WO2012019789A1 - Preparations comprising benzethonium chloride and silver citrate - Google Patents

Abstract

The invention relates to a cosmetic preparation containing a combination of a quaternary ammonium salt and silver citrate and is characterised inter alia in that a synergy is observed in respect of preservation and hence the application concentration needed for preservation is reduced.

Description

 PREPARATIONS WITH BENZETHONIUM CHLORIDE AND SILVER CITRATE

The invention relates to a preparation containing a combination of quaternary ammonium salt and silver citrate. All quantities are - unless otherwise stated - percentages by weight based on the total mass of the preparation.

Silver SDC for the purposes of the present specification is Tinosan SDC from CIBA and consists chemically of Citric Acid + Silver Citrate.

To keep creams and lotions stable for a few months after opening, they must be preserved. Every preservation means a desire on the one hand a good safe product that smells good after a few months, is handsome and does not pose a danger to the consumer through microbial contamination, but on the other hand is also very well tolerated. The decisive factor is the choice of means. Some preservatives are very effective, but cause discomfort to individual consumers. For example, parabens are suspected of causing a certain amount of humanity to tingle, itch, or burn. This problem can be avoided by avoiding these preservatives (Route I). In this case, one is very limited in the choice of preservation. Another option is to use combinations that work very well, but at the same time contain less of the individual components (Route II). Prior art can be found in JP 2007284412, JP 20081 10999, EP 1964543,

WO2005102046, WO 2001041573.

All this could not eliminate the shortcomings of the prior art. The state of the art lacked preparations that allow good preservation while avoiding the use of parabens and thus avoid tingling, itching or burning in many users. Surprisingly and unforeseeable for a person skilled in the art, it has now turned out that a cosmetic preparation containing a combination from quaternary ammonium salt and silver citrate, characterized in that with respect to the preservation of a synergy is observed and is lowered with the necessary concentration for preservation use the shortcomings of the prior art remedies. This ensures that less of a quaternary ammonium salt must be used for the same conservation performance. This is advantageous because quaternary ammonium salts are suspected to cause consumer discomfort, especially with sensitive or damaged skin. Due to the synergy, the concentration of the quaternary ammonium salt can be significantly reduced, and thus the likelihood of discomfort. It is preferred if, the quaternary ammonium compound

Benzethonium chloride is. It is thereby achieved that it is possible to use a quaternary ammonium salt which is already effective at low levels per se even at lower levels. This not only reduces the possibility of discomfort but also offers benefits in terms of formula stability. It is particularly preferred if the preparation is in the form of a w / o emulsion, o / w emulsion, w / o / w emulsion, high internal phase emulsion, w / si emulsion, si / w emulsion, a hydrogel, a gel cream, a Gels or as a solid formulation such as a bar of soap or lipstick is present. Due to the reduced use concentration of the quaternary ammonium salt is achieved that any formula instabilities that are observed by adding cationic substances from time to time are observed even less frequently. Further, it is preferable if

Benzethonium chloride is present in a concentration of 0.001 to 0.1%. This ensures that the likelihood of a malady is significantly reduced. It is very particularly preferred if silver citrate is present in a concentration of 1 to 20 ppm. This ensures that the synergistic effect and thus the possibility of

Reduction of the quaternary ammonium component can be perceived particularly clearly / is particularly efficient. The invention also includes the use of

 Benzethonium chloride and silver citrate for improving the preservation of cosmetic preparations, more preferably in a concentration of 0.001 to 0.1%. The invention also encompasses the use of preparations according to the invention for the production of deodorant preparations and after-save products.

Such preparations may additionally comprise 2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol); Titanium dioxide, zinc oxide, 2,4,6-tris- (biphenyl) -1, 3,5-triazine, (2- {4- [2- (4-diethylamino-2-hydroxybenzoyl) benzoyl] -piperazine- 1-carbonyl} -phenyl) - (4-diethylamino-2-hydroxy-phenyl) -methanone. Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid salts; 2-phenylbenzimidazole-5-sulfonic acid salts; 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and its salts; 4- (2-oxo-3-bomylidenemethyl) benzene sulfonic acid salts; 2-methyl-5- (2-oxo-3-bornylidenemethyl) sulfonic acid salts; 2; 2- (2H-benzyl zotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy nyl] propyl] phenol; 3- (4-methylbenzylidene) camphor; 3-benzylidenecamphor;

Ethylhexyl salicylate, terephthalidene dic- camphorsulfonic acid; 2-ethylhexyl 4- (dimethylamino) benzoate; 4- (dimethylamino) benzoic acid amyl ester; Di (2-ethylhexyl) -4-methoxybenzalmalonate; 4-methoxycinnamate (2-ethylhexyl) ester; 4-methoxycinnamic acid isoamyl ester; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone; Hexyl 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoate, 4- (tert-butyl) -4'-methoxydibenzoylmethane;

homomenthyl; 2-ethylhexyl 2-hydroxybenzoate; 2-ethylhexyl-2-cyano-3,3-diphenylacrylate; dimethicodiethylbenzalmalonate; 3- (4- (2,2-ethoxycarbonylvinyl) phenoxy) propenyl) methoxysiloxane / dimethylsiloxane copolymer; 2,4-bis - {[4- (2-ethyl-hexyl-oxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (I NCI: bis-ethylhexyloxyphenol Methoxyphenyl triazine); Dioctylbutylamidotriazone (I NCI: diethylhexyl-butamidotriazone); 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine having the (CAS Nos 288254-16-0); 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) (also: 2,4,6-tris [anilino - (p-carbo-2'-ethyl-1'-hexyloxy)] - 1, 3,5-triazine (I NCI: ethylhexyl triazone); merocyanines, tapioca starch, distarch phosphate, aluminum or sodium starch, octenyl succinate and the like, Celluloses and cellulose derivatives,

Polymethylsilkenoxanes, emulsifying silicone elastomers, non-emulsifying silicone elastomers, polymethylmethacrylates, polymethylmethacrylate crosspolymer, polyamides, nylon, polyethylene powder, talc, coated talc, e.g. with Dimethicone and

Trimethylsiloxysilicate, mica, silica, titanium dioxide (optionally hydrophilic or hydrophobically coated, or else uncoated) silicone oils, phenethylbenzoate, 2-phenylethylbenzoate, propylheptyl caprylate, isopropyl lauroyl sarcosinate, dibutyl adipate, octyl palmitate, octylcoate, octyl isostearate, octyldodeceyl myristate, octyldodecanol, cetearyl isononanoate,

Isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, stearylheptanoate, oleyl oleate, Oleylerucat, erucyl oleate, erucyl erucate, tridecyl stearate, Tridecyltri- mellitat, and synthetic, semi-synthetic and natural mixtures of such esters, such. B. jojoba oil. Dialkyl ethers and dialkyl carbonates in particular. Dicaprylyl ether and / or di-caprylylcarbona, soicosane, neopentyl glycol diheptanoate, propylene glycol dicaprylate / dicaprate, caprylic / capric / diglyceryl succinate, butylene glycol dicaprylate / dicaprate, Ci ₂ -13-alkyl lactate, di-Ci ₂ -13-alkyl tartrate, triisostearin, dipentaerythrityl hexacaprylate / hexacaprate,

Propylene glycol monoisostearate, tricaprylin, dimethylisosorbide, caprylic / capric triglycerides, octyldodecanol, C12-15 alkyl benzoates, butylene glycol dicaprylate / dicaprate, dicaprylyl carbonate, isopropyl palmitate, ethylhexyl cocoate, cera microcristallina + paraffinum liquidum, Butyrospermum Parkii, Dicaprylyl Ether, Hydrogenated Coco-Glycerides, Simmondsia Chinensis Oil, Tridecyl Stearate, Tridecyl Trimellitate, Dipentaerythrityl

Hexacaprylate / hexacaprate, lanolin alcohol. Glyceryl stearate citrate, glyceryl stearate (self-emulsifying), stearic acid, stearate salts, polyglyceryl-3-methylglycose distearate, ceteareth-20, PEG-40 stearate, PEG-100 stearate, sucrose polystearates in combination with hydrogenated polyisobutene, sodium stearoyl glutamate, cetearyl alcohol in combination with PEG-40 hydrogenated castor oil, sodium cetearyl sulfate, glyceryl stearate, potassium cetyl phosphate, polyglyceryl-3 disiloxanes dimethicone sorbitan stearates, silicone polyether copolymers such as PEG-10 dimethicones, PEG / PPG-14/4 dimethicones, glyceryl stearate citrates and / or sodium stearoyl glutamates, ceteareth-n with n = 5-50, sorbitan oleate, distearyldimonium chloride, stearyl dimethicone, lecithin, sodium dihydroxycetyl phosphate, PG-10 stearate, lauryl PEG / PPG-18/18 methicone, cetyl PEG / PPG-10/1 dimethicone, polyglyceryl-2 caprate , Isostearyl Diglyceryl Succinate, Cetyl Phosphate, Sorbitan Sesquioleate,

Polyglyceryl-3 polydimethylsiloxyethyl dimethicone, acrylates / C 10-30 alkyl acrylates

Crosspolymer, Methyl Glucose Sesquistearate, Polyglyceryl-3 Methylglucose Distearate, Potassium Cetyl Phosphate, Polyglyceryl-2 Sesquiisostearate, Glyceryl Isostearate,

Behentrimonium chlorides, cetearyl glucosides, PEG / PPG-18/18 dimethicones, silicone emulsifiers in general. Examples:

All substances used have-unless otherwise stated-a 100% active content. The bacterium S. aureus (ATCC 12000) was from a according to EN 12353

Cryotubes on a corresponding plate (TSA agar, Heipha) struck and incubated at 37 ° C for 24 hours. From the grown bacteria, a second passage was created, which was used in the suspension test. A loop of the bacteria was added to 10mL LB medium (37g Hin-Herz broth (Merck) to 11 water) and 5g 4mm diameter glass beads and vortexed for 3 minutes. Subsequently, this bacterial suspension was adjusted to an OD of 0.08. The adjusted bacterial suspension was then diluted 1:20 with LB medium to ensure a bacterial count of approximately 2 ^* 10 ⁵ . This bacterial suspension was then used for the test. The suspension test was carried out by means of a TECAN pipetting robot. To this end, 800μΙ_ of the drug solutions to be tested, 10ΟμΙ H20 and 100 μΙ of the bacterial suspension were placed in Eppendorf tubes without lid with welded foil in the thermal shaker. After 20, 60 and 180 minutes at 37 ° C. and 1200 rpm, 100 μl each were taken from the Eppendorf tubes in the thermal shaker and pipetted to 900 μl LB medium (10 μl ⁾ .

Dilution). These dilutions were plated out on agar plates using spiral plates. The only exception is the control, which was diluted 1: 100 again (10 ^"3 dilution) and the controls were plated with both dilutions, including time T = 0 minutes, and finally the plates were allowed to cure at 37 ° C for 24 hours incubated and then evaluated using the Countermaten.

In the evaluation, the reduction factor was determined. The reduction factor is the factor by which the cell number (CFU) of the test substance is reduced compared to the control.

CFU (control)

 ; - = reduction factor

 CFU {test substance) tested drug solutions:

10 ppm Silver SDC

 8 ppm Silver SDC

 0.01% benzethonium chloride

 10 ppm Silver SDC + 0.01% benzethonium chloride

8 ppm Silver SDC + 0.01% Benzethonium Chloride The raw materials were dissolved using a solubilizer (2.5% Peg 40 = Hydrogenated Cator Oil).

The following reduction factors could be achieved:

 10ppm silver show a reduction factor of 3, 0.01% benzethonium chloride show a reduction factor of 4 and the combination 10ppm silver and 0.01% benzethonium chloride do not show the factor 7 as arithmetically expected but surprisingly from 81.

This effect can even be repeated at 8 ppm (see table), so it can not be a randomly observed effect.

Hydrodispersionsqel

 1 2 3 4 5

 Cyclomethicone D5 8 10 5 3 -

 Dimethicone 200 est. - - - - 3

 Dimethiconol (Dow Corning 1501 Fluid) 1 2 3 - 3

 Ethanol 1, 0 5.0 7.5 1, 5 3.0

Sodium polyacrylate (Cosmedia SP) 0.2 0.3 0.3 0.4 0, 10

Methylpropanediol 2 3 4 5 -

 Glycerol 9 15 5 7,5 25

Carbomer (Carbopol 981) 0.2 0.3 0.2 0.4 0.15

Acrylate.es/C10-30Alkyl Acrylate Crosspoly- 0.2 0, 15 0.3 0.4 0, 10 mer (Pemulen TR 2)

 Carrageenan (Chondrus Crispus) (Gelcarin) - - - - 2

 Hamamelis extract Hamamelis (extract PG) 0, 1 0.2 0.3 0.4 -

 Perfume q.s. q.s. q.s. q.s. q.s.

 Silver citrate (Tinosan SDC) 0.4 0.3 0.5 0.4 0.6

Benzethonium chloride 0.5 1, 0 0.05 0.2 0, 1

Water ad 100 ad 100 ad 100 ad 100 ad 100 O / W emulsion

6 7 8 9 10

Glyceryl stearate citrate 2.4 2.0 2.0 2.0 2.4

White medicinal oil (Shell Ondina Oil G 6.0 6.0 6.0

37)

 Myristyl myristate 3.0 - - - 3.0

Isopropyl palmitate - 3.0 3.0 3.0 -

Caprylic / Capric Triglyceride 4.0 - - - 4.0

Linear silicone oil (BRB Silicone Oil DM 100 2.0 1, 0 1, 0 1, 0 2.0 EP)

 Propylparaben 0.2 0, 1 0.1 0, 1 0.2

Sorbitan stearate 0.8 - - - 0.8

Octyldodecanol 1, 0 - - - 1, 0

Cetearyl alcohol 0.8 2.0 2.0 2.0 0.8

Phenoxyethanol 0.6 0.5 0.5 0.5 0.6

Glycerol 6.5 - - - 6.5

Sodium polyacrylate (Cosmedia SP) 0, 19 0, 19 0, 19 0, 19 0.19

Xanthan Gum (Xanthan gum E 415 food 0.2 0.2 grade)

 Methyl paraben 0.3 0.3 0.3 0.3 0.3

Ethanol 3.0 - - - 3.0

Perfume 0.3 0.3 0.3 0.3 0.6

Lauroylethylarginate (aminate G) 1, 0 - 0.5 - -

Silver citrate (Tinosan SDC) 0.4 0.3 0.5 0.4 0.6

Benzethonium chloride - 0, 1 - 0.07 0.05

Water ad 100 ad 100 ad 100 ad 100 ad 100

O / W emulsions

1 2 3 4 5 6

Panthenol 1, 50 - - 0.70 - 0.00

Silver citrate (Tinosan SDC) 0.4 0.3 0.3 0.5 0.4 0.4

Benzethonium chloride 1 0, 12 0, 12 0.5 0.07 0.07

Paraffinum Liquidum (Shell Ondina 933 HRD) - 3.00 3.00

 Isopropyl palmitate 1, 00 - - - - -

Caprylic / Capric Triglyceride - 3.00 3.00 0.00 1.00 1 .00

Cetearyl alcohol - - - 2.50 4.00 4.00

Cetyl alcohol - 3.00 3.00 - - -

Paraffin Liquidum (Shell

Ondina 927) 3.00 3.00

 Dimethicone 200 est - 3.00 3.00 - 0.50 0.50

Cyclomethicone D5 - 3.00 3.00 - - -

C12-15 alkyl benzoate - - - - 2.00 2.00

Butyrospermum Parkii butter

(Shea butter) 0,50 0,50 0,00

 Dicaprylyl ether - - - 10.00 - -

Dicaprylyl carbonate 2.00 - - 0.00 - -

Glyceryl stearates - 1, 20 1, 20 2.40 2.40 2.40

Tapioca starch aq. (Tapioca

Pure) 1, 00

 Glycerine 5.00 8.00 10.00 8.00 10.00 8.00

Butylene glycol - - - 1, 00 - -

Citric acid 0.0050 - - - - -

Sodium hydroxide aq 45% 0.35 0.01 0.01 0.25 1, 00 1, 00

Polyglyceryl-10 myristate - 1, 80 - - 1, 00 0.00

Polyglyceryl-10 Stearate 0.70 - 1, 80 1, 00 - 1, 00

Carbopol 981 0.50 0.02 0.02 - - 0.00

Acrylic Acid / VP Crosspolymer

(Ultrathix P-100) - 0.50 0.75 0.75

Water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100

Trisodium EDTA aq. 1, 00 1, 00 1, 00 1, 00 Ethylhexyl methoxycinnamate +

BHT 2.00

 Butyl Methoxydibenzoylmethane - - - - 2.00 2.00

Phenylbenzimidazolesulfonic acid - - - - 2.00 2.00

Ethylhexyl salicylate - - - - 2.00 2.00

Titanium dioxide + trimethoxycaprylylsilane (Tego Sun T 805) 0.3600

 Octocrylene - - - - 2.00 2.00

Perfume - 0.35 0.35 - 0.20 0.20

W / O emulsions,

 1 2 3 4 5

Triglycerol diisostearate 1, 0 0.5 0.25 2.0 3.0

Diglycerol dipolyhydroxystearate 1, 0 1, 5 1, 75 3.0 2.0

Paraffin oil (Shell Ondina 917) 12.5 10.0 8.0 5.0 1 1, 5

Vaseline (Pioneer 6787) 8.0 6.0 5.0 12.0 2.5

Hydrogenated coconut glycerides 2.0 1, 0 2.5 5.0 0.25

Decyl oleate 0.5 0.75 1, 0 2.0 0.25

Octyldodecanol 0.5 1, 0.75 3.0 0.25

Aluminum stearate 0.4 0.3 0.6 1, 0.05

Dicaprylyl carbonate 0, 1 0.05 0, 15 0.5 1, 0 hydrogenated castor oil 0.5 0.75 1, 0 2.5 5.0

Chitosan - - 0.25 - -

Polyacrylic acid, Na salt (Cosmedia SP) - - - 0.15 0.25

Magnesium chloride 0.5 0.6 0.5 0.7 1, 0

Glycerine 3.0 5.0 10.0 15.0 1, 5

Lactic Acid 0.5 0.9 0.2 - -

Perfume q, s, q, s, q, s, q, s, q, s,

Ethanol 2.0 - 5.0 - -

Caprylic / Capric Acid Triglyceride 2.0 2.5 3.0 5.0 0.5

Lauroylethylarginate (aminate G) 1, 0 - 0.5 - -

Silver citrate (Tinosan SDC) 0.4 0.3 0.5 0.4 0.6

Benzethonium chloride - 0, 12 - 0.07 0.05

Potassium sorbate 0.04 0, 15 0.05 0.03 0.4

Water ad 100 ad 100 ad 100 ad 100 ad 100

Claims

claims Cosmetic preparation containing a combination of quaternary ammonium salt and silver citrate, characterized in that with respect to the preservation of a synergy is observed and thus the necessary for preservation use concentration is lowered. Preparation according to one of the preceding claims, characterized in that the quaternary ammonium compound is benzethonium chloride. Preparation according to one of the preceding claims, characterized in that the preparation is in the form of a w / o emulsion, o / w emulsion, w / o / w emulsion, high internal phase emulsion, w / si emulsion, si / w emulsion, a hydrogel , a jelly cream, a gel or as a solid formulation such as a bar of soap or lipstick. Preparation according to one of the preceding claims, characterized in that benzethonium chloride is present in a concentration of 0.001 to 0, 1%. Preparation according to one of the preceding claims, characterized in that silver citrate is present in a concentration of 1 to 20 ppm. Use of benzethonium chloride and silver citrate for improving the preservation of cosmetic preparations. Use according to claim 5, characterized in that Benzethonium chloride is present in a concentration of 0.001 to 0.1%. Use of preparations according to one of the preceding claims for the production of deodorant preparations and aftershave products.