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WO1999064550A1 - Utilisation de polycondensats basiques en tant que substance active antimicrobienne - Google Patents

Utilisation de polycondensats basiques en tant que substance active antimicrobienne 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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WO
WIPO (PCT)
Prior art keywords
ammonium
basic
test
atcc
dicyandiamide
Prior art date
Application number
PCT/EP1999/003752
Other languages
English (en)
Inventor
Rolf Kuratli
Anita Schmidlin
Werner Kaufmann
Dietmar Ochs
Karin Puchtler
Original Assignee
Ciba Specialty Chemicals Holding Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Specialty Chemicals Holding Inc. filed Critical Ciba Specialty Chemicals Holding Inc.
Priority to AU43720/99A priority Critical patent/AU4372099A/en
Publication of WO1999064550A1 publication Critical patent/WO1999064550A1/fr

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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.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Epidemiology (AREA)
  • Agronomy & Crop Science (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Organic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Dans l'invention, on décrit l'utilisation de polycondensats basiques que l'on peut obtenir (a) en faisant réagir une amine de la formule (1) avec un sel d'ammonium en présence d'un solvant non aqueux, et (b) en faisant réagir le produit obtenu dans la réaction (a), avec un cyanamide, à température élevée. Dans la formule (1) R1, R2, R3 et R4 représentent chacun indépendamment hydrogène, ou alkyle substitué ou non par amino, hydroxy, cyano ou alcoxy C1-C4, et A représente alkylène qui peut être substitué ou non, ou qui peut être interrompu par un ou plusieurs hétéroatomes. Ces composés sont destinés au traitement antimicrobien de la peau humaine, de matériaux en fibre textile, de papier ou de carton et de surfaces dures.
PCT/EP1999/003752 1998-06-11 1999-05-31 Utilisation de polycondensats basiques en tant que substance active antimicrobienne WO1999064550A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43720/99A AU4372099A (en) 1998-06-11 1999-05-31 Use of basic polycondensates as antimicrobial active substance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP98810532.6 1998-06-11
EP98810532 1998-06-11

Publications (1)

Publication Number Publication Date
WO1999064550A1 true WO1999064550A1 (fr) 1999-12-16

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Application Number Title Priority Date Filing Date
PCT/EP1999/003752 WO1999064550A1 (fr) 1998-06-11 1999-05-31 Utilisation de polycondensats basiques en tant que substance active antimicrobienne

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AR (1) AR019638A1 (fr)
AU (1) AU4372099A (fr)
WO (1) WO1999064550A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9572913B2 (en) 2009-11-12 2017-02-21 B. Braun Melsungen Ag Use of polymeric or oligomeric active ingredients for medical articles

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2000164A (en) * 1977-06-10 1979-01-04 Ciba Geigy Ag Polymeric quaternary ammonium salts processes for their preparation and their use
GB1570517A (en) * 1975-10-22 1980-07-02 Kemanobel Ab Antimicrobial or pesticidal guanidine derivatives
DE3237074A1 (de) * 1982-10-07 1984-04-12 Bayer Ag, 5090 Leverkusen Neue polymer-biguanide, ihre herstellung und verwendung in mikrobiziden mitteln
EP0265202A2 (fr) * 1986-10-20 1988-04-27 Unilever Plc Compositions désinfectantes
EP0692511A1 (fr) * 1994-07-12 1996-01-17 Ciba-Geigy Ag Procédé de fabrication d'adjuvant de teinture
US5659011A (en) * 1994-09-23 1997-08-19 Waldmann; John J. Agents having high nitrogen content and high cationic charge based on dicyanimide dicyandiamide or guanidine and inorganic ammonium salts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1570517A (en) * 1975-10-22 1980-07-02 Kemanobel Ab Antimicrobial or pesticidal guanidine derivatives
GB2000164A (en) * 1977-06-10 1979-01-04 Ciba Geigy Ag Polymeric quaternary ammonium salts processes for their preparation and their use
DE3237074A1 (de) * 1982-10-07 1984-04-12 Bayer Ag, 5090 Leverkusen Neue polymer-biguanide, ihre herstellung und verwendung in mikrobiziden mitteln
EP0265202A2 (fr) * 1986-10-20 1988-04-27 Unilever Plc Compositions désinfectantes
EP0692511A1 (fr) * 1994-07-12 1996-01-17 Ciba-Geigy Ag Procédé de fabrication d'adjuvant de teinture
US5659011A (en) * 1994-09-23 1997-08-19 Waldmann; John J. Agents having high nitrogen content and high cationic charge based on dicyanimide dicyandiamide or guanidine and inorganic ammonium salts

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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AU4372099A (en) 1999-12-30
AR019638A1 (es) 2002-02-27

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