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CN1360602A - Method for producing inherently microbicidal polymer surfaces - Google Patents

Method for producing inherently microbicidal polymer surfaces Download PDF

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Publication number
CN1360602A
CN1360602A CN00810290A CN00810290A CN1360602A CN 1360602 A CN1360602 A CN 1360602A CN 00810290 A CN00810290 A CN 00810290A CN 00810290 A CN00810290 A CN 00810290A CN 1360602 A CN1360602 A CN 1360602A
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Prior art keywords
substrate
branching
microbial polymer
preparation
film
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CN00810290A
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Chinese (zh)
Inventor
P·奥特斯巴赫
F·索斯纳
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CREVIS TECHNOLOGY AND CREATION Co Ltd
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CREVIS TECHNOLOGY AND CREATION Co Ltd
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Publication of CN1360602A publication Critical patent/CN1360602A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/10—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to inorganic materials
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • 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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/204—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Inorganic Chemistry (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Molecular Biology (AREA)
  • Biomedical Technology (AREA)
  • Dermatology (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Hematology (AREA)
  • Toxicology (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a method for producing antimicrobial polymers by polymerizing aliphatically unsaturated monomers that are at least mono-functionalized with a tertiary amino group. The antimicrobial polymers produced according to the invention can be used as a microbicidal coating on e.g. hygiene products or in the area of medicine, or in paints or protective coats.

Description

Produce the method for inherently microbicidal polymer surfaces
The present invention relates to a kind ofly prepare the method for anti-microbial polymer and the application of the anti-microbial polymer that obtains by the monomeric polymerization of aminofunctional.
The invention still further relates to and a kind ofly prepare the method for anti-microbial polymer and the application of the antimicrobial substrate that obtains by the graft polymerization of aminofunctional monomer on substrate.
Bacterium is in case settle down or spread at pipeline, container or surface of package, and that will be unusual brain people.Usually be, form slime layer earlier, just occur the sharp increase of microbial population thereupon, these microorganisms since then will be for a long time, constantly destroy the quality of water, beverage or food, even destroy product, harm consumer health.
The sphere of life that is placed on critical role in institute's handlebar health all must be accomplished away from bacterium.This relates to the textiles of direct contact bodies, particularly contacts genital area, and old man and patient care are used.At hospital ward, particularly grave illness is nursed and the Baby Care zone, and especially medical treatment gets involved regional furniture and instrument surface and also must avoid bacterium again, also have at the isolation ward that seriously infects case, and even in the lavatory.
Be used for equipment or furniture or textile surface are carried out the method for antimicrobial treatment at present,, all adopt chemical or its solution or mixture as sterilizing agent with suitable broad-spectrum antibacterial action no matter when needs or be used as preventive measures.The effect right and wrong of this type chemical agent are special, and they itself usually poisonous or with irritating, perhaps generate the degraded product that is harmful to health.Usually be in addition, the people is in case to certain material allergy, and from then on he just show and do not tolerate these materials.
Another kind prevents that the method that the surface of bacterium is spread from being that the material that will have anti-microbial effect is attached in the matrix.
Methacrylic acid tertiary butyl amino-ethyl ester is a ready-made available commercial in the methacrylated, especially is used in the copolyreaction as hydrophilic component.For example, EP 0 290 676 adopts various polyacrylic ester and polymethacrylate as matrix, is used for fixing the microbicidel quaternary ammonium compound.
In another technical field, US-A 4 532 269 discloses the terpolymer of a kind of butyl methacrylate, methacrylic acid tributyl tin and methacrylic acid tertiary butyl amino-ethyl ester.This polymkeric substance is used for various boats and ships as antimicrobial lacquer: hydrophilic methacrylic acid tertiary butyl amino-ethyl ester can impel this polymkeric substance gradually by erosion, thereby discharges this biocide of high toxicity methacrylic acid tributyl tin.
In these application scenarios, adopting the multipolymer of amino methyl acrylate preparation only is a kind of matrix or carrier substance, is intended to make the microbicide of adding to spread in carrier substance or moves.Sooner or later, in case no longer can reach " minimum inhibition concentration " (MIC) on its surface, the polymkeric substance of this type is just lost its effectiveness at once.
European patent application 0 862 858 and 0 862 859 open roads, methacrylic acid tertiary butyl amino-ethyl ester, a kind of methacrylic ester that has secondary amino group functional group, its all-and multipolymer possess the inherently microbicidal performance.For avoiding the undesirable resistance phenomenon of microorganisms, particularly in view of learning that from antibody research bacterium can develop immunity to drugs gradually, the system of exploitation also must continue following the novel composition direction with the effectiveness improved in the future.
Therefore, the objective of the invention is to research and develop a kind of novel polymer with anti-microbial effect.This polymkeric substance is randomly taked coating form, should prevent bacterium settling down and spread from the teeth outwards.
Surprisingly have now found that, by the polymerization of the aliphatic unsaturated monomer of monofunctional at least of uncle's amino group, generate a kind of polymkeric substance with long-acting microbicidel surface, it is not subjected to the erosion of solvent or physical stress and does not show migration yet.This make re-use other microbicides become unnecessary.
The invention provides a kind of method for preparing anti-microbial polymer, it is characterized in that, to by uncle's amino group at least the aliphatic unsaturated monomer of monofunctional carry out polymerization.
That the present invention uses, by uncle's amino group at least the aliphatic unsaturated monomer of monofunctional can have maximum 50 carbon atoms, preferred maximum 30 carbon atoms, the hydrocarbyl group of especially preferred maximum 22 carbon atoms.The substituting group of this amino group can be aliphatic series or vinyl hydrocarbyl group, methyl, ethyl, propyl group or acrylic groups groups such as (acrylic radicals) for example, perhaps cyclic hydrocarbon group group, the replacement of for example maximum 25 carbon atoms or unsubstituted phenyl or cyclohexyl groups.This amino group also can replace ketone group or aldehyde groups, for example group such as acryloyl or oxo.
For reaching enough rates of polymerization, the monomeric molar mass that the present invention uses should be less than 900, preferably less than 550g/mol.
A special embodiment of the present invention can adopt by aliphatic unsaturated monomer uncle's amino group monofunctional and that have following general formula,
R 1NR 2R 3R wherein 1Be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group has maximum 50 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom, and
R 2And R 3Can be identical or different, be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group has maximum 25 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom.
The suitable monomers structural unit is all aliphatic unsaturated monomers with at least one uncle's amido functional group, for example methacrylic acid 2-lignocaine ethyl ester, methacrylic acid 2-dimethylaminoethyl, methacryloyl 3-dimethylamino-propyl amine, vinylformic acid 2-lignocaine ethyl ester, vinylformic acid 2-dimethylaminoethyl, vinylformic acid 3-dimethylamino propyl ester or vinylformic acid 3-dimethylamino-2,2-dimethyl propyl ester.
The inventive method also can by by uncle's amino group at least the polymerization of monomer on substrate of monofunctional obtain.This will generate the physical adsorption coating of a kind of anti-microbial polymer on substrate.
Be fit to do the especially any polymer plastic of material of substrate, for example urethane, polymeric amide, polyester and polyethers, polyether block amide, polystyrene, polyvinyl chloride, polycarbonate, organopolysiloxane, polyolefine, polysulfones, polyisoprene, sovprene, polytetrafluoroethylene (PTFE) or corresponding multipolymer or blend, and also comprise natural or synthetic rubber, can have or be not with the radiation-sensitive group.The inventive method also can be used on body surface of metal, glass or timber top coat or other usefulness plastic-coated.
In another embodiment of the present invention, this anti-microbial polymer can by by uncle's amino group at least aliphatic unsaturated monomer graft polymerization on substrate of monofunctional prepare.Can produce covalent linkage between anti-microbial polymer and the substrate in the grafting on the substrate.Spendable substrate can be any polymeric material, plastics for example above-mentioned.
Before the graft polymerization reaction, the surface of substrate can be activated by variety of processes.Any standard method that is used for the activated polymer surface all can here be used, and for example substrate can activate with methods such as ultraviolet ray, Cement Composite Treated by Plasma, corona treatment, flame treating, ozonize, discharge or gamma-radiations before graft polymerization.Usefully, this surface is removed oil, fat or other pollutents by known way with solvent in advance.
Substrate can adopt ultraviolet activation, and its wavelength region is between 170～400nm, preferred 170～250nm.Suitable radiogenic example is Noblelight UV excimer (excimer) equipment (HERAEUS company (Hanau, a Germany)).Yet mercury vapor light also is suitable for the activation of substrate, as long as they launch the ray of the scope of mentioning above the significant proportion.Irradiation time is generally between 0.1s～20min, preferred 1s～10min.
Standard polymers also can adopt photosensitizers in addition with the activation that uv-radiation carries out.For this reason, photosensitizers paint substrate surface that will be such as benzophenone is carried out irradiation then.Equally, mercury vapor light also can here use, this moment irradiation time between 0.1s～20min, preferred 1s～10min.
According to the present invention, activation also can be passed through Cement Composite Treated by Plasma, uses RF (radio frequency) or microwave plasma (Hexagon, Technics Plasma company, 85551, Kirchheim, Germany) to carry out in air, nitrogen or argon gas atmosphere.Irradiation time is generally between 2s～30min, preferred 5s～10min.Under the situation of lab setup, the energy of supply is between 100～500W, preferred 200～300W.
Corona unit (SOFTAL, hamburger, Germany) also can be used for activation.Irradiation time, in this case generally between 1～10min, preferred 1～60s.
Utilize discharge, electron beam or gamma-radiation (for example from cobalt 60 source), also have the activation of ozonize etc. to allow to take the short irradiation time, generally between 0.1～60s.
Substrate surface also can reach activation by flame treating.Suitable device particularly has those of shielding (barrier) flame front, is easy to make or for example buy from ARCOTEC company (71297 M  nsheim, Germany).They can utilize hydro carbons or hydrogen to operate as combustion gases.Under any circumstance, all must avoid, and this is easy to by allowing the back of the body keep closely contacting being guaranteed with the refrigerative metallic surface towards the substrate side of flame treating one side because of the overheated substrate that damages.Therefore, the flame treating activation method is confined to situation relatively thinner, sheet substrate.Irradiation time is generally between 0.1s～1min, preferred 0.5～2s.The flame here is non-luminous without exception, and the distance between substrate surface and the flame front outside is between 0.2～5cm, preferred 0.5～2cm.
Through like this activatory substrate surface, be coated with by currently known methods, for example dip-coating, spraying or brush gone up by uncle's amino group aliphatic unsaturated monomer of monofunctional at least, randomly, applies with the solution form.Proved that useful solvent is Shui Heshui/alcohol mixture, however other solvents also can use, as long as they can dissolve these monomers and can wetting well substrate surface fully.The example of other solvents is ethanol, methyl alcohol, butanone, Anaesthetie Ether, dioxane, hexane, heptane, benzene, toluene, chloroform, methylene dichloride, tetrahydrofuran (THF) and acetonitrile.Monomer content is between 1～10wt%, and for example the solution of about 5wt% proves success in practice, just can provide after coating together usually and cover substrate surface, thickness can be greater than the adhering coating of 0.1 μ m.
Usefully, the monomeric graft polymerization on the paint activating surface can cause by the irradiation of the long-wave band of the short-wave band of the visible-range of electromagnetic radiation or ultraviolet light range.For example, wavelength is between 250～500nm, and the ray that preferred 290～320nm is sent by the burst of ultraviolel thing is very suitable.Mercury vapor light here also is fit to, as long as the radiation that they have significant proportion is positioned at above-mentioned scope.Irradiation time is generally between 10s～30min, preferred 2～15min.
This graft polymerization also can be implemented by european patent application 0 872 512 described methods, and this method is based on the graft polymerization reaction by swelling bonded monomer molecule and initiator molecule.
With the monomer of going up uncle's amino group, also can use other aliphatic unsaturated monomers except passing through functionalized in the methods of the invention.For example, used monomer mixture can comprise uncle's amino group for example vinylformic acid, methacrylic tert-butyl acrylate or methyl methacrylate, vinylbenzene, vinylchlorid, vinyl ether, acrylamide, vinyl cyanide, alkene (ethene, propylene, butylene and iso-butylene), allylic cpd, vinyl ketone, vinylacetic acid, vinyl acetate or vinyl ester of the aliphatic unsaturated monomer of monofunctional and acrylate or methyl acrylic ester at least.
Even if be not grafted to substrate surface, by the inventive method by uncle's amino group at least the anti-microbial polymer of the aliphatic unsaturated monomer preparation of monofunctional still show microbicidel or antimicrobial behavior.
If the inventive method directly is used in and does not carry out crosslinkedly on the substrate surface, then can adopt traditional radical initiator.The example of available initiator is azonitrile, alkyl peroxide, hydroperoxide, acyl peroxide, ketone peroxide, peroxy esters, peroxycarbonate (ester), peroxydisulfate, persulphate and any light trigger commonly used, for example phenyl methyl ketone, alpha-alcohol ketone, dimethyl ketal and benzophenone.This polyreaction also can adopt thermal initiation or, as noted above, by electromagnetic radiation, for example UV-light or gamma-radiation cause.
The application of polymer-modified substrate
The application that the present invention also provides the anti-microbial polymer by the present invention preparation to be used to produce the antimicrobial acivity product, and the product of so producing itself.This product can comprise the polymeric substrates by modification of the present invention, perhaps is made up of it.This type product be preferably based on employing according to the polymkeric substance of the present invention preparation carry out surface modification following material: polymeric amide, urethane, polyether block amide, polyesteramide or-imide, PVC, polyolefine, siloxanes, polysiloxane, polymethacrylate or polyterephthalate.
The example of this type antimicrobial acivity product is especially: machine parts, air-conditioning system component, roof Material, bathroom and the lavatory of food and drink processing usefulness with article, kitchen tackle, sanitation component, animal (pet) cage or nest, entertainment for children product, water system component, Foods or drinks pack, the operative employee unit (touch control board) and the contact lens of equipment.
Can be used for according to the polymkeric substance of the present invention preparation or graft copolymer any to surperficial release characteristics special concern or require the aseptic as far as possible occasion in its surface, that is, and can microbicidel.The top coat in the especially following field of the example application of this novel polymer or graftomer, protective paint and other coatings:
Ocean: hull, harbour, buoy, drilling unit, Ballast water tank
Building: roof, vault, wall, the shop front, greenhouse, sun-proof, garden hedge, wood protection
Environmental health: convenient public facility, lavatory, shower curtain, lavatory article, swimming pool, sauna bath, junction surface, sealed mixture
Daily necessities: machine, kitchen, kitchen tackle, sponge pad, entertainment for children product, food and drink packing, diary processing, potable water system, makeup
Machine parts: air-conditioning system, ion-exchanger, process water, solar energy equipment, heat exchanger, bio-reactor, film
Medical skill: contact lens, diaper, film, implant
Human consumer's goods: automotive seat, clothes (socks, Sportswear), hospital equipment, door handle, telephone set and mobile phone, convenient public facility (lavatory), animal cage, cash register (cashier's machine), wall-to-wall carpet, wallpaper.
The present invention also provides a kind of application of polymeric substrates aspect production health product or field of medical technology article of having adopted polymkeric substance of the present invention to carry out surface modification.Relate to above preferred material said all correspondingly here all be suitable for.The example of this type health product is toothbrush, toilet seat, comb and wrapping material.Term " sanitary product " also comprises the article that contact with numerous people, for example grasping band or the handle in telephone bandset, banister, door handle, window latch and the public transport.The example of field of medical technology article is stretcher, flexible conduit, film protection or backing and surgery instrument.
The purpose that provides following embodiment is to illustrate in greater detail the present invention, and is not intended to the scope of the invention of claim defined is set restriction.
Embodiment 1:
Polymeric amide-12 film exposes 2min under from the 172nm ray in the excimer source of Heraeus company and 1mbar pressure.So the activatory film is put in radiator shielding gas under and is fixed.Subsequently, on this film, be coated with the mixture that 20mL is made up of 3g methacrylic acid 2-lignocaine ethyl ester (Aldrich company) and 97g methyl alcohol under the counter-current condition of shielding gas.The radiation chamber good seal also is placed on the place of excimer 10cm that distance is sent the Heraeus company of 308nm wavelength.Beginning irradiation also continues 15min.Subsequently, take out film and use the 30mL washed with methanol, dry 12h under 50 ℃, vacuum, and then water again is 30 ℃ of extractions 5 times down, and 6h at every turn is then at 50 ℃ of dry 12h.
Then, the reverse side of film is pressed same program and is handled, so finally obtain the polyamide layer that the two sides scribbles graftomer.
Embodiment 1a:
From a slice coating film of embodiment 1 (5 * 4cm), in 30mL streptococcus aureus test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 15min.This time has been detected less than any streptococcus aureus microorganism after finishing.
Embodiment 1b:
From a slice coating film of embodiment 1 (5 * 4cm), in 30mL Pseudomonas aeruginosa test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 60min.After this time finished, microbe number was by 10 7Be reduced to 10 4
Embodiment 2:
Polymeric amide-12 film exposes 2min under from the 172nm ray in the excimer source of Heraeus company and 1mbar pressure.So the activatory film is put in radiator shielding gas under and is fixed.Subsequently, on this film, be coated with the mixture that 20mL is made up of 3g N-methacryloyl 3-dimethylamino-propyl amine (Aldrich company) and 97g methyl alcohol under the counter-current condition of shielding gas.The radiation chamber good seal also is placed on the place of excimer 10cm that distance is sent the Heraeus company of 308nm wavelength.Beginning irradiation also continues 15min.Subsequently, take out film and use the 30mL washed with methanol, dry 12h under 50 ℃, vacuum, and then water again is 30 ℃ of extractions 5 times down, and 6h at every turn is then at 50 ℃ of dry 12h.
Then, the reverse side of film is pressed same program and is handled, so finally obtain the polyamide layer that the two sides scribbles graftomer.
Embodiment 2a:
From a slice coating film of embodiment 2 (5 * 4cm), in 30mL streptococcus aureus test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 15min.This time has been detected less than any streptococcus aureus microorganism after finishing.
Embodiment 2b:
From a slice coating film of embodiment 2 (5 * 4cm), in 30mL Pseudomonas aeruginosa test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 60min.After this time finished, microbe number was by 10 7Be reduced to 10 4
Embodiment 3:
Polymeric amide-12 film exposes 2min under from the 172nm ray in the excimer source of Heraeus company and 1mbar pressure.So the activatory film is put in radiator shielding gas under and is fixed.Subsequently, on this film, be coated with the mixture that 20mL is made up of 3g vinylformic acid 3-dimethylamino propyl ester (Aldrich company) and 97g methyl alcohol under the counter-current condition of shielding gas.The radiation chamber good seal also is placed on the place of excimer 10cm that distance is sent the Heraeus company of 308nm wavelength.Beginning irradiation also continues 15min.Subsequently, take out film and use the 30mL washed with methanol, dry 12h under 50 ℃, vacuum, and then water again is 30 ℃ of extractions 5 times down, and 6h at every turn is then at 50 ℃ of dry 12h.
Then, the reverse side of film is pressed same program and is handled, so finally obtain the polyamide layer that the two sides scribbles graftomer.
Embodiment 3a:
From a slice coating film of embodiment 3 (5 * 4cm), in 30mL streptococcus aureus test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 15min.This time has been detected less than any streptococcus aureus microorganism after finishing.
Embodiment 3b:
From a slice coating film of embodiment 3 (5 * 4cm), in 30mL Pseudomonas aeruginosa test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 60min.After this time finished, microbe number was by 10 7Be reduced to 10 3
Embodiment 4:
Polymeric amide-12 film exposes 2min under from the 172nm ray in the excimer source of Heraeus company and 1mbar pressure.So the activatory film is put in radiator shielding gas under and is fixed.Subsequently, on this film, be coated with the mixture that 20mL is made up of 3g methacrylic acid 2-lignocaine ethyl ester (Aldrich company), 2g methyl methacrylate (Aldrich) and 95g methyl alcohol under the counter-current condition of shielding gas.The radiation chamber good seal also is placed on the place of excimer 10cm that distance is sent the Heraeus company of 308nm wavelength.Beginning irradiation also continues 15min.Subsequently, take out film and use the 30mL washed with methanol, dry 12h under 50 ℃, vacuum, and then water again is 30 ℃ of extractions 5 times down, and 6h at every turn is then at 50 ℃ of dry 12h.
Then, the reverse side of film is pressed same program and is handled, so finally obtain the polyamide layer that the two sides scribbles graftomer.
Embodiment 4a:
From a slice coating film of embodiment 4 (5 * 4cm), in 30mL streptococcus aureus test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 15min.This time has been detected less than any streptococcus aureus microorganism after finishing.
Embodiment 4b:
From a slice coating film of embodiment 4 (5 * 4cm), in 30mL Pseudomonas aeruginosa test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 60min.After this time finished, microbe number was by 10 7Be reduced to 10 3
Embodiment 5:
Polymeric amide-12 film exposes 2min under from the 172nm ray in the excimer source of Heraeus company and 1mbar pressure.So the activatory film is put in radiator shielding gas under and is fixed.Subsequently, on this film, be coated with the mixture that 20mL is made up of 3g N-(3-dimethylamino-propyl) Methacrylamide (Aldrich company), 2g methyl methacrylate (Aldrich) and 95g methyl alcohol under the counter-current condition of shielding gas.The radiation chamber good seal also is placed on the place of excimer 10cm that distance is sent the Heraeus company of 308nm wavelength.Beginning irradiation also continues 15min.Subsequently, take out film and use the 30mL washed with methanol, dry 12h under 50 ℃, vacuum, and then water again is 30 ℃ of extractions 5 times down, and 6h at every turn is then at 50 ℃ of dry 12h.
Then, the reverse side of film is pressed same program and is handled, so finally obtain the polyamide layer that the two sides scribbles graftomer.
Embodiment 5a:
From a slice coating film of embodiment 5 (5 * 4cm), in 30mL streptococcus aureus test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 15min.This time has been detected less than any streptococcus aureus microorganism after finishing.
Embodiment 5b:
From a slice coating film of embodiment 5 (5 * 4cm), in 30mL Pseudomonas aeruginosa test microbial suspension body, shake.After duration of contact, take out 1mL test microbial suspension body, then the microbe number in the confirmed test mixture through 60min.After this time finished, microbe number was by 10 7Be reduced to 10 3
Except the described function of killing microorganism of top cell at Pseudomonas aeruginosa and streptococcus aureus, all these samples all demonstrate at Klebsiella pneumonia (pneumobacillus), dust Xi Shi intestinal bacteria, Rhizopus oryzae, candida tropicalis and the isocellular function of killing microorganism of Tetrahymenapyriformis.

Claims (11)

1. a method for preparing anti-microbial polymer is characterized in that, make by uncle's amino group at least the aliphatic unsaturated monomer of monofunctional carry out polymerization.
2. the method for claim 1 is characterized in that, use through uncle's amino group aliphatic unsaturated monomer functionalized and that have following general formula,
R 1NR 2R 3R wherein 1Be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group has maximum 50 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom, and
R 2And R 3Identical or different, be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group has maximum 25 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom.
3. claim 1 and one of 2 method is characterized in that polyreaction is carried out under other aliphatic unsaturated monomers participate in.
4. the method for one of claim 1～3 is characterized in that, polyreaction is carried out on substrate.
5. the method for one of claim 1～4 is characterized in that, polyreaction is to implement as the graft polymerization of substrate.
6. the method for claim 5 is characterized in that, substrate utilized uv-radiation, Cement Composite Treated by Plasma, corona treatment, flame treating, ozonize, discharge or gamma-radiation to activate before graft polymerization.
7. the method for claim 5 is characterized in that, substrate activated with photosensitizers by uv irradiation before graft polymerization.
By the anti-microbial polymer of one of claim 1～7 preparation in production with the application in the product of the antimicrobial coatings of this polymkeric substance.
By the anti-microbial polymer of one of claim 1～7 preparation in production with the application in the medical skill articles for use of the antimicrobial coatings of this polymkeric substance.
By the anti-microbial polymer of one of claim 1～7 preparation in production with the application in the sanitary product of the antimicrobial coatings of this polymkeric substance.
11. the application of anti-microbial polymer in producing top coat, protective paint or other coatings by the preparation of one of claim 1～7.
CN00810290A 1999-05-12 2000-03-30 Method for producing inherently microbicidal polymer surfaces Pending CN1360602A (en)

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DE19921897A DE19921897A1 (en) 1999-05-12 1999-05-12 Preparation of antimicrobial polymer for medical and hygiene articles, varnishes, paints and coatings comprises polymerizing monomers that have been functionalized by a tert. amino group
DE19921897.8 1999-05-12

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WO2013114297A1 (en) * 2012-01-31 2013-08-08 Polymers Crc Ltd. Uv polymerization of specific acrylic monomers on reverse osmosis membranes for improved bio-fouling resistance
CN112812324A (en) * 2021-01-08 2021-05-18 暨南大学 Polycation-hyaluronic acid composite hydrogel and preparation method and application thereof

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DE10062201A1 (en) * 2000-12-13 2002-06-20 Creavis Tech & Innovation Gmbh Process for the use of antimicrobial polymers in building and monument protection
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

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WO1991012282A1 (en) * 1990-02-14 1991-08-22 H.B. Fuller Licensing & Financing Inc. Copolymers with inherent antimicrobial action
DE19646965C2 (en) * 1996-11-14 1999-08-12 Roehm Gmbh Acrylate-based biophobic polymers, processes for their production and their use
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Publication number Priority date Publication date Assignee Title
WO2013114297A1 (en) * 2012-01-31 2013-08-08 Polymers Crc Ltd. Uv polymerization of specific acrylic monomers on reverse osmosis membranes for improved bio-fouling resistance
CN112812324A (en) * 2021-01-08 2021-05-18 暨南大学 Polycation-hyaluronic acid composite hydrogel and preparation method and application thereof

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