CH ₂ COOH X ^" (at pH = 2) X ^" = any anion, eg CI ^"

RNH ₂ ⁺ CH ₂ CH ₂ COO ^" (at pH = 7)

RNHCH ₂ CH ₂ COO ^_ B ⁺ (at pH = 12) B ⁺ = any cation, e.g. Na ⁺

Polyether chains are typical of non-ionic surfactants. Non-ionic surfactants do not form ions in an aqueous medium.

The detergent surfactants in cosmetic and dermatological cleaning agents are subject to a very critical assessment with regard to their dermatological and ecological behavior. The latter is particularly important because they are used in considerable quantities and are discharged as intended after use.

Based on the already described central importance of the detergent surfactants for the cleaning process, their behavior on the human skin is of paramount importance.

When the skin is cleaned with water - 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 are also dissolved and washed out to a certain extent by the skin's own surface-active substances. After initial swelling, this causes the skin to dry out subsequently.

It is understandable that detersive surfactants, which are intended to clean the skin and hair of greasy and water-soluble dirt components, also have a degreasing effect on normal skin lipids. Every time the skin is cleaned, intercomomeocytic lipids and sebum components are also removed to different degrees. This means that the natural water-lipid coat of the skin is more or less disturbed with every wash. This can lead to a brief change in the barrier cause the skin to function, although the condition of the treated skin region is of course also of considerable influence on the changes shown. For example, the thickness of the skin, the number of sebum and sweat glands and the sensitivity associated with it can vary considerably.

Accordingly, the basic requirement for wash-active surfactants is that they are as inactive as possible in order to avoid undesirable side effects. They should develop their cleaning effect with optimal mildness, best skin compatibility and low degreasing.

However, there has also been no lack of attempts to find suitable cleansing preparations which regenerate or “regrease” the skin at the same time with good cleaning performance. However, the performance achieved often falls short of the expected, so that the user generally relies on separate care products which must be applied to the skin after cleaning and remain on it (so-called "leave-on" products).

Due to the increasing washing frequency among consumers, however, the desire for mild, compatible and as regenerating preparations as possible continues to increase.

As a rule, cosmetic or dermatological cleaning preparations are very well tailored to an assumed range of applications, since the mechanical parameters, such as the time factor, which vary depending on the application, are of particular importance for a defined, mild cleaning effect. B. clearly if you consider the different times of use (contact) of a foam bath compared to brief hand washing.

Cosmetic cleaning agents usually contain mixtures of different types of surfactants. The selection is primarily based on skin tolerance and the desired cosmetic performance of the surfactants. In addition, foaming power, formulability and a favorable performance / cost ratio play an important role. In a particular embodiment, the present invention relates to cosmetic cleaning agents in the form of shaped soap products. Such means are known per se. These are essentially surface-active substances or mixtures of substances that are offered to the consumer in various preparations. The invention relates in particular to bar soaps with improved smoothness and increased lime soap dispersing capacity due to a content of talc and one or more amphoteric surfactants with the simultaneous absence of alkyl (oligo) glycosides.

Surface-active substances - best known are the alkali salts of higher fatty acids, ie the classic "soaps" - are amphiphilic substances that can emulsify organic non-polar substances in water.

These substances not only wash dirt from the skin and hair, they irritate the skin and mucous membranes to a greater or lesser extent, depending on the choice of surfactant or surfactant mixture. While a large number of fairly mild surfactants are available, the prior art surfactants are either mild, but clean poorly, or they clean well but irritate skin or mucous membranes.

Bar soaps play a major role in body cleansing, which are now produced on an industrial scale by continuously saponifying free fatty acids with alkalis, concentrating basic soaps and spray drying. A distinction is made between real alkali soaps, which only contain fatty acid salts and possibly still free fatty acids, and so-called "combibars", bar soaps, which, in addition to fatty acid salts, also contain other synthetic surfactants, usually fatty alcohol ether sulfates or fatty acid isothionates. A special position, however, occupies syndet bars, so-called "syndet bars", which, apart from impurities, are free of fatty acid salts and contain only synthetic surfactants.

In Germany alone, several million soap bars are sold every year for personal hygiene. However, the demands of the market for these mass consumer goods are becoming ever higher: bar soaps not only have to clean the skin, they also have to take care of it, ie prevent it from drying out, relubricate it and offer protection against external influences. Of course, it is expected that the soap is particularly skin-friendly, but it should nevertheless result in as much and creamy foam as possible and create a pleasant feeling on the skin. In this context, bar soap manufacturers are constantly looking for new ingredients that meet this increased requirement profile.

A distinction is made between solid, mostly bar-shaped, and liquid soaps. The main components are the alkali salts of the fatty acids of natural oils and. Fat, preferably of chain lengths C ₁₂ -C ₁₈ . Since lauric acid soaps foam particularly well, the lauric acid-rich coconut and palm kernel oils are preferred raw materials for fine soap production. The sodium salts of the fatty acid mixtures are solid, the potassium salts are soft-pasty. For saponification, the dilute sodium or potassium hydroxide solution is added to the fat raw materials in a stoichiometric ratio in such a way that an excess of lye of at most 0.05% is present in the finished soap. In many cases, soaps are no longer made directly from fats, but from the fatty acids obtained through fat splitting.

Common soap additives are fatty acids, fatty alcohols, lanolin, lecithin, vegetable oils, partial glycerides and other fat-like substances for regreasing the cleansed skin, antioxidants such as ascorbyl palmitate or tocopherol to prevent the autoxidation of soap (rancidity), complexing agents such as nitrilotriac Binding of heavy metal traces that could catalyze autoxidative spoilage, perfume oils to achieve the desired fragrance notes, dyes to color the soap bars and, if required, special additives.

The most important types of fine soaps are:

Toilet soaps with 20 - 50% coconut oil in the fat base, up to 5% lipid replenishment and 0.5 - 2% perfume oil, they form the largest proportion of fine soaps;

- Luxury soaps with up to 5% particularly valuable perfume oils;

- Deodorant soaps with additives of deodorising agents, such as. B. 3,4,4'-trichlorocarbanilide (triclocarban);

Cream soaps with particularly high proportions of lipid-replenishing and skin-creaming substances;

Baby soaps with good regreasing and additional nourishing components such as B. chamomile extracts, at most very slightly perfumed;

- Skin protection soaps with high proportions of moisturizing substances as well as other nourishing and protective additives such as B. proteins; Transparent soaps with additions of glycerin, sugar and others, which prevent the crystallization of the fatty acid salts in the solidified soap melt and thus create a transparent appearance;

Floating soaps with a density of <1, caused by air bubbles incorporated in a controlled manner during production. Soaps with abrasive additives for cleaning heavily soiled hands.

In a particular embodiment, the present invention relates to liquid soaps or washing lotions. Such products are not only used to clean the hands, but usually also for the whole body, including the face. Accordingly, they are also suitable for use as a shower preparation. The development of these products focuses on the dermatological requirements, since the skin comes into intensive contact with the concentrated surfactant solution. Special emphasis is therefore placed on the selection of mild surfactants in low concentrations. Further criteria are good foaming power as well as a pleasant, refreshing fragrance and the simultaneous care of the skin. Washing lotions and shower baths in particular generally have viscosities of around 3,000 to 10,000 mPa-s, which on the one hand allow the product to be easily distributed with quick foaming, but on the other hand should be high enough to enable perfect use by hand or washcloth ,

Liquid soaps or washing lotions are generally characterized by a more or less high water content, but usually do not have a noticeable care effect, since they have only a low oil content.

In a special embodiment, the present invention relates to a relatively new technical development, namely shower preparations containing surfactants with a high oil content. In this context, German Offenlegungsschrift 44 24 210 describes cosmetic or dermatological shower preparations with a surfactant content of at most 55% by weight and an oil content of more than 45% by weight, the preparations being essentially water-free. Due to the high oil content, these preparations have a regenerating effect on the general skin condition. At the same time, they have good foam development and high cleaning power. Furthermore, WO 96/17591 describes foaming liquid skin cleaning compositions which contain the following substances: 5 to 30% by weight of a moisturizing active ingredient which has a Vaughan Solubility Parameter (VSP) of 5 to 10, 0.3 to 5% by weight. % of a water-dispersible gel-forming polymer, 5 to 30% by weight of a synthetic surface-active substance, 0 to 15% by weight of a C ₈ to C ₁₄ fatty acid soap and water, the preparations having a lipid deposition value (LDV) of at least 5 to 1000 and wherein the synthetic surfactant and the soap have a common CMC equilibrium surface tension value of 15 to 50. However, this document could not show the way to the present invention.

In a particular embodiment, the present invention also relates to cleaning products based on emulsions. These are formulated in such a way that the emulsion is stabilized with emulsifiers and then a surfactant system is adapted.

Emulsifiers also have an amphiphilic structure, so their structure is comparable to that of surfactants. Emulsifiers enable or facilitate the uniform distribution of two or more immiscible phases and at the same time prevent their separation. Since emulsions are generally destroyed by the addition of surfactants, the choice of surfactant system is severely restricted and the cleaning preparations obtained are based on expensive and complicated formulations.

At the end of the 1940s, a system was developed that should make it easier to select emulsifiers. A so-called HLB value (a dimensionless number between 0 and 20) is ascribed to each emulsifier, which indicates whether there is a preferred water or oil solubility. Numbers below 9 indicate oil-soluble, hydrophobic emulsifiers, numbers above 11 water-soluble, hydrophilic. The HLB value says something about the balance between the size and strength of the hydrophilic and lipophilic groups of an emulsifier. From these considerations it can be deduced that the effectiveness of an emulsifier can also be characterized by its HLB value. The following table shows the relationship between the HLB value and the possible area of application: HLB value application area

0 to 3 defoamers

3 to 8 W / O emulsifier

7 to 9 wetting agents

8 to 18 O / W emulsifier

12 to 18 solubilizers

The HLB value of an emulsifier can also be composed of increments, the HLB increments for the various hydrophilic and hydrophobic groups from which a molecule is composed can be found in tables. In principle, HLB values can also be determined for wash-active surfactants in this way, although the HLB system was originally only designed for emulsifiers. It can be seen that wash-active substances generally have HLB values that are significantly greater than 20.

The object of the present invention was to provide cleaning preparations based on emulsions which remedy the disadvantages of the prior art and which are accordingly based on simple and inexpensive formulations. The preparations should also have a high care effect without detracting from the cleaning effect.

In a particular embodiment, the present invention relates to cosmetic and dermatological cleaning preparations in the form of gels

Cosmetic gels are extremely popular with consumers. Since they are mostly transparent, often colored, but should also be so often colorlessly clear, they offer the cosmetic developer additional design options, some of which have a functional character, but some of which only serve to improve the external appearance. For example, the product, which is then usually presented to the viewer in a transparent packaging, can be given interesting optical effects by incorporated color pigments, gas bubbles and the like, or else larger objects. Another object was to provide cleaning preparations which, if desired, can be designed as visually appealing, stable gels.

Ethoxylated glycerol fatty acid esters are used for various purposes in aqueous cleaning formulations. Low ethoxylated glycerin fatty acid esters (EO 3-12) usually serve as refatting agents to improve the feeling on the skin after drying, glycerol fatty acid esters with a degree of ethoxylation of approx. 30-50 serve as solubilizers for non-polar substances such as perfume oils.

Highly ethoxylated glycerin fatty acid esters are used as thickeners. All these substances have in common that they produce a slippery feeling on the skin when used when diluted with water, which is perceived by the consumer as unpleasant.

It was therefore astonishing and unforeseeable for the person skilled in the art that the objects on which the invention is based are achieved by washing-active cosmetic or dermatological preparations comprising:

(a) one or more pre-gelatinized, cross-linked starch derivatives

(b) one or more ethoxylated oils.

It is known that pre-gelatinized, cross-linked starch derivatives from aqueous cleansing formulations draw onto the skin and thereby produce a pleasant feeling on the skin after drying. It was therefore not foreseeable for the person skilled in the art that pregelatinized, cross-linked starch derivatives are able to reduce the slippery feeling on the skin when washing that is produced by ethoxylated glycerol fatty acid esters.

The cosmetic and / or dermatological cleaning preparations in the sense of the present invention are based on simple and inexpensive formulations. They have good foam development and high cleaning power at the same time. The preparations have a regenerating effect on the general skin condition, reduce the feeling of dryness of the skin and make the skin supple.

According to the invention, the ethoxylated oils are advantageously selected from the group of ethoxylated glycerol fatty acid esters, particularly preferably: PEG-10 olive oil glycerides, - PEG- 11 avocado oil glycerides, PEG-11 cocoa butter glycerides, PEG-13 sunflower oil glycerides, PEG-15 glyceryl isostearate, PEG-9 coconut fatty acid glycerides, PEG-54 hydrogenated castor oil, PEG-7 hydrogenated castor oil, PEG-60 hydrogenated castor oil, jojoba oil-jojoba oil -Fatty acids, PEG-26 jojoba alcohol), Glycereth-5 cocoat, PEG-9 coconut fatty acid glycerides, PEG-7 glyceryl cocoat, PEG-45 palm kernel oil glycerides, PEG-35 castor oil, olive oil-PEG-7 ester, PEG-6 caprylic acid / capric acid glyceride 10 olive oil glycerides, PEG-13 sunflower oil glycerides, PEG-7 hydrogenated castor oil, hydrogenated palm kernel oil glyceride-PEG-6 esters, PEG-20 corn oil glycerides, PEG-18 glyceryl oleate cocoate, PEG-40 hydrogenated castor oil, PEG-40 castor oil, PEG-60 hydrogenated , PEG-60 corn oil glycerides, PEG-54 hydrogenated castor oil, PEG-45 palm kernel oil glycerides, PEG-35 castor oil, PEG-80 glyceryl cocoate, PEG-60 almond oil glycerides, PEG-60 "Evening Primrose" glycerides, PEG-200 hydrogenated glyceryl palmat, PEG -90 glycer ylisostearat.

Preferred ethoxylated oils are PEG-7 glyceryl cocoate, PEG-9 coconut glycerides, PEG-40 hydrogenated castor oil, PEG-200 hydrogenated glyceryl palmat.

It is advantageous according to the invention if one or more pregelatinized, crosslinked starch derivatives in a concentration of 0.1 to 20% by weight, preferably in a concentration of 0.3 to 15% by weight and very particularly preferably in a concentration of 0.5 up to 10% by weight, based on the total weight of the preparation, are contained in the preparations according to the invention.

It is advantageous according to the invention if one or more ethoxylated oils in a concentration of 0.1 to 15% by weight, preferably in a concentration of 0.2 to 8% by weight and very particularly preferably in a concentration of 0.3 to 5 % By weight, based on the total weight of the preparation, are contained in the preparations according to the invention.

It is particularly advantageous according to the invention if hydroxypropylated phosphate esters are used as the pregelatinized, crosslinked starch derivatives. Starch derivatives such as those described in US Pat. No. 6,248,338 are particularly advantageous, and hydroxypropyl distarch phosphate is particularly advantageous. The use of a hydroxypropyl distarch phosphate, as sold as the Structure® XL product by National Starch, is very particularly preferred. The cleaning preparations advantageously contain one or more wash-active anionic, cationic, amphoteric and / or non-ionic surfactants according to the invention. It is particularly advantageous to choose the wash-active surfactant or surfactants according to the invention from the group of surfactants which have an HLB value of more than 25, very particularly advantageous are those which have an HLB value of more than 35.

Very particularly advantageous wash-active anionic surfactants in the sense of the present

Are invention

Acylamino acids and their salts, such as

■ acylglutamates, especially sodium acylglutamate

^{"Sarcosinates,} ylsarcosinat for example myristoyl sarcosine, TEA-lauroyl sarcosinate, sodium cocoyl Natriumlauro- and,

Sulfonic acids and their salts, such as

^■ acyl isethionates, eg sodium / Ammoniumcocoyl isethionate,

■ 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

^■ alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium pareth sulfate, and sodium C _12-13,

^■ Alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate

as well as carboxylated triglyceride ethoxylates such as

^■ sodium PEG-4 Olivenölcarboxylate.

Quaternary surfactants are very particularly advantageous washing-active cationic surfactants for the purposes of the present invention. Quaternary surfactants contain at least one N atom that is covalently bonded to 4 alkyl or aryl ^groups'. Benzalkonium chloride, alkyl betaine, alkylamidopropyl betaine and alkyl amidopropyl hydroxysultain are advantageous.

Particularly advantageous washing-active amphoteric surfactants in the sense of the present invention are ^■ acyl / dialkylethylenediamines, for example sodium, Dinatriumacyl- amphodipropionat, disodium, Natriumacylamphohydroxypropyl- sulfonate, and sodium acyl Dinatriumacylamphodiacetat,

Very particularly advantageous washing-active nonionic surfactants in the sense of the present invention are

Alkanolamides, such as Cocamide MEA / DEA / MIPA,

Esters which are formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols,

■ ethers, for example ethoxylated alcohols, ethoxylated lanolin, ethoxylated polysiloxanes, propoxylated POE ethers and alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside.

Other advantageous anionic surfactants are

^■ taurates, for example sodium lauroyl taurate and sodium methyl cocoyl taurate,

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,

■ Alkyl sulfonates, for example sodium coconut monoglyceride sulfate, sodium C12-14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate.

Other advantageous amphoteric surfactants are

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

Further advantageous non-ionic surfactants are alcohols.

Other suitable anionic surfactants for the purposes of the present invention are also ^B Aeylglutamate such as di-TEA-palmitoyiaspartat and sodium caprylic / capric glutamate, ^{"acylpeptides,} for example palmitoyl hydrolysed milk protein, sodium cocoyl hydrolyzed soy protein and sodium / potassium cocoyl hydrolysed collagen and acylated wheat protein Hydrolysates, for example sodium cocoyl hydrolyzed wheat protein, as well as carboxylic acids and derivatives, such as

^■ example, lauric acid, cylenat aluminum stearate, magnesium and Zinkunde-,

^■ ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauramide carboxylate,

■ alkylarylsulfonates.

Other suitable cationic surfactants for the purposes of the present invention are also

■ alkylamines,

Alkylimidazoles and

^■ ethoxylated amines.

Other suitable nonionic surfactants for the purposes of the present invention are also amine oxides, such as cocoamidopropylamine oxide.

In the sense of the present invention, it is advantageous if the content of one or more detergent surfactants in the cosmetic or dermatological cleaning preparations is selected from the range from 5 to 25% by weight, very particularly advantageously from 10 to 20% by weight, each based on the total weight of the preparations.

It is advantageous according to the invention to add such active substance combinations containing complexing agents to the active substance combinations or cosmetic or dermatological preparations used according to the invention.

Complexing agents are known auxiliaries in cosmetology and medical galenics. The complexation of interfering metals such as Mn, Fe, Cu and others can, for example, prevent undesirable chemical reactions in cosmetic or dermatological preparations.

Complexing agents, in particular chelators, form complexes with metal atoms which, if one or more polybasic complexing agents, ie chelators, are metalacycles. Chelates are compounds in which a single ligand occupies more than one coordination site on a central atom. In this case, These elongated connections are closed to form rings by complex formation via a metal atom or ion. The number of ligands bound depends on the coordination number of the central metal. The prerequisite for chelation is that the compound reacting with the metal contains two or more atom groups which act as electron donors.

The complexing agent or complexing agents can advantageously be selected from the group of the usual compounds, preferably at least one substance from the group consisting of tartaric acid and its anions, citric acid and its anions, aminopolycarboxylic acids and their anions (such as, for example, ethylenediaminetetraacetic acid (EDTA) and their anions, Nitrilotriacetic acid (NTA) and its anions, Hydroxyethylenediaminotriessigsäure (HOEDTA) and its anions, Diethylenaminopentaacetic acid (DPTA) and its anions, trans-1,2-diaminocyclohexanetetraacetic acid (CDTA) and its anions).

According to the invention, the complexing agent or complexing agents are advantageous in cosmetic or dermatological preparations, preferably at 0.01% by weight to 10% by weight, preferably at 0.05% by weight to 5% by weight, particularly preferably at 0.1 - 2.0 wt .-%, based on the total weight of the preparations.

An optionally desired oil component of the cosmetic or dermatological cleaning preparations - for example in the form of cleaning emulsions - for the purposes of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 C Atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms, from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyiisononanoate, 2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl-2-ethylhexyl Hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucyl erucate as well as synthetic, semi-synthetic and natural mixtures of such esters, e.g. B. Jojoba oil. Furthermore, the oil component can advantageously be chosen from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also the fatty acid triglycerides, especially the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 to 18, carbon atoms. The fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, e.g. B. olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.

The oil component is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C _2- i ₅ -alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.

Mixtures of C _12-15 alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C _12-15 alkyl benzoate and isotridecyl isononanoate and mixtures of C ₁₂ are particularly advantageous. ₁ 5-alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

Of the hydrocarbons, paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.

The oil component can also advantageously have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.

Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention. But other silicone oils are also advantageous in the sense of to use the present invention, for example hexamethylcyclotrisiloxane, pofydimethylsiloxane, poly (methylphenylsiloxane).

Mixtures of cyclomethicone and isotridecyl isononanoate, cyclomethicone and 2-ethylhexyl isostearate are also particularly advantageous.

The oil component is also advantageously selected from the group of the phospholipids. The phospholipids are phosphoric acid esters of acylated glycerols. Of great importance among the phosphatidylcholines are, for example, the lecithins, which are characterized by the general structure

distinguish, where R and R "typically represent unbranched aliphatic radicals having 15 or 17 carbon atoms and up to 4 cis double bonds.

Cleaning preparations according to the invention are advantageously in the form of gels and contain one or more gel formers or hydrocolloids.

"Hydrocolloid" is the technological short name for the more correct term "hydrophilic colloid". Hydrocolloids are macromolecules that are largely linear in shape and have intermolecular interaction forces that enable secondary and main valence bonds between the individual molecules and thus the formation of a network-like structure. They are partially water-soluble natural or synthetic polymers that form gels or viscous solutions in aqueous systems. They increase the viscosity of the water by either binding water molecules (hydration) or by absorbing and enveloping the water in their intertwined macromolecules, while at the same time restricting the mobility of the water. Such water-soluble polymers represent a large group of chemically very different natural and synthetic polymers, the common feature of which is their solubility in water or aqueous media. The prerequisite for this is that these polymers have a have sufficient number of hydrophilic groups and are not too strongly cross-linked. The hydrophilic groups can be nonionic, anionic or cationic in nature, for example as follows:

- NH ₂ - COOH - COO ^" ^' M ⁺ -NR ₂

- NH - RO - SO ₃ - M ⁺ (CH ₂ ) _n

II

—OH - NH-C-NH ₂ -PO3 ^" M ²⁺ SO ₃ ^"

The group of cosmetically and dermatologically relevant hydrocolloids can be divided as follows: organic, natural compounds, such as agar agar, carrageenan, tragacanth,

Gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum,

Starch, dextrins, gelatin, casein, organic, modified natural substances such as B. carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, organic, fully synthetic compounds, such as. B. polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, inorganic compounds, such as. B. polysilicic acids, clay minerals such as montmorillonites,

Zeolites, silicas.

Hydrocolloids preferred according to the invention are, for example, methyl celluloses, as the methyl ethers of cellulose are referred to. They are characterized by the following structural formula in which R can represent a hydrogen or a methyl group.

Particularly advantageous for the purposes of the present invention are the cellulose mixed ethers, which are generally also referred to as methyl celluloses and which, in addition to a dominant content of methyl, additionally contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl groups. (Hydroxypropyl) methyl celluloses are particularly preferred, for example those sold under the trade name Methocel E4M by Dow Chemical Comp. available.

Also advantageous according to the invention is sodium carboxymethyl cellulose, the sodium salt of the glycolic acid ether of cellulose, for which R in structural formula I can be a hydrogen and / or CH ₂ COONa. Particularly preferred is the sodium carboxymethyl cellulose available under the trade name Natrosol Plus 330 CS from Aqualon, also known as cellulose gum.

For the purposes of the present invention, preference is also given to xanthan (CAS No. 11138-66-2), also called xanthan gum, which is an anionic heteropolysaccharide which is generally formed from corn sugar by fermentation and is isolated as the potassium salt. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 ^χ 10 ⁶ to 24 * 10 ⁶ . Xanthan is formed from a chain with β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. Xanthan is the name for the first microbial anionic heteropolysaccharide. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 10 ⁶ . Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. The number of pyruvate units determines the viscosity of the xanthane. Xanthan is produced in two-day batch cultures with a yield of 70-90%, based on the carbohydrate used. In doing so Yields of 25-30 g / l achieved. The work-up takes place after killing the culture by precipitation with z. B. 2-propanol. Xanthan is then dried and ground.

An advantageous gelling agent in the sense of the present invention is also carrageenan, a gel-forming extract similar to agar from northern Atlantic, belonging to the florida red algae (Chondrus crispus and Gigartina stellata).

The term carrageen is often used for the dried algae product and carrageenan for the extract from it. The carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored powder with a molecular weight range of 100,000-800,000 and a sulfate content of approx. 25%. Carrageenan, which is very easily soluble in warm water; a thixotropic gel forms on cooling, even if the water content is 95-98%. The firmness of the gel is brought about by the double helix structure of the carrageenan. There are three main components in carrageenan: The gel-forming κ fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in 1, 3 and 1, 4 positions (In contrast, agar contains 3,6-anhydro-α-L-galactose). The non-gelling λ fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and the like. Easily soluble in cold water. The i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-α-D-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also designated with Greek letters: α, ß, γ, μ, v, ξ, π, ω, χ. The type of cations present (K ⁺ , NH ₄ ⁺ , Na ⁺ , Mg ²⁺ , Ca ²⁺ ) also influences the solubility of the carrageenans.

Polyacrylates are also advantageous gelators to be used in the sense of the present invention. Polyacrylates are compounds of the general structural formula

whose molecular weight can be between approximately 400,000 and more than 4,000,000. Polyacrylates which are advantageous according to the invention are acrylate-alkyl acrylate copolymers, in particular those which are selected from the group of the so-called carbomers or carbopols (Carbopol® is actually a registered trademark of the BF Goodrich Company). In particular, the acrylate-alkyl acrylate copolymer which is advantageous according to the invention is distinguished by the following structure:

R 'represents a long-chain alkyl radical and x and y numbers which symbolize the respective stoichiometric proportion of the respective comonomers.

According to the invention, particular preference is given to acrylate copolymers and / or acrylate-alkyl acrylate copolymers, which are available from B.F. Goodrich Company under the trade names Carbopol® 1382, Carbopol® 981 and Carbopol® 5984.

Also advantageous are copolymers of Cιo- ₃₀ alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters, which are cross-linked with an allyl ether of sucrose or an allyl ether of pentaerythritol.

Compounds bearing the INCI name "Acrylates / C 10-30 Alkyl Acrylate Crosspolymer" are advantageous. Particularly advantageous are those available under the trade names Pemulen TR1 and Pemulen TR2 from B.F. Goodrich Company.

The total amount of one or more hydrocolloids in the finished cosmetic or dermatological preparations is advantageously chosen to be less than 1.5% by weight, preferably between 0.1 and 1.0% by weight, based on the total weight of the preparations. It is advantageous in the sense of the present invention if the content of one or more polyacrylates in the cosmetic or dermatological cleaning emulsion is in the range from 0.5 to 2% by weight, very particularly advantageously from 0.7 to 1.5% by weight. -% is selected, in each case based on the total weight of the preparations

Cosmetic preparations, which are cosmetic cleaning preparations for the skin, can be in liquid or solid form.

In addition to the substances mentioned above, the compositions according to the invention optionally contain the additives customary in cosmetics, for example perfume, dyes, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescent agents, plant extracts, vitamins, active ingredients, preservatives, bactericides, pigments, which have a coloring effect, thickeners, softening, moisturizing and / or moisturizing substances, or other usual components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

An additional level of antioxidants is generally preferred. According to the invention, all the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.

It is also advantageous to add antioxidants to the preparations according to the invention. The antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L- Camosin and its derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl -, Cholesteryl and glyceryl esters) as well as their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthione sulfoximine, buth Penta-, hexa-, heptathioninsulfoximine) in very low tolerable doses (e.g. pmol to μmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, Lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their Derivatives, vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and their Derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, camosin, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and their derivatives, Mannose and its derivatives, zinc and its derivatives (for example ZnO, ZnSO ₄ ) selenium and its derivatives (for example selenium methionine), stilbenes and their derivatives (for example stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers , Sugar, nucleotides, nucleosides, peptides and lipids) of these active ingredients.

The amount of the aforementioned antioxidants (one or more compounds) in the emulsions is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 0.1 to 10% by weight on the total weight of 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 (s), it is advantageous to use their respective concentrations in the range from 0.001 to 10% by weight, based on the total weight of the formulation, to choose.

The following examples, in which washing preparations for hair and body care are described, are intended to illustrate the compositions according to the invention, but are not intended to restrict the invention to these examples. The numerical values in the examples mean percentages by weight, based on the total weight of the respective preparations. Formulation Examples:

Claims

claims:

1. Cosmetic and dermatological cleaning preparations containing

(a) one or more pre-gelatinized, cross-linked starch derivatives

(b) one or more ethoxylated oils.

2. Preparation according to claim 1, characterized in that hydroxypropylated phosphate esters are used as the pregelatinized, crosslinked starch derivatives.

3. Preparation according to claim 1, characterized in that hydroxypropyl distarch phosphate (CAS number 113894-92-1) is used as the pregelatinized, crosslinked starch derivative

4. Preparations according to one of the preceding claims, characterized in that the or the ethoxylated oils are selected from the group of ethoxylated glycerol fatty acid esters, particularly preferably: PEG-10 olive oil glycerides, PEG-11 avocado oil glycerides, PEG-11 cocoa butter glycerides, PEG -13 sunflower oil glyceride, PEG-15 glyceryl isostearate, PEG-9 coconut fatty acid glyceride, PEG-54 hydrogenated castor oil, PEG-7 hydrogenated castor oil, PEG-60 hydrogenated castor oil, jojoba oil ethoxylate (PEG-26 jojoba fatty acids, PEG-26 jojoba alcohol) 5 cocoat, PEG-9 coconut fatty acid glyceride, PEG-7 glyceryl cocoat, PEG-45 palm kernel oil glyceride, PEG-35 castor oil, olive oil-PEG-7 ester, PEG-6 caprylic acid / capric acid glyceride, PEG-10 olive oil glyceride, PEG-13 sunflower oil Hydrogenated castor oil, hydrogenated palm kernel oil glyceride-PEG-6 esters, PEG-20 corn oil glycerides, PEG-18 glyceryl oil / cocoate, PEG-40 hydrogenated castor oil, PEG-40 castor oil, PEG-60 hydrogenated ric inus oil, PEG-60 corn oil glycerides, PEG-54 hydrogenated castor oil, PEG-45 palm kernel oil glycerides, PEG-35 castor oil, PEG-80 glyceryl cocoate, PEG-60 almond oil glycerides, PEG-60 "Evening Primrose" glycerides, PEG-200 hydrogenated glyceryl palmat, PEG-90 glyceryl isostearate.

5. Preparations according to one of the preceding claims, characterized in that the or the pre-gelatinized, crosslinked starch derivatives in a concentration of 0.1 to 20% by weight, preferably in a concentration of 0.3 to 15% by weight and very particularly preferably in a concentration of 0.5 to 10% by weight, based on the total weight of the preparation contained in the preparations according to the invention.

6. Preparations according to one of the preceding claims, characterized in that the or the ethoxylated oils in a concentration of 0.1 to 15% by weight, preferably in a concentration of 0.2 to 8% by weight and very particularly preferably in one Concentration of 0.3 to 5% by weight, based on the total weight of the preparation, is contained in the preparations according to the invention.

7. Preparations according to one of the preceding claims, characterized in that they are in the form of gels.

8. Preparations according to one of the preceding claims, characterized in that they are in the form of liquid dosage forms.

9. Preparations according to one of the preceding claims, characterized in that they are in the form of solid soap or syndet pieces.

10. Preparation according to one of the preceding claims, characterized in that it additionally contains one or more detergent surfactants selected from the group of anionic, cationic, nonionic or amphoteric surfactants.

11. Preparations according to one of the preceding claims, characterized in that the surfactant or surfactants are selected from the group consisting of myristoyl sarcosine, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate, sodium / ammonium cocoyl isethionate , Dioctyl sodium sulfosuccinate, disodium laureth sulfosuccinate, disodium lauryl sulfosuccinate and disodium undecylenamido MEA sulfosuccinate, sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium ammonium sulfate and sodium C ₁₂ -ι _3- parium sulfate lauryl sulfate, benzalkonium chloride, alkyl betaine, alkylamidopropyl betaine and alkyl amidopropylhydroxy- sultaine, acetate Natriumacylamphoacetat, Dinatriumacylamphodipropionat, Dinatriumalkylamphodia-, Natriumacylamphohydroxypropylsulfonat, Dinatriumacylamphodiacetat and Natriuma- cylamphopropionat, Cocamide MEA / DEA / MIPA, lauryl glucoside, decyl glycoside and co coglycosid.

12. Cosmetic or dermatological cleaning emulsions according to one of the preceding claims, characterized in that they contain an alkyl ether sulfate, preferably lauryl ether sulfate or myristyl ether sulfate.