Aqueous silicone polymer compositions

Abstract

The present invention relates to aqueous compositions comprising one or more silicones and a synergistic combination of anti-microbiological agents, to a process for preparing the aqueous compositions, and to the use of said aqueous compositions, in particular, for the manufacture of home care articles, household cleansing articles, fabric articles, cosmetic articles, hygienic articles, medical articles etc.

Claims

1. An aqueous composition comprising one or more silicones, and a) at least one compound of the general formula (1) ##STR00012## wherein n is 0 or 1, R.sub.1, R.sub.1* and R.sub.1** are independently selected from the group consisting of hydrogen, a linear or branched C1-C9 alkyl group, and a linear or branched C1-C9 alkyloxy group, and R.sub.2 is a linear or branched divalent C2-C5 alkyl group, and b) at least one compound selected from general formula (2) ##STR00013## wherein compound (2) has 5 to 22 carbon atoms, and wherein R.sub.3 is selected from the group consisting of hydrogen, a linear or branched C1 to C12 alkyl group, a linear or branched C1 to C12 alkylaryl group, an aryl group, a linear or branched C1 to C12 alkyloxy group, a linear or branched C1 to C12 alkylaryloxy group, and an aryloxy group, and R.sub.4 and R.sub.5 are the same or different and are selected from the group consisting of a linear or branched C1 to C12 alkyl group, a linear or branched C1 to C12 alkylaryl group, an aryl group, or R.sub.4 and R.sub.5 together form an optionally substituted ring system with at least 5 carbon atoms, and c) optionally one or more compounds selected from the group consisting of the general formulae (4) and (5) ##STR00014## wherein R.sub.6 and R.sub.7 are either both hydrogen or one is a methyl group and the other is hydrogen and R.sub.8 is selected from the group consisting of a linear or branched C6 to C14 alkyl group, a linear or branched C6 to C14 alkyloxy group, a linear or branched C6 to C14 alkyloxyalkyl group, a linear or branched C6 to C14 alkylaryl, a linear or branched C6 to C14 alkylaryloxy and aryloxy group.

2. The aqueous composition according to claim 1, comprising d) one or more substances selected from the group consisting of i) nonionic surfactants, ii) cationic surfactants, iii) anionic surfactants, iv) amphoteric surfactants, v) fatty oils and fats with between 8 and 32 carbon atoms, vi) organic acids and polymeric derivatives thereof, vii) inorganic or polymeric thickeners, viii) antioxidants, and ix) pH adjusting agents.

3. The aqueous composition according to claim 1, comprising at least one surfactant.

4. The aqueous composition according to claim 1, comprising components a) and b) in a quantity producing a synergistic antimicrobial effect.

5. The aqueous composition according to claim 1, wherein the total weight of the sum of the components a), b) and c) is from 0.5 to 12 weight based on the total weight of the aqueous composition.

6. The aqueous composition according to claim 1, wherein the amount of the one or more silicones is in the range of 1 and 50 weight-%, based on the total weight of the aqueous composition.

7. The aqueous composition according to claim 1, wherein the silicones are selected from the group consisting of polyorganosiloxanes which optionally may have one or more functional groups and mixtures thereof.

8. The aqueous composition according to claim 1, comprising 0.1 to 5.0 weight-%, of the total weight of the components a) based on the total weight of the aqueous composition, and said component a).

9. The aqueous composition according to claim 1, comprising 0.1 to 5.0 weight-% of the total weight of the components b) based on the total weight of the aqueous composition, and said component b) is selected from the group consisting of 2-methyl-2,4-pentanediol, 2-methyl-2,4-hexanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol and 2,2-dioctyl-1,3-propanediol, and mixtures thereof.

10. The aqueous composition according to claim 1, comprising 0.1 to 5.0 weight-%, of the total weight of the components c) based on the total weight of the aqueous composition, and said component c) is preferably selected from the group consisting of 1,2-octanediol, 1,2-decanediol, 3-(2-ethylhexyloxy)-1,2-propanediol, 1,2-dodecanediol, 2-methyl-1,3-propanediol, 1,3-propanediol and 1,3-butanediol, and mixtures thereof.

11. An article selected from the group consisting of homecare articles, household articles, industrial articles, fabric articles, cosmetic articles, hygienic articles, personal care articles and medical articles wherein the article comprises the aqueous composition according to claim 1.

12. The article according to claim 11, wherein the aqueous composition further comprises e) one or more functional components, selected from the group consisting of: i) volatile silicone compounds, ii) anionic, nonionic, cationic or amphoteric surfactants, iii) oily phase-forming substance, iv) saturated and unsaturated aliphatic alcohols, which are different from components a), b) and c) of the aqueous composition, v) organic acids and polymeric derivatives thereof, vi) antioxidants, vii) UV absorbers, viii) perfumes and fragrances, ix) dyes and pigments, x) hydrophilic components or polymers, xi) emollients, xii) organic polymeric quaternary ammonium compounds, xiii) antidandruff agents, xiv) antiperspirants, xv) insect repellants, xvi) vitamins or vitamin precursors, xvii) botanical extracts, xviii) inorganic or polymeric thickeners, xix) additional components with antimicrobiological properties, which are different from components a), b) and c) as defined in the aqueous composition, xx) silicone and organic polymer fixatives, and xxi) organic solvents.

13. A method of preserving aqueous compositions, comprising at least one silicone, against microorganisms, which comprises admixing said aqueous composition comprising the at least one silicone, with a mixture of components a) and b), and optionally component c), as defined in claim 1.

14. A preservative composition comprising the aqueous composition of claim 1.

15. The aqueous composition according to claim 1, wherein the total weight of the sum of the components a), b) and c) is from 1.5 to 5.0 wt.-%, based on the total weight of the aqueous composition.

16. The aqueous composition according to claim 1, wherein the amount of the one or more silicones is in the range of 10 and 30 weight-%, based on the total weight of the aqueous composition.

17. The aqueous composition according to claim 1, wherein the silicones are selected from the group consisting of polydimethylsiloxanes, amino group-modified silicones, polyether group-modified silicones, and silicones comprising at least one quaternary ammonium group, and mixtures thereof.

18. The aqueous composition according to claim 1, comprising 0.1 to 2.0 weight-% of the total weight of the components a) based on the total weight of the aqueous composition, and said component a) is 2-phenoxyethanol and/or 3-phenyl-1-propanol.

19. The aqueous composition according to claim 1, comprising 0.1 to 3.0 weight-%, of the total weight of the components b) based on the total weight of the aqueous composition, and said component b) is selected from 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-2,4-hexanediol, or 2-methyl-2-propyl-1,3-propanediol, and combinations thereof.

20. The aqueous composition according to claim 1, comprising 0.1 to 3.0 weight-%, of the total weight of the components c) based on the total weight of the aqueous composition, and said component c) is selected from (3-(2-ethylhexyloxy)-1,2-propanediol, 1,3-propanediol, 1,2-dodecanediol, or 2-methyl-1,3-propanediol, and combinations thereof.

21. The aqueous composition according to claim 1, wherein compound (2) has 6 to 22 carbon atoms.

22. An oil-in-water emulsion comprising 5 and 40 weight-% of one or more silicones based on the weight of the oil-in-water emulsion, and a) at least one compound of the general formula (1) ##STR00015## wherein n is 0 or 1, R.sub.1, R.sub.1* and R.sub.1** are independently selected from the group consisting of hydrogen, a linear or branched C1-C9 alkyl group, and a linear or branched C1-C9 alkyloxy group, and R.sub.2 is a linear or branched divalent C2-C5 alkyl group, and b) at least one compound selected from the group consisting of the general formulae (2) and (3) ##STR00016## wherein compounds (2) has 5 to 22 carbon atoms, and wherein R.sub.3 is selected from the group consisting of hydrogen, a linear or branched C1 to C12 alkyl group, a linear or branched C1 to C12 alkylaryl group, an aryl group, a linear or branched C1 to C12 alkyloxy group, a linear or branched C1 to C12 alkylaryloxy group, and an aryloxy group, and R.sub.4 and R.sub.5 are the same or different and are selected from the group consisting of a linear or branched C1 to C12 alkyl group, a linear or branched C1 to C12 alkylaryl group, an aryl group, or R.sub.4 and R.sub.5 together form an optionally substituted ring system with at least 5 carbon atoms, and c) optionally one or more compounds selected from the group consisting of the general formulae (4) and (5) ##STR00017## wherein R.sub.6 and R.sub.7 are either both hydrogen or one is a methyl group and the other is hydrogen and R.sub.8 is selected from the group consisting of a linear or branched C6 to C14 alkyl group, a linear or branched C6 to C14 alkyloxy group, a linear or branched C6 to C14 alkyloxyalkyl group, a linear or branched C6 to C14 alkylaryl, a linear or branched C6 to C14 alkylaryloxy and aryloxy group.

23. The aqueous composition according to claim 22, wherein compound (2) has 6 to 22 carbon atoms.

Description

EXAMPLES

(1) Unless otherwise stated differently, all percentages given are weight percent related to the total weight of the compositions. In particular, the percentages for components a), components b), and components c) are weight percentages related to the total weight of the compositions. The parts used below for the different components in the examples are weight parts.

(2) The testing of microbiological stability is performed according to the state-of-the-art in that the composition according to the invention is inoculated with 1.0 weight-% of a suspension of microorganisms with 10.sup.4-10.sup.8 KBE/ml (KBE=Koloniebildende Einheiten je ml (colony forming units (cfu) per ml of the sample)) of live bacteria, yeasts or fungi. The mixture is thoroughly mixed then incubated at 25+/2 C. in air.

(3) After incubation for a period of time ranging from 7 to 36 days, a sample of the inoculated emulsion is swabbed onto agar plates of growth medium (caseinpepton-sojapepton-agar for bacteria and sabouraud-dextrose-agar for yeasts and fungi). The agar plates are then incubated at 26+/2 C. for three days, after which time the plates are inspected for colonies of microbiological growth.

(4) The results of the microbiological stress tests are summarized in the Tables 1-4 and denoted as: 0 (no growth), X (minimal growth, less than 5 colonies), XX (moderate growth 5-10 colonies), XXX (strong growth, >10 colonies).

(5) In some cases, all the microorganisms in the inoculated emulsion are only killed after a number of days incubation. This is indicated in the tables as the number of days to destruction of all microorganisms.

(6) Viscosities are determined at 25 C. (unless indicated otherwise) according to the method of Hppier (DIN 53015: ViscometryMeasurement of viscosity by means of the rolling ball viscometer by Floppier).

(7) Solids content is determined using an infrared moisture analyzer model HR73 as sold by Mettler Toledo GmbH (Gieen, Germany).

(8) Color according to Hazen is determined with a LICO 200 Color Analyzer as sold by HachLange GmbH (Weinheim, Germany).

Example 1

(9) An aqueous microemulsion comprising 20% of an amino group-modified silicone with aminoethylaminopropyl pendant groups and an amino content of 0.77 mmol NH.sub.2/g and 19.3% of a mixture of an alkylpolyglycoside and cocosamidopropyl betaine surfactants, was prepared by first mixing 50 parts of the aminosilicone with

(10) 2.25 parts (0.9%) of 2-phenoxyethanol (component a)),

(11) 3.75 parts (1.5%) of 2-butyl-2-ethyl-1,3-propanediol (component b)), and

(12) 1.5 parts (0.6%) ethylhexyl glycerin (component c)),

(13) then adding this mixture to a solution of the 87.5 parts Plantacare 2000 UP (a 50% aqueous solution of C8-C16 alkylpolyglycosides sold by the BASF SE, Ludwigshafen, Germany) and 15.0 parts of Genagen CAB 818 (a 30% aqueous solution of cocosalkylamidopropylbetaine sold by the Clariant GmbH, Frankfurt am Main, Germany) in 84.23 parts water and adjusting the pH with 3.0 parts L-arginine and 2.77 parts acetic acid, the remainder being water, in accordance with WO2011042409. The final microemulsion had a viscosity of 18.3 mPa*s at 25 C., a solids content of 43.5%, a color according to Hazen of 190 and a pH value of 8.

(14) The microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 6, and 13 days after inoculation with 1.0% of a suspension with a titer of 10.sup.8 KBE/ml, comprising a mixture of Gram negative and Gram positive bacteria including Pseudomonas aeruginosa, Pseudomonas putida, Burkholderia cepacia, Klebsiella pneumonia, Enterobacter gergoviae, Straphylocuccus aureus and Straphylocuccus epidermidis. In a separate test, the microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 14 and 28 days after inoculation with 1.0% of a suspension of microorganisms with a titer of 10.sup.7 KBE/ml microorganisms, comprising a mixture of yeasts including Cadida albicans and Cadida parapsilosis. In a third test the emulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 14 and 28 days after inoculation with 1.0% of a suspension of microorganisms with a titer of 10.sup.7 KBE/ml microorganisms, comprising the fungi Aspergillus brasiliensis, and Penicillium pinophilum.

Comparative Example 1

(15) A microemulsion was prepared as in Example 1, but instead adding

(16) 2.25 parts (0.9%) 2-phenoxyethanol (component a)) and

(17) 1.5 parts (0.6%) ethylhexyl glycerin (component c)),

(18) but no component b), to the preformed microemulsion, and the blend mixed at ambient temperature until clear.

(19) The microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 6, and 13 days after inoculation with 1.0% of a suspension of with a titer of 10.sup.8 KBE/ml, comprising a mixture of Gram negative and Gram positive bacteria as in Example 1. In a separate test, the emulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 14 and 28 days after inoculation with 1.0% of a suspension of microorganisms with a titer of 10.sup.7 KBE/ml microorganisms, comprising a mixture of yeasts including Cadida albicans and Cadida parapsilosis. In a third test the emulsion exhibited moderate microbiological growth upon incubation at 25+/2 C. for 14 and 28 days after inoculation with 1.0% of a suspension of microorganisms with a titer of 10.sup.7 KBE/ml microorganisms, comprising Aspergillus brasiliensis, and Penicillium pinophilum.

Example 2

(20) A microemulsion comprising 20% of a silicone polymer comprising at least one quaternary ammonium group, Silicone Quaternium-18, and 10% of a mixture of nonionic surfactants was prepared by first mixing 20 parts of the silicone quat polymer as a microemulsion with 10 parts of the non-ionic surfactants and then adding 70 parts of water and mixed at ambient temperature until clear. The final unpreserved emulsion had a viscosity of 17.8 mPa*s at 25 C., a solids content of 30.3%, a pH value of 8.0 and a color according to Hazen of 71.

(21) To 95.7 parts of this microemulsion were added

(22) 3.3 parts (3.3%) 2-phenoxyethanol (component a)),

(23) 1.0 part (1.0%) 2-butyl-2-ethyl-1,3-propanediol (component b))

(24) and mixed at ambient temperature until clear. The microemulsion exhibited moderate microbiological growth upon incubation at 25+/2 C. for 7 days, but no microbiological growth 14 days, after inoculation with 1.0% of a suspension of microorganisms with a titer of 10.sup.5 KBE/ml microorganisms, comprising Aspergillus niger, and Penicillium funiculosum.

Comparative Example 2

(25) To 95.7 parts of the microemulsion in Example 2 was instead added

(26) 4.3 parts (4.3%) 2-phenoxyethanol (component a)),

(27) but no component (b), and mixed at ambient temperature until clear. The microemulsion exhibited strong to moderate microbiological growth upon incubation at 25+/2 C. for 7 and 14 days, but no microbiological growth 28 days, after inoculation with 1.0% of the suspension of microorganisms used in Example 2.

Comparative Example 3

(28) To 95.7 parts of the microemulsion in Example 2 was instead added

(29) 4.3 parts (4.3%) 2-butyl-2-ethyl-1,3-propanediol (component b)),

(30) but no component a), and mixed at ambient temperature until clear. The microemulsion exhibited strong microbiological growth upon incubation at 25+/2 C. for 7, 14, 28 and 36 days after inoculation with 1.0% of the suspension of microorganisms used in Example 2.

Example 3

(31) To 95.7 parts of the microemulsion in Example 2 were instead added

(32) 1.0 part (1.0%) 3-phenyl-1-propanol (component a)),

(33) 3.3 parts (3.3%) 2-butyl-2-ethyl-1,3-propanediol (component b))

(34) and mixed at ambient temperature until clear. The microemulsion exhibited moderate microbiological growth upon incubation at 25+/2 C. for 7 days, but no microbiological growth 14 and 28 days, after inoculation with 1.0% of the suspension of microorganisms used in Example 2.

Example 4

(35) To 95 parts of the microemulsion in Example 2 were instead added

(36) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(37) 3.1 parts (3.1%) 2-butyl-2-ethyl-1,3-propanediol (component b)), and

(38) 1.0 part (1.0%) 2-methyl-2-propyl-1,3-propanediol (component b)) and mixed at ambient temperature until clear. The microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 7, 14 and 28 days after inoculation with 1.0% of the suspension of microorganisms used in Example 2.

Comparative Example 4

(39) To 95 parts of the microemulsion in Example 2 were instead added

(40) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(41) 2.1 parts (2.1%) ethylhexylglycerin (component c)), and

(42) 2.0 parts (2.0%) 1,2-octanediol (component c)),

(43) but no component (b), and mixed at ambient temperature until clear. The microemulsion exhibited strong microbiological growth upon incubation at 25+/2 C. for 7, 14 and 28 days after inoculation with 1.0% of the suspension of microorganisms used in example 2.

Example 5

(44) To 95 parts of the microemulsion in Example 2 were instead added

(45) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(46) 2.0 parts (2.0%) 2-butyl-2-ethyl-1,3-propanediol (component b)),

(47) 0.5 parts (0.5%) 2-methyl-1,3-propanediol (component c)),

(48) 0.5 parts (0.5%) 1,3-propanediol (component c)), and

(49) 1.1 parts (1.1%) ethylhexyl glycerin (component c)) and mixed at ambient temperature until clear. The microemulsion exhibited minor microbiological growth upon incubation at 25+/2 C. for 7 days, but no microbiological growth 14 and 28 days, after inoculation with 1.0% of the suspension of microorganisms used in Example 2.

Comparative Example 5

(50) To 97 parts of the microemulsion in Example 2 were instead added

(51) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(52) 0.5 parts (0.5%) 2-methyl-1,3-propanediol (component c)),

(53) 0.5 parts (0.5%) 1,3-propanediol (component c)), and

(54) 1.1 parts (1.1%) ethylhexyl glycerin (component c)), but no component (b), and mixed at ambient temperature until clear. The microemulsion exhibited strong to moderate microbiological growth upon incubation at 25+/2 C. for 7 and 14 days, and minimal growth 28 days after inoculation with 1.0% of the suspension of microorganisms used in Example 2.

Comparative Example 6

(55) To 95.9 parts of the microemulsion in Example 2 were instead added

(56) 2.0 parts (2.0%) 2-butyl-2-ethyl-1,3-propanediol (component b)),

(57) 0.5 parts (0.5%) 2-methyl-1,3-propanediol (component c)),

(58) 0.5 parts (0.5%) 1,3-propanediol (component c)), and

(59) 1.1 parts (1.1%) ethylhexyl glycerin (component c)),

(60) but no component (a), and mixed at ambient temperature until clear. The microemulsion exhibited strong to moderate microbiological growth upon incubation at 25+/2 C. for 7, 14 and 28 days after inoculation with 1.0% the suspension of microorganisms used in example 2.

Example 6

(61) A microemulsion comprising 20% of an amino group-modified silicone with aminoethylaminopropyl pendant groups and an amino content of 0.77 mmol NH.sub.2/g was prepared as in Example 1 but without first mixing the aminosilicone with any component a), b) or c). The microemulsion had a viscosity of 27.1 mPa*s at 25 C., a solids content of 42.5%, a color according to Hazen of 222 and a pH value of 8.5. To 95 parts of this microemulsion were added

(62) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(63) 3.1 parts (3.1%) 2-butyl-2-ethyl-1,3-propanediol (component b)), and

(64) 1.0 part (1.0%) 2,2-dimethyl-1,3-propanediol (component b))

(65) and mixed at ambient temperature until clear. The microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 7 and 14 days after inoculation with 1.0% of a suspension of microorganisms with a titer of 10.sup.4 KBE/ml microorganisms, comprising Aspergillus niger, and Penicillium funiculosum.

Example 7

(66) To 96.0 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), were instead added

(67) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(68) 2.0 Parts (2.0%) 2-butyl-2-ethyl-1,3-propanediol (component b)), and

(69) 1.1 parts (1.1%) ethylhexyl glycerin (component c))

(70) to the emulsion and mixed until clear. The microemulsion exhibited minor microbiological growth upon incubation at 25+/2 C. for 7 and 14 days, but no microbiological growth 24 days after inoculation with 1.0% of the suspension of microorganisms used Example 6.

Example 8

(71) To 97.5 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), were instead added

(72) 0.9 parts (0.9%) 2-phenoxyethanol (component a)) and

(73) 1.6 parts (1.6%) 2-butyl-2-ethyl-1,3-propanediol (component b)).

(74) The microemulsion exhibited minor microbiological growth upon incubation at 25+/2 C. for 14 and 24 days, but no microbiological growth 36 days after inoculation with 1.0% of the suspension of the microorganisms used in Example 6.

Example 9

(75) To 97.5 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), were instead added

(76) 2.0 parts (2.0%) 2-phenoxyethanol (component (a)) and

(77) 0.5 parts (0.5%) 2-methyl-2,4-hexanediol (component (b)).

(78) The microemulsion exhibited moderate microbiological growth upon incubation at 25+/2 C. for 7 days, but no microbiological growth 14 and 24 days, after inoculation with 1.0% of the suspension of microorganisms as used in Example 6.

Comparative Example 7

(79) To 97.5 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), was instead added

(80) 2.5 parts (2.5%) 2-phenoxyethanol (component a))

(81) but no component (b). The microemulsion exhibited moderate microbiological growth upon incubation at 25+/2 C. for 7 and 14 days, but no microbiological growth 28 days after inoculation with 1.0% of the suspension of microorganisms used in Example 6.

Comparative Example 8

(82) To 97.5 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), was instead added

(83) 2.5 parts (2.5%) 2-butyl-2-ethyl-1,3-propanediol (component b)),

(84) but no component (a). The microemulsion exhibited strong to moderate microbiological growth upon incubation at 25+/2 C. for 7, 14 and 28 days after inoculation with 1.0% of the suspension of microorganisms used in Example 6.

Comparative Example 9

(85) To 98 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), were instead added

(86) 0.9 parts (0.9%) 2-phenoxyethanol (component (a)) and

(87) 1.1 parts (1.1%) ethylhexyl glycerin (component (c)),

(88) but no component b). The microemulsion exhibited strong to moderate microbiological growth upon incubation at 25+/2 C. for 14 and 28 days after inoculation with 1,0% of the suspension of microorganisms used in Example 6.

Comparative Example 10

(89) To 95 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), were instead added

(90) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(91) 1.75 (1.75%) ethylhexyl glycerin, and

(92) 2.35 parts (2.35%) 1,2-octanediol (both components c)),

(93) but no component b). The microemulsion exhibited strong to moderate microbiological growth upon incubation at 25+/2 C. for 7, 14 and 28 days, but no microbiological growth 36 days, after inoculation with 1.0% of the suspension of microorganisms used in Example 6.

Example 10

(94) To 95 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), were instead added

(95) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(96) 3.0 parts (3.0%) 2-butyl-2-ethyl-1,3-propanediol (component b)),

(97) 0.6 parts (0.6%) ethylhexyl glycerin (component c)) and

(98) 0.5 parts (0.5%) 1,3-propanediol (component c))

(99) and mixed at ambient temperature until clear. The microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 7, 14 and 24 days after inoculation with 1.0% of the suspension of microorganisms used in Example 6.

Example 11

(100) To 95 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), were added

(101) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(102) 1.5 parts (1.5%) 2,2-dimethyl-1,3-propanediol (component b)),

(103) 1.5 parts (1.5%) 2-methyl-2-propyl-1,3-propanediol (component b)),

(104) 0.6 parts (0.6%) ethylhexyl glycerin (component c)) and

(105) 0.5 parts (0.5%) 1,3-propanediol (component c))

(106) and mixed at ambient temperature until clear. The microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 7, 14 and 28 days after inoculation with 1.0% of the suspension of microorganisms used in Example 6.

Example 12

(107) To 95 parts of the microemulsion comprising 20% of an amino group-modified silicone in Example 6, but without any component a), b) or c), were added

(108) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(109) 3.0 parts (3.0%) 2-methyl-2,4-hexanediol (component b)),

(110) 0.6 parts (0.6%) ethylhexyl glycerin (component c)) and

(111) 0.5 parts (0.5%) 1,3-propanediol (component c))

(112) and mixed at ambient temperature until clear. The microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 14 and 28 days after inoculation with 1.0% of the suspension of microorganisms used in Example 6.

Example 13

(113) To 98 parts of an aqueous emulsion comprising 30% of a polydimethylsiloxane with a viscosity of 100 mPa*s at 25 C. and 4.3% of a mixture of non-ionic surfactants with an average HLB value of 15.4 were added

(114) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(115) 1.0 part (1.0%) 2-butyl-2-ethyl-1,3-propanediol (component b)) and

(116) 0.1 parts (0.1%) ethylhexyl glycerin (component c))

(117) and mixed at ambient temperature for 1 hour. The microemulsion had a solids content of 39.1%, a viscosity at 25 C. of 13.7 mPa*s, an average particle size of 0.29 microns and a pH value of 4.

(118) The microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 6, and 13 days after inoculation with 1.0% of a suspension of with a titer of 10.sup.8 KBE/ml, comprising a mixture of Gram negative and Gram positive bacteria including Pseudomonas aeruginosa, Pseudomonas putida, Burkholderia cepacia, Klebsiella pneumonia, Enterobacter gergoviae, Staphylocuccus aureus and Staphylocuccus epidermidis. In a separate test, the microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 14 and 28 days after inoculation with 1.0% of a suspension of microorganisms with a titer of 10.sup.7 KBE/ml microorganisms, comprising a mixture of yeasts including Candida albicans and Candida parapsilosis. In a third test, the microemulsion exhibited no microbiological growth upon incubation at 25+/2 C. for 14 and 28 days after inoculation with 10% of a suspension of microorganisms with a titer of 10.sup.7 KBE/ml microorganisms, comprising the fungi Aspergillus brasiliensis, and Penicillium pinophilum.

Example 14

(119) A typical shampoo formulation was prepared by mixing at ambient temperature 33.3 parts of a 27% aqueous solution of sodium lauryl sulfate, with 10 parts of a 30% aqueous solution of cocosamidopropyl betaine, and 51.7 parts of waterand adding 5 parts of the unpreserved silicone microemulsion according to Example 2, comprising 20% of Silicone Quaternium-18, and 10% of a mixture of nonionic surfactants.

(120) To 97 parts of this shampoo formulation were added

(121) 1.0 part (1.0%) 3-phenyl-1-propanol (component a)) and

(122) 2.0 parts (2.0%) 2-butyl-2-ethyl-1,3-propanediol (component b)).

(123) The shampoo formulation had a viscosity of 14.4 mPa*s at 25 C., a solids content of 28.6%, a pH value of 8 and a color according to Hazen of 116. The final shampoo formulation was neutralized with 0.4 parts of a 20% solution of citric acid in water to a final pH value of 6.5.

(124) The shampoo formulation exhibited no microbiological growth upon incubation at 25+/2 C. for 7, 14 and 28 days after inoculation with 1.0% of a suspension of microorganisms with a titer of 10.sup.4 KBE/ml, comprising Aspergillus niger, and Penicillium funiculosum.

Example 15

(125) A shampoo formulation was prepared as in Example 14 with 5 parts of the unpreserved silicone microemulsion according to Example 2, comprising 20% of Silicone Quaternium-18, 10% of a mixture of nonionic surfactants.

(126) To 95 parts of this shampoo formulation were added

(127) 0.9 parts (0.9%) 2-phenoxyethanol (component a)),

(128) 3.0 parts (3.0%) 2-butyl-2-ethyl-1,3-propanediol (component b)),

(129) 0.1 parts (0.1%) ethylhexyl glycerin (component c)), and

(130) 1.0 parts (1.0%) 1,3-propanediol (component c)) and thoroughly mixed. The final shampoo formulation was neutralized with 0.4 parts of a 20% solution of citric acid in water to a final pH value of 6.5.

(131) The shampoo formulation exhibited no microbiological growth upon incubation at 25+/2 C. for 7, 14 and 28 days after inoculation with 1.0% of the suspension of microorganisms used in Example 14.

Example 16

(132) A shampoo formulation was prepared as in Example 14 with 5 parts of the unpreserved silicone microemulsion according to Example 2, comprising 20% of Silicone Quaternium-18, and 10% of a mixture of nonionic surfactants.

(133) To 95 parts of this shampoo formulation were added

(134) 1.0 parts (1.0%) 3-phenyl-1-propanol (component a)),

(135) 1.5 parts (1.5%) 2-butyl-2-ethyl-1,3-propanediol (component b)),

(136) 1.5 parts (1.5%) 2-methyl-2,4-hexanediol (component b)) and

(137) 1.0 parts (1.0%) 1,3-propanediol (component c)). The final shampoo formulation was neutralized with 0.4 parts of a 20% solution of citric acid in water to a final pH value of 6.5.

(138) The shampoo formulation exhibited minor microbiological growth upon incubation at 25+/2 C. for 7 days but no microbiological growth upon incubation for 14 and 28 days after inoculation with 1.0% of the suspension of microorganisms used in Example 14.

Comparative Example 11

(139) A shampoo formulation was prepared as in Example 14 with 5 g of the unpreserved silicone microemulsion according to Example 2, comprising 20% of Silicone Quaternium-18, 10% of a mixture of nonionic surfactants, and water. To 96.75 parts of this shampoo formulation was added 3.25 parts 2-phenoxyethanol (component a)), but no component b), and thoroughly mixed. The final shampoo formulation was neutralized with 0.4 parts of a 20% solution of citric acid in water to a final pH value of 6.5.

(140) The shampoo formulation exhibited strong to moderate microbiological growth upon incubation at 25+/2 C. for 7 and 14, but no microbiological growth upon incubation for 24 days, after inoculation with 1.0% of the suspension of microorganisms used in Example 14.

Comparative Example 12

(141) A shampoo formulation was prepared as in Example 14 with 5 g of the unpreserved silicone microemulsion according to Example 2, comprising 20% of Silicone Quaternium-18, 10% of a mixture of nonionic surfactants, and water. To 96.7 parts of this shampoo formulation were added

(142) 2.5 parts (2.5%) 2-butyl-2-ethyl-1,3-propanediol component b)),

(143) 0.75 parts (0.75%) 2-methyl-2,4-hexanediol (component b)) and

(144) 0.05 parts (0.05%) 1,3-propanediol (component c)),

(145) but no component (a), and mixed until homogeneous. The final shampoo formulation was neutralized with 0.4 parts of a 20% solution of citric acid in water to a final pH value of 6.5.

(146) The shampoo formulation exhibited strong to moderate microbiological growth upon incubation at 25+/2 C. for 7, 14 and 28 days after inoculation with 1.0% of the suspension of microorganisms used in Example 14.

(147) Tables

(148) TABLE-US-00001 TABLE 1 Example 1 C1 2 C2 C3 3 4 C4 5 C5 C6 Component a) PE 0.9 0.9 3.3 4.3 0.9 0.9 0.9 0.9 PP 1.00 Component b) BEPD 1.5 1.0 4.3 3.3 3.1 2.0 2.0 MPPD 1.0 Component c) EHG 0.6 0.6 2.1 1.1 1.1 1.1 OD 2.0 MPD 0.5 0.5 0.5 PD 0.5 0.5 0.5 Sum a)-c) 3.0 1.5 4.3 4.3 4.3 4.3 5.0 5.0 5.0 3.0 4.1 1 week XX XXX XXX XX 0 X X XXX XXX 2 week 0 XX 0 XX XXX 0 0 XX 0 XX XXX Days to destruction <14 >28 14 28 >42 <14 <7 >24 14 >28 >28 Component additives: PE = 2-phenoxyethanol, PP = 3-phenyl-1-propanol, BEPD = 2-butyl-2-ethyl-1,3-propanediol, DMPD = 2,2-dimethyl-1,3-propanediol, MPPD = 2-methyl-2-propyl-1,3-propanediol, EHG = ethylhexylglycerin, OD, 1,2-octanediol, DD = 1,2-dodecanediol, MPD = 2-methyl-1,3-propanediol, PD = 1,3-propanediol. HG = 2-methyl-2,4-hexanediol 0 = no growth; X = minimal growth (<5 colonies); XX = moderate growth (5-10 colonies); XXX = strong growth (>10 colonies)

(149) TABLE-US-00002 TABLE 2 Example 6 7 8 9 C7 C8 C9 C10 10 Component a) PE 0.9 0.9 0.9 2.0 2.5 0.9 0.9 0.9 PP Component b) BEPD 3.1 2 1.6 2.5 3.0 DMPD 1.0 HG 0.50 Component c) EHG 1.1 1.1 1.75 0.6 OD 2.35 PD 0.5 Sum a)-c) 5.0 4.0 2.5 2.5 2.5 2.5 2.0 5.0 5.0 1 week 0 XX XX XX XXX XXX XXX 0 2 week 0 X X 0 XX XXX XXX XXX 0 Days to <7 24 36 14 24 >24 >36 36 <7 destruction

(150) TABLE-US-00003 TABLE 3 Example 11 12 13 Component a) PE 0.9 0.9 0.9 PP Component b) BEPD 1.0 DMPD 1.5 MPPD 1.5 HG 3 Component c) EHG 0.6 0.6 0.1 PD 0.5 0.5 Sum a)-c) 5.0 5.0 2.0 1 week 0 2 week 0 0 0 Days to destruction <7 <14 <14

(151) TABLE-US-00004 TABLE 4 Example 14 15 16 C11 C12 Component a) PE 0.9 3.25 PP 1.0 1.0 Component b) BEPD 2.0 3.0 1.5 2.5 HG 1.5 0.75 Component c) EHG 0.1 PD 1.0 1.0 0.05 Sum a)-c) 3.0 5.0 5.0 3.25 3.3 1 week 0 0 X XXX XXX 2 week 0 0 0 XX XXX Days to distruction <7 <7 14 24 >24