WO1999064550A1 - Use of basic polycondensates as antimicrobial active substance - Google Patents

Use of basic polycondensates as antimicrobial active substance Download PDF

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Publication number
WO1999064550A1
WO1999064550A1 PCT/EP1999/003752 EP9903752W WO9964550A1 WO 1999064550 A1 WO1999064550 A1 WO 1999064550A1 EP 9903752 W EP9903752 W EP 9903752W WO 9964550 A1 WO9964550 A1 WO 9964550A1
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WIPO (PCT)
Prior art keywords
ammonium
basic
test
atcc
dicyandiamide
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PCT/EP1999/003752
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French (fr)
Inventor
Rolf Kuratli
Anita Schmidlin
Werner Kaufmann
Dietmar Ochs
Karin Puchtler
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Ciba Specialty Chemicals Holding Inc.
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Priority to AU43720/99A priority Critical patent/AU4372099A/en
Publication of WO1999064550A1 publication Critical patent/WO1999064550A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/74—Synthetic polymeric materials
    • A61K31/785—Polymers containing nitrogen

Definitions

  • the present invention relates to the use of basic polycondensates as antimicrobial active substance.
  • such basic polycondensates are also antimicrobially active against microorganisms (gram-positive and gram-negative bacteria and fungi) and that they are therefore particularly suitable for the antimicrobial treatment of the human skin and of textile fibre materials as well as for the antimicrobial treatment of hard surfaces, for example as household detergents, rinsing agents, surface disinfectants, washing powders, softeners and the like.
  • this invention relates to the use of basic polycondensates, which are obtainable by reacting
  • Rj, R , R 3 and R 4 are each independently of one another hydrogen, or alkyl which is unsubstituted or substituted by amino, hydroxy, cyano or d-C 4 alkoxy, and
  • A is alkylene which is unsubstituted or substituted or which may be interrupted by one or more than one heteroatom, for the antimicrobial treatment of the human skin, of paper and of textile fibre materials and hard surfaces.
  • a in formula (1 ) is preferably C 2 -C 20 alkylene which may be interrupted by -O-, -S-, -NH- or -N(C ⁇ -C 4 alkyl)- and/or substituted by OH.
  • A is preferably C 2 -C 20 alkylene which is interrupted once or several times by -NH-.
  • Ri, 2 , R 3 and R are each independently of one another preferably hydrogen or C C alkyl.
  • Examples of suitable compounds of formula (1 ) are, for example, 1 ,4-butanediamine, 1 ,6- hexanediamine, dipropylenetriamine, N-(2-aminoethyl)-1 ,3-propanediamine, N,N-bis(2- aminopropyl)methylamine, polyethylenimine or polyethylenepolyamines, such as diethylene- thamine, triethylenetetramine, tetraethylenepentamine or pentamethylenehexamine.
  • Preferred compounds of formula (1) are polyethylenepolyamines and, in particular, dihexylene- triamine.
  • Suitable ammonium salts are, for example, ammonium salts of organic or inorganic acids, e.g. ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium formiate or ammonium acetate.
  • ammonium chloride is preferred.
  • the non-aqueous solvent is, for example, a hydroxyl group-containing solvent, preferably a solvent having a boiling point of above 150°C and, more preferably, of above 180°C, or a mixture of different such solvents.
  • a hydroxyl group-containing solvent preferably a solvent having a boiling point of above 150°C and, more preferably, of above 180°C, or a mixture of different such solvents.
  • examples are ethylene glycol, 1 ,2- or 1 ,3-propylene gly- col, butylene glycol, di-, tri- or tetraethylene glycol and the ethers thereof, as well as polyethylene glycols having a molecular weight of e.g. 600 to 5000, and mixtures thereof.
  • Suitable cyanamides (b) are, for example, cyanamide, dicyandiamide, guanidine and biguanidine. The use of dicyandiamide is preferred.
  • the compound of formula (1 ) and the ammonium salt are used in step (a) e.g. in a molar ratio of 1 :0.1 to 1 :2.5, preferably of 1 :0.7 to 1 :2 and, particularly preferably, of 1 :1 to 1 :1.5.
  • the amount of hydroxyl group-containing solvent can vary within wide limits and is, for example, from 0.2 to 20 mol and preferably from 0.4 to 5 mol per mol of the compound of formula (1).
  • the reaction according to step (a) preferably takes place at elevated temperature, e.g. from 80 to 200°C, preferably from 80 to 140°C and, particularly preferably, from 80 to 120°C.
  • the compound of formula (1 ) is preferably placed in the hydroxyl group-containing solvent or solvent mixture and the ammonium compound is added.
  • the reaction step is carried out under inert conditions, for example under nitrogen atmosphere.
  • the protonated compound of formula (1) obtained according to (a) is then reacted with, for example, 0.5 to 4 mol, preferably with 0.8 to 3 mol, of dicyandiamide per mol of starting compound of formula (1 ).
  • the reaction according to (b) is advantageously carried out in the presence of one or several of the above hydroxyl group-containing solvents at elevated temperature which may be, for example, in the range from 80 to 250°C and, preferably, from 100 to 150°C.
  • reaction products are solid at room temperature and have basic properties affording clear solutions in water; they can be converted into their water-soluble salts by neutralisation with inorganic or organic acids, such as hydrochloric acid or acetic acid.
  • the reaction mixture obtained according to (b) is preferably worked up by being diluted with water and adjusted thus to a predetermined product end concentration which may be, for example, in the range from 20 to 80 % by weight, preferably from 35 to 75 % by weight, based on the entire mixture.
  • the polycondensates used according to this invention have marked microbistatic and micro- bicidal action. They are therefore particularly suitable as antimicrobial active substance in body-care products, for example soaps, shampoos, foot-care products and, especially, deodorants, and as additives in washing and cleaning agents and disinfectants. Accordingly, this invention also relates to a body-care product, which comprises at least one inventive basic polycondensate as well as cosmetically compatible carriers or assistants.
  • the novel body-care product preferably comprises 0.01 to 15, more preferably 0.5 to 10 % by weight, based on the total weight of the composition, of a basic polycondensate and also cosmetically compatible assistants.
  • the body-care product comprises other components besides the basic polycondensate, for example sequestrants, colourants, perfume oils, thickeners or consistency regulators, emollients, UV absorbers, skin protectives, antioxidants, additives improving the mechanical properties, such as dicarboxylic acids and/or the aluminium, zinc, calcium and magnesium salts of C 14 -C 22 fatty acids and, where required, preservatives.
  • the basic polycondensate for example sequestrants, colourants, perfume oils, thickeners or consistency regulators, emollients, UV absorbers, skin protectives, antioxidants, additives improving the mechanical properties, such as dicarboxylic acids and/or the aluminium, zinc, calcium and magnesium salts of C 14 -C 22 fatty acids and, where required, preservatives.
  • the basic polycondensates can be incorporated into the respective formulations without any problems.
  • the novel body-care product can be formulated as water-in-oil or oil-in-water emulsion, as surfactant formulation (washing product), as alcoholic or alcohol-containing formulation, as vesicular dispersion of a ionic or non-ionic amphiphilic lipid, as gel, oil or lotion, solid stick, spray, powder, make-up or as aerosol formulation.
  • the cosmetically compatible assistant comprises preferably 5 to 50% of an oil phase, 5 to 20% of an emulsifier and 30 to 90% of water.
  • the oil phase can in this case contain any oil suitable for the cosmetic formulation, for example one or several hydrocarbon oils, a wax, a natural oil, a siiicone oil, a fatty acid ester or a fatty alcohol.
  • Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
  • An antimicrobial soap has, for example, the following composition:
  • a shampoo has, for example, the following composition: 0.01 to 5 % by weight of the inventive basic polycondensate, 12.0 % by weight of sodium-laureth-2-sulfate, 4.0 % by weight of cocamidopropylbetain, 3.0 % by weight of NaCI, and water ad 100%.
  • a deodorant has, for example, the following composition:
  • the basic polycondensates used according to this invention are also suitable for the treatment and antimicrobial finishing of textile fibre materials.
  • textile fibre materials are undyed and dyed or printed fibre materials made, for example, of silk, leather, wool, polyamide or poly- urethanes and, in particular, of cellulosic fibre materials of all kinds.
  • Such fibre materials are typically natural cellulose fibres, such as cotton, linen, jute and hemp, and also cellulose and regenerated cellulose.
  • Preferred suitable textile fibre materials are made of cotton.
  • the basic polycondensates used according to this invention are also suitable for the treatment and antimicrobial finishing of paper and cardboard.
  • a germ reduction of 75% (Staphylococcus aureus ATCC 9144) is found at an application concentration of lOOOppm and at a bacterial dissemination of 1-3x10 7 KBE/ml after a contact time of 3 hours. After a contact time of 24 hours, the germ reduction for Escherichia coli is 99.88% and for Staphylococcus aureus 99.999%.
  • Example Metering time Metering time Stirring time Stirring Avera ⁇ e diethylenedicyandiamide Kminl temperature molecular triamine [(mini PCI weight
  • the ammonia gas is washed out of the N 2 stream in an NH_-absorption apparatus and titrated. After addition is complete, the mixture is allowed to react at the same TF for another 240 minutes. A clear, colourless and homogeneous product is thus obtained.
  • the end product is composed as follows [%]: condensate 30
  • a germ reduction of 71% ( Staphylococcus aureus ATCC 9144) is found at an application concentration of lOOOppm and at a bacterial dissemination of 1-3 x 10 7 KBE/ ml after a contact time of 3 hours and, after a contact time of 24 hours, a germ re - duction of 99.8% is found for Escherichia coli and of 97.5% for Staphylococcus aureus.
  • Example18 metering time bis-3-(aminopropyl)amine [min]: 40 metering time dicyandiamide [min]: 90 stirring time [min]: 120 stirring temperature [°C]: 120 average molecular weight Mn/Mw 305/400
  • the ammonia gas is washed out of the N 2 stream in an NH 3 -absorption apparatus and titrated.
  • the TF is raised to 130°C (128-132°C) and the clear yellow solution is allowed to react for another 270 minutes at this TF.
  • the polycondensate so obtained is then diluted with X g of deionised water to a concentration of 30% active substance.
  • Example 23 shows in the dilution test a germ reduction of 99.999% (Escherichia coli NCTC 8196) and 98% (Staphylococcus aureus ATCC 9144) at an application concentration of 200ppm and at a bacterial dissemination of 1-3x10 7 KBE/ml after a contact time of 3 hours. After a contact time of 24 hours, the germ reduction both for Escherichia coli and for Staphylococcus aureus is 99.999%.
  • the ammonia gas is washed out of the N 2 stream in an NH 3 -absorption apparatus and titrated. After the addition is complete, 97.6 g of octylamine are added over 15-25 minutes at TF 120°C (118-122°C), resulting in a clear yellow solution. The TF is then lowered to 110°C (108-112°C) and the reaction solution is allowed to react for another 120 minutes.
  • the polycondensate so obtained is then diluted with X g of water de ⁇ 0n to a concentration of 30% active substance.
  • Staphylococcus aureus ATCC 9144 200ppm Staphylococcus epidermidis ATCC 12228 100ppm Corynebacterium xerosis ATCC 373 100ppm Escherichia coli NCTC 8196 500ppm Pseudomonas aeruginosa CIP A-22 lOOOppm Candida albicans ATCC 10'231 500ppm Aspergillus niger ATCC 6275 500ppm
  • Example 24 shows in the dilution test a germ reduction of 99.9% (Escherichia coli NCTC 8196) and 95% (Staphylococcus aureus ATCC 9144) at an application concentration of 500ppm (Escherichia coli) and 200ppm (Staphylococcus aureus) and at a bacterial dissemination of 1 -3x10 7 KBE/ml after a contact time of 3 hours. After a contact time of 24 hours, the germ reduction both of Escherichia coli and of Staphylococcus aureus is 99.999%.
  • Germ reduction after a contact time of 3 and 24 hours Germ reduction Escherichia coli NCTC 8196 Staphylococcus aureus ATCC 9144 after a 3 hour
  • Example 25 26 27 28 29 metering time diethylenetriamine 40 40 40 40 40 40 40
  • the TF is raised to 120°C (117-123°C) and 196.7 g of dicyandiamide are added at this TF over 90 minutes. Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out of the N 2 stream in an NH -absorption apparatus and titrated. After the addition is complete, the TF is lowered to 110°C (108- 112°C) and the reaction solution is allowed to react for another 60 minutes. The polycondensate so obtained is then diluted with X g of water de ⁇ on to a concentration of 30% active substance.
  • the TF is raised to 120°C (117-123°C) and 196.7 g of dicyandiamide are added at this TF over 90 minutes. Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out of the N 2 stream in an NH 3 -ab- sorption apparatus and titrated. After the addition is complete, the TF is lowered to 110°C (108-112°C) and the reaction solution is allowed to react for another 120 minutes. The polycondensate so obtained is then diluted with X g of water dei o n to a concentration of 30% active substance.
  • Example 31 shows in the dilution test a germ reduction of 99.6% for Staphylococcus aureus and, after a contact time of 24 hours, a complete germ reduction of 99.999%, at an application concentration of 200ppm (Escherichia coli) and 50ppm (Staphylococcus aureus) and at a bacterial dissemination of 1-3x10 7 KBE/ml after 3 hours.
  • the germ numbers of Escherichia coli were reduced by 99.999% already after a contact time of 3 hours.
  • Example 32 33 metering time ammonium chloride [min] 40 min 40 min metering time dicyandiamide [min] 90 min 90 min stirring time [min] 180 min 240 min stirring temperature [°C] 110°C 110°C
  • Example 101 Dishwasher formulation basic polycondensate 0.01-10 % sodium lauryl sulfate 7.0 sodium myreth sulfate 7.0 lauryl glucoside 4.0 cocobetain 1.1 ethanol 5.0
  • Example 102 All-purpose cleaner basic polycondensate 0.01-10 % cocamidopropylbetain 2.9 % lauramine oxide 3.0 % sodium laureth sulfate 4.2 sodium citrate 4.0 sodium carbonate 3.0 ethanol 3.0 water d eion ad 100.0 %
  • Example 103 Surface cleaner basic polycondensate 0.01 -10 % octyl alcohol 4 EO 3.0 %
  • Test method Determination of the minimum inhibitory concentration ( MHK) in the aoar incorporation test (MHK-test)
  • Test solution 1% aqueous stock solutions are prepared from all the test substances and diluted in dilution series to end concentrations from lOOOppm to 10ppm.
  • Test principle 0.3 ml of the respective dilution grade is mixed with 15 ml of still-liquid nutrient medium. After the culture medium has solidified, 10 ⁇ l of the following germ dilution in 0.85% of NaCI solution are applied in spots on the agar medium:
  • Staphylococcus aureus ATCC 9144 100 Staphylococcus epidermidis ATCC 12228 100 Corynebacterium xerosis ATCC 373 100 Escherichia coli NCTC 8196 1000 Pseudomonas aeruginosa CIP A-22 1000 Candida albicans ATCC 10'231 10 Aspergillus niger ATCC 6275 10
  • the plates are incubated for 24 hours at 37°C ( A.niger 3 days at 28°C) and then just that end concentration of the test substance is determined at which no further growth is possible.
  • medium Mueller-Hinton-Agar (Merck) Sabouraud 4% glucose agar dilution medium: sterile 0.85% NaCI solution
  • test germs Staphylococcus aureus ATCC 9144 Staphylococcus epidermidis ATCC 12228 Corynebacterium xerosis ATCC 373 Escherichia coli NCTC 8196 Pseudomonas aeruginosa CIP A-22 Candida albicans ATCC 10'231 Aspergillus niger ATCC 6275
  • Test method Determination of the bactericidal activity in the dilution test
  • Test solution The test substances 1-6 are adjusted to the minimum inhibitory concentration (MIC) by dilution with water and are tested against the test germs Staphylococcus aureus ATCC 9144 and Escherichia coli NCTC 8196:
  • Test princir 3le Batches of 8ml nutrient solution each are char and 1 ml of germ suspension. (16-24 hour cultivation, diluted to a germ concentration of 1 - 3x10 8 KBE/ml.) The resulting germ concentration in the test batch is 1-3x10 7 KBE/ml.
  • test batch After contact times of 3 hours and 24 hours, 1ml of test batch is sampled and diluted in 9 ml of inactivation medium in 1 :10 steps, and 100 ⁇ l of the dilution stages 10 "1 , 10 "3 , 10 '5 are plated out by means of a spiralometer. After incubation, the survival germ numbers are determined and the germ number reduction over the water controls is calculated.
  • Escherichia coli NCTC 8196 contact times 3 hours, 24 hours incubation: 24 hours at 37°C
  • test sample a.
  • Example 31 5% solution in water
  • Example 32 5% solution in water
  • wash cycles are carried out by the following method:
  • washing powder 0.35 g washing powder / ad 70 g water textile: 7g of cotton temperature: 40°C duration: 10 minutes rinsing: 2 x 30 seconds drying: air
  • Antimicrobially finished circular cotton pads are placed on seeded nutrient agar plates and incubated.
  • the active substance which diffuses into the agar during incubation inhibits the growth of the test germs in the environment and under the circular cotton pad.
  • the inhibitory zone around the round pad is given in nm as a measure of the antimicrobial activity of the active substance.
  • Test organism Staphylococcus aureus ATCC 9144
  • Circular pads having a diameter of 20 nm are punched out of the cotton sample to be tested and are placed in the centre of a seeded agar plate.
  • the plates are incubated for 18-24 hours at 37°C.
  • Inhibitory zones are measured and indicated in mm.

Abstract

A description is given of the use of basic polycondensates, which are obtainable by reacting (a) an amine of formula (1), with an ammonium salt in the presence of a non-aqueous solvent, and (b) by reacting the protonated product obtained according to (a) with a cyanamide at elevated temperature, wherein R1, R2, R3 and R4 are each independently of one another hydrogen, or alkyl which is unsubstituted or substituted by amino, hydroxy, cyano or C1-C4alkoxy, and A is alkylene which is unsubstituted or substituted or which may be interrupted by one or more than one heteroatom, for the antimicrobial treatment of the human skin, of textile fibre materials, paper or card-board and hard surfaces.

Description

Use of basic polycondensates as antimicrobial active substance
The present invention relates to the use of basic polycondensates as antimicrobial active substance.
It is known that certain basic polycondensates or their salts are suitable as aftertreatment agents for improving the fastness to wet treatment of dyed or printed textile material.
Surprisingly, it has been found that such basic polycondensates are also antimicrobially active against microorganisms (gram-positive and gram-negative bacteria and fungi) and that they are therefore particularly suitable for the antimicrobial treatment of the human skin and of textile fibre materials as well as for the antimicrobial treatment of hard surfaces, for example as household detergents, rinsing agents, surface disinfectants, washing powders, softeners and the like.
Accordingly, this invention relates to the use of basic polycondensates, which are obtainable by reacting
(a) an amine of formula
Figure imgf000003_0001
with an ammonium salt in the presence of a non-aqueous solvent, and
(b) by reacting the protonated product obtained according to (a) with a cyanamide at elevated temperature, wherein
Rj, R , R3 and R4 are each independently of one another hydrogen, or alkyl which is unsubstituted or substituted by amino, hydroxy, cyano or d-C4alkoxy, and
A is alkylene which is unsubstituted or substituted or which may be interrupted by one or more than one heteroatom, for the antimicrobial treatment of the human skin, of paper and of textile fibre materials and hard surfaces. A in formula (1 ) is preferably C2-C20alkylene which may be interrupted by -O-, -S-, -NH- or -N(Cι-C4alkyl)- and/or substituted by OH. A is preferably C2-C20alkylene which is interrupted once or several times by -NH-.
Ri, 2, R3 and R are each independently of one another preferably hydrogen or C C alkyl.
Examples of suitable compounds of formula (1 ) are, for example, 1 ,4-butanediamine, 1 ,6- hexanediamine, dipropylenetriamine, N-(2-aminoethyl)-1 ,3-propanediamine, N,N-bis(2- aminopropyl)methylamine, polyethylenimine or polyethylenepolyamines, such as diethylene- thamine, triethylenetetramine, tetraethylenepentamine or pentamethylenehexamine. Preferred compounds of formula (1) are polyethylenepolyamines and, in particular, dihexylene- triamine.
Suitable ammonium salts are, for example, ammonium salts of organic or inorganic acids, e.g. ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium formiate or ammonium acetate.
The use of ammonium chloride is preferred.
The non-aqueous solvent is, for example, a hydroxyl group-containing solvent, preferably a solvent having a boiling point of above 150°C and, more preferably, of above 180°C, or a mixture of different such solvents. Examples are ethylene glycol, 1 ,2- or 1 ,3-propylene gly- col, butylene glycol, di-, tri- or tetraethylene glycol and the ethers thereof, as well as polyethylene glycols having a molecular weight of e.g. 600 to 5000, and mixtures thereof.
Suitable cyanamides (b) are, for example, cyanamide, dicyandiamide, guanidine and biguanidine. The use of dicyandiamide is preferred.
The preparation of the basic polycondensates used according to this invention is described in detail in EP-A-0,692,511.
To prepare the basic polycondensates used according to this invention, the compound of formula (1 ) and the ammonium salt are used in step (a) e.g. in a molar ratio of 1 :0.1 to 1 :2.5, preferably of 1 :0.7 to 1 :2 and, particularly preferably, of 1 :1 to 1 :1.5. The amount of hydroxyl group-containing solvent can vary within wide limits and is, for example, from 0.2 to 20 mol and preferably from 0.4 to 5 mol per mol of the compound of formula (1).
The reaction according to step (a) preferably takes place at elevated temperature, e.g. from 80 to 200°C, preferably from 80 to 140°C and, particularly preferably, from 80 to 120°C. The compound of formula (1 ) is preferably placed in the hydroxyl group-containing solvent or solvent mixture and the ammonium compound is added. Advantageously, the reaction step is carried out under inert conditions, for example under nitrogen atmosphere.
The protonated compound of formula (1) obtained according to (a) is then reacted with, for example, 0.5 to 4 mol, preferably with 0.8 to 3 mol, of dicyandiamide per mol of starting compound of formula (1 ). The reaction according to (b) is advantageously carried out in the presence of one or several of the above hydroxyl group-containing solvents at elevated temperature which may be, for example, in the range from 80 to 250°C and, preferably, from 100 to 150°C.
Further details on the preparation of the polycondensates used according to this invention are to be found in the above-mentioned literature reference.
The reaction products are solid at room temperature and have basic properties affording clear solutions in water; they can be converted into their water-soluble salts by neutralisation with inorganic or organic acids, such as hydrochloric acid or acetic acid.
The reaction mixture obtained according to (b) is preferably worked up by being diluted with water and adjusted thus to a predetermined product end concentration which may be, for example, in the range from 20 to 80 % by weight, preferably from 35 to 75 % by weight, based on the entire mixture.
The polycondensates used according to this invention have marked microbistatic and micro- bicidal action. They are therefore particularly suitable as antimicrobial active substance in body-care products, for example soaps, shampoos, foot-care products and, especially, deodorants, and as additives in washing and cleaning agents and disinfectants. Accordingly, this invention also relates to a body-care product, which comprises at least one inventive basic polycondensate as well as cosmetically compatible carriers or assistants.
The novel body-care product preferably comprises 0.01 to 15, more preferably 0.5 to 10 % by weight, based on the total weight of the composition, of a basic polycondensate and also cosmetically compatible assistants.
Depending on the form of the body-care product, it comprises other components besides the basic polycondensate, for example sequestrants, colourants, perfume oils, thickeners or consistency regulators, emollients, UV absorbers, skin protectives, antioxidants, additives improving the mechanical properties, such as dicarboxylic acids and/or the aluminium, zinc, calcium and magnesium salts of C14-C22fatty acids and, where required, preservatives.
Owing to their good solubility in water, the basic polycondensates can be incorporated into the respective formulations without any problems.
The novel body-care product can be formulated as water-in-oil or oil-in-water emulsion, as surfactant formulation (washing product), as alcoholic or alcohol-containing formulation, as vesicular dispersion of a ionic or non-ionic amphiphilic lipid, as gel, oil or lotion, solid stick, spray, powder, make-up or as aerosol formulation.
As water-in-oil or oil-in-water emulsion, the cosmetically compatible assistant comprises preferably 5 to 50% of an oil phase, 5 to 20% of an emulsifier and 30 to 90% of water. The oil phase can in this case contain any oil suitable for the cosmetic formulation, for example one or several hydrocarbon oils, a wax, a natural oil, a siiicone oil, a fatty acid ester or a fatty alcohol. Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
An antimicrobial soap has, for example, the following composition:
0.01 to 5 % by weight of the inventive basic polycondensate,
0.3 to 1 % by weight of titanium dioxide,
1 to 10 % by weight of stearic acid, ad 100% of soap base, for example the sodium salts of tallow fatty acid and coconut fatty acid or glycerols. A shampoo has, for example, the following composition: 0.01 to 5 % by weight of the inventive basic polycondensate, 12.0 % by weight of sodium-laureth-2-sulfate, 4.0 % by weight of cocamidopropylbetain, 3.0 % by weight of NaCI, and water ad 100%.
A deodorant has, for example, the following composition:
0.01 to 5 % by weight of the inventive polycondensate,
60 % by weight of ethanol,
0.3 % by weight of perfume oil, and water ad 100 %.
The basic polycondensates used according to this invention are also suitable for the treatment and antimicrobial finishing of textile fibre materials. These materials are undyed and dyed or printed fibre materials made, for example, of silk, leather, wool, polyamide or poly- urethanes and, in particular, of cellulosic fibre materials of all kinds. Such fibre materials are typically natural cellulose fibres, such as cotton, linen, jute and hemp, and also cellulose and regenerated cellulose. Preferred suitable textile fibre materials are made of cotton.
The basic polycondensates used according to this invention are also suitable for the treatment and antimicrobial finishing of paper and cardboard.
The following Examples illustrate the invention in more detail.
Example 1 :
Starting compounds Amount used r%1 ammonium chloride 11.7
1 ,2-propylene glycol 19.7 diethylene triamine 34.2 dicyandiamide 34.4 Reaction parameters: metering time diethylenethamine: 40 min metering time dicyandiamide: 60 min stirring time: 300 min stirring temperature: 130°C
Molar ratio:
Monomers Molar amount Molar ratio ammonium chloride 1.249 0.66 diethylenetriamine 1.895 1.00 dicyandiamide 2.339 1.23
Execution:
Under inert gas (N2), 112.3 g of 1 ,2-propylene glycol and 66.8 g of ammonium chloride are placed in a 1.5 litre ground glass flask at room temperature (20-25°C). The resulting white suspension is heated to a temperature in the flask (=TF) of 78-82°C over 20 to 30 minutes. When the prescribed TF is reached, 195.5 g of diethylenetriamine are added within 40 minutes (38-42 min), resulting in a clear, yellow, low viscous solution (<200mPas at D=200/80°C).
The TF is then raised to 120°C (117-123°C) and 196.7 g of dicyandiamide are added at this temperature over 60 minutes. Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out from the N2 stream in an NH3-absorption apparatus and titrated. After addition is complete, the TF is raised to 130°C (128-132°C) and the clear, yellow to yellowish-brown and slightly viscous (>200 mPas at D=200/80°C) solution is allowed to react for another 300 minutes at this temperature. The polycondensate so obtained is then diluted with X g of deionised water to a concentration of 30% active substance.
titrated amount of ammonia: 5.2 mol average molecular weight: Mn/Mw = 365/630 composition of the end product [%]: condensate 30
1 ,2-propylene glycol 8-10 waterde,on 60-62 Antimicrobial action:
(The microbiological test methods are described at the end of the Examples.)
1. Determination of the minimum inhibitory concentration in the aαar incorporation test (MHK values in ppm of active substance)
Test strains Polycondensate of Example 1
Staphylococcus aureus ATCC 9144 >1000ppm Staphylococcus epidermidis ATCC 12228 200ppm
Corynebacte um xerosis ATCC 373 200ppm Escherichia coli NCTC 8196 lOOOppm Pseudomonas aeruginosa CIP A-22 >1000ppm Candida albicans ATCC 10'231 lOOOppm Aspergillus niger ATCC 6275 >1000ppm
2. Determination of the bactericidal activity (dilution test)
In the dilution test, a germ reduction of 75% (Staphylococcus aureus ATCC 9144) is found at an application concentration of lOOOppm and at a bacterial dissemination of 1-3x107 KBE/ml after a contact time of 3 hours. After a contact time of 24 hours, the germ reduction for Escherichia coli is 99.88% and for Staphylococcus aureus 99.999%.
Germ reduction after a contact time of 3 and 24 hours
Germ reduction Escherichia coli NCTC 8196 Staphylococcus aureus ATCC 9144 after a 3 hour 3.4% 75% contact time after a 24 hour 99.88% 99.999% contact time
Additional Examples: Example Metering time Metering time Stirring time Stirring Averaαe diethylenedicyandiamide Kminl temperature molecular triamine [(mini PCI weight
Kminl Mn/Mw
2 40 60 240 130 570/950
3 40 60 60 130 395/580
4 40 60 30 130 350/500
5 40 60 300 110 400/550
6 40 60 240 110 405/520
7 40 60 60 110 295/365
8 40 60 30 110 275/350
9 40 90 300 130 465/775
10 40 90 240 130 440/725
11 40 90 60 130 415/595
12 40 90 30 130 350/520
13 40 90 300 110 370/555
14 40 90 240 110 365/520
15 40 90 60 110 310/405
16 40 90 30 110 265/330
Example 17:
Starting compounds Amount used f%l ammonium chloride 10.7 1 ,2-propylene glycol 18.0 bis-3-(aminopropyl)amine 39.8 dicyandiamide 31.5 Reaction parameters: metering time bis-3-(aminopropyl)amine: 40 min metering time dicyandiamide: 90 min stirring time: 240 min stirring temperature: 120°C
Molar ratio:
Monomers Molar amount used Molar ratio ammonium chloride 1.249 0.66 bis-3-(aminopropyl)amine 1.890 1.00 dicyandiamide 2.339 1.23
Execution:
Under inert gas (N2), 112.3 g of 1 ,2-propylene glycol and 66.8 g of ammonium chloride are placed in a 1.5 litre ground glass flask at room temperature (20-25°C). The resulting white suspension is heated to TF = 78-82°C over 20-30 minutes. When the prescribed TF is reached, 248.0 g of bis-3-(aminopropyl)amine are added over 40-50 minutes, resulting in a clear, colourless solution. The TF is then raised to 120°C (117-123°C) and 196.7 g of dicyandiamide are added at this temperature over 90 minutes. Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out of the N2 stream in an NH_-absorption apparatus and titrated. After addition is complete, the mixture is allowed to react at the same TF for another 240 minutes. A clear, colourless and homogeneous product is thus obtained. The polycondensate so obtained is then diluted with X g of deionised water to a concentration of 30% active substance, titrated amount of ammonia: 4.2 mol average molecular weight: Mn/Mw = 380/520
The end product is composed as follows [%]: condensate 30
1 ,2-propylene glycol 7-9 waterdeιon 61-63 Antimicrobial action:
1. Determination of the minimum inhibitory concentration in the agar incorporation test (MHK values in ppm active substance)
Test strains Polycondensate of Example 17
Staphylococcus aureus ATCC 9144 0OOppm
Staphylococcus epidermidis ATCC 12228 500ppm
Corynebacterium xerosis ATCC 373 200ppm
Escherichia coli NCTC 8196 lOOOppm
Pseudomonas aeruginosa CIP A-22 >1000ppm
Candida albicans ATCC 10'231 >1000ppm
Aspergillus niger ATCC 6275 >1000ppm
2. Determination of the bactericidal activity (dilution test)
In the dilution test, a germ reduction of 71% ( Staphylococcus aureus ATCC 9144) is found at an application concentration of lOOOppm and at a bacterial dissemination of 1-3 x 107 KBE/ ml after a contact time of 3 hours and, after a contact time of 24 hours, a germ re - duction of 99.8% is found for Escherichia coli and of 97.5% for Staphylococcus aureus.
Germ reduction after a contact time of 3 and 24 hours
Germ reduction Escherichia coli NCTC 8196 Staphylococcus aureus ATCC 9144
after a 3 hour 6.9% 71% contact time after a 24 hour 99.8% 97.5% contact time
Additional tests of the same chemical type are listed below. Example18: metering time bis-3-(aminopropyl)amine [min]: 40 metering time dicyandiamide [min]: 90 stirring time [min]: 120 stirring temperature [°C]: 120 average molecular weight Mn/Mw 305/400
Figure imgf000013_0001
Example 23:
Starting compounds Amount used [%1 ammonium chloride 9.0
1 ,2-propylene glycol 36.3
1 ,5-diamino-2-methylpentane 28.1 dicyandiamide 26.5 Reaction parameters: metering time 1 ,5-diamino-2-methylpentane [min]: 40 metering time dicyandiamide [min]: 90 stirring time [min]: 270 stirring temperature [°C]: 130
Molar ratio:
Monomers Molar amount used Molar ratio ammonium chloride 0.699 0.70
1 ,5-diamino-2-methylpentane 1.000 1.00 dicyandiamide 1.300 1.30
Execution:
Under inert gas (N2), 150.0 g of 1 ,2-propylene glycol and 37.4 g of ammonium chloride are placed in a 1.5 litre ground glass flask at room temperature (20-25°C). The resulting white suspension is then heated to TF = 78-82°C over 20-30 minutes. When the prescribed TF is reached, 116.2 g of 1 ,5-diamino-2-methylpentane are added over 40 min (38-42 min), resulting in a clear, pale yellow solution. The TF is then raised to 120°C (117-123°C) and 109.3 g of dicyandiamide are added at this TF over 90 minutes. Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out of the N2 stream in an NH3-absorption apparatus and titrated. After the addition is complete, the TF is raised to 130°C (128-132°C) and the clear yellow solution is allowed to react for another 270 minutes at this TF. The polycondensate so obtained is then diluted with X g of deionised water to a concentration of 30% active substance.
titrated amount of ammonia: 1.4 mol average molecular weight: Mn/Mw = 560/670 composition of the end product [%]: condensate 30
1 ,2-propylene glycol 17-19 waterdeion 5-53 Antimicrobial action:
1. Determination of the minimum inhibitory concentration in the agar incorporation test (MHK values in ppm of active substance)
Test strains
Polycondensate of Example 23
Staphylococcus aureus ATCC 9144 200ppm Staphylococcus epidermidis ATCC 12228 100ppm
Corynebacterium xerosis ATCC 373 50ppm
Escherichia coli NCTC 8196 200ppm
Pseudomonas aeruginosa CIP A-22 >1000ppm
Candida albicans ATCC 10'231 lOOOppm
Aspergillus niger ATCC 6275 lOOOppm
2. Determination of the bactericidal activity (dilution test)
Example 23 shows in the dilution test a germ reduction of 99.999% (Escherichia coli NCTC 8196) and 98% (Staphylococcus aureus ATCC 9144) at an application concentration of 200ppm and at a bacterial dissemination of 1-3x107 KBE/ml after a contact time of 3 hours. After a contact time of 24 hours, the germ reduction both for Escherichia coli and for Staphylococcus aureus is 99.999%.
Germ reduction after a contact time of 3 and 24 hours
Germ reduction Escherichia coli NCTC 8196 Staphylococcus aureus ATCC 9144 after a 3 hour 99.999% 98% contact time after a 24 hour 99.999% 99.999% contact time Example 24:
Starting compounds Amount used [%1 ammonium chloride 10.0
1 ,2-propylene glycol 16.8 diethylenetriamine 29.2 dicyandiamide 29.4 octylamine 14.6
Reaction parameters: metering time diethylenetriamine [min]: 40 metering time dicyandiamide [min]: 210 metering time octylamine [min]: 20 stirring time [min]: 120 stirring temperature [°C]: 110
Molar ratio:
Monomers Molar amount used Molar ratio ammonium chloride 1.249 0.66 diethylenetriamine 1.894 1.00 dicyandiamide 2.339 1.23 octylamine 0.755 0.40
Execution:
Under inert gas (N2), 112.3 g of 1 ,2-propylene glycol and 66.8 g of ammonium chloride are placed in a 1.5 litre ground glass flask at room temperature (20-25°C). The resulting white suspension is then heated for 20-30 minutes to TF = 78-82°C. When the prescribed TF is reached, 195.5 g of diethylenetriamine are added over 40 minutes (38-42 min), resulting in a clear, yellow and low-viscous solution. The TF is then raised to 120°C (117-123°C) and 196.7 g of dicyandiamide are added at this temperature over 210 minutes. Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out of the N2 stream in an NH3-absorption apparatus and titrated. After the addition is complete, 97.6 g of octylamine are added over 15-25 minutes at TF 120°C (118-122°C), resulting in a clear yellow solution. The TF is then lowered to 110°C (108-112°C) and the reaction solution is allowed to react for another 120 minutes.
The polycondensate so obtained is then diluted with X g of waterdeι0n to a concentration of 30% active substance.
titrated amount of ammonia: 3.4 mol average molecular weight: Mn/Mw = 350/440 composition of the end product [%] condensate 30
1.2-propylene glycol 6-8 waterdeι0n 62-64
Antimicrobial action:
1. Determination of the minimum inhibitory concentration in the agar incorporation test (MHK values in ppm active substance)
Test strains Polycondensate of Example 24
Staphylococcus aureus ATCC 9144 200ppm Staphylococcus epidermidis ATCC 12228 100ppm Corynebacterium xerosis ATCC 373 100ppm Escherichia coli NCTC 8196 500ppm Pseudomonas aeruginosa CIP A-22 lOOOppm Candida albicans ATCC 10'231 500ppm Aspergillus niger ATCC 6275 500ppm
2. Determination of the bactericidal activity (dilution test)
Example 24 shows in the dilution test a germ reduction of 99.9% (Escherichia coli NCTC 8196) and 95% (Staphylococcus aureus ATCC 9144) at an application concentration of 500ppm (Escherichia coli) and 200ppm (Staphylococcus aureus) and at a bacterial dissemination of 1 -3x107 KBE/ml after a contact time of 3 hours. After a contact time of 24 hours, the germ reduction both of Escherichia coli and of Staphylococcus aureus is 99.999%.
Germ reduction after a contact time of 3 and 24 hours: Germ reduction Escherichia coli NCTC 8196 Staphylococcus aureus ATCC 9144 after a 3 hour
99.9% 95% contact time after a 24 hour
99.999% 99.999% contact time
Additional tests of the same chemical type are listed below.
Example 25 26 27 28 29 metering time diethylenetriamine 40 40 40 40 40
[min]: metering time dicyandiamide 210 90 90 90 90
[min] stirring time [min] 60 60 120 180 240 stirring temperature [°C] 110 110 110 110 110
Molar ratio of the monomers: ammonium chloride 0.7 0.7 0.7 0.7 0.7 diethylenetriamine 1.0 1.0 1.0 1.0 1.0 dicyandiamide 1.3 1.3 1.3 1.3 1.3 octylamine 0.4 0.2 0.2 0.2 0.2 average molecular weight 355/450 280/340 295/380 330/420 380/500
Mn/Mw
Example 30:
Starting compounds Batch r%l bis(6-aminohexyl)amine 35.1
1 ,2-propylene glycol 19.4 ammonium chloride 11.5 dicyandiamide 34.0 Reaction parameters: metering time ammonium chloride [min]: 40 metering time dicyandiamide [min]: 0 stirring time [min]: 60 stirring temperature [°C]: 110
Molar ratio:
Monomers Molar amount used Molar ratio ammonium chloride 1.249 1.32 bis(6-aminohexyl)amine 0.945 1.00 dicyandiamide 2.339 2.48
Execution:
Under inert gas (N2), 112.3 g of 1 ,2-propylene glycol and 203.5 g of bis(6-aminohexyl)amine are placed in a 1.5 litre ground glass flask at room temperature (20-25°C). This suspension is then heated for 20-30 minutes to TF = 78-82°C. Aspect: clear, pale yellow solution. When the prescribed TF is reached, 66.8 g of ammonium chloride are added over 40 min (38 - 42 min). Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out of the N2 stream in an NH -absorption apparatus and titrated. The reaction solution turns cloudy. After the addition is complete, the TF is raised to 120°C (117-123°C) and 196.7 g of dicyandiamide are added at this TF over 90 minutes. Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out of the N2 stream in an NH -absorption apparatus and titrated. After the addition is complete, the TF is lowered to 110°C (108- 112°C) and the reaction solution is allowed to react for another 60 minutes. The polycondensate so obtained is then diluted with X g of waterdeιon to a concentration of 30% active substance.
titrated amount of ammonia: 0.7 mol average molecular weight: Mn/Mw = 350/420 composition of the end product [%]: condensate 30
1 ,2-propylene glycol 7-9 waterdeιon 61-63 Antimicrobial action:
1. Determination of the minimum inhibitory concentration in the agar incorporation test (MHK values in ppm active substance)
Test strains Polycondensate of Example 30
Staphylococcus aureus ATCC 9144 500ppm
Staphylococcus epidermidis ATCC 12228 100ppm
Corynebacterium xerosis ATCC 373 100ppm
Escherichia coli NCTC 8196 lOOOppm
Pseudomonas aeruginosa CIP A-22 >1000ppm
Candida albicans ATCC 10'231 50ppm
Aspergillus niger ATCC 6275 100ppm
Example 31 :
Starting compounds Amount used [%1 bis(6-aminohexyl)amine 35.1 1.2-propylene glycol 19.4 ammonium chloride 11.5 dicyandiamide 34.0
Reaction parameters: metering time ammonium chloride [min]: 40 metering time dicyandiamide [min]: 90 stirring time [min]: 120 stirring temperature [°C]: 110 Molar ratio:
Monomers Molar amount used Molar ratio ammonium chloride 1.249 1.32 bis(6-aminohexyl)amine 0.945 1.00 dicyandiamide 2.339 2.48
Execution:
Under inert gas (N2), 112.3 g of 1 ,2-propylene glycol and 203.5 g of bis(6-aminohexyl)amine are placed in a 1.5 litre ground glass flask at room temperature (20-25°C). This suspension is then heated to TF = 78-82°C over 20-30 minutes. Aspect: clear, pale yellow solution. When the prescribed TF is reached, 66.8g of ammonium chloride are added over 40 min (38-42 min). Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out of the N2 stream in an NH -absorption apparatus and titrated. The reaction solution turns cloudy. After the addition is complete, the TF is raised to 120°C (117-123°C) and 196.7 g of dicyandiamide are added at this TF over 90 minutes. Foam forms during the addition as a result of ammonia gas escaping as byproduct of the reaction. The ammonia gas is washed out of the N2 stream in an NH3-ab- sorption apparatus and titrated. After the addition is complete, the TF is lowered to 110°C (108-112°C) and the reaction solution is allowed to react for another 120 minutes. The polycondensate so obtained is then diluted with X g of waterdeion to a concentration of 30% active substance.
titrated amount of ammonia: 0.7 mol average molecular weight: Mn/Mw = 410/500 composition of the end product [%]: condensate 30
1 ,2-propylene glycol 7-9 waterdei0n 61-63 Antimicrobial action:
1. Determination of the minimum inhibitory concentration in the agar incorporation test (MHK values in ppm active substance)
Test strains Polycondensate of Example 31
Staphylococcus aureus ATCC 9144 50ppm
Staphylococcus epidermidis ATCC 10ppm
12228
Corynebacterium xerosis ATCC 373 10ppm
Escherichia coli NCTC 8196 200ppm
Pseudomonas aeruginosa CIP A-22 >1000ppm
Candida albicans ATCC 10'231 50ppm
Aspergillus niger ATCC 6275 50ppm
2. Determination of the bactericidal activity (dilution test)
Example 31 shows in the dilution test a germ reduction of 99.6% for Staphylococcus aureus and, after a contact time of 24 hours, a complete germ reduction of 99.999%, at an application concentration of 200ppm (Escherichia coli) and 50ppm (Staphylococcus aureus) and at a bacterial dissemination of 1-3x107 KBE/ml after 3 hours. The germ numbers of Escherichia coli were reduced by 99.999% already after a contact time of 3 hours.
Germ reduction after a contact time of 3 and 24 hours
Germ reduction Escherichia coli NCTC 8196 Staphylococcus aureus ATCC 9144 after a 3 hour 99.999% 99.6% contact time after a 24 hour 99.999% 99.999% contact time Additional Examples:
Example 32 33 metering time ammonium chloride [min] 40 min 40 min metering time dicyandiamide [min] 90 min 90 min stirring time [min] 180 min 240 min stirring temperature [°C] 110°C 110°C
Molar ratio of the monomers: ammonium chloride 0.5 0.5 bis(6-aminohexyl)amine 0.5 0.5 dicyandiamide 1.3 1.3 average molecular weight Mn/Mw 350/460 390/540
Comparison starting products/end products:
The following Table shows the antimicrobial action of the monomers in comparison with the end product prepared therefrom. The results show that the action of the products is not based on the activity of possibly remaining unreacted monomers. The two last Examples show equally clearly that using the same educts but different process parameters has an influence on the action.
Figure imgf000024_0001
*) The Examples differ not in their composition but in their reaction parameters. Examples 34 to 100: Variation of the molar ratios
Monomers Molar ratio (a) Molar ratio (b) ammonium chloride 1.32 0.5 (1.0) bis(6-aminohexyl)amine 1.00 0.5 (1.0) dicyandiamide 2.48 1.3 (2.6) corresponding to Examples 30 and 31 32 and 33
The molar ratio variants (a) and (b) can be used for the Examples listed in the following Table 1 :
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Example 101 : Dishwasher formulation basic polycondensate 0.01-10 % sodium lauryl sulfate 7.0 sodium myreth sulfate 7.0 lauryl glucoside 4.0 cocobetain 1.1 ethanol 5.0
NaCI 1.0 citric acid 50% to pH 6.5 perfume/preservative q.s. waterdeion ad 100.0 %
Example 102: All-purpose cleaner basic polycondensate 0.01-10 % cocamidopropylbetain 2.9 % lauramine oxide 3.0 % sodium laureth sulfate 4.2 sodium citrate 4.0 sodium carbonate 3.0 ethanol 3.0 waterdeion ad 100.0 %
Example 103: Surface cleaner basic polycondensate 0.01 -10 % octyl alcohol 4 EO 3.0 %
C8-Cι0fatty alcohol polyglucoside 1.3 % isopropyl alcohol 3.0 % waterdei0n ad 100.0 % Example 104: Softener basic polycondensate 0.01-10 % tallow acid ethylhydroxyethyl ammonium methosulfate 15.0 %
MgCI (sat. solution) 2.0 % coceth-10 2.0 % siiicone emulsion 0.5 % isopropyl alcohol 3.0 % perfume/preservative q.s. waterdei0n ad 100.0 %
Test methods
1. Test method: Determination of the minimum inhibitory concentration ( MHK) in the aoar incorporation test (MHK-test)
Test solution: 1% aqueous stock solutions are prepared from all the test substances and diluted in dilution series to end concentrations from lOOOppm to 10ppm.
Test principle: 0.3 ml of the respective dilution grade is mixed with 15 ml of still-liquid nutrient medium. After the culture medium has solidified, 10μl of the following germ dilution in 0.85% of NaCI solution are applied in spots on the agar medium:
Staphylococcus aureus ATCC 9144 100 Staphylococcus epidermidis ATCC 12228 100 Corynebacterium xerosis ATCC 373 100 Escherichia coli NCTC 8196 1000 Pseudomonas aeruginosa CIP A-22 1000 Candida albicans ATCC 10'231 10 Aspergillus niger ATCC 6275 10
The plates are incubated for 24 hours at 37°C ( A.niger 3 days at 28°C) and then just that end concentration of the test substance is determined at which no further growth is possible. medium: Mueller-Hinton-Agar (Merck) Sabouraud 4% glucose agar dilution medium: sterile 0.85% NaCI solution
test germs: Staphylococcus aureus ATCC 9144 Staphylococcus epidermidis ATCC 12228 Corynebacterium xerosis ATCC 373 Escherichia coli NCTC 8196 Pseudomonas aeruginosa CIP A-22 Candida albicans ATCC 10'231 Aspergillus niger ATCC 6275
incubation: 24 hours at 37°C 3 days at 28°C
2. Test method: Determination of the bactericidal activity in the dilution test
Test solution: The test substances 1-6 are adjusted to the minimum inhibitory concentration (MIC) by dilution with water and are tested against the test germs Staphylococcus aureus ATCC 9144 and Escherichia coli NCTC 8196:
Staphylococcus aureus ATCC 9144
Examples Test concentration
Example 1 : lOOOppm
Example 2: lOOOppm
Example 3: 200ppm
Example 4: 200ppm
Example 6: 50ppm Escherichia coli NCTC 8196
Examples Test concentration
Example 1 lOOOppm
Example 2 lOOOppm
Example 3 200ppm
Example 4 500ppm
Example 6 200ppm
Test princir 3le: Batches of 8ml nutrient solution each are char and 1 ml of germ suspension. (16-24 hour cultivation, diluted to a germ concentration of 1 - 3x108 KBE/ml.) The resulting germ concentration in the test batch is 1-3x107 KBE/ml.
After contact times of 3 hours and 24 hours, 1ml of test batch is sampled and diluted in 9 ml of inactivation medium in 1 :10 steps, and 100μl of the dilution stages 10"1, 10"3, 10'5 are plated out by means of a spiralometer. After incubation, the survival germ numbers are determined and the germ number reduction over the water controls is calculated.
nutrient solution: Mueller-Hinton-Broth (Merck) dilution medium: 0.85% NaCI solution inactivation medium: TS-Broth, pH7.2, containing 10.0% Tween 80, 3.0% lecithin, 0.5% sodium thiosulfate, 01% L-histidine test germs: Staphylococcus aureus ATCC 9144
Escherichia coli NCTC 8196 contact times: 3 hours, 24 hours incubation: 24 hours at 37°C
Example 105: Treatment of cotton
test sample: a. Example 31 (5% solution in water) b. Example 32 (5% solution in water)
starting solutions: 1 -1 Og/I of a 5% solution 2-30g/l of a 5% solution 3-50g/l of a 5% solution 4-1 OOg/l of a 5% solution
padding: liquor up-take of 70-90% drying: 1 10-130°C
The wash cycles are carried out by the following method:
Washing conditions washing powder 0.35 g washing powder / ad 70 g water textile: 7g of cotton temperature: 40°C duration: 10 minutes rinsing: 2 x 30 seconds drying: air
Microbiological test method:
Determination of the bacteriostatic activity of padded cotton in the agar diffusion test:
Test principle:
Antimicrobially finished circular cotton pads are placed on seeded nutrient agar plates and incubated. The active substance which diffuses into the agar during incubation inhibits the growth of the test germs in the environment and under the circular cotton pad.
The inhibitory zone around the round pad is given in nm as a measure of the antimicrobial activity of the active substance. Preparation of the agar plates:
Casein soybean flour peptone seeded with 1-5*106 KBE/ml of the test organism.
Test organism: Staphylococcus aureus ATCC 9144
Preparation of the test sample
Circular pads having a diameter of 20 nm are punched out of the cotton sample to be tested and are placed in the centre of a seeded agar plate.
Incubation of the plates and evaluation
The plates are incubated for 18-24 hours at 37°C.
Inhibitory zones are measured and indicated in mm.
Results activity of the treated cotton
Figure imgf000033_0001
Inhibition of growth in the contact zone The results in Table 2 show that the inventive formulations have antimicrobial action on cotton.
Activity of the treated cotton after 5 wash cycles
Figure imgf000034_0001

Claims

What is claimed is
1 . Use of a basic polycondensate, which is obtainable by reacting
(a) an amine of formula
R, A
(1 ) NΓÇö AΓÇö N
R2 R4
with an ammonium salt in the presence of a non-aqueous solvent, and
(b) by reacting the protonated product obtained according to (a) with a cyanamide at elevated temperature, wherein
R╬╣. R2, R3 and R are each independently of one another hydrogen, or alkyl which is unsubstituted or substituted by amino, hydroxy, cyano or C C4alkoxy, and
A is alkylene which is unsubstituted or substituted or which may be interrupted by one or more than one heteroatom, for the antimicrobial treatment of the human skin and of textile fibre materials and of paper or cardboard.
2. Use according to claim 1 , wherein A in formula (1 ) is C2-C2oalkylene which may be interrupted by -O-, -S-, -NH- or -N(C C4alkyl)- and/or substituted by OH and, preferably, C2-C20- alkylene which is interrupted once or several times by -NH-.
3. Use according to either claim 1 or claim 2, wherein the compound of formula (1 ) is dihe- xylenetriamine.
4. Use according to any one of claims 1 to 3, wherein the ammonium compound is ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium formiate or ammonium acetate and, preferably, ammonium chloride.
5. Use according to any one of claims 1 to 4, wherein the non-aqueous solvent is a hydroxyl group-containing solvent.
6. Use according to any one of claims 1 to 5, wherein the non-aqueous solvent is ethylene glycol, 1 ,2- or 1 ,3-propylene glycol, butylene glycol, di-, tri- or tetraethylene glycol or an ether thereof, a polyethylene glycol having a molecular weight of 600 to 5000 or a mixture of two or more of the cited solvents.
7. Use according to any one of claims 1 to 6, wherein the cyanamide (b) is dicyandiamide.
8. Use of the basic polycondensate according to any one of claims 1 to 7 as antimicrobial active substance against gram-positive and gram-negative bacteria and fungi.
9. Use of the basic polycondensate according to any one of claims 1 to 8 in body-care products.
10. A body-care product, which comprises a basic polycondensate according to claim 1.
11. A body-care product according to claim 10 in the form of a soap, shampoo or deodorant.
12. Use of the basic polycondensate according to any one of claims 1 to 8 in textile fibre materials.
13. Use of the basic polycondensate according to any one of claims 1 to 8 in paper or cardboard.
14. Use of the basic polycondensate according to any one of claims 1 to 8 in cleaning agents and disinfectants for hard surfaces.
PCT/EP1999/003752 1998-06-11 1999-05-31 Use of basic polycondensates as antimicrobial active substance WO1999064550A1 (en)

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US9572913B2 (en) 2009-11-12 2017-02-21 B. Braun Melsungen Ag Use of polymeric or oligomeric active ingredients for medical articles

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