Laundry detergent

Abstract

A biocidal composition is provided, which comprise a mixture of the biocides Poly-(hexamethylene-guanidium chloride) and N,N-didecyl-N-methyl-poly(oxyethyl) ammonium propionate, which biocides have a synergistic biocidal effect against bacteria and fungi. Specifically, the provided composition can be as disinfectants and general biocidal products; preservatives; pest control; control; preservatives for food or feedstocks; antifouling products; embalming and taxidermist fluids; and control of other vertebrates; vermin control on domestic animals, livestock or pets; alga control; and products for use in spas or swimming pools.

Claims

1. A composition comprising a mixture of the biocides Poly-(hexamethylene-guanidium chloride) and N,N-didecyl-N-methyl-poly(oxyethyl) ammonium propionate, said biocides having synergistic effect in regard to the total biocidal activity, wherein said composition does not comprise a surfactant.

2. A detergent composition comprising a mixture of the biocides Poly-(hexamethylene-guanidium chloride) and N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate, said biocides having synergistic effect in regard to the total biocidal activity and one or more surfactants selected from the group consisting of non-ionic surfactants and monovalent cationic surfactants, wherein said one or more surfactants are of the general formula (I):
R(OCH.sub.2CH.sub.2)xOH wherein i) R is C.sub.7-20-alkyl whereby the alkyl is of 7-20 carbon atoms; wherein R is optionally substituted with: a) one or more substituents selected from the group consisting of alkyl, C.sub.3-8-cycloalkyl, C.sub.3-8-cycloalkyl-C.sub.1-6-alkyl, C.sub.1-6-alkyl-C.sub.3-8-cycloalkyl, aryl-C.sub.1-6-alkyl, C.sub.1-6-alkyl-aryl, C.sub.1-6-alkyl-oxy, C.sub.3-8-cycloalkyl-oxy, C.sub.3-8-cycloalkyl-C.sub.1-6-alkyl-oxy, C.sub.3-8-cycloalkyl-oxy-C.sub.1-6-alkyl, C.sub.1-6-alkyl-oxy-C.sub.3-8-cycloalkyl, C.sub.1-6-alkyl-C.sub.3-8-cycloalkyl-oxy, aryl-C.sub.1-6-alkyl-oxy, and aryl; or b) one or two groups selected from the group consisting of —C.sub.7-20-alkyl(OCH.sub.2CH.sub.2).sub.yOH and —C.sub.7-20-alkyl-(OCH.sub.2CH.sub.2).sub.zOH; wherein each of y and z is an integer selected from 2-12; whereby the polyethyleneglycol comprises 2-12 repetitions of OCH.sub.2CH.sub.2; and ii) x is an integer selected from 2-12, whereby the polyethyleneglycol comprises 2-12 repetitions of OCH.sub.2CH.sub.2; and iii) with the proviso that when R is C.sub.18-alkyl then y is not greater than x; and z is not greater than x; and the surfactant may not comprise an alkoxylated moiety that comprises higher alkoxides than the ethylene oxides.

3. The composition according to claim 2, which further comprises i) one or more liquid carriers; and ii) one or more chelating agents.

4. The composition according to claim 2, wherein x is 4-8.

5. The composition according to claim 2, wherein R is C.sub.12-14-alkyl.

6. The composition according to claim 2, wherein at least 80% by weight of R is C.sub.12-alkyl, C.sub.13-alkyl or C.sub.14-alkyl or mixtures thereof.

7. The composition according to claim 2, said composition comprising a surfactant of formula (I) wherein R is substituted with one or more substituents selected from the group consisting of C.sub.1-6-alkenyl, C.sub.1-6-alkynyl, C.sub.3-8-cycloalkenyl, C.sub.3-8-cycloalkenyl-C.sub.1-6-alkenyl, C.sub.3-8-scycloalkenyl-C.sub.1-6-alkynyl, C.sub.1-6-alkenyl-C.sub.3-8-cycloalkenyl, C.sub.1-6-alkynyl-C.sub.3-8-cycloalkenyl, aryl-C.sub.1-6-alkenyl, aryl-C.sub.1-6-alkynyl, C.sub.1-6-alk enyl-aryl, C.sub.1-6-alkynyl-aryl, C.sub.1-6-alkenyl-oxy, C.sub.1-6-alkynyl-oxy, C.sub.3-8-cycloalkenyl-oxy, C.sub.3-8-cycloalkenyl-C.sub.1-6-alkenyl-oxy, C.sub.3-8-scycloalkenyl-C.sub.1-6-alkynyl-oxy, C3-s-cycloalkenyl-oxy-C.sub.1-6-alkenyl, C.sub.3-8-cycloalkenyloxy-C.sub.1-6-alkynyl, C.sub.1-6-alkenyl-oxy-C.sub.3-8-cycloalkenyl, C.sub.1-6-alkynyl-oxy-C.sub.3-8-cycloalkenyl, C.sub.1-6-alkenyl-C.sub.3-8-cycloalkenyl-oxy, C.sub.1-6-alkynyl-C.sub.3-8-cycloalkenyl-oxy, aryl-C.sub.1-6-alkenyloxy, aryl-C.sub.1-6-alkenyl-oxy, aryl-oxy-C.sub.1-6-alkenyl, aryl-oxy-C.sub.1-6-alkynyl and aryl.

8. The composition according to claim 2, said composition comprising a surfactant of formula (I) wherein R is substituted with one or two groups selected from —C.sub.7-20-alkyl-(OCH.sub.2CH.sub.2).sub.yOH and —C.sub.7-20-alkyl-(OCH.sub.2CH.sub.2).sub.zOH.

9. The composition according to claim 2, said composition comprising a surfactant of formula (I) wherein R is not substituted.

10. The composition according claim 2, wherein the one or more surfactants are selected from the group consisting of nonionic surfactants.

11. The composition according to claim 2, wherein the one or more surfactants are selected from the group consisting of a C.sub.12-14 alcohol polyethylene glycol ether mixture.

12. The composition according to claim 2, said composition comprising only one surfactant which is selected from the group consisting of a C.sub.12-14 alcohol polyethylene glycol ether mixture.

13. The composition according to claim 2, said composition comprising only one surfactant which is selected from the group consisting of iso-C.sub.12-14 alcohol ethoxylates and combinations thereof.

14. The composition according to claim 2, which is characterized in that CMC(biocid)>MIC(biocid).

15. The composition according to claim 2, which is characterized in that CMC(detergent)>MIC(biocid).

16. The composition according to claim 1, said composition comprising one or more liquid carriers selected from the group consisting of water, ethanol, glycerol, propylene glycol, glycerin, and combinations thereof.

17. The composition according to claim 1, said composition comprising one or more liquid carriers selected from propylene glycol and water and mixtures thereof.

18. The composition according to claim 1, said composition comprising one or more chelating agents selected from the group consisting of amino-tri(methylene) phophonic acid sodium salt (ATMP), methylglycinediacetic acid, potassium tripolyphosphate, and combinations thereof.

19. The composition according to claim 2, wherein the composition is suitable for washing at low temperatures in a range of 5° C. to 40° C.

20. The composition according claim 2, wherein the composition is a delicate laundry detergent composition.

21. The composition according to claim 2, wherein the composition is for washing of clothing or textiles considered to be a source of infection.

22. The composition according to claim 2, wherein the composition does not comprise enzymes.

23. The composition according to claim 2, which is a liquid laundry detergent.

24. The composition according to claim 1, for use as: a) disinfectants and general biocidal products; b) preservatives; c) pest control; d) preservatives for food or feedstocks; e) antifouling products; f) embalming and taxidermist fluids; and control of other vertebrates g) vermin control on domestic animals, livestock or pets h) alga control; or i) products for use in spas or swimming pools.

25. The composition according to claim 2, said composition comprising only one surfactant which is selected from the group consisting of a mixture of fatty alcohols with 9 mol ethylene oxide and fatty alcohols with 3 mol ethylene oxide.

26. The composition according claim 10, wherein the one or more surfactants are alkoxylated nonionic surfactants.

27. The composition according to claim 11, wherein the one or more surfactants are selected from the group consisting of a mixture of fatty alcohols with 9 mol ethylene oxide, fatty alcohols with 3 mol ethylene oxide, and iso-C13 alcohol ethoxylate, and combinations thereof.

28. The composition according to claim 12, wherein the mixture is a mixture of fatty alcohols with 9 mol ethylene oxide and fatty alcohols with 3 mol ethylene oxide.

29. The composition according to claim 13, said composition comprising the surfactant is iso-C13 alcohol ethoxylate.

30. A composition comprising a mixture of the biocides Poly-(hexamethylene-guanidium chloride) and N, N-didecyl-N-methyl-poly(oxyethyl) ammonium propionate, said biocides having synergistic effect in regard to the total biocidal activity.

31. The composition according to claim 30, said composition comprising one or more liquid carriers selected from the group consisting of water, ethanol, glycerol, propylene glycol, glycerin, and combinations thereof.

32. The composition according to claim 30, said composition comprising one or more liquid carriers selected from propylene glycol and water and mixtures thereof.

33. The composition according to claim 30, said composition comprising one or more chelating agents selected from the group consisting of amino-tri(methylene) phophonic acid sodium salt (ATM)), methylglycinediacetic acid, potassium tripolyphosphate, and combinations thereof.

34. The composition according to claim 30, for use as: a) disinfectants and general biocidal products; b) preservatives; c) pest control; d) preservatives for food or feedstocks; e) antifouling products; f) embalming and taxidermist fluids; and control of other vertebrates g) vermin control on domestic animals, livestock or pets h) alga control; or i) products for use in spas or swimming pools.

Description

FIGURES

(1) FIGS. 1 and 2 display the CMC absorption data obtained for diluted Detergent A (table 8a)

(2) FIGS. 3 and 4 display the CMC absorption data obtained for diluted Detergent B (table 8c)

(3) FIGS. 5 and 6 display the CMC absorption data obtained for diluted Akacid Forte

EXAMPLES

(4) The following non-limiting examples are illustrative of the present invention. Percentages are by weight unless otherwise specified.

Example 1

Delicate Liquid Laundry Detergent for Wool and Fine Textiles

(5) The below table provides a detergent composition to be combined with one or more biocides as described herein. This particular detergent composition is preferably for washing wool, and may be used for other fine textiles.

(6) TABLE-US-00001 Ingredient Amount (% by weight) Marlipal 24/939 25.0%  Mackadet 40K 5.0% Sodium Citrate 10.0%  Masquol P320 Na 4-5% Alcoperse 240 1-2% Alcoperse 747 1-2% Lanolin, PEG-75/50 LV   2% MGP, Glycerol 7.5% Ethanol 2.5% Water Up to 100%

Example 2

Delicate Liquid Laundry Detergent for Silk and Fine Textiles

(7) The below table provides a detergent composition to be combined with one or more biocides as described herein. This particular detergent composition is preferably for washing silk, and may be used for other fine textiles.

(8) TABLE-US-00002 Ingredient Amount (% by weight) Daclor 70-1-23 10.3%  Stepanol WA-extra E 16.7%  Mackadet 40K 1.0% Marlipal 24/939 3.4% Cosmacol ESI 0.5% Integra 44 0.3% opacifier q.s. Perfume q.s. Water Up to 100%

Example 3

Liquid Laundry for Textiles

(9) The below table provides a detergent composition to be combined with one or more biocides as described herein. This particular detergent composition is for washing textiles in general and may be used for fine textiles.

(10) TABLE-US-00003 Ingredient Amount (% by weight) Soft soap 10-20%  Sodium lauryl sulphate 5-10% Triton M (MGDA) 0.5-2.0%  Potassium tripolyphosphate 5-10% Lutensol TO 89 5-10% Plurafac LF300  1-3% Glycerine  1-3% Perfume and colour q.s. Water 60-65% 

Example 4

Assay for Biocidal Effect

(11) The one or more biocides are assayed for in vitro biocidal effect. There may either be assayed one biocide alone or two or more biocides in combination. Five different concentrations of the one or more biocides may be assayed at e.g. two different temperatures in the range of 20-40° C. The exposure time of biocide to microorganism may be selected to represent the desired washing process for the laundry detergent composition in question. For example 1 hour for a delicate laundry detergent suitable for wool or silk wash, or 2 hours for a laundry detergent suitable for heavy-duty wash of e.g. hospital textiles.

(12) The one or more biocide may be assayed against the following microorganisms: Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Candida albicans. Escherichia coli have been chosen in order to represent a gram negative faecal bacteria; Staphylococcus aureus have been chosen in order to represent a gram positive, heat tolerant bacteria; Pseudomonas aeruginosa have been chosen in order to represent a disease causing bacteria that in some cases are difficult to treat; and Candida albicans represent the presence of fungi.

(13) The reduction in the different microorganisms is quantified. This assay may be used to determine the biocidal effect of one specific biocide, or a combination of biocides. The later determining whether a synergistically effect is obtained.

Example 4A

Biocidal Effect

Dosage Response

(14) The assay is based on the requirements to chemical disinfectants and antiseptic agent with regard to a reduction in fungus and bacteria of 4 and 5 log units respectively. These requirements are stated in DS/EN 1276:1997 and DS/EN 1275:2005, respectively.

(15) Microorganisms and Stock Cultures

(16) The following microorganisms were chosen for this dosage response assays: Staphylococcus aureus, ATCC 6538, representing grampositive bacteria; Escherichia coli, ATCC 11229, representing gramnegative bacteria; and Candida albicans, ATCC 2091, representing yeast fungi.

(17) The bacterial cultures were cultivated in the growth medium TSB (Tryptic Soy Bouillon) for 24 h at 37° C. before use. Colony forming units (CFU) were determined by plating Tryptic Soy Agar (TSA).

(18) Candida albicans was cultivated on malt extract agar (MEA) for 24 h at 37° C. before use. Then the yeast cells were harvested in 0.9% saline by use of a drigalski spatula. CFU were determined by plating on MEA.

(19) The above described cultures are termed the stock cultures.

(20) Biocides

(21) The biocides and concentrations assayed can be seen in Table 1.

(22) TABLE-US-00004 TABLE 1 Test concentrations of biocides Test concentrations** Biocide 700 ppm 200 ppm 160 ppm 120 ppm 80 ppm 40 ppm (% active) active active active active active active Akacid (25%) 2800 ppm 800 ppm 640 ppm 480 ppm 320 ppm 160 ppm CAS 37457-91-5 Akacid Forte (25%) 2800 ppm 800 ppm 640 ppm 480 ppm 320 ppm 160 ppm CAS 57028-96-3 Akacid Plus * (25%) 2800 ppm 800 ppm 640 ppm 480 ppm 320 ppm 160 ppm CAS 37457-91-5 CAS 57028-96-3 Lonzabac BG (20%) 3500 ppm 1000 ppm  800 ppm 600 ppm 400 ppm 200 ppm CAS 27083-27-8 Bardap-26 (70%) 1000 ppm 286 ppm 229 ppm 171 ppm 114 ppm  57 ppm CAS 94667-33-1 Barquat PQ-2 (50%) 1400 ppm 400 ppm 320 ppm 240 ppm 160 ppm  80 ppm CAS 25988-97-0 * Akacid Plus is a mixture of Akacid and Akacid Forte in a 1:1 ratio. **The test solutions were prepared in aqueous solutions in a concentration corresponding to 10 times the desired. (ppm = mg per kg/liter)
Exposure to Biocide

(23) The exposure to biocide was performed at pH 6-6.5, which was obtained by addition of 100 mM potassium phosphate buffer. To test tubes with 8 mL sterile 100 mM phosphate buffer were added 1 mL test solution (i.e. biocide solution) and 1 mL stock culture. After thorough mixing the assay mixtures were exposed to heating in water bath at 30° C. for 9 minutes. After exposure the test tubes were immediately removed from the water bath and the surviving microorganisms were determined by plating.

(24) Reference samples were prepared by adding 1 mL sterile water instead of 1 mL test solution.

(25) Plating on Agar

(26) From appropriate dilutions of starting material (mixture of biocide solution, stock culture and buffer) was taken 0.1 mL onto agar plates, and the material was spread with Drigalski spatulas. The plates were incubated at 37° C. 1 day for bacteria and 2 days for yeast.

(27) For determining CFU of the bacteria after exposure, with and without biocide, was used incubation on TSA for 24 h at 37° C. For determining CFU of Candida albicans before and after exposure was used incubation on MEA for 48 h at 37° C.

(28) Where a large reduction in organisms was expected (test concentrations of 700 and 200 ppm) 1 mL and 0.1 mL solution, respectively, were mixed with 100 ml sterile water and filtered through a 47 mm Millipore EZ-Pak® membrane filter, mesh 0.22 μm. The filter was rinsed with 100 mL sterile water, and thereafter placed directly on the agar plate. The mixing in water and subsequent rinsing ensures that the biocide is heavily diluted and thus will not have any effect after plating. For dilutions of 100× and more, regular plating were used, as the biocide at these concentrations is considered to not provide any further reduction in the microorganisms during plating on agar.

(29) Plates with between 20 and 500 CFU were chosen for counting. Number of CFU (colony forming units) per g or mL sample was calculated by multiplying the number of colonies per plate with the dilution and further by 10, as only 0.1 mL was used on each plate.

(30) After incubation, CFU was determined and reduction in organisms was calculated. All tests were performed in triplicate.

(31) Results

(32) In relation to E. Coli, see Table 2, especially Bardap-26 and Akacid Forte showed a good effect. The counting gave a reduction in organisms of >10.sup.7 for Bardap in a concentration of 160 ppm. The effect was smaller for Akacid Forte where the reduction in organisms only was >10.sup.5. The remaining biocides showed no or limited effect.

(33) Barquat PC-2 showed no effect, and may be used as a negative control. These findings show the importance of choosing the appropriate biocide for the intended microorganism.

(34) TABLE-US-00005 TABLE 2 Reduction obtained in E. coli Test concentrations** 700 ppm 200 ppm 160 ppm 120 ppm 80 ppm 40 ppm Biocide active active active active active active (% active) C1 C2 C3 C4 C5 C6 Akacid (25%) ~10.sup.6 10.sup.2-10.sup.3 No reduction CAS 37457-91-5 Akacid Forte (25%) >10.sup.7 ~10.sup.5 ~10.sup.5 ~10.sup.3 10.sup.2-10.sup.3 No CAS 57028-96-3 reduction Akacid Plus * (25%) >10.sup.7 10.sup.3-10.sup.4 10.sup.2-10.sup.3 No reduction CAS 37457-91-5 CAS 57028-96-3 Lonzabac BG (20%) >10.sup.7 10.sup.3-10.sup.4 10.sup.2-10.sup.3 No reduction CAS 27083-27-8 Bardap-26 (70%) >10.sup.7 >10.sup.7 >10.sup.7 10.sup.4-10.sup.5 ~10.sup.4 ~10.sup.4 CAS 94667-33-1 Barquat PQ-2 (50%) No reduction CAS 25988-97-0 * Akacid Plus is a mixture of Akacid and Akacid Forte in a 1:1 ratio. **The test solutions were prepared in aqueous solutions in a concentration corresponding to 10 times the desired. (ppm = mg per kg/liter)

(35) In relation to Staphylococcus Aureus, see Table 3, especially Bardap-26 at 160 ppm and in part Akacid Forte showed a good effect, while the remaining biocides showed no or very limited effect. Bardap-26 reduced Staphylococcus Aureus by >10.sup.7 at 160 ppm. Akacid Forte reduced by >10.sup.4. Barquat PQ-2 showed no effect, and may be used as a negative control. These findings again show the importance of choosing the appropriate biocide for the intended microorganism.

(36) TABLE-US-00006 TABLE 3 Reduction obtained in Staphylococcus Aureus Test concentrations** 700 ppm 200 ppm 160 ppm 120 ppm 80 ppm 40 ppm Biocide active active active active active active (% active) C1 C2 C3 C4 C5 C6 Akacid (25%) >10.sup.8 <10.sup.5 <10.sup.5 ~10 No reduction CAS 37457-91-5 Akacid Forte (25%) >10.sup.6 10.sup.5-10.sup.4 ~10.sup.4 No reduction CAS 57028-96-3 Akacid Plus * (25%) >10.sup.7 ~10.sup.2 No reduction CAS 37457-91-5 CAS 57028-96-3 Lonzabac BG (20%) >10.sup.7 10.sup.5-10.sup.4 10.sup.5-10.sup.4 10.sup.2-10.sup.3 10.sup.2-10.sup.3 ~10.sup.  CAS 27083-27-8 Bardap-26 (70%) >10.sup.7 >10.sup.7 >10.sup.7 10.sup.2-10.sup.3 10.sup.2-10.sup.3 ~10.sup.2 CAS 94667-33-1 Barquat PQ-2 (50%) <10.sup.5 No reduction CAS 25988-97-0 * Akacid Plus is a mixture of Akacid and Akacid Forte in a 1:1 ratio. **The test solutions were prepared in aqueous solutions in a concentration corresponding to 10 times the desired. (ppm = mg per kg/liter)

(37) In relation to Candida Albicans, see Table 4, especially Bardap-26 showed a good effect, while the remaining biocides showed no or very limited effect. Bardap-26 reduced Candida Albicans by 10.sup.4. Barquat PQ-2 showed no effect, and may be used as a negative control. These findings again show the importance of choosing the appropriate biocide for the intended microorganism.

(38) TABLE-US-00007 TABLE 4 Reduction obtained in Candida Albicans Test concentrations** 700 ppm 200 ppm 160 ppm 120 ppm 80 ppm 40 ppm Biocide active active active active active active (% active) C1 C2 C3 C4 C5 C6 Akacid (25%) ~10.sup.4 ~10 No reduction CAS 37457-91-5 Akacid Forte (25%) ~10.sup.4 No reduction CAS 57028-96-3 Akacid Plus * (25%) ~10.sup.4 ~10 No reduction CAS 37457-91-5 CAS 57028-96-3 Lonzabac BG (20%) ~10.sup.4 No reduction ~10 CAS 27083-27-8 Bardap-26 (70%) 10.sup.4-10.sup.5 .sup. ~10.sup.4 ~10.sup.4 ~10.sup.3 10.sup.2-10.sup.3 No reduction CAS 94667-33-1 Barquat PQ-2 (50%) ~10.sup.4 No reduction CAS 25988-97-0

Example 4B

Biocidal Effect

Synergistical Effect

(39) The optimal biocides, Bardap-26 and Akacid Forte, found in Example 4A, were further assayed for synergistically effect. Bardap-26 and Akacid Forte was mixed in a 50:50 ratio, and the applied concentrations can be seen from Table 5. The methods and solutions were otherwise as described in example 4A herein.

(40) TABLE-US-00008 TABLE 5 Test concentrations of 50:50 mixtures of Bardap-26 and Akacid Forte Test concentrations Biocide 700 ppm 200 ppm 160 ppm 120 ppm 80 ppm 40 ppm (% active) active active active active active active Bardap-26 (70%) 500 ppm + 143 ppm + 114 ppm + 86 ppm + 57 ppm + 29 ppm + CAS 94667-33-1 + 1400 ppm 400 ppm 320 ppm 240 ppm 160 ppm 80 ppm Akacid Forte (25%) CAS 57028-96-3
Results

(41) As can be seen from Table 6, there was found a clear and surprising synergistical effect for all of the assayed organisms. The synergistical effect was especially evident for E. coli, as there was found a total elimination. For Staphylococcus Aureus and Candida Albicans were likewise found a synergistical effect, as the combination gave a significant increase in reduction compared to the effects previously observed for either biocide alone.

(42) TABLE-US-00009 TABLE 6 Reductions obtained in three organisms by use of 50:50 mixture of Bardap-26 and Akacid Forte Gray indicates high effect.

Example 5

Assay for Washing and Biocidal Effect

(43) The microorganisms, as mentioned in example 4, are inoculated on the textile in question. For a delicate laundry detergent the textile is wool and/or silk, and for a detergent composition for heavy-laundry duty the textile may be cotton, a cotton containing textile, a polyester containing textile etc.

(44) The inoculated textile is washed by standardises methods with the laundry detergent to be assayed. The wash is performed at different temperatures, concentrations, and under conditions suitable for the intended use of the laundry detergent composition.

(45) The reduction in the different microorganisms is quantified.

(46) This assay is used to determine the biocidal effect of the laundry detergent under washing conditions.

Example 6

Liquid Laundry Detergent for Fine Textiles

(47) The below table provides a liquid laundry detergent composition for fine textiles, i.e. a delicate laundry detergent, to be combined with one or more biocides as described herein; preferably Bardap-26 or Akacid Forte, or a mixture thereof.

(48) TABLE-US-00010 TABLE 7 Test concentrations of biocides Ingredient Amount (in g pr. Kg) Marlipal 24/939 250 g Ampholac 200 g Trilon M  30 g Propyleneglycol  50 g Water 470 g

(49) The liquid laundry may be prepared by adding the components to the specified amount of water and stirring after addition of each component. Thereafter the pH is adjusted to pH 6.0-6.5.

Example 7

Liquid Laundry Detergent for Fine Textiles

(50) The exemplified liquid laundry detergents for fine textiles, i.e. delicate laundry detergents, comprise: one or more chelating agents such as but not limited to Trilon M, one or more non-ionic surfactants or monovalent cationic surfactants such as but not limited to the surfactants selected from the group consisting of Lutensol TO 89 and Marlipal 24/93 one or more liquid carriers such as but not limited to water and propylene glycol optionally one or more biocides such as but not limited to biocides selected from the group consisting of Bardap-26 and Akacid Forte.

(51) Below detergents A, B and C were prepared with and without biocides (Tables 8a-f):

(52) TABLE-US-00011 TABLE 8a Detergent A with biocides Ingredient Amount % (w/w) Water 69.5 Propylene glycol 5 Trilon ® M 3 Lutensol TO 89 12.5 (90% (w/w) isotridecanolethoxylat, polymer (CAS nr. 69011-36-5)) Bardap-26 comprising 70% CAS 94667-33-1 * 5 Akacid Forte comprising 25% CAS 57028-96-3 ** 5

(53) TABLE-US-00012 TABLE 8b Detergent A without biocides Ingredient Amount % (w/w) Water 79.5 Propylene glycol 5 Trilon ® M 3 Lutensol TO 89 12.5 (90% (w/w) isotridecanolethoxylat, polymer (CAS nr. 69011-36-5))

(54) TABLE-US-00013 TABLE 8c Detergent B with biocides Ingredient Amount % (w/w) Water 69.5 Propylene glycol 5 Trilon M 3 Marlipal 24/939 12.5 (90% CAS-NR 68439-50-9 (w/w)) Bardap-26 comprising 70% CAS 94667-33-1 * 5 Akacid Forte comprising 25% CAS 57028-96-3 ** 5

(55) TABLE-US-00014 TABLE 8d Detergent B without biocides Ingredient Amount % (w/w) Water 79.5 Propylene glycol 5 Trilon M 3 Marlipal 24/939 12.5 (90% CAS-NR 68439-50-9 (w/w))

(56) TABLE-US-00015 TABLE 8e Detergent C with biocides Ingredient Amount % (w/w) Water 69.5 Propylene glycol 5 Trilon ® M 3 Plurafac LF 300 12.5 (90% (w/w) CAS nr. 69227-21-0)) Bardap-26 comprising 70% CAS 94667-33-1 * 5 Akacid Forte comprising 25% CAS 57028-96-3 ** 5

(57) TABLE-US-00016 TABLE 8f Detergent C without biocides Ingredient Amount % (w/w) Water 79.5 Propylene glycol 5 Trilon ® M 3 Plurafac LF 300 12.5 (90% (w/w) CAS nr. 69227-21-0))

(58) Liquid laundry detergents A, B and C with and without biocides may be prepared by adding the components to the specified amount of water and stirring after addition of each component. Thereafter the pH is adjusted to pH 6-7 using e.g. lactic acid. * A content of 5% (w/w) Bardap-26 comprising 70% CAS 94667-33-1 in each of detergents A, B and C gives a content of 3.5% (w/w) CAS 94667-33-1, which is the active ingredient in Bardap-26.** A content of 5% (w/w) Akacid Forte comprising 25% CAS 57028-96-3 in each of detergents A, B and C gives a content of 1.25% (w/w) CAS 57028-96-3, which is the active ingredient in Akacid Forte.

(59) The stability of liquid laundry detergents A, B and C with comprising 5% (w/w) Bardap-26 and 5% (w/w) Akacid Forte were analyzed after 1 week storage at −18° C., 5° C., 20° C. and 58° C.:

(60) TABLE-US-00017 TABLE 9 Results obtained in stability test Storage temperature −18° C. 5° C. 20° C. 58° C. Detergent A stable stable stable stable Detergent B stable stable stable stable Detergent C stable stable stable stable

(61) Detergent C without biocides is the only detergent of detergents A without biocides, B without biocides and C without biocides which was not stable.

(62) Conclusion

(63) No precipitate occurred in detergent A with biocides upon storage for 1 week at −18° C.-58° C. No precipitate occurred in composition B with biocides upon storage for 1 week at −18° C.-58° C. No precipitate occurred in composition C with biocides upon storage for 1 week at −18° C.-58° C. In conclusion, liquid laundry detergents A, B and C are stable.

(64) Detergent C without biocides is not stable.

Example 8

(65) Biocidal Effect of Detergent and Detergent with Biocides

(66) Bacteria and Yeast Stock Cultures

(67) Staphylococcus aureus, ATCC 6538 representing Gram-positive bacteria.

(68) Escherichia coli, ATCC 11229 representing Gram-negative bacteria.

(69) Candida albicans, ATCC 2091 representing yeasts.

(70) Bacteria were cultivated in TSB (Tryptic Soy Bouillon) at 37° C. for 24 hours. This culture was designated bacterial stock culture.

(71) Candida albicans was cultivated on MEA (Malt extract Agar) at 37° C. for 24 hours. The yeast was harvested by adding 10 mL 0.9% NaCl per plate and the yeast loosened with a Drigalski spatula. The yeast suspension was collected in a jar with glass beads and whirled to ensure an even distribution of the cells. This culture was designated yeast stock culture. Counts of yeast CFU after exposure was carried out using normal plate counts on MEA at 37° C. for 48 hours.

(72) Biocide Stock Solution

(73) A 12000 ppm biocides stock solution comprising 6000 ppm of the active ingredient in Akacid Forte (CAS 57028-96-3)+6000 ppm of the active ingredient in Bardap-26 (CAS 94667-33-1) was made in potassium phosphate buffer, pH 6.0.

(74) Test Solution 1

(75) Test solution 1 was prepared by addition of 0.5 ml biocides stock solution and 8.5 ml potassium phosphate buffer to sterile test tubes. Test solution 1 comprises no detergent.

(76) Test Solution 2

(77) Test solution 2 was prepared by addition of 1.0 ml biocides stock solution and 8 ml potassium phosphate buffer to sterile test tubes. Test solution 2 comprises no detergent.

(78) Prior to use in test solutions 3-8, detergent solutions A and B with and without biocides were made in accordance with Example 7 and pH was adjusted to 6.0-6.5 by adding of 1M NaOH.

(79) Test Solution 3

(80) Detergent A without biocides (table 8b) was diluted with water to a concentration of 5.4 g/liter test solution: Detergent A comprises 11.25% (w/w) of the active ingredient in Lutensol TO 89 (CAS nr. 69011-36-5). Thereby test solution 3 comprises CAS nr. 69011-36-5 in an amount of 0.61 g/liter test solution.

(81) Test solution 3 comprises no biocide.

(82) Test Solution 4

(83) Detergent A with biocides (table 8a) was diluted with water to a concentration of 6 g/900 ml test solution: Detergent A comprises 11.25% (w/w) of the active ingredient in Lutensol TO 89 (CAS nr. 69011-36-5). Thereby test solution 4 comprises CAS nr. 69011-36-5 in an amount of 0,675 g/900 ml test solution. Detergent A comprises 3.5% (w/w) of the active ingredient in Bardap-26 (CAS NR 94667-33-1). Thereby test solution 4 comprises CAS 94667-33-1 in an amount of 0.21 g/900 ml test solution. Detergent A comprises 1.25% (w/w) of the active ingredient in Akacid Forte (CAS NR 57028-96-3). Thereby test solution 4 comprises CAS 57028-96-3 in an amount of 0,075 g/900 ml test solution.

(84) In total, test solution 4 comprises biocides in the amount of (0.21+0.075) g/900 ml=0,285 g biocides/900 ml test solution

(85) Test Solution 5

(86) Detergent A with biocides (table 8a) was diluted with water to a concentration of 12 g/900 ml test solution: Detergent A comprises 11.25% (w/w) of the active ingredient in Lutensol TO 89 (CAS nr. 69011-36-5). Thereby test solution 5 comprises CAS nr. 69011-36-5 in an amount of 1.35 g/900 ml test solution. Detergent A comprises 3.5% (w/w) of the active ingredient in Bardap-26 (CAS NR 94667-33-1). Thereby test solution 4 comprises CAS 94667-33-1 in an amount of 0.42 g/900 ml test solution. Detergent A comprises 1.25% (w/w) of the active ingredient in Akacid Forte (CAS NR 57028-96-3). Thereby test solution 4 comprises CAS 57028-96-3 in an amount of 0.15 g/900 ml test solution.

(87) In total, test solution 5 comprises biocides in the amount of (0.42+0.15) g/900 ml=0.57 g biocides/900 ml test solution

(88) Test Solution 6

(89) Detergent B without biocides (table 8d) was diluted with water to a concentration of 5.4 g/liter test solution: Detergent B comprises 11.25% (w/w) of the active ingredient in Marlipal 24/939 (CAS-NR 68439-50-9). Thereby test solution 6 comprises CAS-NR 68439-50-9 in an amount of 0.61 g/liter test solution.

(90) Test solution comprises no biocide.

(91) Test Solution 7

(92) Detergent B with biocides (table 8c) was diluted with water to a concentration of 6 g/900 ml test solution: Detergent B comprises 11.25% (w/w) of the active ingredient in Marlipal 24/939 (CAS-NR 68439-50-9). Thereby test solution 7 comprises CAS-NR 68439-50-9 in an amount of 0,675 g/900 ml test solution. Detergent B comprises 3.5% (w/w) of the active ingredient in Bardap-26 (CAS NR 94667-33-1). Thereby test solution 4 comprises CAS 94667-33-1 in an amount of 0.21 g/900 ml test solution. Detergent B comprises 1.25% (w/w) of the active ingredient in Akacid Forte (CAS NR 57028-96-3). Thereby test solution 4 comprises CAS 57028-96-3 in an amount of 0,075 g/900 ml test solution.

(93) In total, test solution 7 comprises biocides in the amount of (0.21+0.075) g/900 ml=0,285 g biocides/900 ml test solution

(94) Test Solution 8

(95) Detergent B with biocides (table 8c) was diluted with water to a concentration of 12 g/900 ml test solution: Detergent B comprises 11.25% (w/w) of the active ingredient in Marlipal 24/939 (CAS-NR 68439-50-9). Thereby test solution 8 comprises CAS nr. CAS-NR 68439-50-9 in an amount of 1.35 g/900 ml test solution. Detergent B comprises 3.5% (w/w) of the active ingredient in Bardap-26 (CAS NR94667-33-1). Thereby test solution 4 comprises CAS 94667-33-1 in an amount of 0.42 g/900 ml test solution. Detergent B comprises 1.25% (w/w) of the active ingredient in Akacid Forte (CAS NR 57028-96-3). Thereby test solution 4 comprises CAS 57028-96-3 in an amount of 0.15 g/900 ml test solution.

(96) In total, test solution 8 comprises biocides in the amount of (0.42+0.15) g/900 ml=0.57 g biocides/900 ml test solution

(97) Experimental

(98) 9 ml of test solution 1, 2, 3, 4, 5, 6, 7 or 8 was added into a sterile test tube. 1 ml of bacterial stock culture or yeast stock culture was added immediately before exposure.

(99) Thus, the concentration during exposure was as follows:

(100) TABLE-US-00018 TABLE 10 Exposure concentrations Concentration (ppm) during exposure Product Concentration 1 2 3 4 5 6 7 8 Lutensol CAS nr. — — 610 675 1350  — — — TO 89 69011-36-5* Marlipal CAS-NR — — — — — 610 675 1350  24/939 68439-50-9** Bardap- CAS NR 300 600 — 210 420 — 210 420 26 94667-33- 1*** Akacid CAS NR 300 600 —  75 150 —  75 150 Forte 57028-96- 3**** Total 600 1200  285 570 285 570 biocides

(101) Test solutions were exposed to micro organisms for 9 minutes at 30° C.

(102) The number of surviving bacteria was determined immediately after exposure. The bacterial CFU (colony forming units) after exposure to bacteria was carried out using normal plate counts on TSA plates (Tryptic Soy Agar) at 37° C. for 24 hours. Counts of yeast CFU after exposure was carried out using normal plate counts on MEA at 37° C. for 48 hours.

(103) All tests were performed in triplicate.

(104) Results and Conclusion:

(105) TABLE-US-00019 TABLE 11 Results from exposure Test solution Candida albicans Staph. aureus E. coli 1 ~10.sup.6 ~10.sup.7 ~10.sup.7 2 >10.sup.6 ~10.sup.7 ~10.sup.7 3 <10.sup.  None None 4 >10.sup.5 ~10.sup.7 ~10.sup.7 5 >10.sup.6 ~10.sup.7 ~10.sup.7 6 <10.sup.  None None 7 >10.sup.5 ~10.sup.7 ~10.sup.7 8 >10.sup.6 ~10.sup.7 ~10.sup.7

(106) When incorporating detergent C comprising Plurafac LF 300 (prepared in accordance with example 7) into a test solution comprising Bardap-26 and Akacid Forte, then reductions as low as 10.sup.2 of yeast are obtained.

(107) The results show that (table 11): A reduction of 10.sup.5 of yeast was obtained at the lower biocide concentration present in test solutions 4 and 7. A reduction of 10.sup.6 of yeast was obtained t the higher biocide concentration present in test solutions 4 and 7. A reduction of 10.sup.7 of bacteria was obtained at the biocide concentration of test solutions 5 and 8 The same reduction was obtained for all test solutions when exposed to Staph. Aureus and E. coli. The same results were obtained for Lutensol TO 89 and Marlipal 24/939 There is no difference in the reduction of bacteria obtained for test solutions 1 and 2 as compared to test solutions 4, 5, 6 and 7 There is no difference in the reduction of yeast obtained for test solutions 1 and 2 as compared to test solutions 5 and 8 The addition of Lutensol TO 89 and Marlipal 24/939 did not have any significant impact on the biocide effect of the biocides No reduction of the tested organisms was seen when exposed to test solutions 3 and 6. Addition of Plurafac LF300 comprised in detergent C leads to a reduction of yeast as low as a factor 100.

(108) A reduction as high as 10.sup.5 of yeast was obtained after exposure to the biocidal detergent compositions wherein the biocide concentration was as low as 285 ppm. Accordingly, in a non-limiting example, exposure under the same conditions to biocidal compositions wherein the biocide concentration was as high as 600 or 1200 ppm without detergent only increased the reduction of yeast with a factor 10 to a reduction of yeast of 10.sup.6.

(109) In one embodiment, the same reduction of yeast was obtained when exposing to a biocidal composition without detergent and when exposing to a biocidal detergent composition. Accordingly, in a non-limiting example, the same reduction of 10.sup.6 of yeast was obtained after exposure to biocidal detergent compositions comprising 570 ppm biocide and 600 or 1200 ppm biocide composition without detergent.

(110) In one embodiment, at least the same antibacterial effect was obtained when exposing to a biocidal composition without detergent and when exposing to a biocidal detergent composition. Accordingly, in a non-limiting example, the same reduction of 10.sup.7 of bacteria was obtained after exposure to biocidal detergent compositions comprising 285 or 570 ppm biocide and 600 or 1200 ppm biocide composition without detergent.

(111) The same reduction was obtained independently of the bacteria tested.

(112) Conclusion

(113) Based on the above results, it is concluded that addition of Lutensol TO 89 and Marlipal 24/939 does not significantly have an impact on the biocide effect of Marlipal 24/939 and Bardap-26.

Example 9

(114) Test Solutions

(115) Detergent A with biocides and detergent B with biocides obtained from Example 7 tables 8a+c were tested.

(116) Furthermore a solution comprising

(117) TABLE-US-00020 Water 75% (w/w); and Akacid Forte was tested 25% (w/w)
Experimental

(118) The critical micelle concentration is measured using Sudan Black B dissolved in the test solutions at different concentrations. Sudan Black B is dissolvable in micelles, only. A difference in the absorbance measured is thus a valid measure of the critical micelle concentration in the test solutions.

(119) Sudan black is of the below structure:

(120) ##STR00002##

(121) Absorbance was measured using a Shimadzu UV-1800 spectrofotometer and the absorbance is measured at 600 nm.

(122) Dilutions were made in water and Sudan Black B by adding first water, then Sudan Black B and at last the test solutions to 4 ml cuvettes. The dilutions were then stirred and left for at least 6 hours at room temperature. Then the absorbance was measured.

(123) Results

(124) CMC for Detergent A (Table 8a)

(125) CMC for diluted Detergent A (table 8a) was measured to 0,097 g/l (FIGS. 1 and 2) Detergent A (table 8a) comprises 11.25% (w/w) of the active ingredient in Lutensol TO 89 (CAS nr. 69011-36-5). Thereby, diluted detergent A comprises CAS nr. 69011-36-5 in an amount of 10.9 mg/l solution.
CMC for Detergent B (Table 8c) CMC for diluted Detergent B (table 8c) was measured to 0.03 g/l (FIGS. 3 and 4) Detergent B (table 8a) comprises 11.25% (w/w) of the active ingredient in Marlipal 24/939 (CAS-NR 68439-50-9). Thereby diluted detergent B comprises CAS-NR 68439-50-9 in an amount of 3.38 mg/l solution.
CMC for Akacid Forte CMC for diluted Akacid Forte was measured to 15 g/l (FIGS. 5 and 6) This 15 g/l dilution is diluted from a 25% (w/w) solution of Akacid Forte and thus comprises 3.75 g/l. Akacid Forte comprises the active ingredient CAS 57028-96-3 in an amount of 25% (w/w). Thereby the 15 g/l dilution comprises CAS 57028-96-3 in an amount of 0,938 g/l

(126) CMC for Bardap-26 is about 0.7-1.0 mmol/l (data not shown)