CA2384427A1 - Copolymers of acryloylaminoalkyl compounds - Google Patents
Copolymers of acryloylaminoalkyl compounds Download PDFInfo
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- CA2384427A1 CA2384427A1 CA002384427A CA2384427A CA2384427A1 CA 2384427 A1 CA2384427 A1 CA 2384427A1 CA 002384427 A CA002384427 A CA 002384427A CA 2384427 A CA2384427 A CA 2384427A CA 2384427 A1 CA2384427 A1 CA 2384427A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/30—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
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- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Epidemiology (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
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- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Vascular Medicine (AREA)
- Dermatology (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Polymers & Plastics (AREA)
- Hematology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The invention relates to antimicrobial polymer, which can be obtained by copolymerisation of a monomer of formula (I) where R1 = -H or -CH3, R2 = branched or straight chain aliphatic hydrocarbon radical with 1 to 5 carbon atoms, Y=NR3R4, N+R3R4R5 X-R3, R4, R5 = H, a branched or straight chain aliphatic hydrocarbon radical with 1 to 5 carbon atoms, whereby R3, R4 and R 5 are identical or different and X- CH3SO-4, NO-3, F-, Cl-, Br-, I-, CH3CH2-, NO2-, NO-, CN-, SCN-, CNO-, ClO-, ClO2-, ClO3-, ClO4-. ClO4- with other aliphatic, unsaturated monomers. The invention also relates to a method for production of said polymers. Said polymers can also be produced by graft copolymerisation of a substrate, whereby a covalently bonded coating is obtained on the substrate surface. The inventive antimicrobial polymers can be used inter alia as microbiocidal coatings on hygiene articles or in the medical field and in paints or protective coatings.
Description
O.Z. 5493-WO
Copolymers of acrvloylaminoalkyl compounds The invention relates to antimicrobial polymers which are obtained by copolymenzing acryloylaminoalkyl compounds with other monomers. The invention further relates to a process for preparing these antimicrobial polymers, and to their use.
The invention also relates to antimicrobial polymers which are obtained by graft copolymerization of acryloylaminoalkyl compounds with other 1 o monomers on a substrate, and also to a process for their preparation, and to their use.
For the purposes of the present invention, acryloylaminoalkyl compounds are in particular dialkylaminoalkyl acrylates and acryloylaminoalkyl ammonium salts.
It is highly undesirable for bacteria to become established or to spread on the surfaces of piping, or of containers or packaging. Frequently, slime layers form and permit sharp rises in microbial populations, and these can 2 0 lead to persistent impairment of the quality of water or of drinks or foods, and even to spoilage of the product and harm to the health of consumers.
Bacteria must be kept away from all fields of life where hygiene is important. This affects textiles for direct body contact, especially in the genital area, and those for the care of the sick or elderly. Bacteria must also be kept away from surfaces of the furniture and instruments used in patient-care areas, especially in areas for intensive care or for neonatal care, and in hospitals, especially in areas for medical intervention, and also in isolation wards for critical cases of infection, and in toilets.
Copolymers of acrvloylaminoalkyl compounds The invention relates to antimicrobial polymers which are obtained by copolymenzing acryloylaminoalkyl compounds with other monomers. The invention further relates to a process for preparing these antimicrobial polymers, and to their use.
The invention also relates to antimicrobial polymers which are obtained by graft copolymerization of acryloylaminoalkyl compounds with other 1 o monomers on a substrate, and also to a process for their preparation, and to their use.
For the purposes of the present invention, acryloylaminoalkyl compounds are in particular dialkylaminoalkyl acrylates and acryloylaminoalkyl ammonium salts.
It is highly undesirable for bacteria to become established or to spread on the surfaces of piping, or of containers or packaging. Frequently, slime layers form and permit sharp rises in microbial populations, and these can 2 0 lead to persistent impairment of the quality of water or of drinks or foods, and even to spoilage of the product and harm to the health of consumers.
Bacteria must be kept away from all fields of life where hygiene is important. This affects textiles for direct body contact, especially in the genital area, and those for the care of the sick or elderly. Bacteria must also be kept away from surfaces of the furniture and instruments used in patient-care areas, especially in areas for intensive care or for neonatal care, and in hospitals, especially in areas for medical intervention, and also in isolation wards for critical cases of infection, and in toilets.
3 o A current method of treating equipment, or the surfaces of furniture or of textiles, to resist bacteria either when this becomes necessary or else as a precautionary measure is to use chemicals or solutions of these, or else mixtures which are disinfectant and therefore have fairly broad general antimicrobial action. Chemical agents of this type act nonspecifically and are themselves frequently toxic or irritant, or form degradation products which are hazardous to health. In addition, people frequently exhibit intolerance to these materials once they have become sensitized.
O.Z. 5493-WO - 2 -Another procedure to counteract the surface spread of bacteria is the incorporation of antimicrobial substances into a matrix.
In another technical sector, US 4 532 269 discloses a terpolymer of butyl methacrylate, tributyltin methacrylate, and tert-butylaminoethyl methacrylate. This polymer is used as an antimicrobial paint for ships: the hydrophilic tert-butylaminoethyl methacrylate promotes gradual erosion of the polymer, thus liberating the highly toxic tributyltin methacrylate as 1 o antimicrobial agent.
In these applications, the copolymer prepared using aminomethacrylates is merely a matrix or carrier substance for added microbial agents which can diffuse or migrate out of the carrier substance. Sooner or later, polymers of this type lose their effectiveness once the necessary "minimum inhibitory concentration" (MIC) at the surface has been lost.
European patent applications 0 862 858 and 0 8fi2 859 have disclosed that homo- and copolymers of tert-butylaminoethyl methacrylate, a 2 o methacrylate having a secondary amino function, have inherent microbicidal properties. For effective avoidance of undesirable resistance phenomena in microbes, particularly bearing in mind that the development of resistance by microbes is known from antibiotics research, systems developed in the future will again have to be based on novel compositions 2 5 with improved effectiveness.
Tert-butylaminoethyl methacrylate is a commercially available monomer in methacrylate chemistry and is used in particular as a hydrophilic constituent in copolymerization reactions. For example, EP 0 290 676 3 o describes the use of various polyacrylates and polymethacrylates as a matrix for immobilizing bactericidal quaternary ammonium compounds.
Dialkylaminoalkylmethacrylamides are widely used as a comonomer unit, in particular as a constituent of materials which improve dispersion and viscosity in lubricating oils. For example, EP 0 750 031 describes a 35 terpolymer from two alkyl acrylates, the alkyl chains present in each case being of different lengths, and from a nitrogen-containing monomer, including dimethylaminoacrylamides. US 5 821 313 describes analogous ' CA 02384427 2002-03-08 O.Z. 5493-WO 3 replacement sheet systems with a proportion by weight of up to 45% of amino-containing monomer.
As described in EP 0 416 762, dimethylaminopropylmethacrylamide is also used as a terpolymer constituent in cationic electrodeposition paint s compositions.
The preparation of antimicrobial copolymers using dialkylaminoalkylacrylamides is not known.
The object on which the invention is based is therefore to develop novel antimicrobial polymers which prevent bacteria from colonizing surfaces and io spreading thereon.
Surprisingly, it has now been found that copolymerization of acryloylaminoalkylamines with aliphatically unsaturated monomers or graft copolymerization of these components on a substrate gives polymers with a surface which is lastingly microbicidal, is not damaged by solvent or physical is action, and exhibits no migration. There is no need here to use any other biocidal active ingredient.
The use of 2-methacryloyloxyethyl derivatives as a cationic constituent in copolymerization reactions is known from other technical sectors. In this connection, EP 0 322 234 describes the synthesis of terpolymers which are 2o dewatering auxiliaries auxiliaries for dye systems, as described in US 4 976. There is no discussion in this context of acryloylaminoalkyl derivatives, which are in chemical terms a different class of substance.
FR-A-2757866 discloses polymers or copolymers having quaternary amino groups, the quaternary amino group containing an alkyl or aryl radical having 2s from 5 to 20 carbon atoms.
EP 331 528 describes copolymers composed of from 40 to 95% by weight of ethylene and from 5 to 60% by weight of at least one dialkylaminoalkylacrylamide.
3o The present invention therefore provides antimicrobial copolymers which are obtained by copolymerizing a monomer of the formula I
O.Z. 5493-WO 4 replacement sheet R' H
HzC =C' C--N-Rz-Y
(1) O
where R' - -H or -CH3, R2 - a branched or unbranched aliphatic hydrocarbon s radical having from 1 to 5 carbon atoms, R3, R4 - H or a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, where R3 and R4 may be identical or different, io with at least one other aliphatically unsaturated monomer excluding ethylene.
The invention further provides a process for preparing antimicrobial copolymers, where monomers of the formula I
R' HZC =C~ H
'C- ~ -RZ--Y
(I) O
is where R' - -H or -CH3, R2 - a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, Zo R3, R4 - H or a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon O.Z. 5493-WO 5 replacement sheet atoms, where R3 and R4 may be identical or different, are copolymerized with at least one other aliphatically unsaturated monomer excluding ethylene.
s The monomers of the formula I which may be used to prepare the inventive copolymers may therefore also be described by the formulae II
(dialkylaminoacrylamides) and III (acryloylaminoalkylammonium salts):
R' Ra z , Ra C-N-R -N
(II) O
R~
Rs C-N-R2-Nr R4 X' R5 (III}
O
To obtain adequate antimicrobial action from the copolymer or graft polymer, io the proportion of monomers of formula I or, respectively, 3-methacrylaminopropyltrimethylammonium chloride or 3-acryl-amidopropyltrimethylammonium chloride in the reaction mixture during the preparation of the antimicrobial copolymers or in the process according to the invention should be from 5 to 98 mol%, preferably from 30 to 98 mol%, is particularly preferably from 40 to 98 mol%, based on the entirety of the monomers.
The aliphatically unsaturated monomers used may be any of the monomers which copolymerize with the monomers of formula I. Examples of those suitable are acrylates and methacrylates, such as acrylic acid, tert-butyl 2o methacrylate, or methyl methacrylate, styrene, vinyl chloride, vinyl ethers, acrylamides, acrylonitriles, olefins (propylene, butylene, isobutylene), allyl compounds, vinyl ketones, vinylacetic acid, O.Z. 5493-WO 6 replacement sheet vinyl acetate, and vinyl esters, e.g. in particular methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butylaminoethyl esters, 2-diethylaminoethyl methacrylate, 2-diethylaminoethyl vinyl ether, 2-meth-s acryloyloxyethyltrimethylammonium methosulfate, and 2-meth-acryloyloxyethyltrimethylammonium chloride.
The aliphatically unsaturated monomers are preferably the compounds of acrylic or methacrylic acid, particularly preferably esters of acrylic or to methacrylic acid.
The monomer used in the formula II is preferably dimethylaminopropylmethacrylamide, diethylaminopropylmethacrylamide, or N-3-dimethylaminopropylacrylamide.
The monomer used in the formula III is 3-methacrylaminopropyltrimethylammonium chloride or 3-acrylamidopropyltrimethylammonium chloride.
2o The antimicrobial copolymers of the invention may be obtained by copolymerizing monomers of the formula I or II or III with one or more aliphatically unsaturated monomers. The polymerization advantageously takes place by a free-radical route using a free-radical initiator, or with initiation by radiation. The examples describe typical procedures.
The antimicrobial copolymers of the invention may also be obtained by copolymerizing monomers of the formula I or II or III with at least one aliphatically unsaturated monomer on a substrate. This gives a physisorbed coating made from the antimicrobial copolymer on the substrate.
O.Z. 5493-WO - 7 -Particularly suitable substrate materials are any of the synthetic polymers, e.g. polyurethanes, polyamides, polyesters, polyethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), and corresponding copolymers and blends, and also natural or synthetic rubbers, with or without radiation-sensitive groups. The process of the invention may also be employed on surfaces of products which have been made from metal, from glass, or from wood and which have been painted or otherwise 1 o plastic-coated.
In another embodiment of the present invention, the copolymers may be obtained by graft polymerization of a substrate using monomers of the formula I or II or III and using at least one aliphatically unsaturated monomer. The grafting of the substrate permits covalent linking of the antimicrobial copolymer to the substrate. The substrates used may be any polymeric material, such as the abovementioned plastics.
Prior to the graft copolymerization, the surfaces of the substrates may be 2 o activated by various methods. Any standard method for activating polymer surfaces may be used here. For example, the substrate may be activated prior to the graft polymerization by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge, or y-radiation.
The surfaces are advantageously freed in advance in a known manner 2 5 from oils, fats, or other contamination, using a solvent.
The substrates may be activated using UV radiation in the wavelength range from 170-400 nm, preferably from 170-250 nm. An example of a suitable radiation source is a Noblelight UV excimer apparatus from 3 o HERAEUS, Hanau, Germany. However, mercury vapor lamps are also suitable for substrate activation as long as they emit substantial proportions of radiation in the abovementioned ranges. The exposure time is generally from 0.1 second to 20 minutes, preferably from 1 second to 10 minutes.
The activation of the substrate using UV radiation prior to the graft polymerization may also be effected using an additional photosensitizer.
For this, the photosensitizer, such as benzophenone, is applied to the O.Z. 5493-WO - 8 -substrate surface and irradiated. A mercury vapor lamp may again be used here, with exposure times of from 0.1 second to 20 minutes, preferably from 1 second to 10 minutes.
According to the invention, the activation may also be achieved by plasma treatment using an RF or microwave plasma (Hexagon, Technics Plasma, 85551 Kirchheim, Germany) in air, nitrogen, or argon atmospheres. The exposure times are generally from 2 seconds to 30 minutes, preferably from 5 seconds to 10 minutes. The energy supplied in the case of to laboratory devices is from 100 to 500 W, preferably from 200 to 300 W.
Corona devices (SOFTAL, Hamburg, Germany) may also be used for activation. The exposure times in this case are generally from 1 to 10 minutes, preferably from 1 to 60 seconds.
Activation by electrical discharge, electron beam, or y-radiation (e.g. from a cobalt 60 source), and also ozonization, permit short exposure times, generally from 0.1 to 60 seconds.
2 o Substrate surfaces may also be activated by flame treatment. Suitable devices, in particular those with a barrier flame front, can readily be constructed or, for example, purchased from ARCOTEC, 71297 Monsheim, Germany. They may be operated using hydrocarbons or hydrogen as combustion gas. In all cases it is necessary to avoid damage to the substrate by overheating, and this can readily be ensured if that surface of the substrate facing away from the flame treatment side is in intimate contact with a cooled metal surface. Activation by flame treatment is therefore restricted to relatively thin, sheet-like substrates. The exposure times are generally from 0.1 second to 1 minute, preferably from 0.5 to 2 3 o seconds. The flames are exclusively nonluminous, and the distances between the substrate surfaces and the outer side of the flame front are from 0.2 to 5 cm, preferably from 0.5 to 2 cm.
The substrate surfaces activated in this way are coated by known methods, such as dipping, spraying, or spreading, using monomers of the formula I or II or III (component I) and using one or more aliphatically unsaturated monomers (component II), where appropriate in solution.
Solvents which have proven useful are water and waterlethanol mixtures, O.Z. 5493-WO - 9 -but other solvents may also be used as long as they are sufficiently capable of dissolving the monomers and give good wetting of the substrate surfaces. Solutions with monomer contents of from 1 to 10% by weight, for example about 5% by weight, have proven successful in practice and generally give, in a single pass, coherent coatings which cover the substrate surface and have thicknesses which can be more than 0.1 Nm.
The graft copolymerization of the monomers applied to the activated surfaces may usefully be initiated by radiation in the short-wave segment l o of the visible range, or in the long-wave segment of the UV range of electromagnetic radiation. For example, the radiation from a UV excimer to wavelengths of from 250 to 500 nm, preferably from 290 to 320 nm, is very suitable. Mercury vapor lamps are also suitable here as long as they emit substantial proportions of radiation in the abovementioned ranges. The exposure times are generally from 10 seconds to 30 minutes, preferably from 2 to 15 minutes.
Graft copolymerization of the comonomer compositions of the invention may also be achieved by a process described in European patent 2 o application 0 872 512 and based on graft polymerization of molecules of monomer and of initiator incorporated by swelling. The monomer used for the swelling process may be component II.
The antimicrobial copolymers of the invention made from monomers of formula I or II or III (component I) and from at least one other aliphatically unsaturated monomer (component II) exhibit microbicidal or antimicrobial behavior, even without grafting onto a substrate surface. In another embodiment of the present invention, components I and II are copolymerized on a substrate.
The components may be in solution when applied to the substrate.
Examples of suitable solvents are water, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran, and acetonitrile. It is also possible to use component II as solvent for component I.
The novel antimicrobial copolymers may also be used directly, i.e. not by polymerizing the components on a substrate but as an antimicrobial O.Z. 5493-WO - 10 -coating. Suitable coating methods are application of the copolymers in solution or as a melt.
The solution of the polymers of the invention may be applied to substrates by dipping, spraying, or painting, for example.
If the copolymers of the invention are produced directly on the substrate surface without grafting, conventional free-radical initiators may be added.
Examples of initiators which may be used in preparing the copolymers of 1 o the invention are azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate, and any of the usual photoinitiators, such as acetophenones, a hydroxyketones, dimethylketals, and benzophenone. The polymerization may also be initiated thermally or, as previously stated, by electromagnetic radiation, such as UV light or y-radiation.
Use of the modified polymer substrates The present invention also provides the use of the antimicrobial 2 o copolymers of the invention for producing antimicrobial products, and provides the resultant products per se. The products may comprise polymer substrates modified according to the invention, or consist of these.
Products of this type are preferably based on polyamides, on polyurethanes, on polyether block amides, on polyesteramides, or on polyesterimides, on PVC, on polyolefins, on silicones, on polysiloxanes, on polymethacrylate, or on polyterephthalates, which have surfaces modified using polymers of the invention.
Examples of antimicrobial products of this type are machine parts for the 3 o processing of food or drink, components of air conditioning systems, roofing, bathroom or toilet items, kitchen items, components of sanitary equipment, components of animal cages or of animal houses, recreational products for children, components of water systems, packaging for food or drink, operating units (touch panels) of devices, and contact lenses.
The copolymers or graft copolymers of the invention may be used wherever importance is placed on surfaces which are as free as possible from bacteria, i.e. microbicidal surfaces or surfaces with release properties.
O.Z. 5493-WO - 11 -Examples of the use of the copolymers or graft polymers of the invention are in particular surface coatings, protective paints, and other coatings in the following sectors:
- marine: ships' hulls, docks, buoys, drilling platforms, ballast water tanks - construction: roofing, basements, walls, facades, greenhouses, sun protection, garden fences, wood protection - sanitary: public conveniences, bathrooms, shower curtains, toilet items, swimming pools, saunas, jointing, sealing compounds - food and drink: machines, kitchens, kitchen items, sponges, recreational products for children, packaging for food or drink, milk processing, drinking water systems, cosmetics - machine parts: air conditioning systems, ion exchangers, process water, solar-powered units, heat exchangers, bioreactors, membranes - medical technology: contact lenses, diapers, membranes, implants - consumer articles: automobile seats, clothing (socks, sports clothing), hospital equipment, door handles, telephone handsets, public conveyances, animal cages, cash registers, carpeting, wall coverings.
2 o The copolymers of the invention or coatings made from these copolymers are also used as components for formulating inks or paints, e.g. as an additive or as a coating for an additive or for a pigment.
The present invention also provides the use of the inventive polymer substrates surface-modified using polymers of the invention or using the process of the invention for producing hygiene products or items for medical technology. The same descriptions of preferred materials are applicable. Examples of hygiene products of this type are toothbrushes, toilet seats, combs, and packaging material. The term hygiene item also 3 o includes other objects which may come into contact with a large number of people, for example telephone handsets, stair rails, door handles, window catches, and grab straps and grab handles in public conveyances.
Examples of items in medical technology are catheters, tubing, protective or backing films, and surgical instruments.
The following examples are given to describe the present invention in greater detail, but are not intended to limit its scope as set out in the patent claims.
O.Z. 5493-WO - 12 -Example 1:
16 g of 3-methacryloylaminopropyltrimethylammonium chloride (50% by weight solution in water) (Aldrich), 9 g of tert-butyl methacrylate (Aldrich), and 60 ml of ethanol are charged to a three-necked flask and heated to 65°C under a stream of argon. 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone is then slowly added dropwise, with stirring.
The mixture is heated to 70°C and stirred for 72 h at this temperature.
1 o After expiry of this time, the reaction mixture is stirred into 0.5 I of deionized water, whereupon the polymeric product precipitates. After the product has been isolated by filtration, the filter residue is washed with 100 ml of deionized water in order to remove any residual monomers still present. The product is then dried in vacuo at 52°C for 24 hours.
is Examale 1 a:
0.05 g of the product from example 1 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of 2 o microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 104.
Example 1 b:
0.05 g of the product from example 1 is shaken in 20 ml of a test microbial 2 5 suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 104.
3 o Example 2:
16 g of 3-methacryloylaminopropyltrimethylammonium chloride (50% by weight solution in water) (Aldrich), 9 g of butyl methacrylate (Aldrich), and 60 ml of ethanol are charged to a three-necked flask and heated to 65°C
under a stream of argon. 0.15 g of azobisisobutyronitrile dissolved in 4 ml 35 Of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred for 72 h at this temperature.
After expiry of this time, the reaction mixture is stirred into 0.5 I of deionized water, whereupon the polymeric product precipitates. After the product has O.Z. 5493-WO - 13 -been isolated by filtration, the filter residue is washed with 100 ml of deionized water in order to remove any residual monomers still present.
The product is then dried in vacuo at 50°C for 24 hours.
Example 2a:
0.05 g of the product from example 2 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the 1 o number of microbes has fallen from 10' to 103.
Example 2b:
0.05 g of the product from example 2 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 104.
Example 3:
2 0 12 g of 3-acrylamidopropyltrimethylammonium chloride (75% strength by weight solution in water) (Aldrich), 9 g of tert-butyl methacrylate (Aldrich), and 60 ml of ethanol are charged to a three-necked flask and heated to 65°C under a stream of argon. 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone is then slowly added dropwise, with stirring.
The mixture is heated to 70°C and stirred for 72 h at this temperature.
After expiry of this time, the reaction mixture is stirred into 0.51 of deionized water, whereupon the polymeric product precipitates. After the product has been isolated by filtration, the filter residue is washed with 100 ml of deionized water in order to remove any residual monomers still 3 o present. The product is then dried in vacuo at 50°C for 24 hours.
Example 3a:
0.05 g of the product from example 3 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 103.
O.Z. 5493-WO - 14 -Example 3b:
0.05 g of the product from example 3 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10'to 104.
Example 4:
12 g of 3-acrylamidopropyltrimethylammonium chloride (75% strength by to weight solution in water) (Aldrich), 9 g of butyl methacrylate (Aldrich), and 60 ml of ethanol are charged to a three-necked flask and heated to 65°C
under a stream of argon. 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred for 72 h at this temperature.
After expiry of this time, the reaction mixture is stirred into 0.51 of deionized water, whereupon the polymeric product precipitates. After the product has been isolated by filtration, the filter residue is washed with 100 ml of deionized water in order to remove any residual monomers still present.
The product is then dried in vacuo at 50°C for 24 hours.
Examale 4a:
0.05 g of the product from example 4 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 103.
Example 4b:
0.05 g of the product from example 4 is shaken in 20 ml of a test microbial 3 o suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10'to 104.
Examale 5:
A nylon-12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from a Heraeus excimer source. The film activated in this way is placed into an irradiator under an inert gas, and secured. Under a O.Z. 5493-WO - 15 -counterstream of inert gas, the film is then covered with 20 ml of a mixture of 16 g of 3-methacryloylaminopropyltrimethylammonium chloride (50%
strength by weight solution in water) (Aldrich), 9 g of tert-butyl methacrylate (Aldrich), and 60 g of ethanol. The irradiation chamber is sealed and placed at a distance of 10 cm from a Heraeus excimer source emitting at wavelength 308 nm. Irradiation is begun and continues for 15 minutes. The film is then removed and rinsed with 30 ml of ethanol, then dried in vacuo at 50°C for 12 hours, then extracted 5 times with water for 6 hours at 30°C, and then dried for 12 hours at 50°C.
The reverse side of the film is then treated in the same way, so that the polyamide film finally obtained has been coated on both sides with grafted polymer.
Example 5a:
A piece of coated film from example 5 (5 x 4 cm) is shaken in 30 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this 2 o time, the number of microbes has fallen from 10' to 104.
Examale 5b:
A piece of coated film from example 5 (5 x 4 cm) is shaken in 30 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact 2 s time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 104.
Example 6:
3 o A nylon-12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from a Heraeus excimer source. The film activated in this way is placed into an irradiator under an inert gas, and secured. Under a counterstream of inert gas, the film is then covered with 20 ml of a mixture of 12 g of 3-acrylamidopropyltrimethylammonium chloride (75% strength by 35 weight solution in water) (Aldrich), 9 g of tert-butyl methacrylate (Aldrich), and 60 g of ethanol. The irradiation chamber is sealed and placed at a distance of 10 cm from a Heraeus excimer source emitting at wavelength 308 nm. Irradiation is begun and continues for 15 minutes. The film is then O.Z. 5493-WO - 16 -removed and rinsed with 30 ml of ethanol, then dried in vacuo at 50°C
for 12 hours, then extracted 5 times with water for 6 hours at 30°C, and then dried for 12 hours at 50°C.
The reverse side of the film is then treated in the same way, so that the polyamide film finally obtained has been coated on both sides with grafted polymer.
Example 6a:
to A piece of coated film from example 6 (5 x 4 cm) is shaken in 30 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10'to 104.
Example 6b:
A piece of coated film from example 6 (5 x 4 cm) is shaken in 30 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and 2 o the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 104.
Example 7:
17 g of dimethylaminopropylmethacrylamide (Aldrich), 7 g of butyl methacrylate (Aldrich) and 120 ml of ethanol are charged to a three necked flask and heated to 65°C under a stream of argon. 0.3 g of azobisisobutyronitrile dissolved in 8 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred at this temperature for 72 h. After expiry of this time, the reaction mixture is 3 o stirred into 0.6 I of cyclohexane, whereupon the polymeric product precipitates. After the product has been isolated by filtration, the filter residue is washed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50°C for hours.
Example 7a:
0.05 g of the product from example 7 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, O.Z. 5493-WO - 17 -1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, no remaining Staphylococcus aureus microbes are detectable.
Example 7b:
0.05 g of the product from example 7 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the 1 o number of microbes has fallen from 10' to 103.
Example 8:
13 g of dimethylaminopropylmethacrylamide (Aldrich), 11 g of butyl methacrylate (Aldrich) and 120 ml of ethanol are charged to a three necked flask and heated to 65°C under a stream of argon. 0.3 g of azobisisobutyronitrile dissolved in 8 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred at this temperature for 72 h. After expiry of this time, the reaction mixture is stirred into 0.6 I of demineralized water, whereupon the polymeric product 2 o precipitates. After isolation of the product by filtration, the filter residue is washed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50°C for hours.
2 5 Example 8a:
0.05 g of the product from example 8 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the 3 o number of microbes has fallen from 10' to 103.
Example 8b:
0.05 g of the product from example 8 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 35 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 104.
O.Z. 5493-WO - 18 -Example 9:
14 g of dimethylaminopropylmethacrylamide (Aldrich), 10 g of tert-butyl methacrylate (Aldrich) and 120 ml of ethanol are charged to a three-necked flask and heated to 65°C under a stream of argon. 0.3 g of azobisisobutyronitrile dissolved in 8 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred at this temperature for 72 h. After expiry of this time, the reaction mixture is stirred into 0.6 I of demineralized water, whereupon the polymeric product precipitates. After isolation of the product by filtration, the filter residue is to washed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50°C for hours.
Example 9a:
0.05 g of the product from example 9 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10'to 103.
Example 9b:
0.05 g of the product from example 9 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 103.
Example 10:
14 g of dimethylaminopropylmethacrylamide (Aldrich), 10 g of ethyl 3 o methacrylate (Aldrich) and 120 ml of ethanol are charged to a three necked flask and heated to 65°C under a stream of argon. 0.3 g of azobisisobutyronitrile dissolved in 8 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred at this temperature for 72 h. After expiry of this time, the reaction mixture is 3 5 stirred into 0.6 I of cyclohexane, whereupon the polymeric product precipitates. After isolation of the product by filtration, the filter residue is washed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50°C for O.Z. 5493-WO - 19 -hours.
Example 10a:
0.05 g of the product from example 10 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 103.
Example 10b:
0.05 g of the product from example 10 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 104.
O.Z. 5493-WO - 2 -Another procedure to counteract the surface spread of bacteria is the incorporation of antimicrobial substances into a matrix.
In another technical sector, US 4 532 269 discloses a terpolymer of butyl methacrylate, tributyltin methacrylate, and tert-butylaminoethyl methacrylate. This polymer is used as an antimicrobial paint for ships: the hydrophilic tert-butylaminoethyl methacrylate promotes gradual erosion of the polymer, thus liberating the highly toxic tributyltin methacrylate as 1 o antimicrobial agent.
In these applications, the copolymer prepared using aminomethacrylates is merely a matrix or carrier substance for added microbial agents which can diffuse or migrate out of the carrier substance. Sooner or later, polymers of this type lose their effectiveness once the necessary "minimum inhibitory concentration" (MIC) at the surface has been lost.
European patent applications 0 862 858 and 0 8fi2 859 have disclosed that homo- and copolymers of tert-butylaminoethyl methacrylate, a 2 o methacrylate having a secondary amino function, have inherent microbicidal properties. For effective avoidance of undesirable resistance phenomena in microbes, particularly bearing in mind that the development of resistance by microbes is known from antibiotics research, systems developed in the future will again have to be based on novel compositions 2 5 with improved effectiveness.
Tert-butylaminoethyl methacrylate is a commercially available monomer in methacrylate chemistry and is used in particular as a hydrophilic constituent in copolymerization reactions. For example, EP 0 290 676 3 o describes the use of various polyacrylates and polymethacrylates as a matrix for immobilizing bactericidal quaternary ammonium compounds.
Dialkylaminoalkylmethacrylamides are widely used as a comonomer unit, in particular as a constituent of materials which improve dispersion and viscosity in lubricating oils. For example, EP 0 750 031 describes a 35 terpolymer from two alkyl acrylates, the alkyl chains present in each case being of different lengths, and from a nitrogen-containing monomer, including dimethylaminoacrylamides. US 5 821 313 describes analogous ' CA 02384427 2002-03-08 O.Z. 5493-WO 3 replacement sheet systems with a proportion by weight of up to 45% of amino-containing monomer.
As described in EP 0 416 762, dimethylaminopropylmethacrylamide is also used as a terpolymer constituent in cationic electrodeposition paint s compositions.
The preparation of antimicrobial copolymers using dialkylaminoalkylacrylamides is not known.
The object on which the invention is based is therefore to develop novel antimicrobial polymers which prevent bacteria from colonizing surfaces and io spreading thereon.
Surprisingly, it has now been found that copolymerization of acryloylaminoalkylamines with aliphatically unsaturated monomers or graft copolymerization of these components on a substrate gives polymers with a surface which is lastingly microbicidal, is not damaged by solvent or physical is action, and exhibits no migration. There is no need here to use any other biocidal active ingredient.
The use of 2-methacryloyloxyethyl derivatives as a cationic constituent in copolymerization reactions is known from other technical sectors. In this connection, EP 0 322 234 describes the synthesis of terpolymers which are 2o dewatering auxiliaries auxiliaries for dye systems, as described in US 4 976. There is no discussion in this context of acryloylaminoalkyl derivatives, which are in chemical terms a different class of substance.
FR-A-2757866 discloses polymers or copolymers having quaternary amino groups, the quaternary amino group containing an alkyl or aryl radical having 2s from 5 to 20 carbon atoms.
EP 331 528 describes copolymers composed of from 40 to 95% by weight of ethylene and from 5 to 60% by weight of at least one dialkylaminoalkylacrylamide.
3o The present invention therefore provides antimicrobial copolymers which are obtained by copolymerizing a monomer of the formula I
O.Z. 5493-WO 4 replacement sheet R' H
HzC =C' C--N-Rz-Y
(1) O
where R' - -H or -CH3, R2 - a branched or unbranched aliphatic hydrocarbon s radical having from 1 to 5 carbon atoms, R3, R4 - H or a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, where R3 and R4 may be identical or different, io with at least one other aliphatically unsaturated monomer excluding ethylene.
The invention further provides a process for preparing antimicrobial copolymers, where monomers of the formula I
R' HZC =C~ H
'C- ~ -RZ--Y
(I) O
is where R' - -H or -CH3, R2 - a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, Zo R3, R4 - H or a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon O.Z. 5493-WO 5 replacement sheet atoms, where R3 and R4 may be identical or different, are copolymerized with at least one other aliphatically unsaturated monomer excluding ethylene.
s The monomers of the formula I which may be used to prepare the inventive copolymers may therefore also be described by the formulae II
(dialkylaminoacrylamides) and III (acryloylaminoalkylammonium salts):
R' Ra z , Ra C-N-R -N
(II) O
R~
Rs C-N-R2-Nr R4 X' R5 (III}
O
To obtain adequate antimicrobial action from the copolymer or graft polymer, io the proportion of monomers of formula I or, respectively, 3-methacrylaminopropyltrimethylammonium chloride or 3-acryl-amidopropyltrimethylammonium chloride in the reaction mixture during the preparation of the antimicrobial copolymers or in the process according to the invention should be from 5 to 98 mol%, preferably from 30 to 98 mol%, is particularly preferably from 40 to 98 mol%, based on the entirety of the monomers.
The aliphatically unsaturated monomers used may be any of the monomers which copolymerize with the monomers of formula I. Examples of those suitable are acrylates and methacrylates, such as acrylic acid, tert-butyl 2o methacrylate, or methyl methacrylate, styrene, vinyl chloride, vinyl ethers, acrylamides, acrylonitriles, olefins (propylene, butylene, isobutylene), allyl compounds, vinyl ketones, vinylacetic acid, O.Z. 5493-WO 6 replacement sheet vinyl acetate, and vinyl esters, e.g. in particular methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butylaminoethyl esters, 2-diethylaminoethyl methacrylate, 2-diethylaminoethyl vinyl ether, 2-meth-s acryloyloxyethyltrimethylammonium methosulfate, and 2-meth-acryloyloxyethyltrimethylammonium chloride.
The aliphatically unsaturated monomers are preferably the compounds of acrylic or methacrylic acid, particularly preferably esters of acrylic or to methacrylic acid.
The monomer used in the formula II is preferably dimethylaminopropylmethacrylamide, diethylaminopropylmethacrylamide, or N-3-dimethylaminopropylacrylamide.
The monomer used in the formula III is 3-methacrylaminopropyltrimethylammonium chloride or 3-acrylamidopropyltrimethylammonium chloride.
2o The antimicrobial copolymers of the invention may be obtained by copolymerizing monomers of the formula I or II or III with one or more aliphatically unsaturated monomers. The polymerization advantageously takes place by a free-radical route using a free-radical initiator, or with initiation by radiation. The examples describe typical procedures.
The antimicrobial copolymers of the invention may also be obtained by copolymerizing monomers of the formula I or II or III with at least one aliphatically unsaturated monomer on a substrate. This gives a physisorbed coating made from the antimicrobial copolymer on the substrate.
O.Z. 5493-WO - 7 -Particularly suitable substrate materials are any of the synthetic polymers, e.g. polyurethanes, polyamides, polyesters, polyethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), and corresponding copolymers and blends, and also natural or synthetic rubbers, with or without radiation-sensitive groups. The process of the invention may also be employed on surfaces of products which have been made from metal, from glass, or from wood and which have been painted or otherwise 1 o plastic-coated.
In another embodiment of the present invention, the copolymers may be obtained by graft polymerization of a substrate using monomers of the formula I or II or III and using at least one aliphatically unsaturated monomer. The grafting of the substrate permits covalent linking of the antimicrobial copolymer to the substrate. The substrates used may be any polymeric material, such as the abovementioned plastics.
Prior to the graft copolymerization, the surfaces of the substrates may be 2 o activated by various methods. Any standard method for activating polymer surfaces may be used here. For example, the substrate may be activated prior to the graft polymerization by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge, or y-radiation.
The surfaces are advantageously freed in advance in a known manner 2 5 from oils, fats, or other contamination, using a solvent.
The substrates may be activated using UV radiation in the wavelength range from 170-400 nm, preferably from 170-250 nm. An example of a suitable radiation source is a Noblelight UV excimer apparatus from 3 o HERAEUS, Hanau, Germany. However, mercury vapor lamps are also suitable for substrate activation as long as they emit substantial proportions of radiation in the abovementioned ranges. The exposure time is generally from 0.1 second to 20 minutes, preferably from 1 second to 10 minutes.
The activation of the substrate using UV radiation prior to the graft polymerization may also be effected using an additional photosensitizer.
For this, the photosensitizer, such as benzophenone, is applied to the O.Z. 5493-WO - 8 -substrate surface and irradiated. A mercury vapor lamp may again be used here, with exposure times of from 0.1 second to 20 minutes, preferably from 1 second to 10 minutes.
According to the invention, the activation may also be achieved by plasma treatment using an RF or microwave plasma (Hexagon, Technics Plasma, 85551 Kirchheim, Germany) in air, nitrogen, or argon atmospheres. The exposure times are generally from 2 seconds to 30 minutes, preferably from 5 seconds to 10 minutes. The energy supplied in the case of to laboratory devices is from 100 to 500 W, preferably from 200 to 300 W.
Corona devices (SOFTAL, Hamburg, Germany) may also be used for activation. The exposure times in this case are generally from 1 to 10 minutes, preferably from 1 to 60 seconds.
Activation by electrical discharge, electron beam, or y-radiation (e.g. from a cobalt 60 source), and also ozonization, permit short exposure times, generally from 0.1 to 60 seconds.
2 o Substrate surfaces may also be activated by flame treatment. Suitable devices, in particular those with a barrier flame front, can readily be constructed or, for example, purchased from ARCOTEC, 71297 Monsheim, Germany. They may be operated using hydrocarbons or hydrogen as combustion gas. In all cases it is necessary to avoid damage to the substrate by overheating, and this can readily be ensured if that surface of the substrate facing away from the flame treatment side is in intimate contact with a cooled metal surface. Activation by flame treatment is therefore restricted to relatively thin, sheet-like substrates. The exposure times are generally from 0.1 second to 1 minute, preferably from 0.5 to 2 3 o seconds. The flames are exclusively nonluminous, and the distances between the substrate surfaces and the outer side of the flame front are from 0.2 to 5 cm, preferably from 0.5 to 2 cm.
The substrate surfaces activated in this way are coated by known methods, such as dipping, spraying, or spreading, using monomers of the formula I or II or III (component I) and using one or more aliphatically unsaturated monomers (component II), where appropriate in solution.
Solvents which have proven useful are water and waterlethanol mixtures, O.Z. 5493-WO - 9 -but other solvents may also be used as long as they are sufficiently capable of dissolving the monomers and give good wetting of the substrate surfaces. Solutions with monomer contents of from 1 to 10% by weight, for example about 5% by weight, have proven successful in practice and generally give, in a single pass, coherent coatings which cover the substrate surface and have thicknesses which can be more than 0.1 Nm.
The graft copolymerization of the monomers applied to the activated surfaces may usefully be initiated by radiation in the short-wave segment l o of the visible range, or in the long-wave segment of the UV range of electromagnetic radiation. For example, the radiation from a UV excimer to wavelengths of from 250 to 500 nm, preferably from 290 to 320 nm, is very suitable. Mercury vapor lamps are also suitable here as long as they emit substantial proportions of radiation in the abovementioned ranges. The exposure times are generally from 10 seconds to 30 minutes, preferably from 2 to 15 minutes.
Graft copolymerization of the comonomer compositions of the invention may also be achieved by a process described in European patent 2 o application 0 872 512 and based on graft polymerization of molecules of monomer and of initiator incorporated by swelling. The monomer used for the swelling process may be component II.
The antimicrobial copolymers of the invention made from monomers of formula I or II or III (component I) and from at least one other aliphatically unsaturated monomer (component II) exhibit microbicidal or antimicrobial behavior, even without grafting onto a substrate surface. In another embodiment of the present invention, components I and II are copolymerized on a substrate.
The components may be in solution when applied to the substrate.
Examples of suitable solvents are water, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran, and acetonitrile. It is also possible to use component II as solvent for component I.
The novel antimicrobial copolymers may also be used directly, i.e. not by polymerizing the components on a substrate but as an antimicrobial O.Z. 5493-WO - 10 -coating. Suitable coating methods are application of the copolymers in solution or as a melt.
The solution of the polymers of the invention may be applied to substrates by dipping, spraying, or painting, for example.
If the copolymers of the invention are produced directly on the substrate surface without grafting, conventional free-radical initiators may be added.
Examples of initiators which may be used in preparing the copolymers of 1 o the invention are azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate, and any of the usual photoinitiators, such as acetophenones, a hydroxyketones, dimethylketals, and benzophenone. The polymerization may also be initiated thermally or, as previously stated, by electromagnetic radiation, such as UV light or y-radiation.
Use of the modified polymer substrates The present invention also provides the use of the antimicrobial 2 o copolymers of the invention for producing antimicrobial products, and provides the resultant products per se. The products may comprise polymer substrates modified according to the invention, or consist of these.
Products of this type are preferably based on polyamides, on polyurethanes, on polyether block amides, on polyesteramides, or on polyesterimides, on PVC, on polyolefins, on silicones, on polysiloxanes, on polymethacrylate, or on polyterephthalates, which have surfaces modified using polymers of the invention.
Examples of antimicrobial products of this type are machine parts for the 3 o processing of food or drink, components of air conditioning systems, roofing, bathroom or toilet items, kitchen items, components of sanitary equipment, components of animal cages or of animal houses, recreational products for children, components of water systems, packaging for food or drink, operating units (touch panels) of devices, and contact lenses.
The copolymers or graft copolymers of the invention may be used wherever importance is placed on surfaces which are as free as possible from bacteria, i.e. microbicidal surfaces or surfaces with release properties.
O.Z. 5493-WO - 11 -Examples of the use of the copolymers or graft polymers of the invention are in particular surface coatings, protective paints, and other coatings in the following sectors:
- marine: ships' hulls, docks, buoys, drilling platforms, ballast water tanks - construction: roofing, basements, walls, facades, greenhouses, sun protection, garden fences, wood protection - sanitary: public conveniences, bathrooms, shower curtains, toilet items, swimming pools, saunas, jointing, sealing compounds - food and drink: machines, kitchens, kitchen items, sponges, recreational products for children, packaging for food or drink, milk processing, drinking water systems, cosmetics - machine parts: air conditioning systems, ion exchangers, process water, solar-powered units, heat exchangers, bioreactors, membranes - medical technology: contact lenses, diapers, membranes, implants - consumer articles: automobile seats, clothing (socks, sports clothing), hospital equipment, door handles, telephone handsets, public conveyances, animal cages, cash registers, carpeting, wall coverings.
2 o The copolymers of the invention or coatings made from these copolymers are also used as components for formulating inks or paints, e.g. as an additive or as a coating for an additive or for a pigment.
The present invention also provides the use of the inventive polymer substrates surface-modified using polymers of the invention or using the process of the invention for producing hygiene products or items for medical technology. The same descriptions of preferred materials are applicable. Examples of hygiene products of this type are toothbrushes, toilet seats, combs, and packaging material. The term hygiene item also 3 o includes other objects which may come into contact with a large number of people, for example telephone handsets, stair rails, door handles, window catches, and grab straps and grab handles in public conveyances.
Examples of items in medical technology are catheters, tubing, protective or backing films, and surgical instruments.
The following examples are given to describe the present invention in greater detail, but are not intended to limit its scope as set out in the patent claims.
O.Z. 5493-WO - 12 -Example 1:
16 g of 3-methacryloylaminopropyltrimethylammonium chloride (50% by weight solution in water) (Aldrich), 9 g of tert-butyl methacrylate (Aldrich), and 60 ml of ethanol are charged to a three-necked flask and heated to 65°C under a stream of argon. 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone is then slowly added dropwise, with stirring.
The mixture is heated to 70°C and stirred for 72 h at this temperature.
1 o After expiry of this time, the reaction mixture is stirred into 0.5 I of deionized water, whereupon the polymeric product precipitates. After the product has been isolated by filtration, the filter residue is washed with 100 ml of deionized water in order to remove any residual monomers still present. The product is then dried in vacuo at 52°C for 24 hours.
is Examale 1 a:
0.05 g of the product from example 1 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of 2 o microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 104.
Example 1 b:
0.05 g of the product from example 1 is shaken in 20 ml of a test microbial 2 5 suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 104.
3 o Example 2:
16 g of 3-methacryloylaminopropyltrimethylammonium chloride (50% by weight solution in water) (Aldrich), 9 g of butyl methacrylate (Aldrich), and 60 ml of ethanol are charged to a three-necked flask and heated to 65°C
under a stream of argon. 0.15 g of azobisisobutyronitrile dissolved in 4 ml 35 Of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred for 72 h at this temperature.
After expiry of this time, the reaction mixture is stirred into 0.5 I of deionized water, whereupon the polymeric product precipitates. After the product has O.Z. 5493-WO - 13 -been isolated by filtration, the filter residue is washed with 100 ml of deionized water in order to remove any residual monomers still present.
The product is then dried in vacuo at 50°C for 24 hours.
Example 2a:
0.05 g of the product from example 2 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the 1 o number of microbes has fallen from 10' to 103.
Example 2b:
0.05 g of the product from example 2 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 104.
Example 3:
2 0 12 g of 3-acrylamidopropyltrimethylammonium chloride (75% strength by weight solution in water) (Aldrich), 9 g of tert-butyl methacrylate (Aldrich), and 60 ml of ethanol are charged to a three-necked flask and heated to 65°C under a stream of argon. 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone is then slowly added dropwise, with stirring.
The mixture is heated to 70°C and stirred for 72 h at this temperature.
After expiry of this time, the reaction mixture is stirred into 0.51 of deionized water, whereupon the polymeric product precipitates. After the product has been isolated by filtration, the filter residue is washed with 100 ml of deionized water in order to remove any residual monomers still 3 o present. The product is then dried in vacuo at 50°C for 24 hours.
Example 3a:
0.05 g of the product from example 3 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 103.
O.Z. 5493-WO - 14 -Example 3b:
0.05 g of the product from example 3 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10'to 104.
Example 4:
12 g of 3-acrylamidopropyltrimethylammonium chloride (75% strength by to weight solution in water) (Aldrich), 9 g of butyl methacrylate (Aldrich), and 60 ml of ethanol are charged to a three-necked flask and heated to 65°C
under a stream of argon. 0.15 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred for 72 h at this temperature.
After expiry of this time, the reaction mixture is stirred into 0.51 of deionized water, whereupon the polymeric product precipitates. After the product has been isolated by filtration, the filter residue is washed with 100 ml of deionized water in order to remove any residual monomers still present.
The product is then dried in vacuo at 50°C for 24 hours.
Examale 4a:
0.05 g of the product from example 4 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10' to 103.
Example 4b:
0.05 g of the product from example 4 is shaken in 20 ml of a test microbial 3 o suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this period, the number of microbes has fallen from 10'to 104.
Examale 5:
A nylon-12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from a Heraeus excimer source. The film activated in this way is placed into an irradiator under an inert gas, and secured. Under a O.Z. 5493-WO - 15 -counterstream of inert gas, the film is then covered with 20 ml of a mixture of 16 g of 3-methacryloylaminopropyltrimethylammonium chloride (50%
strength by weight solution in water) (Aldrich), 9 g of tert-butyl methacrylate (Aldrich), and 60 g of ethanol. The irradiation chamber is sealed and placed at a distance of 10 cm from a Heraeus excimer source emitting at wavelength 308 nm. Irradiation is begun and continues for 15 minutes. The film is then removed and rinsed with 30 ml of ethanol, then dried in vacuo at 50°C for 12 hours, then extracted 5 times with water for 6 hours at 30°C, and then dried for 12 hours at 50°C.
The reverse side of the film is then treated in the same way, so that the polyamide film finally obtained has been coated on both sides with grafted polymer.
Example 5a:
A piece of coated film from example 5 (5 x 4 cm) is shaken in 30 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this 2 o time, the number of microbes has fallen from 10' to 104.
Examale 5b:
A piece of coated film from example 5 (5 x 4 cm) is shaken in 30 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact 2 s time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 104.
Example 6:
3 o A nylon-12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from a Heraeus excimer source. The film activated in this way is placed into an irradiator under an inert gas, and secured. Under a counterstream of inert gas, the film is then covered with 20 ml of a mixture of 12 g of 3-acrylamidopropyltrimethylammonium chloride (75% strength by 35 weight solution in water) (Aldrich), 9 g of tert-butyl methacrylate (Aldrich), and 60 g of ethanol. The irradiation chamber is sealed and placed at a distance of 10 cm from a Heraeus excimer source emitting at wavelength 308 nm. Irradiation is begun and continues for 15 minutes. The film is then O.Z. 5493-WO - 16 -removed and rinsed with 30 ml of ethanol, then dried in vacuo at 50°C
for 12 hours, then extracted 5 times with water for 6 hours at 30°C, and then dried for 12 hours at 50°C.
The reverse side of the film is then treated in the same way, so that the polyamide film finally obtained has been coated on both sides with grafted polymer.
Example 6a:
to A piece of coated film from example 6 (5 x 4 cm) is shaken in 30 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10'to 104.
Example 6b:
A piece of coated film from example 6 (5 x 4 cm) is shaken in 30 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and 2 o the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 104.
Example 7:
17 g of dimethylaminopropylmethacrylamide (Aldrich), 7 g of butyl methacrylate (Aldrich) and 120 ml of ethanol are charged to a three necked flask and heated to 65°C under a stream of argon. 0.3 g of azobisisobutyronitrile dissolved in 8 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred at this temperature for 72 h. After expiry of this time, the reaction mixture is 3 o stirred into 0.6 I of cyclohexane, whereupon the polymeric product precipitates. After the product has been isolated by filtration, the filter residue is washed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50°C for hours.
Example 7a:
0.05 g of the product from example 7 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, O.Z. 5493-WO - 17 -1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, no remaining Staphylococcus aureus microbes are detectable.
Example 7b:
0.05 g of the product from example 7 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the 1 o number of microbes has fallen from 10' to 103.
Example 8:
13 g of dimethylaminopropylmethacrylamide (Aldrich), 11 g of butyl methacrylate (Aldrich) and 120 ml of ethanol are charged to a three necked flask and heated to 65°C under a stream of argon. 0.3 g of azobisisobutyronitrile dissolved in 8 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred at this temperature for 72 h. After expiry of this time, the reaction mixture is stirred into 0.6 I of demineralized water, whereupon the polymeric product 2 o precipitates. After isolation of the product by filtration, the filter residue is washed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50°C for hours.
2 5 Example 8a:
0.05 g of the product from example 8 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the 3 o number of microbes has fallen from 10' to 103.
Example 8b:
0.05 g of the product from example 8 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 35 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 104.
O.Z. 5493-WO - 18 -Example 9:
14 g of dimethylaminopropylmethacrylamide (Aldrich), 10 g of tert-butyl methacrylate (Aldrich) and 120 ml of ethanol are charged to a three-necked flask and heated to 65°C under a stream of argon. 0.3 g of azobisisobutyronitrile dissolved in 8 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred at this temperature for 72 h. After expiry of this time, the reaction mixture is stirred into 0.6 I of demineralized water, whereupon the polymeric product precipitates. After isolation of the product by filtration, the filter residue is to washed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50°C for hours.
Example 9a:
0.05 g of the product from example 9 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10'to 103.
Example 9b:
0.05 g of the product from example 9 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 103.
Example 10:
14 g of dimethylaminopropylmethacrylamide (Aldrich), 10 g of ethyl 3 o methacrylate (Aldrich) and 120 ml of ethanol are charged to a three necked flask and heated to 65°C under a stream of argon. 0.3 g of azobisisobutyronitrile dissolved in 8 ml of ethyl methyl ketone is then slowly added dropwise, with stirring. The mixture is heated to 70°C and stirred at this temperature for 72 h. After expiry of this time, the reaction mixture is 3 5 stirred into 0.6 I of cyclohexane, whereupon the polymeric product precipitates. After isolation of the product by filtration, the filter residue is washed with 100 ml of n-hexane in order to remove any residual monomers still present. The product is then dried in vacuo at 50°C for O.Z. 5493-WO - 19 -hours.
Example 10a:
0.05 g of the product from example 10 is shaken in 20 ml of a test microbial suspension of Staphylococcus aureus. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 103.
Example 10b:
0.05 g of the product from example 10 is shaken in 20 ml of a test microbial suspension of Pseudomonas aeruginosa. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After expiry of this time, the number of microbes has fallen from 10' to 104.
Claims (26)
1. An antimicrobial copolymer obtainable by copolymerizing a monomer of the formula I
where R1 = -H or -CH3, R2 = a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, Y = NR3R4 R3, R4 = H or a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, where R3 and R4 may be identical or different, with at least one other aliphatically unsaturated monomer excluding ethylene.
where R1 = -H or -CH3, R2 = a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, Y = NR3R4 R3, R4 = H or a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, where R3 and R4 may be identical or different, with at least one other aliphatically unsaturated monomer excluding ethylene.
2. An antimicrobial copolymer obtainable by copolymerizing 3-methacrylaminopropyltrimethylammonium chloride or 3-acrylamidopropyltrimethylammonium chloride with at least one other aliphatically unsaturated monomer excluding ethene.
3. The antimicrobial copolymer as claimed in claim 1 or 2, wherein the aliphatically unsaturated monomers are compounds of methacrylic acid.
4. The antimicrobial copolymer as claimed in claim 1 or 2, wherein the aliphatically unsaturated monomers are compounds of acrylic acid.
5. The antimicrobial copolymer as claimed in claim 1 or 2, wherein the aliphatically unsaturated monomers used comprise methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butylaminoethyl esters, 2-diethylaminoethyl methacrylate, 2-diethylaminoethyl vinyl ether, 2-methacryloyloxyethyl-trimethylammonium methosulfate, or 2-methacryloyloxyethyltri-methylammonium chloride.
6. The antimicrobial copolymer as claimed in any of claims 1 to 5, wherein the copolymerization is carried out on a substrate.
7. The antimicrobial copolymer as claimed in any of claims 1 to 5, wherein the copolymerization is carried out as a graft polymerization of a substrate.
8. The antimicrobial copolymer as claimed in claim 7, wherein prior to the graft polymerization, the substrate is activated by UV
radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge, or .gamma.-radiation.
radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge, or .gamma.-radiation.
9. The antimicrobial copolymer as claimed in claim 7, wherein prior to the graft polymerization, the substrate is activated by UV
radiation using a photoinitiator.
radiation using a photoinitiator.
10. The antimicrobial copolymer as claimed in any of claims 1 to 9, wherein the monomer used of the formula I is dimethylaminopropylmethacrylamide, diethylamino-propylmethacrylamide, or N-3-dimethylaminopropylacrylamide.
11. The antimicrobial copolymer as claimed in any of claims 1 to 10, wherein the proportion of monomers of the formula I or, respectively, 3-methacrylaminopropyltrimethylammonium chloride or 3-acryl-amidopropyltrimethylammonium chloride in the reaction mixture during preparation of the antimicrobial copolymers is from 5 to 98 mol%.
12. A process for preparing antimicrobial copolymers, which comprises copolymerizing a monomer of the formula I
where R1 = -H or -CH3, R2 = a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, Y = NR3R4 R3, R4 = H or a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, where R3 and R4 may be identical or different, with at least one other aliphatically unsaturated monomer excluding ethylene.
where R1 = -H or -CH3, R2 = a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, Y = NR3R4 R3, R4 = H or a branched or unbranched aliphatic hydrocarbon radical having from 1 to 5 carbon atoms, where R3 and R4 may be identical or different, with at least one other aliphatically unsaturated monomer excluding ethylene.
13. A process for preparing antimicrobial copolymers by copolymerizing 3-methacryloylaminopropyltrimethylammonium chloride or 3-acrylamidopropyltrimethylammonium chloride with at least one other aliphatically unsaturated monomer excluding ethene.
14. The process as claimed in claim 12 or 13, wherein the aliphatically unsaturated monomers are compounds of methacrylic acid.
15. The process as claimed in claim 12 or 13, wherein the aliphatically unsaturated monomers are compounds of acrylic acid.
16. The process as claimed in claim 12 or 13, wherein the aliphatically unsaturated monomers used comprise methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butylaminoethyl esters, 2-diethylaminoethyl methacrylate, 2-diethylaminoethyl vinyl ether, 2-methacryloyl-oxyethyltrimethylammonium methosulfate, or 2-meth-acryloyloxyethyltrimethylammonium chloride.
17. The process as claimed in any of claims 12 to 16, wherein the copolymerization is carried out on a substrate.
18. The process as claimed in any of claims 12 to 16, wherein the copolymerization is carried out as a graft polymerization of a substrate.
19. The process as claimed in claim 18, wherein prior to the graft polymerization, the substrate is activated by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge, or .gamma.-radiation.
20. The process as claimed in claim 18, wherein prior to the graft polymerization, the substrate is activated by UV radiation, using a photoinitiator.
21. The process as claimed in any of claims 12 to 20, wherein the monomer used of the formula I is dimethylaminopropylmethacrylamide, diethylaminopropylmethacrylamide, or N-3-dimethylaminopropylacrylamide.
22. The process as claimed in any of claims 12 to 21, wherein the proportion of monomers of the formula I or, respectively, 3-methacrylaminopropyltrimethylammonium chloride or 3-acrylamidopropyltrimethylammonium chloride in the reaction mixture during the preparation of the antimicrobial copolymers is from 5 to 98 mol%.
23. The use of the antimicrobial polymers as claimed in any of claims 1 to 11 for producing products with an antimicrobial coating made from the polymer.
24. The use of the antimicrobial polymers as claimed in any of claims 1 to 11 for producing items for medical technology with an antimicrobial coating made from the polymer.
25. The use of the antimicrobial polymers as claimed in any of claims 1 to 11 for producing hygiene items with an antimicrobial coating made from the polymer.
26. The use of the antimicrobial polymers as claimed in any of claims 1 to 11 in surface coatings, protective paints, or other coatings.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19943344.5 | 1999-09-10 | ||
| DE19943344A DE19943344A1 (en) | 1999-09-10 | 1999-09-10 | Antimicrobial copolymer of permanently antimicrobial surface obtained by graft copolymerization of an alkylaminoalkylamide with an unsaturated monomer useful for medical and hygiene items |
| DE19952222.7 | 1999-10-29 | ||
| DE1999152222 DE19952222A1 (en) | 1999-10-29 | 1999-10-29 | Preparation of antimicrobial copolymer used for hygiene articles and in paints, by copolymerizing ethylamino alkyl amide(s) and aliphatically unsaturated comonomer(s) |
| PCT/EP2000/006487 WO2001019878A1 (en) | 1999-09-10 | 2000-07-08 | Copolymers of acryloylaminoalkyl compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2384427A1 true CA2384427A1 (en) | 2001-03-22 |
Family
ID=26054914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002384427A Abandoned CA2384427A1 (en) | 1999-09-10 | 2000-07-08 | Copolymers of acryloylaminoalkyl compounds |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1228112A1 (en) |
| JP (1) | JP2003509546A (en) |
| AU (1) | AU6690300A (en) |
| CA (1) | CA2384427A1 (en) |
| WO (1) | WO2001019878A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10351716B2 (en) | 2014-07-15 | 2019-07-16 | Akzo Nobel Coatings International B.V. | Antifouling coating composition comprising at least two salt-containing copolymers |
| US11384172B2 (en) | 2015-12-14 | 2022-07-12 | Jsr Corporation | Polymer, antimicrobial agent, disinfectant, antimicrobial material, disinfectant material, antimicrobial method, and disinfecting method |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10022406A1 (en) * | 2000-05-09 | 2001-11-15 | Creavis Tech & Innovation Gmbh | New antimicrobial copolymers used for disinfection of water or production of microbicidal coatings, obtained by copolymerisation of amino-functional acrylate or acrylamide with non-functionalised monomers |
| DE10110885A1 (en) * | 2001-03-07 | 2002-09-12 | Creavis Tech & Innovation Gmbh | Mocrobicidal separation systems |
| DE10117106A1 (en) * | 2001-04-06 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Antimicrobial food preservation systems |
| CA2521249A1 (en) * | 2003-04-07 | 2004-10-21 | Rimon Therapeutics Ltd. | Ancient defense polymer |
| EP1518870B1 (en) * | 2003-09-17 | 2018-11-28 | Gambro Lundia AB | Separating material |
| US8142844B2 (en) | 2003-09-17 | 2012-03-27 | Gambro Lundia Ab | Separating material |
| JP2007327008A (en) * | 2006-06-09 | 2007-12-20 | Nippon Shokubai Co Ltd | Manufacturing process of antibacterial water-absorbing resin |
| FR2976485B1 (en) * | 2011-06-20 | 2013-10-11 | Oreal | USE AS ANTI-TRANSPARENT AGENT OF A FLOCCULATING HYDRODISPERSIBLE POLYMER COMPRISING NON-QUATERNIZED AMINE GROUPS |
| JP6329229B2 (en) * | 2015-09-30 | 2018-05-23 | 株式会社日本触媒 | Antibacterial agent |
| JP6871266B2 (en) * | 2016-10-17 | 2021-05-12 | 株式会社日本触媒 | Copolymer for cleaning agent |
| JP7161856B2 (en) * | 2017-09-29 | 2022-10-27 | 株式会社日本触媒 | Fiber treatment agent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4237218A (en) * | 1979-02-09 | 1980-12-02 | Bio-Rad Laboratories, Inc. | Micro-carrier cell culture |
| JP2661241B2 (en) * | 1988-03-03 | 1997-10-08 | 住友化学工業株式会社 | Disinfectant and disinfectant resin composition containing ethylene copolymer as active ingredient |
| DE19646965C2 (en) * | 1996-11-14 | 1999-08-12 | Roehm Gmbh | Acrylate-based biophobic polymers, processes for their production and their use |
| FR2757866B1 (en) * | 1996-12-30 | 2004-12-17 | Catalyse | POLYMERS COMPRISING QUATERNARY AMMONIUM GROUPS, THEIR USE FOR THE MANUFACTURE OF AN ANTIBACTERIAL PROPERTY MATERIAL AND THEIR PREPARATION METHODS |
| DE19709076A1 (en) * | 1997-03-06 | 1998-09-10 | Huels Chemische Werke Ag | Process for the production of antimicrobial plastics |
-
2000
- 2000-07-08 JP JP2001523655A patent/JP2003509546A/en active Pending
- 2000-07-08 WO PCT/EP2000/006487 patent/WO2001019878A1/en not_active Application Discontinuation
- 2000-07-08 AU AU66903/00A patent/AU6690300A/en not_active Abandoned
- 2000-07-08 EP EP00954450A patent/EP1228112A1/en not_active Withdrawn
- 2000-07-08 CA CA002384427A patent/CA2384427A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10351716B2 (en) | 2014-07-15 | 2019-07-16 | Akzo Nobel Coatings International B.V. | Antifouling coating composition comprising at least two salt-containing copolymers |
| US11384172B2 (en) | 2015-12-14 | 2022-07-12 | Jsr Corporation | Polymer, antimicrobial agent, disinfectant, antimicrobial material, disinfectant material, antimicrobial method, and disinfecting method |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1228112A1 (en) | 2002-08-07 |
| JP2003509546A (en) | 2003-03-11 |
| WO2001019878A1 (en) | 2001-03-22 |
| AU6690300A (en) | 2001-04-17 |
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