Cosmetic products and cleaning products stabilized against microbial attack

Abstract

The invention relates to the use of guanidine and / or at least one salt of guanidine for stabilizing aqueous products, such as cosmetic products and washing and cleaning products, against microbial attack.

Description

[0001] Cosmetic and cleaning products stabilized against microbial attack

[0002] The invention relates to the use of guanidine and / or at least one salt of guanidine for stabilizing aqueous products, such as cosmetic products and detergents and cleaning agents, against microbial attack.

[0003] Water-containing products, such as detergents and cleaning agents or cosmetic products, are typically manufactured using natural or biodegradable raw materials. These raw materials and the water used as a solvent are often contaminated with germs such as bacteria, yeasts, and fungi. If these products are not preservative-free, they can exhibit high bacterial counts just one day after production.

[0004] In order to ensure that these products and, where applicable, the components used in their manufacture meet the hygiene requirements and to ensure the durability of the technical products, so-called biocides are usually added to the products or their components.

[0005] One class of biocides used to preserve aqueous products, such as detergents and cleaning agents or cosmetic products, is the so-called 3-isothiazolin-3-ones. This class of substances includes highly effective antimicrobial compounds, some with different activity profiles. Synergistic combinations of different 3-isothiazolin-3-ones are often used to reduce the amount of biocide needed. For example, WO 99 / 08530 A1 proposes the combined use of methylisothiazolin-3-one and l,2-benzisothiazolin-3-one. Another class of biocides are the so-called alkylguanidinium salts and polyguanidinium salts.For example, it is known from the "Directory of microbicides for the protection of materials", Springer 2005, pages 726 to 731, that medium and long-chain guanidines and biguanidines, such as cocospropylenediamine-l,5-bis-guanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylene-biguanidine) hydrochloride, di(4'-chlorophenyldiguanido)hexane, chlorhexidine digluconate, chlorhexidine diacetate, have an antimicrobial effect.

[0006] In addition to their use as preservatives, alkylguanidine compounds are used in cosmetics, particularly in hair care, as disclosed in EP 1 646 429 A1.

[0007] Despite the numerous known active ingredients, active ingredient combinations and the measures that have now been taken, there is an increased demand for novel preservation methods for cosmetic products as well as detergents and cleaning agents, which preferably do not contain or have a reduced content of conventional preservatives or biocides, particularly due to the increasing regulatory restrictions.

[0008] The invention solves this problem by the novel use of guanidine and / or at least one salt of guanidine for stabilizing aqueous products, selected from cosmetic products and washing and cleaning agents, against microbial attack.

[0009] Within the scope of the invention, it was surprisingly found that aqueous products, i.e. water-based products, require significantly less, and in some cases even none, of the preservatives usually contained in these products for preservation due to the content of guanidine and / or a salt of guanidine, which were previously unknown as antimicrobial agents. Nevertheless, these products are characterized by excellent resistance to microbial attack, particularly during storage. The products stabilized against microbial attack exhibit significantly improved stability against attack by microorganisms such as bacteria, yeasts and fungi compared to products that do not contain guanidine or a salt of guanidine, and are therefore less prone to contamination. Furthermore, the cosmetic products, orthe detergents and cleaning agents have been significantly improved in terms of their environmental compatibility and also exhibit all known properties with regard to good and safe application properties.

[0010] Guanidine is the compound according to the formula shown below:

[0011] The salts of guanidine or guanidine salts within the meaning of the present invention are non-substituted guanidine or guanidinium salts of the general formula shown below: where n is 1, 2 or 3, and where the counterion X n ' for example chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, formate, acetate or citrate.

[0012] According to a preferred embodiment of the invention, guanidine hydrochloride and / or guanidine carbonate is used as the salt of guanidine.

[0013] At least one salt of guanidine means in the context of the invention that one or two, three, four or more, i.e. also a mixture of salts of guanidine are used in the aqueous products or are contained in these products.

[0014] The amount of guanidine or its salt used for stabilization against microbial attack can vary widely and is generally in the range of 0.033 to 2.0 wt.%, preferably in the range of 0.066 to 1.5 wt.%, particularly preferably in the range of 0.1 to 1.0 wt.%, in each case based on the guanidine content in the entire product. Any counterions other than H are therefore not taken into account when determining the guanidine content.

[0015] In the context of the present invention, the terms "wt%" refer to the total aqueous product.

[0016] The pH of the aqueous products in which the guanidine and / or its salt(s) is / are used for stabilization against microbial attack can vary widely and is generally in a range from pH 6.5 to pH 11.5, preferably in the range from pH 7.0 to pH 11.0, particularly preferably in the range from pH 7.5 to pH 10.5. The pH can be adjusted to the claimed range using measures familiar to the person skilled in the art.

[0017] The water content of the aqueous products in which guanidine and / or its salt(s) are used for stabilization against microbial attack can vary widely. Typically, the product is characterized by a water content of greater than 1 wt.%, preferably greater than 5 wt.%, particularly preferably greater than 10 wt.%, based on the total product.

[0018] The present invention relates to the use of guanidine and / or at least one salt of guanidine for stabilizing aqueous products, such as cosmetic products and detergents and cleaning agents, against microbial attack.

[0019] Cosmetic products include products from the cosmetics sector. These include, for example, products selected from the group consisting of shower gels, shower baths, tooth cleaning and care products, mouthwashes, hair shampoos, hair conditioners, conditioning shampoos, hair sprays, hair rinses, hair treatments, hair packs, hair tonics, self-tanners, facial toners, permanent wave fixing solutions, hair coloring shampoos, hair dyes, hair setting lotions, hair styling preparations, hair styling lotions, mousses, hair gels, hair waxes, shaving foam, perfume preparations, wet wipes, care products, and dermatological products for topical application, such as body creams, lotions, face creams, sunscreen preparations, and deodorants.

[0020] Products from the area of ​​washing and cleaning agents that come into consideration are, for example, selected from the group consisting of household cleaners, washing, cleaning or pre-treatment agents, refreshing sprays for textiles, fabric softeners, window cleaners, bathroom cleaners, toilet cleaners and dishwashing detergents.

[0021] As already described above, the present invention relates to the novel use of guanidine and / or at least one salt of guanidine for stabilizing aqueous products, such as cosmetic products and detergents and cleaning agents, against microbial attack. This novel use of the aforementioned compound, which was previously unknown as an antimicrobial agent, allows for significantly fewer, and in some cases even none at all, of the commonly used preservatives. The products stabilized against microbial attack by the guanidine content are nevertheless characterized by excellent resistance to microbial attack, particularly during storage.

[0022] According to one embodiment of the invention, the product in which guanidine or its salt is used for stabilization against microbial attack is characterized in that it contains one or more ingredients with antimicrobial action as additional preservatives, which are selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, 2,2'-dithiobis(N-methylbenzamide), benzalkonium chloride, didecyldimethylammonium chloride, cetrimonium bromide, benzethonium chloride, polyhexamethylene biguanide, bronopol, bronidox, Chlorphenesin, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynylbutylcarbamate, silver chloride, ethylhexylglycerol, hexylglycerol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-decanediol, glyceryl caprylate, glyceryl caprate,Glyceryl laurate, parabens, phenoxyethanol, phenylpropanol, phenethyl alcohol, benzyl alcohol, phenoxyisopropanol, isopropanol, ethylenediaminetetraacetic acid, sodium pyrithione, zinc pyrithione, piroctone olamine, o-phenylphenol, sorbic acid, formic acid, benzoic acid, propionic acid, salicylic acid, lactic acid, undecylenic acid, dehydroacetic acid, 4-hydroxyacetophenone, o-cymen-5-ol, phenethyl alcohol, glyceryl caprylate, propanediol caprylate, climbazole, 4-(3-ethoxy-4-hydroxyphenyl)-2-butanone, anisic acid, levulinic acid, parabens, and citric acid. The amount of these additional preservatives can vary widely. According to a preferred embodiment of the invention, this or these are contained in a total amount of less than 15,000 ppm, preferably less than 10,000 ppm, particularly preferably less than 5,000 ppm, based on the total product.

[0023] According to a further embodiment of the invention, the product in which the guanidine or its salt is used for stabilization against microbial attack is substantially free, preferably completely free, of preservatives that are usually used for preserving cosmetic products and detergents and cleaning agents. According to this embodiment of the invention, the aqueous product is characterized in that it contains one or more ingredients selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, 2,2'-dithiobis[N-methylbenzamide], benzalkonium chloride, didecyldimethylammonium chloride, cetrimonium bromide, benzethonium chloride, polyhexamethylene biguanide, bronopol, bronidox, chlorphenesin,

[0024] Dibromonitrilopropionamide, Dibromodicyanobutane, Iodopropynyl butylcarbamate, Silver chloride, Ethylhexylglycerin, Hexylglycerin, 1,2-Pentanediol, 1,2-Hexanediol, 1,2-Heptanediol, 1,2-Octanediol, 1,2-Decanediol, Glyceryl caprylate, Glyceryl caprate, Glyceryl laurate, Parabens, Phenoxyethanol, Phenylpropanol, Phenethyl alcohol, Benzyl alcohol, Phenoxyisopropanol, Isopropanol, Ethylenediaminetetraacetic acid, Sodium pyrithione, Zinc pyrithione, Piroctone olamine, o-Phenylphenol, Sorbic acid, Formic acid, Benzoic acid, Propionic acid, Salicylic acid, Lactic acid, Undecylenic acid, Dehydroacetic acid, 4-Hydroxyacetophenone, o- Contains cymen-5-ol, phenethyl alcohol, glyceryl caprylate, propanediol caprylate, climbazole, 4-(3-ethoxy-4-hydroxyphenyl)-2-butanone, anisic acid, levulinic acid, parabens and citric acid in a total amount of less than 100 ppm, preferably less than 50 ppm, particularly preferably less than 10 ppm, based on the entire product.

[0025] The following examples serve to further illustrate the present invention:

[0026] To demonstrate the stabilization of aqueous products against microbial contamination, selected from detergents and cleaning agents and cosmetic products, a cleaning agent, a skin lotion and a shampoo were mixed with various amounts of guanidine salts and tested for their stability against microbial contamination:

[0027] The cleaning agent tested was an all-purpose cleaner without preservatives with a pH of 7.7, the skin lotion was a body lotion without preservatives with a pH of 7.1, and the shampoo was a hair shampoo without preservatives with a pH of 6.9.

[0028] Precaution:

[0029] The cleaning agent was mixed with specific concentrations of guanidine carbonate or guanidine hydrochloride and homogenized. The body lotion and hair shampoo were mixed with guanidine hydrochloride and 1,2-octanediol, either alone or in combination, and homogenized.

[0030] The product batches thus obtained were inoculated several times at specific intervals with bacteria or yeast mixtures, which are standardly used for microbiological contamination tests of technical products or cosmetic products (bacteria mixture 1 and 2, yeast mixture 1 and 2).

[0031] The cleaning agent was additionally inoculated several times at specific intervals with a special inoculum consisting of a mixture of alkaliphilic bacteria (bacterial mixture 3) isolated from a bacterially contaminated cleaning agent with a pH of 9.8. Bacterial mixture 1:

[0032] Alcaligenes faecalis NCIMB 13145 Escherichia coli DSM 13631 Bakterien-Gemisch 3 : Burkholderia cepacia DSM 9241 Nesterenkonia spec. Thor 860 Staphylococcus aureus DSM 799 30 Nesterenkonia spec. Thor 861 Pseudomonas aeruginosa DSM 50071 Pseudomonas putida DSM 13624 Hefepilz-Gemisch 1 : Pseudomonas spp. (Pseudomonas Pichia manshurica DSM 12249 oleovorans group) DSM 33933 Rhodotorula mucilaginosa DSM 12248 Pseudomonas aeruginosa DSM 33935 35 Candida boidinii DSM 13622 Pseudomonas oleovorans DSM 33936 Candida albicans DSM 1386 Pseudomonas putida DSM 33937 Pseudomonas aeruginosa DSM 33938 Hefepilz-Gemisch 2:

[0033] Candida albicans ATCC 10231

[0034] Bakterien-Gemisch 2: 40 Candida parapsilosis ATCC 22019

[0035] Pseudomonas aeruginosa ATCC 9027 Pseudomonas putida ATCC 31483 Burkholderia cepacia ATCC 25416 Klebsiella pneumoniae ATCC 10031 Pluralibacter gergoviae ATCC 33028 Escherichia coli ATCC 8739 Staphylococcus aureus ATCC 6538 Staphylococcus epidermidis ATCC 12228 The inoculum was added to the respective sample at 2% (v / w) as a fresh cell suspension in a physiological saline solution (0.9% NaCl). The cell count of the added inoculum for the bacterial mixtures was 10 8 -10 9 / ml, for yeast mixtures 10 7 -10 8 / ml, consisting of equal parts of the individual bacterial and yeast strains.

[0036] The cell suspension of the bacterial mixtures was prepared by culturing the individual bacteria for 24 hours at 30 °C in liquid culture on a shaker. Müller-Hinton liquid medium served as the culture medium for bacterial mixtures 1 and 2. The bacteria from bacterial mixture 3 were cultured in Müller-Hinton liquid medium, which had previously been adjusted to pH 9.5 to 9.7 with an alkaline buffer solution. After culture, the individual liquid cultures were centrifuged, and the cells were resuspended in physiological saline. To adjust the mixtures to a total cell count of 10 8 up to 10 9 / ml, the individual bacterial suspensions were diluted accordingly before combining with saline solution if necessary. The cell count of the inoculation suspensions was determined using the chamber counting method.

[0037] To prepare the cell suspension of the yeast mixtures, the yeast strains were grown on Sabouraud glucose agar for 48 hours at 25 °C, and the cell layer was washed off using physiological saline (0.9% NaCl). Further steps were used to adjust the cell count of the inoculation suspension to 10 7 bisl0 8 / ml were carried out analogously to the preparation of the bacterial suspensions.

[0038] In the examples, the samples were inoculated with the respective cell suspensions three times at weekly intervals (2% v / w), and the development of the bacteria or yeasts was monitored using a semi-quantitative assessment method. After each inoculation, the microbial contamination in the samples was assessed after 6 to 7 days of incubation at 30 °C. For this purpose, an aliquot was taken from each sample after homogenization using a sterile plastic inoculation tube (10 μl) and spread evenly on agar plates (bacterial mixtures 1 and 2 on tryptone soy agar, bacterial mixture 3 on alkaline nutrient agar DSMZ 31, and Sabouraud glucose agar for yeasts). The spread agar plates were then incubated for 48 hours (bacterial mixtures 1 and 2) or 5 to 7 days (bacterial mixture 3) at 30 °C, or 72 hours at 25 °C (yeast mixtures). After incubation, the bacteria or yeast cultures grown on the agar plates were incubated.Yeast colonies were visually assessed and quantified according to the following scheme:.

[0039] The results for the examples are shown in Tables 1 to 5: Example 1 / Table 1:

[0040] Inoculation 2% (w / v) with bacterial mixture 1, cell count 10 9 / ml

[0041] *pH 9.5 adjusted with NaOH As can be seen from the test results shown in Table 1, the addition of 659 ppm guanidine in the form of guanidine carbonate at a pH value of pH 9.2 or pH 9.5 results in a significantly improved stability of the all-purpose cleaner against microbial attack by bacteria.

[0042] Example 2 / Table 2:

[0043] Inoculation 2% (w / v) with bacterial mixture 3, cell count 10 9 / ml

[0044] *pH 11.2 adjusted with NaOH. As can be seen from the test results presented in Table 2, the addition of just 330 ppm of guanidine in the form of guanidine carbonate at a pH of 9.1 significantly improved the stability of the all-purpose cleaner against microbial attack. Example 3 / Table 3:

[0045] Inoculation 2% (w / v) with yeast mixture 1, cell count 10 8 / ml

[0046] *pH 10.5 adjusted with NaOH. As can be seen from the test results presented in Table 3, the addition of just 659 ppm of guanidine in the form of guanidine carbonate at a pH of 9.9 or 1516 ppm of guanidine in the form of guanidine hydrochloride at a pH of 7.7 significantly improved the stability of the all-purpose cleaner against microbial attack by yeast fungi. Example 4 / Table 4:

[0047] Inoculation 2% (w / v) with bacterial mixture 3, cell count 10 8 / ml

[0048] As can be seen from the test results presented in Table 4, the addition of 3,035 ppm guanidine in the form of guanidine hydrochloride at a pH value of pH 7.0 can already achieve a significantly improved stability of the body lotion against microbial attack by bacteria.

[0049] Example 5 I Table 5:

[0050] Inoculation 2% (w / v) with yeast mixture 2, cell count 10 7 / ml As can be seen from the test results presented in Table 5, the addition of 4,553 ppm guanidine in the form of guanidine hydrochloride at a pH value of 6.9 can already achieve a significantly improved stability of the body lotion against microbial attack by yeast fungi.

[0051] Example 6 / Table 6:

[0052] Inoculation 2% (w / v) with yeast mixture 2, cell count 10 7 / ml As can be seen from the test results presented in Table 6, the addition of just 4,553 ppm guanidine in the form of guanidine hydrochloride at a pH value of 6.9 can significantly improve the stability of the body lotion against microbial attack by yeast fungi.

Claims

Patent claims 1. Use of guanidine and / or at least one salt of guanidine for stabilizing aqueous products selected from cosmetic products and washing and cleaning agents against microbial attack.

2. Use according to claim 1, characterized in that the guanidine and / or its salt is / are used in an amount in the range of 0.033 to 2.0% by weight, based on the content of guanidine in the total product.

3. Use according to claim 1 or 2, characterized in that guanidine hydrochloride and / or guanidine carbonate is used as the salt of guanidine.

4. Use according to one of claims 1 to 3, characterized in that the aqueous product has a pH in the range of pH 6.5 to pH 11.

5.

5. Use according to one of claims 1 to 4, characterized in that the aqueous product has a water content of greater than 1% by weight, preferably greater than 5% by weight, particularly preferably greater than 10% by weight, based on the total product.

6. Use according to one of claims 1 to 5, characterized in that the cosmetic product is selected from the group consisting of shower gels, shower baths, tooth cleaning and care products, mouthwashes, hair shampoos, hair conditioners, conditioning shampoos, hair sprays, hair rinses, hair treatments, hair packs, hair tonics, self-tanners, facial toners, permanent wave fixing solutions, hair coloring shampoos, hair dyes, hair setting products, hair styling preparations, blow-dry lotions, mousses, hair gels, hair waxes, shaving foam, perfume preparations, wet wipes, care products and dermatological products for topical application, such as Body creams, lotions, face creams, sunscreens or deodorants.

7. Use according to one of claims 1 to 5, characterized in that the washing and cleaning agent is selected from the group consisting of household cleaners, washing, cleaning or pretreatment agents, refreshing sprays for textiles, laundry fabric softeners, window cleaners, bathroom cleaners, toilet cleaners and dishwashing detergents.

8. Use according to one of claims 1 to 7, characterized in that the aqueous product is characterized in that it contains one or more ingredients selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2- Benzisothiazolin-3-on, N-Butyl-l,2-Benzisothiazolin-3-on, N-Methyl-1,2- Benzisothiazolin-3-on, Octylisothiazolinon, 2,2'-Dithiobis[N-methylbenzamid], Benzalkoniumchlorid, Didecyldimethylammoniumchlorid, Cetrimoniumbromid, Benzethoniumchlorid, Polyhexamethylenbiguanid, Bronopol, Bronidox, Chlorphenesin, Dibromnitrilopropionamid, Dibromdicyanobutan, lodpropinylbutylcarbamat, Silberchlorid, Ethylhexylglycerin, Hexylglycerin, 1,2- Pentandiol, 1 ,2-Hexandiol, 1 ,2-Heptandiol, 1 ,2-Octandiol, 1 ,2-Decandiol, Glycerylcaprylate, Glycerylcaprate, Glyceryllaurate, Parabene, Phenoxyethanol, Phenylpropanol, Phenethylalkohol, Benzylalkohol, Phenoxyisopropanol, Isopropanol, Ethylendiamintetraessigsäure, Natriumpyrithion, Zinkpyrithion, Pirocton Olamin, o-Phenylphenol, Sorbinsäure, Ameisensäure, Benzoesäure, Propionsäure, Salicylsäure, Milchsäure, Undecylensäure, Dehydracetsäure, 4- Hydroxyacetophenon, o-Cymen-5-ol, Phenetylalkohol, Glycerylcaprylat, Propanediolcaprylat, Climbazol,Contains 4-(3-ethoxy-4-hydroxyphenyl)-2-butanone, anisic acid, levulinic acid, parabens and citric acid in a total amount of less than 100 ppm, based on the total product.

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