Cosmetics and cleaning products stabilized against microbial attack

Abstract

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

Description

[Technical Field]

[0001] The present invention relates to the use of guanidine and / or at least one salt of guanidine for the stabilization of aqueous products, such as cosmetics and washing and cleaning compositions, against microbial infestation. [Background technology]

[0002]

[0003] Water-containing products, such as detergent and cleaning compositions or other cosmetics, are typically manufactured 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 manufactured without preservatives, they may have high microbial counts already one day after manufacture.

[0003] To ensure that hygiene requirements are met by these products and, if appropriate, also by the components used in their production, and thus that the shelf life of the industrial product is guaranteed, so-called biocides are usually added to the products or to their components.

[0004] One class of biocides used in washing and cleaning compositions or otherwise preserving aqueous products such as cosmetics are the 3-isothiazolin-3-ones. This class of substances includes highly antimicrobially active compounds with somewhat different action profiles. To reduce the amount of biocide used, synergistic combinations of different 3-isothiazolin-3-ones are often used. For example, WO 99 / 08530 proposes the use of methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one in combination.

[0005] A further class of biocides is the so-called alkylguanidinium salts and also polyguanidinium salts. It is known, for example from "Directory of microbicides for the protection of materials", Springer 2005, pp. 726-731, that antibacterial effect is possessed by medium- and long-chain guanidines and biguanidines, such as cocopropylenediamine-1,5-bisguanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylenebiguanidine) hydrochloride, di(4'-chlorophenyldiguanido)hexane, chlorhexidine digluconate, chlorhexidine diacetate.

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

[0007] Despite the large number of known active ingredients and combinations of active ingredients or measures employed so far, increasing regulatory constraints in particular are causing an increasing demand for new preservation methods for cosmetic and washing and cleaning compositions, which preferably do away with or require only a reduced content of conventional preservatives or biocides. Summary of the Invention

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

[0009] In the context of the present invention, it has surprisingly been found that aqueous products, i.e., water-based products, contain guanidine and / or guanidine salts, which have not been known to date as antimicrobial active agents, and therefore require significantly less preservatives, or even none at all, that are typically present in these products for preservation.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 infestation by microorganisms such as bacteria, yeasts, and fungi, and therefore have a reduced tendency to be colonized by microorganisms.Furthermore, the cosmetic or cleaning and washing compositions are significantly improved in terms of their environmental compatibility, and also have all the known properties of good and safe use characteristics. DETAILED DESCRIPTION OF THE INVENTION

[0010] Guanidine has the formula: [ka] is a compound of

[0011] In the context of the present invention, salts of guanidine or guanidine salts have the general formula: [ka] (wherein n is 1, 2 or 3; and the counter ion X n- is, for example, chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, formate, acetate or citrate) is an unsubstituted guanidine or guanidinium salt of

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

[0013] By "at least one salt of guanidine" in the context of the present invention is meant that one, two, three, four or more salts of guanidine, i.e., a mixture, are used in or present in the aqueous product.

[0014] The amount of guanidine or its salts used for stabilization against microbial infestation can vary over a wide range, generally ranging from 0.033% to 2.0% by weight, preferably from 0.066% to 1.5% by weight, and more preferably from 0.1% to 1.0% by weight, based in each case on the guanidine content of the entire product. Thus, any counterions other than H are not taken into account in determining the guanidine content.

[0015] In the context of the present invention, the unit "% by weight" in each case relates to the aqueous product as a whole.

[0016] The pH of aqueous products in which guanidine and / or its salt(s) is / are used for stabilization against microbial infestation can vary over a wide range, generally within the range of pH 6.5 to pH 11.5, preferably within the range of pH 7.0 to pH 11.0, more preferably within the range of pH 7.5 to pH 10.5. The pH can be adjusted to the ranges stated in the claims using means well known to those skilled in the art.

[0017] The water content of aqueous products in which guanidine and / or its salt(s) is used for stabilization against microbial infestation can vary over a wide range, and the products are typically characterized as having 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 total product.

[0018] The present invention relates to the use of guanidine and / or at least one salt of guanidine for the stabilization of aqueous products, such as cosmetics and washing and cleaning compositions, against microbial infestation.

[0019] Useful cosmetic products are products from the cosmetics sector, such as products selected from the group consisting of shower gels, shower washes, dental cleaning and care products, mouthwashes, hair shampoos, hair conditioners, conditioning shampoos, hair sprays, hair rinses, hair treatments, hair wraps, hair tonics, self-tanning agents, facial tonics, permanent wave fixatives, hair coloring shampoos, hair dyes, hair setting preparations, hair styling preparations, blow waving lotions, hair setting foams, hair gels, hair waxes, shaving foams, perfume preparations, wet wipes, body creams, body lotions, facial creams, care products for topical use such as sunscreens and deodorants, and dermatological products.

[0020] Useful washing and cleaning compositions include products in the field of washing and cleaning compositions selected from the group consisting of household cleaners, detergents, cleaning or pre-wash compositions, fabric refreshing sprays, fabric softeners, window cleaners, bathroom cleaners, toilet cleaners and dish detergents.

[0021] As 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 cosmetics and cleaning and washing compositions, against microbial infestation. This novel use of the aforementioned compounds, which have not previously been known as antimicrobial active substances, makes it possible to use significantly less of the customarily used preservatives, and in some cases even to completely dispense with them. Nevertheless, products stabilized against microbial infestation by their guanidine content are characterized by excellent resistance to microbial infestation, especially during storage.

[0022] In one embodiment of the present invention, the product in which guanidine or its salts are used for stabilization against microbial infestation is 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-methylbenzisothiazolin-3-one] ... nzamide], benzalkonium chloride, didecyldimethylammonium chloride, cetrimonium bromide, benzethonium chloride, polyhexamethylene biguanide, bronopol, bronidox, chlorphenesin, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, silver chloride, ethylhexylglycerol, hexylglycerol, pentane-1,2-diol, hexane-1,2-diol, heptane-1, 2-diol, octane-1,2-diol, decane-1,2-diol, 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 amounts of these additional preservatives used can vary over a wide range, In a preferred embodiment of the invention, the additional preservatives are present in a total amount of less than 15000 ppm, preferably less than 10000 ppm, more preferably less than 5000 ppm, based on the total product.

[0023] In a further embodiment of the present invention, the products in which guanidine or its salts are used for stabilization against microbial infestation are essentially free, and preferably completely free, of preservatives customarily used for preserving cosmetics and washing and cleaning compositions. In this embodiment of the present invention, the aqueous products are preferably 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, 1,2'-benzisothiazolin-3-one, 2 ... Benzethonium bromide, cetrimonium chloride, polyhexamethylene biguanide, bronopol, bronidox, chlorphenesin, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, silver chloride, ethylhexylglycerol, hexylglycerol, pentane-1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octane-1,2-diol, decane-1,2-diol , 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 in a total amount of less than 100 ppm, preferably less than 50 ppm, and more preferably less than 10 ppm, based on the entire product. [Example]

[0024] The following examples serve to further illustrate the present invention:

[0025] To demonstrate the stabilization against microbial infestation of aqueous products selected from washing and cleaning compositions and cosmetics, cleaning compositions, skin lotions and shampoos were mixed with various amounts of guanidine salts and tested for stability against microbial infestation:

[0026] The cleaning composition tested was a preservative-free all-purpose cleaner with a pH of 7.7, the skin lotion was a preservative-free body lotion with a pH of 7.1, and the shampoo was a preservative-free hair shampoo with a pH of 6.9.

[0027] procedure: The cleaning compositions were blended and homogenized with specific concentrations of guanidine carbonate and guanidine hydrochloride. The body lotions and hair shampoos were each blended and homogenized with guanidine hydrochloride and octane-1,2-diol, either alone or in combination.

[0028] The batches of product thus obtained were repeatedly inoculated at specific intervals with bacterial or yeast mixtures (bacterial mixtures 1 and 2, yeast mixtures 1 and 2) used as standards for microbial stress tests of industrial or cosmetic products.

[0029] The cleaning composition was further repeatedly inoculated at specific intervals with a special inoculum consisting of a mixture of alkaliphilic bacteria (bacterial mixture 3) isolated from a cleaning composition contaminated with bacteria having a pH of 9.8.

[0030] Bacteria mixture 1: Alcaligenes faecalis NCIMB 13145 Escherichia coli DSM 13631 Burkholderia cepacia DSM 9241 Staphylococcus aureus DSM 799 Pseudomonas aeruginosa DSM 50071 Pseudomonas putida DSM 13624 Pseudomonas spp. (Pseudomonas oleovorans group) DSM 33933 Pseudomonas aeruginosa DSM 33935 Pseudomonas oleovorans DSM 33936 Pseudomonas putida DSM 33937 Pseudomonas aeruginosa DSM 33938

[0031] Bacterial mixture 2: 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

[0032] Bacterial mixture 3: Nesterenkonia spec. Thor 860 Nesterenkonia spec. Thor 861

[0033] Yeast mixture 1: Pichia manshurica DSM 12249 Rhodotorula mucilaginosa DSM 12248 Candida boidinii DSM 13622 Candida albicans DSM 1386

[0034] Yeast mixture 2: Candida albicans ATCC 10231 Candida parapsilosis ATCC 22019

[0035] The inoculum was added to each sample as a fresh cell suspension in saline (0.9% NaCl) at 2% for each inoculum. The cell count of the added inoculum was 10 for the bacterial mixture. 8 ~10 9 / ml, 10 in yeast mixture 7 ~10 8 / ml and consisted of equal amounts of each bacterial or yeast strain.

[0036] Cell suspensions of bacterial mixtures were prepared by growing individual bacteria in liquid culture on a shaker at 30°C for 24 hours. The medium used to grow bacteria from bacterial mixtures 1 and 2 was Mueller-Hinton liquid medium. Bacteria from bacterial mixture 3 were grown in Mueller-Hinton liquid medium previously adjusted to pH 9.5-9.7 with an alkaline buffer solution. After growth, the individual liquid cultures were centrifuged, and the cells were resuspended in saline. The mixtures were then mixed for 10 min. 8 ~10 9 To adjust the total cell count to 1 / ml, the individual bacterial suspensions were diluted accordingly, if necessary, before being combined with saline. The cell number of the inoculum suspension was determined each time by chamber counting.

[0037] The cell suspensions of the yeast mixtures were prepared by growing the yeast strains on Sabouraud dextrose agar for 48 hours at 25°C and in each case washing off the cell lawn with saline solution (0.9% NaCl). 7 / ml~10 8 Further steps for determining cell counts / ml were performed similar to the preparation of the bacterial suspension.

[0038] In the examples, samples were inoculated three times at weekly intervals with the respective cell suspensions (2% v / w), after which bacterial or yeast growth was followed by a semiquantitative evaluation method. After each inoculation, the prevalence of microorganisms in the samples was evaluated after incubation for 6 to 7 days at 30°C in each case. For this purpose, after homogenization, aliquots were taken from each sample using a sterile plastic inoculation loop (10 μl) and uniformly streaked 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, bacterial or yeast colonies grown on the agar plates were visually evaluated and quantified according to the following scheme:

[0039] TIFF2026505252000003.tif80149

[0040] The results of the examples are shown in Tables 1-5:

[0041] Example 1 / Table 1: [Table 1]

[0042] As can be inferred from the test results shown in Table 1, the addition of 659 ppm of guanidine in the form of guanidine carbonate at a pH of either pH 9.2 or pH 9.5 can achieve a distinct improvement in the stability of the general-purpose cleaner against bacterial infestation.

[0043] Example 2 / Table 2: [Table 2]

[0044] As can be inferred from the test results shown in Table 2, even the addition of 330 ppm of guanidine in the form of guanidine carbonate at a pH of 9.1 can achieve a distinct improvement in the stability of the general-purpose cleaner against bacterial infestation.

[0045] Example 3 / Table 3: [Table 3]

[0046] As can be inferred from the test results shown in Table 3, the addition of 659 ppm of guanidine in the form of guanidine carbonate at a pH of 9.9, or even 1516 ppm of guanidine in the form of guanidine hydrochloride at a pH of 7.7, can achieve a distinct improvement in the stability of the general-purpose cleaner against microbial infestation by yeast.

[0047] Example 4 / Table 4: [Table 4]

[0048] As can be inferred from the test results shown in Table 4, even the addition of 3035 ppm of guanidine in the form of guanidine hydrochloride at a pH of pH 7.0 can achieve a distinct improvement in the stability of the body lotion against bacterial infestation.

[0049] Example 5 / Table 5: [Table 5]

[0050] As can be gathered from the test results shown in Table 5, even the addition of 4553 ppm of guanidine in the form of guanidine hydrochloride at a pH of 6.9 can achieve a distinct improvement in the stability of the body lotion against microbial infestation by yeasts.

[0051] Example 6 / Table 6: [Table 6]

[0052] As can be gathered from the test results shown in Table 6, even the addition of 4553 ppm of guanidine in the form of guanidine hydrochloride at a pH of 6.9 can achieve a distinct improvement in the stability of the body lotion against microbial infestation by yeasts.

Claims

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

2. 2. Use according to claim 1, characterized in that guanidine and / or its salts are used in an amount ranging from 0.033% to 2.0% by weight, based on the guanidine content of the entire product.

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

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

5.

5. Use 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 total product.

6. 6. Use according to any one of claims 1 to 5, characterized in that the cosmetic product is selected from the group consisting of shower gels, shower washes, dental cleaning and care products, mouthwashes, hair shampoos, hair conditioners, conditioning shampoos, hair sprays, hair rinses, hair treatments, hair wraps, hair tonics, self-tanning agents, facial tonics, permanent wave fixatives, hair colouring shampoos, hair dyes, hair setting agents, hair styling preparations, blow waving lotions, hair setting foams, hair styling gels, hair waxes, shaving foams, perfume preparations, wet wipes, body creams, lotions, facial creams, care products for topical use such as sunscreens or deodorants, and dermatological products.

7. Use according to any one of claims 1 to 5, characterized in that the laundry detergents and cleaning compositions are selected from the group consisting of household cleaners, detergents, cleaning or pre-wash products, textile refreshing sprays, fabric softeners, window cleaners, bathroom cleaners, toilet cleaners and dish detergents.

8. The aqueous product contains 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. um, benzethonium chloride, polyhexamethylene biguanide, bronopol, bronidox, chlorphenesin, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, silver chloride, ethylhexylglycerol, hexylglycerol, pentane-1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octane-1,2-diol, decane-1,2-diol, caprylic / capric triglyceride 8. The use according to any one of claims 1 to 7, characterized in that the product contains one or more ingredients selected from the group consisting of glyceryl caprate, 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 in a total amount of less than 100 ppm based on the whole product.

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