Cosmetic and cleaning product stabilized

Abstract

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

Description

[0001] The present invention relates to the use of guanidine and / or at least one guanidine salt for stabilizing aqueous products such as cosmetics and washing and cleaning compositions against infestation by microorganisms.

[0002] Aqueous products, such as washing and cleaning compositions or cosmetics, are often produced using natural or biodegradable raw materials. These raw materials and the water used as a solvent are often contaminated with microorganisms such as bacteria, yeasts, and fungi. If these products are produced without preservatives, they may already have high microbial counts one day after production.

[0003] In order to ensure that these products and, if appropriate, their ingredients used in production, comply with hygiene requirements and thus guarantee the shelf life of industrial products, so-called biocides are usually added to the products or directly to their ingredients.

[0004] One class of biocides used for preserving aqueous products, such as washing and cleaning compositions or cosmetics, is 3-isothiazolin-3-ones. This substance class includes compounds with very strong antimicrobial activity, with somewhat varying spectrums of action. Synergistic combinations of different 3-isothiazolin-3-ones are often used to reduce the amount of biocide used. For example, WO 99 / 08530 A1 proposes the combined use of methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one.

[0005] Another class of biocides is the so-called alkylguanidinium salts and polyguanidinium salts. For example, it is known from "Directory of microbicides for the protection of materials", Springer 2005, pp. 726 to 731 that medium-chain and long-chain guanidines and biguanides have antimicrobial effects, such as cocopropylenediamine-1,5-biguanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylenebiguanide) hydrochloride, bis(4'-chlorophenylbiguanidino)hexane, chlorhexidine digluconate, chlorhexidine diacetate.

[0006] Besides their use as preservatives, alkylguanidine compounds are also used in cosmetics, in particular in hair care, as disclosed in EP 1 646 429 A1.

[0007] Despite the numerous known active ingredients, as well as combinations of active ingredients or measures employed simultaneously, increasing regulatory restrictions have led to an increasing need for novel preservation methods, particularly for cosmetics and washing and cleaning compositions, which preferably do not comprise or require only reduced amounts of conventional preservatives or biocides.

[0008] The present invention achieves this object by the novel use of guanidine and / or at least one guanidine salt for stabilizing aqueous products selected from cosmetics and washing and cleaning compositions against infestation by microorganisms.

[0009] In the present invention, it has surprisingly been found that aqueous products, i.e., water-based products, require significantly less, and in some cases, no preservatives typically present in these products for preservation, due to the presence of guanidine and / or guanidine salts, which have hitherto been unknown antimicrobial active substances. Nevertheless, these products are characterized by excellent stability against microbial infestation, especially during storage. Compared to products that do not contain guanidine or guanidine salts, products stabilized against microbial infestation have significantly improved stability against microorganisms such as bacteria, yeasts, and fungi and therefore have a lower tendency to microbial colonization. Furthermore, the environmental compatibility of the cosmetic or washing and cleaning compositions is significantly improved and all known properties for good and safe use are also present.

[0010] Guanidine is a compound with the following structural formula:

[0011] .

[0012] Guanidine salts or guanidinium salts in the present invention are unsubstituted guanidine or guanidinium salts of the general formula shown below:

[0013]

[0014] wherein n is 1, 2 or 3, and wherein the counterion X n- These are, for example, chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, formate, acetate or citrate.

[0015] In a preferred embodiment of the present invention, the guanidine salt used is guanidine hydrochloride and / or guanidine carbonate.

[0016] “At least one guanidine salt” in the context of the present invention means that one guanidine salt, or two, three, four or more guanidine salts, ie a mixture of guanidine salts, is used in the aqueous products or is present in these products.

[0017] The amount of guanidine or its salt used for stabilization against microbial attack can vary within wide ranges and is generally in the range of 0.033% to 2.0% by weight, preferably in the range of 0.066% to 1.5% by weight, more preferably in the range of 0.1% to 1.0% by weight, in each case based on the guanidine content of the entire product. Therefore, any non-H counterions are not taken into account in the determination of the guanidine content.

[0018] In the present invention, the unit "% by weight" relates in each case to the entire aqueous product.

[0019] The pH of aqueous products in which guanidine and / or its salts are stabilized against microbial infestation can vary widely and is generally in the range of pH 6.5 to pH 11.5, preferably in the range of pH 7.0 to pH 11.0, and more preferably in the range of pH 7.5 to pH 10.5. The pH can be adjusted to the claimed range by means of measures familiar to those skilled in the art.

[0020] The water content of aqueous products in which guanidine and / or its salts are used for stabilization against microbial infestation can vary within wide ranges. Such products are generally characterized in that they have a water content of greater than 1% by weight, preferably greater than 5% by weight, and more preferably greater than 10% by weight, based on the entire product.

[0021] The present invention relates to the use of guanidine and / or at least one guanidine salt for stabilizing aqueous products, such as cosmetics and washing and cleaning compositions, against infestation by microorganisms.

[0022] Useful cosmetic products are products from the cosmetics sector. These are, for example, products selected from the group consisting of shower gels, shower gels, tooth cleaning and care products, mouthwashes, shampoos, conditioners, conditioning shampoos, hair sprays, conditioners, hair masks, hair conditioning creams, hair tonics, self-tanning agents, lotions, permanent styling solutions, hair coloring shampoos, hair colorings, hair setting lotions, conditioners, hair styling preparations, hair dryer lotions, hair styling foams, hair sprays, hair waxes, shaving foams, perfume preparations, wet wipes, care products, and dermatological products for topical use, such as body creams, body lotions, face creams, sunscreen preparations, and deodorants.

[0023] Useful washing and cleaning compositions include products from the field of washing and cleaning compositions selected from household cleaners, washing, cleaning or pretreatment compositions, textile refresher sprays, fabric softeners, window cleaners, bathroom cleaners, toilet cleaners and dishwashing detergents.

[0024] As described above, the present invention relates to the novel use of guanidine and / or at least one guanidine salt for stabilizing aqueous products, such as cosmetics and washing and cleaning compositions, against microbial infestation. These compounds are hitherto unknown as antimicrobial active substances, and this novel use makes it possible to use significantly fewer, and in some cases even completely eliminate, conventional preservatives. Nevertheless, products stabilized against microbial infestation by the presence of guanidine are characterized by excellent resistance to microbial infestation, especially during storage.

[0025] In one embodiment of the invention, the product in which guanidine or its salts is used for stabilization against microbial infestation is characterized in that the product contains one or more ingredients with antimicrobial action as additional preservatives, which are selected from 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, cetyltrimethylammonium bromide , benzethonium chloride, polyhexamethylene biguanide, bronopol, bronidox, chlorphenesin, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, silver chloride, ethylhexylglycerin, hexylglycerin, pentane-1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octan-1,2-diol, decane-1,2-diol, glyceryl caprylate, glyceryl caprate, glyceryl laurate, parabens, phenoxyethanol, phenylpropanol, phenylethyl alcohol, benzyl alcohol, phenoxyisopropyl alcohol, isopropyl alcohol, EDTA, sodium pyrithione, zinc pyrithione, piroctone olamine The amount of these additional preservatives can vary widely. In a preferred embodiment of the present invention, the additional preservative(s) are present in a total amount of less than 15,000 ppm, preferably less than 10,000 ppm, and more preferably less than 5,000 ppm, based on the total product.

[0026] In a further embodiment of the invention, the product in which guanidine or its salt is used for stabilization against microbial infestation is substantially free, preferably completely free, of preservatives conventionally used for the preservation of cosmetics and washing and cleaning compositions. In this embodiment of the invention, the aqueous product is characterized in that it contains less than 100 ppm, preferably less than 50 ppm, more preferably less than 10 ppm of 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, cetyltrimethylammonium bromide, benzethonium chloride, polyhexamethylene biguanide, bronopol, bronido x, chlorphenesin, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, silver chloride, ethylhexylglycerin, hexylglycerin, pentane-1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octan-1,2-diol, decane-1,2-diol, glyceryl caprylate, glyceryl caprate, glyceryl laurate, parabens, phenoxyethanol, phenylpropanol, phenylethyl alcohol, benzyl alcohol, phenoxyisopropyl alcohol, isopropyl alcohol, ethylenediaminetetraacetic acid, sodium pyrithione, zinc pyrithione, piroctone olamine (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, phenylethyl alcohol, glyceryl caprylate, propylene glycol caprylate, climbazole, 4-(3-ethoxy-4-hydroxyphenyl)-2-butanone, anisic acid, levulinic acid, parahydroxybenzoates, and citric acid.

[0027] The following examples are used to further illustrate the present invention:

[0028] In order to demonstrate the stabilization of aqueous products selected from washing and cleaning compositions and cosmetics against microbial infestation, cleaning compositions, skin care lotions and shampoos were mixed with different amounts of guanidine salts and their stability against microbial infestation was tested:

[0029] The cleansing composition tested was an all-purpose cleanser without preservatives and having a pH of 7.7, the skin care lotion was a body lotion (Bodylotion) without preservatives and having a pH of 7.1, and the shampoo was a shampoo without preservatives and having a pH of 6.9.

[0030] program:

[0031] The cleansing composition was mixed with guanidine carbonate or guanidine hydrochloride at a specific concentration and homogenized. The body lotion and shampoo were each mixed with guanidine hydrochloride and octan-1,2-diol, either alone or in combination, and homogenized.

[0032] Batches of the product thus obtained were repeatedly inoculated at specific time intervals with bacterial mixtures or yeast mixtures (bacterial mixtures 1 and 2, yeast mixtures 1 and 2) used as standards for microbial stress tests on industrial products or cosmetics.

[0033] The cleaning composition was additionally inoculated repeatedly at specific time intervals with a special inoculum consisting of a mixture of alkaliphilic bacteria (Bacterial Mixture 3) that had been isolated from a cleaning composition contaminated with bacteria at pH 9.8.

[0034] Bacterial mixture 1:

[0035] Alcaligenes faecalis NCIMB 13145

[0036] Escherichia coli DSM 13631

[0037] Burkholderia cepacia DSM 9241

[0038] Staphylococcus aureus DSM 799

[0039] Pseudomonas aeruginosa DSM 50071

[0040] Pseudomonas putida DSM 13624

[0041] Pseudomonas spp., Pseudomonas oleovorans group DSM 33933

[0042] Pseudomonas aeruginosa DSM 33935

[0043] Pseudomonas oleovorans DSM 33936

[0044] Pseudomonas putida DSM 33937

[0045] Pseudomonas aeruginosa DSM 33938

[0046] Bacterial mixture 2:

[0047] Pseudomonas aeruginosa ATCC 9027

[0048] Pseudomonas putida ATCC 31483

[0049] Burkholderia cepacia ATCC 25416

[0050] Klebsiella pneumoniae ATCC 10031

[0051] Pluralibacter gergoviae ATCC 33028

[0052] Escherichia coli ATCC 8739

[0053] Staphylococcus aureus ATCC 6538

[0054] Staphylococcus epidermidis ATCC 12228

[0055] Bacterial cocktail 3:

[0056] Nesterenkonia spec. Thor 860

[0057] Nesterenkonia spec. Thor 861

[0058] Yeast mixture 1:

[0059] Pichia manshurica DSM 12249

[0060] Rhodotorula mucilaginosa DSM 12248

[0061] Candida boidinii DSM 13622

[0062] Candida albicans DSM 1386

[0063] Yeast mixture 2:

[0064] Candida albicans ATCC 10231

[0065] Candida parapsilosis ATCC 22019

[0066] In each inoculation, 2% (v / w) of inoculum was added to the corresponding sample as a fresh cell suspension in physiological saline solution (0.9% NaCl). The cell count of the added inoculum was 10 in the case of the bacterial mixture. 8 -10 9 / ml, in the case of yeast mixtures 10 7 -10 8 / ml, consisting of equal parts of each bacterial strain or yeast strain.

[0067] The cell suspensions of the bacterial mixtures were prepared by culturing each bacterium in liquid culture on a shaker at 30°C for 24 hours. The medium used to culture the bacteria from bacterial mixtures 1 and 2 was Müller-Hinton liquid medium. The bacteria from bacterial mixture 3 were cultured in Müller-Hinton liquid medium that had been previously adjusted to pH 9.5 to 9.7 with an alkaline buffer solution. After culturing, each liquid culture was centrifuged and the cells were resuspended in physiological saline. In order to adjust the mixture to 10 8 to 10 9 The cell count of the inoculum suspension was determined by chamber counting in each case.

[0068] A cell suspension of the yeast mixture was prepared by growing the yeast strains on Sabouraud dextrose agar at 25° C. for 48 hours and washing the cell lawn with physiological saline solution (0.9% NaCl) in each case. 7 / ml to 10 8 The remaining steps of cell counting of the inoculum suspension of 100 μg / ml are carried out analogously to the preparation of the bacterial suspension.

[0069] In the examples, samples were inoculated three times weekly with the respective bacterial suspension (2% v / w), and the evolution of bacteria or yeast was tracked using a semiquantitative evaluation method. After each inoculation, the samples were evaluated for microbial infection after incubation at 30°C for 6 to 7 days. To do this, a 10 µl aliquot was removed from each sample using a sterile plastic inoculating loop after homogenization and streaked evenly onto agar plates (tryptone soy agar for bacterial mixtures 1 and 2, DSMZ 31 alkaline nutrient agar for bacterial mixture 3, and Sabouraud dextrose agar for yeast). The streaked agar plates were then incubated at 30°C for 48 hours (bacterial mixtures 1 and 2) or 5 to 7 days (bacterial mixture 3), or at 25°C for 72 hours (yeast mixture). After incubation, the bacterial or yeast colonies growing on the agar plates were visually assessed and quantified according to the following protocol:

[0070]

[0071] The results of the examples are shown in Tables 1 to 5:

[0072] Example 1 / Table 1:

[0073] Inoculate 2% (w / v) of the bacterial mixture 1 and count 10 cells. 9 / ml

[0074]

[0075] Establish pH 9.5 with NaOH

[0076] From the test results shown in Table 1 it can be concluded that the addition of 659 ppm of guanidine in the form of guanidine carbonate at a pH of pH 9.2 or pH 9.5 allows a significant improvement in the stability of the universal cleaner against microbial attack by bacteria to be achieved.

[0077] Example 2 / Table 2:

[0078] Inoculate 2% (w / v) with bacterial mixture 3 and count 10 cells. 9 / ml

[0079]

[0080] Establish pH 11.2 with NaOH

[0081] From the test results shown in Table 2 it can be concluded that the addition of 330 ppm of guanidine in the form of guanidine carbonate even at a pH of pH 9.1 allows a significant improvement in the stability of the universal cleaner against microbial attack by bacteria to be achieved.

[0082] Example 3 / Table 3:

[0083] Inoculate 2% (w / v) with yeast mixture 1 and count 10 cells. 8 / ml

[0084]

[0085] Establish pH 10.5 with NaOH

[0086] From the test results shown in Table 3 it can be concluded that even the addition of 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 can achieve a significant improvement in the stability of the universal cleaner against microbial infection by yeasts.

[0087] Example 4 / Table 4:

[0088] Inoculate 2% (w / v) with bacterial mixture 3 and count 10 cells. 8 / ml

[0089]

[0090] From the test results shown in Table 4 it can be inferred that the addition of 3035 ppm of guanidine in the form of guanidine hydrochloride even at a pH of 7.0 can achieve a significant improvement in the stability of the body lotion against microbial infestation by bacteria.

[0091] Example 5 / Table 5:

[0092] Inoculate with 2% (w / v) yeast mixture 2 and count 10 cells. 7 / ml

[0093]

[0094] From the test results shown in Table 5 it can be inferred that the addition of 4553 ppm of guanidine in the form of guanidine hydrochloride even at a pH of pH 6.9 allows a significant improvement in the stability of the body lotion against microbial infestation by yeasts.

[0095] Example 6 / Table 6:

[0096] Inoculate with 2% (w / v) yeast mixture 2 and count 10 cells. 7 / ml

[0097]

[0098] From the test results shown in Table 6 it can be inferred that the addition of 4553 ppm of guanidine in the form of guanidine hydrochloride even at a pH of pH 6.9 allows a significant improvement in the stability of the body lotion against microbial infestation by yeasts.

Claims

1. Use of guanidine and / or at least one guanidine salt for stabilizing aqueous products selected from cosmetics and washing and cleaning compositions against microbial infestation.

2. The use according to claim 1, characterized in that The guanidine and / or its salt is used in an amount ranging from 0.033% by weight to 2.0% by weight based on the guanidine content in the entire product.

3. The use according to claim 1 or 2, characterized in that The guanidine salt used is guanidine hydrochloride and / or guanidine carbonate.

4. The method according to any 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. The method according to any one of claims 1 to 4, characterized in that The aqueous product has a water content of more than 1% by weight, preferably more than 5% by weight, more preferably more than 10% by weight, based on the entire product.

6. The use according to any one of claims 1 to 5, characterized in that The cosmetic product is selected from shower gels, shower creams, tooth cleaning and care products, mouthwashes, shampoos, conditioners, conditioning shampoos, hair sprays, conditioners, hair masks, hair repair creams, hair nourishing lotions, self-tanners, lotions, permanent styling lotions, hair coloring shampoos, hair coloring lotions, hair setting lotions, conditioners, hair styling preparations, blow-drying styling lotions, hair styling foams, hair sprays, hair waxes, shaving foams, perfume preparations, wet wipes, care products and dermatological products for topical use, such as body creams, body lotions, face creams, sun protection preparations and deodorants.

7. The use according to any one of claims 1 to 5, characterized in that The laundry detergent and cleaning composition is selected from household cleaners, washing, cleaning or pretreatment products, textile refresher sprays, fabric softeners, window cleaners, bathroom cleaners, toilet cleaners and dishwashing detergents.

8. The use according to any one of claims 1 to 7, characterized in that The aqueous product is characterized in that it contains less than 100 ppm of 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, hexadecyltrimethylammonium bromide, benzethonium chloride, polyhexamethylene biguanide, bronopol, bronidox, chlorphenesin, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, silver chloride, ethylhexylglycerin, hexylglycerin, pentan-1, 2-Diol, Hexane-1,2-diol, Heptane-1,2-diol, Octan-1,2-diol, Decane-1,2-diol, Glyceryl Caprylate, Glyceryl Caprate, Glyceryl Laurate, Parabens, Phenoxyethanol, Phenylpropanol, Phenethyl Alcohol, Benzyl Alcohol, Phenoxyisopropyl Alcohol, Isopropyl Alcohol, 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, Propylene Glycol Caprylate, Climbazole, 4-(3-Ethoxy-4-hydroxyphenyl)-2-butanone, Anisic Acid, Levulinic Acid, Parabens, and Citric Acid.

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