Storage-stable microbicidal concentrates and use thereof as preservatives

Abstract

A chemical preservative including phenoxyethanol, 2-butyl-1,2-benzisothiazolin-3-one and N,N-bis(3-aminopropyl) dodecylamine; its use to inhibit and/or to control the growth of microorganisms in a technical composition.

Claims

1. A chemical preservative comprising: a) phenoxyethanol, b) 2-butyl-1,2-benzisothiazolin-3-one, and c) N,N-bis(3-aminopropyl) dodecylamine, wherein the weight ratio of compound b) to compound a) (b/a) is greater than or equal to (>) 10.sup.−3 and less than or equal to 10.sup.−1, and the weight ratio of compound c) to compound a) (c/a) is greater than or equal to 5×10.sup.−4 and less than or equal to 6×10.sup.−2.

2. The chemical preservative according to claim 1, in which the concentration of component a) expressed in percentage by weight of the chemical preservative, is from 93.5% to 99.4%.

3. The chemical preservative according to claim 2, in which the concentration of component b) expressed in percentage by weight of the chemical preservative, is from 0.5% to 5%.

4. The chemical preservative according to claim 3, in which the concentration of component c), expressed in percentage by weight of the chemical preservative, is from 0.1% to 1.5%.

5. The chemical preservative according to claim 2, in which the concentration of component a) expressed in percentage by weight of the chemical preservative, is from 97.75% to 99%.

6. The chemical preservative according to claim 5, in which the concentration of component b) expressed in percentage by weight of the chemical preservative, is from 0.75% to 1.25%.

7. The chemical preservative according to claim 6, in which the concentration of component c), expressed in percentage by weight of the chemical preservative, is from 0.25% to 1.0%.

8. The chemical preservative according to claim 1, in which the weight ratio (b/a) is superior or equal to 5×10.sup.−3 and less than or equal to 5×10.sup.−2 and the weight ratio (c/a) is superior or equal to 10.sup.−3 and less than or equal to 10.sup.−2.

9. The chemical preservative according to claim 8, in which the weight ratio (b/a) is superior or equal to 8×10.sup.−3 and less than or equal to 1.5×10.sup.−2 and the weight ratio (c/a) is superior or equal to 2.5×10.sup.−3 and less than or equal to 5×10.sup.−3.

10. The chemical preservative according to claim 5, in which the concentration of component b) expressed in percentage by weight of the chemical preservative is from 0.75% to 1.25%, and the concentration of component c) expressed in percentage by weight of the chemical preservative is from 0.25% to 0.7%.

11. A process to inhibit and/or to control the growth of microorganisms in a water-based composition, which comprises successive additions in said water-based composition of: a) phenoxyethanol, b) 2-butyl-1,2-benzisothiazolin-3-one, and c) N,N-bis(3-aminopropyl) dodecylamine, wherein the weight ratio of compound b) compound a) (b/a) is greater than or equal to (>) 10.sup.−3 and less than or equal to 10.sup.−1, and the weight ratio of compound c) to compound a) (c/a) is greater than or equal to 5×10.sup.−4 and less than or equal to 6×10.sup.−2, in order that said water-based composition finally contains for 100% of a weight of the water-based composition from 0.01% to 2.00% by weight of the chemical preservative according to claim 1.

12. A process to inhibit and/or to control the growth of microorganisms in a water-based composition, which comprises adding the chemical preservative according to claim 1, in order that said water-based composition finally contains for 100% of a weight of the water-based composition from 0.01% to 2.00% by weight of said chemical preservative.

13. The process according to claim 11, in which said water-based composition is a water-based product chosen from a polymer dispersions, a paint, plasters, an adhesive, a sealing composition, a paper coating composition, a textile softening, a sizing composition, a washing raw material, a cleaning and domestic product, a surfactant, a polishing composition, a spinning bath, a cooling lubricant, a leather treatment composition, a silicone and bitumen emulsion or a concrete admixture.

14. The chemical preservative according to claim 2, in which the weight ratio (b/a) is superior or equal to 5×10.sup.−3 and less than or equal to 5×10.sup.−2 and the weight ratio (c/a) is superior or equal to 10.sup.−3 and less than or equal to 10.sup.−2.

15. The chemical preservative according to claim 3, in which the weight ratio (b/a) is superior or equal to 5×10.sup.−3 and less than or equal to 5×10.sup.−2 and the weight ratio (c/a) is superior or equal to 10.sup.−3 and less than or equal to 10.sup.−2.

16. The chemical preservative according to claim 4, in which the weight ratio (b/a) is superior or equal to 5×10.sup.−3 and less than or equal to 5×10.sup.−2 and the weight ratio (c/a) is superior or equal to 10.sup.−3 and less than or equal to 10.sup.−2.

17. The chemical preservative according to claim 5, in which the weight ratio (b/a) is superior or equal to 5×10.sup.−3 and less than or equal to 5×10.sup.−2 and the weight ratio (c/a) is superior or equal to 10.sup.−3 and less than or equal to 10.sup.−2.

18. The chemical preservative according to claim 6, in which the weight ratio (b/a) is superior or equal to 5×10.sup.−3 and less than or equal to 5×10.sup.−2 and the weight ratio (c/a) is superior or equal to 10.sup.−3 and less than or equal to 10.sup.−2.

19. The chemical preservative according to claim 7, in which the weight ratio (b/a) is superior or equal to 5×10.sup.−3 and less than or equal to 5×10.sup.−2 and the weight ratio (c/a) is superior or equal to 10.sup.−3 and less than or equal to 10.sup.−2.

20. A process to inhibit and/or to control the growth of microorganisms in a water-based composition, which comprises successive additions in said water-based composition of: a) phenoxyethanol, b) 2-butyl-1,2-benzisothiazolin-3-one, and c) N,N-bis(3-aminopropyl) dodecylamine, wherein the weight ratio of compound b) to compound a) (b/a) is greater than or equal to (>) 10.sup.−3 and less than or equal to 10.sup.−1, and the weight ratio of compound c) to compound a) (c/a) is greater than or equal to 5×10.sup.−4 and less than or equal to 6×10.sup.−2, in order that said water-based composition finally contains for 100% of a weight of the water-based composition from 0.01% to 2.00% by weight of the chemical preservative according to claim 2.

Description

(1) Therefore, the invention relates to a chemical preservative comprising: a)—phenoxyethanol, b)—N-butyl 1,2-benzisothiazolin-3-one and c)—N,N-bis(3-aminopropyl) dodecylamine,
in which the weight ratio compound b) on compound a) (b/a) is superior or equal to (≥) 10.sup.−3 and less than or equal to (≤) 10.sup.−1, and the weight ratio compound c) on compound a) (c/a) is greater than or equal to 5×10.sup.−4 and less than or equal to 6×10.sup.−2.

(2) The concentration of component a) in the chemical preservative as hereinbefore defined, expressed in percentage by weight of the composition, is generally from 85% to 99.85%, preferably from 93.5% to 99.4%, more preferably from 97.75% to 99%.

(3) The concentration of component b) in the chemical preservative as hereinbefore defined, expressed in percentage by weight of the composition, is generally from 0.1% to 10%, preferably from 0.5% to 5%, more preferably from 0.75% to 1.25%.

(4) The concentration of component c) in the chemical preservative as hereinbefore defined, expressed in percentage by weight of the composition, is generally from 0.05% to 5%, preferably from 0.1% to 1.5%, more preferably from 0.25% to 1.0%.

(5) In the chemical preservative as hereinbefore defined, the weight ratio (b/a) is particularly superior or equal to 5×10.sup.−3 and less than or equal to 5×10.sup.−2 and the weight ratio (c/a) is particularly greater than or equal to 10.sup.−3 and less than or equal to 10.sup.−2; according to a more particular embodiment, the weight ratio (b/a) is greater than or equal to 8×10.sup.−3 and less than or equal to 1.5×10.sup.−2 and the weight ratio (c/a) is greater than or equal to 2.5×10.sup.−3 and less than or equal to 5×10.sup.−3.

(6) According to a particular embodiment, the chemical preservative as hereinbefore defined also comprises: d) At least one solvent such as water, glycols, such as ethylene glycol, propyleneglycol, dipropyleneglycol, butanediols, glycol ethers, such as butyl glycol, butyl diglycol, polyols, such as glycerol, alkanediols and alkyl glycerol ethers, or a mixture thereof.

(7) According to another particular embodiment, the chemical preservative as hereinbefore defined, also comprises: e) At least one additive such as a complexing agent, for example EDTA or NTA, a stabilizer, for example vitamin E, BHA or BHT, a corrosion inhibitor, for example benzotriazole or a mixture thereof.

(8) According to another particular embodiment, the chemical preservative as hereinbefore defined, also comprises: f) At least one or more auxiliary, such as a surfactant, for example a wetting agent, a defoamer or a mixture thereof.

(9) If the chemical preservative according to the invention comprises one more component d), e) and/or f), the total proportion of these components, expressed in percentage by weight of the composition, is less than 40% by weight, such as for example less than 10% by weight.

(10) According to a more particular aspect, the chemical preservative as hereinbefore defined comprises at least a component d) and at least one component e).

(11) According to another more particular aspect, the chemical preservative as hereinbefore defined comprises at least a component d) and at least one component f).

(12) According to another more particular aspect, the chemical preservative as hereinbefore defined comprises at least a component e) and at least one component f).

(13) According to the very specific aspect, the chemical preservative as hereinbefore defined comprises at least a component d), at least one component e) and at least one component f).

(14) According to a preferable embodiment, the invention as hereinbefore defined, consists in components a) b) and c) and are free from components d), e) and f).

(15) The chemical preservative as hereinbefore defined is preferably a clear and homogeneous composition and is preferably a liquid composition. It is adequately colour-stable, low-temperature-stable, storage-stable and active-ingredient-stable. Alternatively, it can also be a form of a low-viscosity to medium-viscosity composition which can flow or in the form of a semisolid, pasty composition.

(16) The invention more particularly relates to a chemical preservative according to claim 5, comprising, as active ingredients:

(17) a)—From 97.75% by weight to 99% by weight of phenoxyethanol,

(18) b)—From 0.75% by weight to 1.25% by weight of N-butylbenzisothiazolin-3-one and

(19) c)—From 0.25% by weight to 1.0% by weight of N,N-bis(3-aminopropyl) dodecylamine.

(20) The invention also relates to a process to inhibit and/or to control the growth of microorganisms in a technical composition, which comprises successive additions in said technical composition of efficient proportions of:

(21) a)—phenoxyethanol,

(22) b)—N-butyl 1,2-benzisothiazolin-3-one and

(23) c)—N,N-bis(3-aminopropyl) dodecylamine,

(24) in such quantities that the weight ratio compound b) on compound a) (b/a) is superior or equal to (≥) 10.sup.−3 and less than or equal to 10.sup.−1, and the weight ratio compound c) on compound a) (c/a) is greater than or equal to 5×10.sup.−4 and less than or equal to 6×10.sup.−2, and in order that said technical composition finally contains for 100% of its weight, from 0.01% to 2.00% by weight of the chemical preservative as hereinbefore defined.

(25) The invention also relates to a process to inhibit and/or to control the growth of microorganisms in a technical composition, which comprises adding the chemical preservative as hereinbefore defined, in order that said technical composition finally contains for 100% of its weight, from 0.01% to 2.00% by weight of said chemical preservative.

(26) In the context of the invention a technical composition, generally means a water-based product such as a polymer dispersion, a paint, plasters, an adhesive, a sealing composition, a paper coating composition, a textile softening, a sizing composition, a washing raw material, a cleaning product, a domestic product, a surfactant, a polishing composition, a spinning bath, a cooling lubricant, a leather treatment composition, a silicone and bitumen emulsion or a concrete admixture.

(27) In the context of the invention microorganisms generally mean, bacteria, yeast, moulds and fungi.

(28) The invention also relates to the use of the chemical preservative as hereinbefore defined, to inhibit and/or to control the growth of microorganisms in a technical composition, and more particularly in a water-containing, water-dilutable or water dispersible technical composition or domestic products.

(29) Experimental Part

(30) Preparation of a Preservative According to the Invention (Composition 1)

(31) A chemical preservative according to the invention was prepared by mixing its components together.

(32) A clear, homogeneous, slightly yellowish, preparation is obtained, containing for 100% of its weight, 98.5% by weight of phenoxyethanol, 1.0% by weight of N-butylbenzisothiazolin-3-one and 0.5% by weight of N, N-bis(3-aminopropyl) dodecylamine (91% of active ingredient).

(33) Germ Count Reduction Test

(34) Dilutions of the samples are prepared with sterile tap water. 25 ml portions of the end solutions are inoculated with 0.1 ml microorganism suspension (initial microorganism count approx. 10.sup.7 cfu/ml) and stirred.

(35) TABLE-US-00001 Test organisms ATCC/DSM-No. Aspergillus brasiliensis 16404 Staphylococcus aureus 6538

(36) For the reduction test with Staphylococcus aureus the solutions are streaked out onto tryptone soya agar after 2,5,10 and 60 minutes.

(37) For testing the reduction with Aspergillus brasiliensis the solutions are streaked out onto Sabouraud-dextrose 4% agar after 1, 3, 6 and 24 hours.

(38) The cultures are incubated for 48 hours at 37° C., except for Aspergillus brasiliensis, which is incubated for 72 hours at 25-27° C. The evaluation is made on the basis of semi-quantitative assessment of the microbial growth of the streaks.

(39) TABLE-US-00002 Symbol Finding Germ count/ml − = no growth <100 + = slight growth approx. 10.sup.2 ++ = moderate growth approx. 10.sup.3 +++ = heavy growth approx. 10.sup.4 ++++ = massive growth approx. 10.sup.5 C = surface covered approx. 10.sup.6

(40) Results

(41) Aspergillus brasiliensis Germ Count Reduction Test

(42) TABLE-US-00003 Contact time [h] Use-concentration [%] 1 3 6 24 Sterile hard water according to EN 14348 C C C C +0.50% Composition 1 ++ + − − +0.0025% N,N bis(3-aminopropyl)- C C ++++ ++++ dodecylamine +0.0050% 2-butyl-1,2-benzisothiazolin-3-one ++++ ++++ ++++ ++++ +0.50% phenoxyethanol C C C C 0.50% phenoxyethanol + 0.0025% C C C C bis(3-aminopropyl)-dodecylamine +0.50% phenoxyethanol + 0.0050% 2-butyl- +++ +++ +++ ++ 1,2-benzisothiazolin-3-one +0.0025% N,N-bis(3-aminopropyl)- ++++ ++++ ++++ ++++ dodecylamine + 0.0050% 2-butyl-1,2- benzisothiazolin-3-one
Staphylococcus aureus Germ Count Reduction Test

(43) TABLE-US-00004 Contact time [min] Use-concentration [%] 2 5 10 60 Sterile hard water according to EN 14348 ++++ ++++ ++++ ++++ +0.50% Composition 1 − − − − +0.0025% Bis-(3-Aminopropyl)-dodecylamine +++ ++ ++ − +0.0050% 2-Butyl-1,2-benzisothiazolin-3-one ++++ ++++ ++++ +++ +0.50% Phenoxyethanol ++++ ++++ ++++ ++++ +0.50% Phenoxyethanol + 0.0025% Bis-(3- ++ + − − Aminopropyl)-dodecylamine +0.50% Phenoxyethanol + 0.0050% 2-Butyl- +++ +++ +++ +++ 1,2-benzisothiazolin-3-one +0.0025% Bis-(3-Aminopropyl)- +++ ++ + − dodecylamine + 0.0050% 2-Butyl-1,2- benzisothiazolin-3-one
These results show that the components of the composition 1 according to the invention, exhibit a synergistic effect against the tested germs. Such a synergy was not deductible from the prior art.