EP3423026A1

EP3423026A1 - Packaging-compatible aerosol shower foam

Info

Publication number: EP3423026A1
Application number: EP17704761.0A
Authority: EP
Inventors: Rixa Dippe; Romy Kienast; Kirsten Schneider; Ina Schornstein; Britta Fischer
Original assignee: Beiersdorf AG
Current assignee: Beiersdorf AG
Priority date: 2016-03-02
Filing date: 2017-02-13
Publication date: 2019-01-09
Also published as: WO2017148689A1; US20190021960A1; CN108463205A; DE202016002099U1; DE102016203440A1

Abstract

The invention relates to aerosol shower foam preparations that are suitably mild, have a creamy dense foam and are packaging-compatible.

Description

Beiersdorf Aktiengesellschaft

Hamburg

description

Packaging-compatible aerosol shower foam

The present invention describes cosmetic aerosol shower foam preparations characterized by a good mildness, a creamy, dense foam and packaging compatibility.

To cleanse yourself is a need that people have had for millennia. During cleaning, the dirt particles on the skin should be loosened and then rinsed off. To achieve this, there have been many different forms of detergents. Since the cleaning not only the dirt particles are removed from the skin, but also skin-specific lipids and skin-natural water-binding substances (NMF) with dissolved out and rinsed, the desire of consumers is great to use the mildest possible cleaning products, so This is not done to such a great extent and therefore the skin is not stressed so much. The strain on the skin can be dry, chapped, reddened and / or irritating. These phenomena are gaining in importance against the background that many people shower or bathe daily, if necessary, even several times a day. In this cleaning behavior, it is crucial that the products used are mild so that the skin is stressed as little as possible.

In addition to this basic need for cleaning, the consumer increasingly wants to indulge in body cleansing and indulge in the "little luxuries" in the bathroom, such as the product's distinctive product shape and its application of pleasurable sensory impressions One way to bring about these pleasurable sensations is to make sure that the feel of the products is pleasant to the touch when taken and applied to the skin, for example through a foam characterized by creaminess and fine bubbles. In order for the product form to be considered luxurious, it should be different from the current product form, shower preparations in plastic bottles, and stand out from it. This can be achieved, for example, by aerosol foams, which are advantageously provided in cans.

It is therefore an object of the present invention to provide mild cleansing preparations in a product form which satisfies consumer demands for special, luxurious products.

Surprisingly, mild cleaning preparations with a creamy, fine-bubble foam could be made available by introducing these preparations into aerosol containers as foamable and / or post-foaming preparations.

There are a variety of cleaning products known that realize various ways to provide the skin with mild preparations. By way of example, EP 1430884 B1 is cited, which discloses an oil bath containing a mild surfactant mixture and oil body.

Aerosol foams in aerosol containers are also known and frequently found in the cosmetic segments for hair preparations, shaving foams or sunscreen preparations in foam form. As an example, EP 1374837 B1 may be mentioned here. This document discloses hair spray aerosol foam products containing certain polymers and a solvent system and packed in a pressure-resistant package together with propellants.

Even older documents of the prior art already disclose preparations which are nachschäumend and offered in pressurized gas containers. The document

No. 3,541,581 mentions water, soap (water-soluble salts of higher fatty acids), gel structuring agents and post-foaming agents as essential constituents of such a composition.

It is proposed in US Pat. No. 4,405,489 to dispense with a gel-forming agent, but in this case a special and expensive process is required for the production and filling of such compositions.

Document DE 3839349 A1 discloses low-viscosity, surfactant-containing cleaning solutions which are converted into a cleansing gel by pressurization with volatile gases. As can be seen from the StdT, the production process of such preparations is sometimes quite expensive. Nevertheless, there is still a need to produce such preparations, since they meet the consumer's wishes for special, even unusual products.

It has been found that mild cosmetic cleansing preparations can be provided if the surfactant content does not exceed 10% by weight, based on the active content. In order to achieve a creamy, fine bubble foam in such preparations, the cleaning preparations are filled with a propellant as aerosol foams in aerosol containers.

However, it has been shown that the aerosol containers are attacked by the cleaning preparations; it comes to corrosion. The use of aerosol containers with inner protective lacquer does not help either. Through the cosmetic cleaning preparations, the inner protective lacquer is infiltrated, it dissolves and corrosion begins. Corrosion of aerosol containers can lead to leaking of the containers and bursting of the containers. The detachment of the inner protective lacquer can also lead to blockage of the valve, thereby the product is unusable.

This results in the task of providing mild cleaning preparations which form a creamy and fine-bubble foam and can be made available in aerosol containers without the inner protective lacquer of the aerosol containers being damaged.

Surprisingly, the object has been achieved by cosmetic cleaning preparations containing

<0.5 wt .-% NaCl, based on the cleaning preparation,

<10% by weight of surfactant or surfactants, based on the active content and the cleaning preparation, selected from the group of anionic, amphoteric and nonionic surfactants,

wherein the cosmetic cleansing preparations contain 0 to 1, 5 wt .-% of uncharged organic molecules having a molecular weight <250 g / mol, and

wherein the cleaning preparations and a propellant in aerosol containers are filled with inner protective lacquer.

It is preferred that the cleaning preparations according to the invention are free of soaps. Soaps in the sense of the present invention are understood as meaning the water-soluble salts of higher fatty acids. For the purposes of the present invention, "free from" means that less than 0, 1 wt .-% of the respective substance, based on the weight of the cleaning preparation, are present. If traces of soaps are present in the preparations according to the invention, they come from impurities of the constituents or premixes which are used to prepare the preparations.

It is essential to the invention that the statement <10% by weight of surfactant or surfactants always refers to the total amount of surfactant or surfactants in the cleaning preparation.

It is preferred if the anionic surfactant (s) is / are selected from the group of sodium laureth sulfate, disodium laureth sulfosuccinate and / or sodium coconut sulfate. The anionic surfactant or anionic surfactants are present at a level of from 1 to 10% by weight, preferably from 3 to 7% by weight. If the content of the anionic surfactant (s) is 10% by weight, no further surfactants are present in the cosmetic preparations. If other surfactants, for example amphoteric and / or nonionic surfactants, are present in addition to an anionic surfactant (s), then the total amount of surfactants must not exceed the value of 10% by weight.

Preferred amphoteric surfactants are low-salt forms of alkylamphoacetates such as disodium cocoamphodiacetate, disodium cocoamphomonoacetate. Preferred embodiments are completely without amphoteric surfactants.

Advantageous nonionic surfactants may be selected from the group of alcohols, cocamides such as MEA, DEA or MI PA, esters formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols, PEG-200 Hydro genated Glyceryl Palmat , the ethoxylated and / or propoxylated triglyceride esters, the propoxylated POE ethers and alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside, the sucrose ester, the sucrose ether, the polyglycerol esters, the diglycerin ter, the monoglycerol esters, the methyl glucose esters and the esters of hydroxy acids.

Surfactant combinations of large surfactant molecules are preferred, because the large surfactant molecules do not interact with the inner protective varnish. An advantageous surfactant combination consists of sodium laureth sulfate and disodium laureth sulfosuccinate, in a preferred weight ratio in the range of 2: 1 to 1: 2.

It is preferable that the content of all surfactants contained in the cleaning preparation is selected from a range of 1 to 10% by weight, preferably 2 to 8% by weight, based on the weight of the cleaning preparation. In an advantageous embodiment, only one or more anionic (s) surfactant (s) are included in the cleaning preparation.

It is essential to the invention that the cosmetic cleansing preparations 0 to

1, 5 wt .-% of uncharged organic molecules having a molecular weight <250 g / mol, based on the weight of the cleaning preparation. Here, the perfume ingredient (s), in particular selected from alpha-isomethyl-ionone, benzyl alcohol, butylphenyl, methylpropional, citronellol, coumarin, geraniol, limonene and linalool, individually or in combination present, together with their solvents to said uncharged organic molecules with a molar mass <250 g / mol counted. Examples of further uncharged organic molecules with a molecular mass <250 g / mol, which also have an aromatic ring system, are phenoxyethanol (molar mass

138, 16 g / mol) and parabens such as ethylparaben (166.15 g / mol) or propylparaben

(180.2 g / mol). It could be shown that products according to example formulations 2 and 13, whose formulation on the one hand on the incorporation of certain uncharged organic molecules with a molecular mass <250 g / mol, namely parabens and phenoxyethanol, was omitted and on the other such molecules were incorporated , react differently with the packaging unit. When products according to example formulation 2, which do not contain any of the above-mentioned uncharged organic molecules, are packaged in an inner coating and stored for 4 months at 40 ° C., the inner coating remains intact (see Figure 1, lower part). For products according to example recipe 13, which contain such molecules, the interior painting is attacked, see Figure 1, upper part. Limited amounts of uncharged organic molecules with a molar mass <250 g / mol can be tolerated in the cosmetic cleansing preparations according to the invention, such as the above-described perfume ingredients, as long as the amount of uncharged organic molecules with a molecular weight <250 g / mol has a value of 1, 5 wt .-%, based on the total weight of the preparation does not exceed. The uncharged organic molecules with a molar mass <250 g / mol can also reach the preparations via impurities and / or additives of the raw materials used. However, it is more advantageous according to the invention if 0 to 1, 2 wt .-%, particularly preferably 0 to 1, 0 wt .-%, uncharged organic molecules having a molecular weight <250 g / mol, each based on the weight of the cleaning preparations are. These quantities contain the amount of perfume ingredients and their solvents. Preferred cleaning formulations according to the invention contain no parabens and no phenoxyethanol. Further preferred cleaning formulations according to the invention comprise <0.05% by weight NaCl, based on the weight of the cleaning preparation and no parabens and no phenoxyethanol. The molar mass M of a substance is the quotient of the mass and the amount of substance. The molar mass is given by the formula where m is mass, n amount of substance, NA avogadro constant and mM molecular weight. If the molecular formula of a chemical compound is known, the molar mass can be calculated. For more complex organic molecules, there are various methods for determining the molar mass, for example, mass spectrometry.

Furthermore, it is essential to the invention that the cleaning preparations contain at most 0.5% by weight of NaCl, based on the weight of the cleaning preparation. It is preferred that NaCl be present at <0.05% by weight, based on the weight of the cleaning formulation. The preparations are not NaCl with added. Traces of NaCl contained in the cleaning preparations may originate from recipe ingredients and / or their premixes.

The strict limitation in the amount of uncharged organic molecules with a molar mass <250 g / mol in the cosmetic cleaning preparations and the substantial absence of NaCl in the cleaning preparations cause the corrosion phenomena of the aerosol container can be prevented; this is evidenced by a so-called electrochemical corrosion test (ECKP) and electrochemical impedance spectroscopy (EIS). The methodology for ECKP and EIS is described in the diploma thesis of Marc Wilck, submitted on 3.2.2014. The ECKP serves to estimate the corrosion potential of a preparation that is filled into a metal container. It also allows a statement as to whether an interior protective coating is required. Since the EIS is carried out with aerosol cans, lacquered with inner protective lacquers and preparations over a long period of time (2 weeks), statements are possible as to whether the investigated combinations of preparation, inner protective lacquer and aerosol can tend to form corrosion or not. By way of example, the results of tests according to ECKP for the preparations according to example recipe 13 (chloride content 1, 2 mg / kg) and 14 (chloride content 3900 mg / kg) are shown in FIG. It becomes clear that preparations with a high chloride content lead to corrosion of the aerosol containers. Therefore, no NaCl is added to the formulations according to the present invention.

It is likewise preferred for the pH of the cleaning preparations to be adjusted to a substantially skin-neutral pH of 4.1 to 5.8. According to the invention therefore substances are selected which are usually used to adjust the pH stable in cosmetic preparations and to keep them stable. Advantageously, these substances can be selected from the group of citric acid and lactic acid.

Since substances commonly used for the preservation of cosmetic preparations, such as, for example, phenoxyethanol and parabens, fall into the group of uncharged organic molecules with a molar mass <250 g / mol, such substances can not be used for the preservation of the preparations according to the invention. The preservation of the cosmetic cleansing preparations according to the invention therefore takes place with benzoic acid and / or a salt of benzoic acid, with salicylic acid and / or a salt of salicylic acid and / or with sorbic acid and / or a salt of sorbic acid. Preference is given to preserving with sodium benzoate. The preservatives according to the invention are present at levels of 0.1 to 1.0% by weight, preferably 0.3 to 0.6% by weight, based on the weight of the cleaning preparation.

The cleaning preparations according to the invention are particularly suitable for forming shower foams.

The present invention also provides a method for preventing corrosion of aerosol containers, in particular aerosol containers made of aluminum, coated with an interior paint, in particular coated with epoxy-phenol paint, which is characterized in that the said aerosol containers with cleaning preparations,

containing <0.5 wt.% NaCl, based on the weight of the cleaning preparation and 0 to 1, 5 wt.% of uncharged organic molecules with a molar mass <250 g / mol, based on the weight of the cleaning preparation .

and be filled with propellant.

It is preferable that the content of NaCl is <0.05% by weight. It is further preferred if the uncharged organic molecules having a molar mass <250 g / mol, with a content of 0 to 1, 2 wt .-%, preferably 0 to 1, 0 wt .-% present. The amounts given above each relate to the weight of the cleaning preparation.

It is likewise preferred if NaCl with a content of <0.05% by weight is present and the uncharged organic molecules with a molar mass <250 g / mol, with a content of 0 to 0, 1 wt .-%, preferably 0 to 0.01 wt .-% are present. The amounts given above each relate to the weight of the cleaning preparation.

Perfumes usually consist of the fragrances and the solvents, usually alcohols or other suitable solvents, optionally also in combination with water. The fragrances are essential oils of vegetable or animal origin and increasingly synthetic fragrances nowadays. For the purposes of the present invention, the terms fragrances and perfume ingredients are synonyms. Perfumes are generally present at levels of from 0.3 to 1.2% by weight, preferably from 0.5 to 1.0% by weight, based on the cleaning preparation.

The present invention further provides a method for preventing corrosion of aerosol containers, in particular aerosol containers made of aluminum, coated with an inner coating, in particular coated with an epoxy phenol paint, which is characterized in that the said aerosol containers containing cleaning preparations

<0.5% by weight NaCl, based on the weight of the cleaning preparation,

<10% by weight of surfactants, based on the active content and the weight of the cleaning preparation, selected from the group of anionic, amphoteric and nonionic surfactants,

wherein the cosmetic cleaning preparations contain 0 to 1, 5 wt .-% of uncharged organic molecules having a molecular weight <250 g / mol, containing and filled with propellant.

By "post-foaming" or "foamable" are meant formulations which form a foam, wherein it is preferred that the foam forms on exit from the nozzle. In foams, gas bubbles are (arbitrarily) distributed in one (or more) liquid phase (s).

In aerosols, liquid droplets are distributed (arbitrarily) in a gaseous phase.

In the context of the present invention, in the case of aerosol foams, the gaseous blowing agents are present in the cleaning preparation, which is in a liquid phase, the liquid phase enclosing the gaseous phase (s). The preparations according to the invention are preferably present as foamable preparations. The preparations according to the invention are particularly preferably in the form of aerosol foams.

Other anionic and / or amphoteric and / or nonionic surfactants can be used in the preparations according to the invention, with the proviso that they do not counteract the solution of the present task.

The anionic surfactants include the following compounds:

Acylamino acids (and their salts), such as

1. acylglutamates, for example sodium acylglutamate, sodium cocoylglutamate, di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,

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

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

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

5. Acyl lactylates, lauroyl lactylate, caproyl lactylate.

Carboxylic acids and derivatives, such as

1. Ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6-citrate and sodium PEG-4-lauramide carboxylate,

2. 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 dilaureth-phosphate,

Sulfonic acids and salts, such as

1. Acyl-isethionates, e.g. Sodium / ammonium cocoyl isethionate, sodium lauryl methyl isethionate,

2. alkylaryl sulphonates,

3. Alkyl sulfonates, for example sodium coconut monoglyceride sulfate, sodium C 12-14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate, 4. other sulfosuccinates, for example dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate, disodium undecylenamido MEA sulfosuccinate and PEG-5 lauryl citrate sulfosuccinate. such as

Sulfuric acid esters, such as

1. further alkyl ether sulfates having different degrees of ethoxylation and mixtures thereof, for example ammonium, magnesium, MIPA, TIPA-laureth-X-sulfate, sodium myrith-X-sulfate and sodium C12-13-pareth-X-sulfate, with X. = 1 -5 ethoxy groups.

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

The following compounds can be counted among the amphoteric surfactants:

1. further acyl / dialkylethylenediamines, for example disodium acylamphodipropionate, sodium acylamphohydroxypropylsulfonate and sodium acylamphopropionate,

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

3. Sultaines, for example Lauryl Hydroxy Sultaine.

The following compounds can be counted among the nonionic surfactants:

1. amine oxides, such as cocoamidopropylamine oxide,

2. Ethers, for example ethoxylated / propoxylated alcohols, laureth-X where X = 2 to 10, where X is ethoxy group, ethoxylated / propoxylated esters, ethoxylated / propoxylated cholesterols, ethoxylated propoxylated lanolin, ethoxylated / propoxylated polysiloxanes.

It is also possible to incorporate natural oils in the preparations according to the invention, but only in small amounts, i. Amounts <0, 1 wt .-%, based on the weight of the cleaning preparation, are used. For example, almond oil and / or sunflower oil can be used in these amounts. Natural oils are understood to mean triglycerides which are obtained primarily from plants but also from animal organisms and are in liquid form at room temperature.

Compositions according to the invention may contain one or more polymeric structurants. The polymeric structurants can be selected from the group of natural, nature-based or synthetic polymers. Synthetic polymers are advantageously acrylate based, preferably acrylate-based copolymers. Particularly preferred is the use of the compound acrylate copolymer.

However, natural polymers are also just as suitable, and the use of xanthan gum is particularly preferred. Furthermore, the combination of acrylate copolymer and xanthan gum is advantageous to use.

Xanthan gum is generally used in concentrations of 0, 1 to 0.5 wt .-%, based on the cleaning preparation. Acrylates copolymer is used in concentrations of 0.5 to 3 wt .-%, based on the cleaning preparation.

Propellants which are advantageous according to the invention are propellants such as propane, n-butane and / or isobutane. According to the invention, mixtures of these gases are preferred. Mixtures A of propellants which are particularly advantageous according to the invention have the following composition: Mixture A: 72% isobutane, 23% propane, 5% butane,

Mixture B: 79.4% isobutane, 15.3% propane, 5.3% butane,

Mixture C: 60% butane, 20% isobutane, 20% propane.

Advantageous in the context of the present invention, the proportion by weight of blowing agent from the range of 1, 0 to 15 wt .-%, in particular 2.0 to 10.0 wt .-%, based on the total weight of filling material and blowing agent chosen. Under contents is the cleaning preparation according to the invention to understand. The contents are therefore present in a proportion by weight of 99 to 85 wt .-%, in particular 98 to 90 wt .-% in the overall preparation. Total preparation is to be understood as meaning the cleaning preparation together with the propellant.

The cleaning preparations according to the invention are advantageously in the form of foamable or foamable preparations, which are taken from aerosol containers and foam on leaving the nozzle. According to the invention advantageous aerosol containers are spray devices with a filling of largely liquid cleaning preparations, which are under the pressure of a propellant. Such containers may be equipped with valves of very different types, which allow foaming in the removal of the contents. In the context of the present invention, pressurized gas containers are in particular cylindrical vessels made of metal (aluminum, tinplate, content <1000 ml), in the selection of which pressure and fracture resistance, corrosion resistance, easy filling, etc., but also aesthetic aspects, handiness, Printability etc. play a role. The maximum permissible operating pressure of metal spray cans at 50 ° C is 12 bar and the maximum filling volume at this temperature is approx. 90% of the total volume.

Particularly advantageous in the context of the present invention are tinplate or aluminum cans. For corrosion protection reasons, metal cans can be painted on the inside (silver- or gold-lacquered), for which all commercially available interior protective lacquers are suitable. Preferred for the purposes of the present invention are polyester, epoxy-phenolic and polyamide-imide coatings. Foil laminations of polyethylene (PE), polypropylene (PP) and / or polyethylene terephthalate (PET) inside the cans are also advantageous, especially for tinplate cans.

The compressed gas containers are usually one or two, but usually three-piece cylindrical, conical or otherwise shaped.

The internal structure of the spray cans and the valve design are depending on the purpose and the physical nature of the content -. B. whether as a two- or three-phase system - very varied and can be determined by the skilled person by simple trial without inventive step. For suitable embodiments, reference is made to the "Aerosol Technology Handbook of Aersosol Packaging" (Wolfgang Tauscher, Melcher Verlag GmbH Heidelberg / Munich, 1996).

According to the invention advantageous valves may be formed with or without riser. The individual parts of which valves according to the invention are usually constructed preferably consist of the following materials:

Plate: Tinplate: bright, gold or clear lacquered, foil-laminated (PE, PP or PET)

Aluminum: bright, silver or gold lacquered, different lacquer variants, Stoner-Mudge-version.

Seal: natural or synthetic elastomers or thermoplastic (sleeve sleeves, foil-laminated PE or PP). Inner and outer seals, eg. B. from Perbunan, Buna, neoprene, butyl, CLB, LDPE, Viton, EPDM, chlorobutyl, bromobutyl and / or various compounds. Cone: polyamide (PA), polyoxymethylene (POM), brass and various special materials, standard bores (eg: 0.25 to 0.70 mm or 2 x 0.45 to 2 x 1.00 mm), various shaft diameter

Spring: metal, more preferably V2A, stainless steel; Plastic and also elastomer.

Housing: standard and impact

VPH holes, RPT holes or slotted for overhead applications Materials: z. As polyacetal, PA, PE, POM and the like

Riser: plastic (polymer resin), e.g. PE, PP, PA or polycarbonate.

Advantageous spray heads for the purposes of the present invention, for example, foam heads for upright use (can hold vertically) or foam heads for overhead application with one or more channels.

It is inventively preferred if the aerosol container is an aluminum can, which is coated on the inside with a protective lacquer, especially with Epoxyphenol lacquer.

Optionally, if necessary, the customary in cosmetics additives and excipients are incorporated into the preparations, such as deodorizing substances, antiperspirants, insect repellents, vitamins, dyes, pigments with coloring effect, flavoring agents, denaturants, softening substances, moistening and / or moisturizing substances, antioxidants, UV filter substances, sensory additives, film formers, active ingredients or other customary constituents of a cosmetic formulation, such as foam stabilizers or silicone derivatives, with the proviso that the additives and auxiliaries of the solution do not counteract the stated object. By way of example, two preparations according to the invention were examined for their mildness; the results are shown in the inserted table:

For determination of mildness, an RBC assay is performed.

The standard RBC assay (10 minutes incubation) is used to estimate in vivo ocular mucosal irritation potentials of surfactants and surfactant-containing products.

1. Hemolysis:

A defined aliquot of isolated calf RBCs is incubated with a series of increasing concentrations of the WAS test sample to be tested (stock solution with formulations 1: 100 w / v and for raw materials 0.1% active in PBS) for 10 minutes with shaking at room temperature (RT). After centrifugation, the supernatants obtained are analyzed photometrically for their content of released hemoglobin (HbO 2) at 530 nm. From this, the relative degree of hemolysis is calculated and the concentration-response curve with the H50 value [μΙ / ml] is determined as a parameter. This indicates the concentration of the test sample at which 50% of hemoglobin is released.

2. Hb0 ₂ denaturation:

A defined aliquot of isolated calf RBCs is incubated with a fixed concentration of the test sample (1% w / v or 0.1% active content) for 10 minutes with shaking at RT and then centrifuged. The change in spectral absorption at 575 nm and 540 nm is measured in comparison to native HbÜ2. From the ratio of the absorption values to each other, the denaturation index DI [%] is calculated. The 100% standard is sodium lauryl sulphate (0.1% active content).

3. L / D quotient:

The quotient represents the ratio of the parameters of hemolysis (H50) and denaturation (DI) and is used to characterize and classify the tested samples. The methodology is described in detail in Mol. Toxicol. 1 (4), 1987-1988, page 525ff.

The results show that both preparations have only a moderate irritation potential for the ocular mucosa. The preparation according to example formulation 15 is the preparation according to the invention without parabens and phenoxyethanol. The product according to this preparation performs better in the above-mentioned test than the comparative product. Since this test is for the determination of the irritation potential of the ocular mucosa, the values obtained are also an indicator of the overall mildness of products, whereby products with a moderately irritating potential for the ocular mucosa can be classified as mild products altogether.

Products according to example formulations 14 and 13 were subjected to an ECKP, the results are shown in FIG. The results of the ECKP test indicate a passivation for the combination preparation according to example formulation 13 and aluminum can. When prepared according to example formulation 14, the results and the image indicate pitting corrosion. The difference between the two preparations is essentially in the chloride concentration. The preparation according to example recipe 13 contains substantially less chloride ions.

With the aid of the EIS, it was possible to identify an inner protective lacquer for a product according to example recipe 16 in an aluminum can, which counteracts corrosion of the aerosol container. The identified paint was an epoxy phenolic paint.

Figure 1 shows two cut aerosol containers. The upper part shows that the inner protective varnish made of epoxy phenol separates from the aluminum aerosol can. The cleansing formulation which had been filled in this can contained 1, 6% by weight of uncharged organic molecules with a molar mass <250 g / mol, in the form of methylparaben, ethylparaben and phenoxyethanol. The cleaning preparation stored 4 months in the aerosol can at 40 ° C.

In the lower part of the figure, an aerosol can is shown, which was filled with a cleaning preparation containing no methylparaben, ethylparaben and phenoxyethanol. The inner protective lacquer was not attacked. Thus, the negative effects of methylparaben, ethylparaben and phenoxyethanol on the durability of the interior paint have been demonstrated. Once the inner protective lacquer is damaged, the corrosion of the aerosol container begins. Examples:

Example formulations Cleaning preparations, without propellant:

Example No. 1 2 3 4 5 6

Sodium Laureth Sulfate 3 3.8 4 4.5 5 4

Disodium Laureth Sulfosuccinate 3 4.9 2.2 3

Decyl glycosides 5 4

Cocoglycosides 2

Natriumacylglutamate

Disodium cocoylglutamate 1 1

PEG-200 Hydrogenated Glyceryl

Palmate 1 0.5 0, 1

PEG-14 M 0.2 0, 1 0.4

PEG-90 M 0.2 0.4

Acrylates Copolymer 1 3

Perfume 1 0.8 1 1, 2 1 0.8

PEG-40 Hydrogenated Castor Oil 0.7 0.5 0.7 0.9 0.6 0.6

Glycerol 2 1 2 3

Citric Acid 0.6 0.8 0.7 0.5 0.8 0.4

Sodium benzoate 0.5 0.45 0.45 0.4 0.3 0.5

Xanthan gum 0.4 0.3 0.2 0, 1

Sunflower oil or almond oil 0.1 0.05

Aqua ad 100 ad 100 ad 100 ad 100 ad 100 ad 100

Example No. 7 8 9 10 11 12

Sodium Laureth Sulfate 2

Disodium Laureth Sulfosuccinate 2 3

Decyl glycosides 4 3

Cocoglycosides 3,3 3 5

Sodium acylglutamate 4 4 5.9 3 3

Disodium cocoylglutamate 4

cocoamidopropyl

PEG-200 Hydrogenated Glyceryl

Palmate 1 0.5 0, 1

PEG-14 M 0.2 0, 1 0.4

PEG-90 M 0.2 0.4

Acrylates Copolymer 1 3

Perfume 1 0.8 1 1, 2 1 0.8

PEG-40 Hydrogenated Castor Oil 0.7 0.5 0.7 0.9 0.6 0.6

Glycerol 2 1 2 3

Citric Acid 0.6 0.8 0.7 0.5 0.8 0.4

Sodium benzoate 0.5 0.45 0.45 0.4 0.3 0.5

Ethylparaben

Methyl paraben

phenoxyethanol

Xanthan gum 0.4 0.3 0.2 0, 1

Sunflower oil or almond oil 0.1 0.05

Polyquaternium-7

Aqua ad 100 ad 100 ad 100 ad 100 ad 100 ad 100

Example No. 13 14 15 16

Sodium Laureth Sulfate 3.7 3.5 3.3 4

Disodium Laureth Sulfosuccinate 3.5 3.3 3.5

Decylglycoside

Cocoglycoside

Natriumacylglutamate

Dinatriumcocoylglutamate

Cocoamidopropylbetaine 3,5

PEG-200 Hydrogenated Glyceryl

palmate

PEG-14 M 0, 1 0.2 0, 1

PEG-90M

Acrylates copolymer

Perfume 0.8 1 0.9 0.8

PEG-40 Hydrogenated Castor Oil 0.5 0.7 0.5 0.8

Glycerin 2.5 1 2 1, 5

Citric Acid 0.6 0.75

Sodium benzoate 0.5 0.35

Ethylparaben 0.4 0.3

Methylparaben 0.4 0.3

Phenoxyethanol 0.9-0.8

Xanthan gum 0,5 0,5 0, 1

Sunflower oil or almond oil 0.05 0.01 0, 1 0.01

Polyquaternium-7 0.3

Aqua ad 100 ad 100 ad 100 ad 100

Claims

claims

Cosmetic cleaning preparations, in particular suitable for the formation of shower foams, containing

- <0.5 wt .-% NaCl, based on the total weight of the cleaning preparation,

- <10% by weight of surfactant or surfactants, based on the active content and the weight of the cleaning preparation, selected from the group of anionic, amphoteric and nonionic surfactants, wherein the cosmetic cleaning preparations 0 to 1, 5 wt.% Of uncharged organic molecules containing a molar mass <250 g / mol and wherein the cleaning preparations and a propellant are filled in aerosol containers with inner protective lacquer.

Cleaning preparation according to claim 1, characterized in that the propellant is a propellant or a mixture of propellant gases, is selected from the group propane, n-butane and isobutane.

Cleaning preparation according to claim 1 and / or 2, characterized in that the blowing agent in contents of 1, 0 to 15 wt .-%, in particular 2.0 to 10.0 wt .-%, based on the weight of the total preparation.

Cleaning preparation according to one of the preceding claims, characterized in that the aerosol container is an aluminum can.

Cleaning preparation according to one of the preceding claims, characterized in that the aerosol container is an aluminum can, which is coated on the inside with protective lacquer.

Cleaning preparation according to claim 5, characterized in that the protective lacquer is an epoxy phenol lacquer.

7. Cleaning preparation according to one of the preceding claims, characterized in that the preparations are free of soaps.

8. Cleaning preparation according to one of the preceding claims, characterized in that the surfactant or surfactants with a content of 1 to 10 wt .-%, preferably 2 to 8 wt .-%, based on the active content and the weight of the cleaning preparation, are present ,

9. Cleaning preparation according to one of the preceding claims, characterized in that the anionic surfactant or anionic surfactants are selected from the group of sodium laureth sulfate, disodium Laureth sulfosuccinate and sodium cocosulfate.

10. Cleaning preparation according to one of the preceding claims, characterized in that the cleaning preparation contains only one anionic surfactant or only several anionic surfactants.

11. A cleaning composition according to any one of the preceding claims, characterized in that the nonionic surfactant (s) are alkyl polyglycosides and / or PEG-200 hydrogenated palmates.

12. Cleaning preparation according to claim 1 1, characterized in that the one or more alkylpolyglycoside (s) decyl glycoside and / or cocoglycoside.

13. Cleaning preparation according to one of the preceding claims, characterized in that the cleaning preparations 0 to 1, 2 wt .-%, in particular 0 to

1, 0 wt .-%, based on the cleaning preparation, uncharged organic molecules having a molecular weight <250 g / mol.

14. Cleaning preparation according to one of the preceding claims, characterized in that the cleaning preparation contains no parabens and no phenoxyethanol.

15. Cleaning preparation according to one of the preceding claims, characterized in that as preservatives acting benzoic acid and / or a salt benzoic acid, salicylic acid and / or a salt of salicylic acid and / or sorbic acid and / or a salt of sorbic acid, preferably sodium benzoate.

16. Cleaning preparation according to one of the preceding claims, characterized in that the preservative substances with contents of 0, 1 to

1, 0 wt .-%, preferably 0.3 to 0.6 wt .-%, based on the weight of the cleaning preparation, are present.

17. Cleaning preparation according to one of the preceding claims, characterized in that the cleaning preparations <0.05 wt .-% NaCl based on the weight of the cleaning preparation.

18. Cleaning preparation according to one of the preceding claims, characterized in that the pH of the cleaning preparation is between 4.1 and 5.8.

19. A method for preventing corrosion of aerosol containers, in particular aerosol containers made of aluminum, coated with an inner coating, in particular coated with epoxy-phenolic lacquer, which is characterized in that the said aerosol container with cleaning preparations,

the <0.5 wt.% NaCl, based on the weight of the cleaning preparation and

and 0 to 1, 5 wt .-% of uncharged organic molecules having a molecular weight <250 g / mol, based on the weight of the cleaning preparation

and be filled with propellant.

20. A method for preventing corrosion of aerosol containers, in particular aerosol containers made of aluminum, coated with an inner coating, in particular with Epoxyphenol paint, characterized in that said aerosol container with cleaning preparations according to claim 1 or cleaning preparations according to at least one of claims 7 to 18 and Propellants are filled.