CN1361797A - Microbicidal copolymers - Google Patents
Microbicidal copolymers Download PDFInfo
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- CN1361797A CN1361797A CN00810327A CN00810327A CN1361797A CN 1361797 A CN1361797 A CN 1361797A CN 00810327 A CN00810327 A CN 00810327A CN 00810327 A CN00810327 A CN 00810327A CN 1361797 A CN1361797 A CN 1361797A
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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
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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
- 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
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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
- A01N37/44—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
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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
- A61L15/42—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
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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
- A61L27/50—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
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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- 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
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- 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
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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
- 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
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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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- 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
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- 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
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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
- C09D151/08—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
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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
- 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
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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
- 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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- 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
- A61L2300/45—Mixtures of two or more drugs, e.g. synergistic mixtures
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- Medicinal Chemistry (AREA)
- Wood Science & Technology (AREA)
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- General Health & Medical Sciences (AREA)
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- Veterinary Medicine (AREA)
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Abstract
The invention relates to antimicrobial polymers, obtained by the copolymerisation of aliphatically unsaturated monomers which are at least simply functionalised by a secondary amino group (component I), with an additional aliphatically unsaturated monomer which is at least simply functionalised by a secondary amino group (component II), whereby component I and component II are different from one another. Additional aliphatically unsaturated monomers can be used as component III for copolymerisation. The antimicrobial polymers can be used as a microbicidal coating, among others, especially for hygiene articles or in the medical field and can also be used in lacquers or protective paint coatings.
Description
The present invention relates to anti-microbial polymer, they be by two or more kinds of by secondary amino group at least the copolymerization between the aliphatic unsaturated monomer of monofunctional obtain.The invention still further relates to the method and the application thereof of this anti-microbial polymer of preparation.
The invention still further relates to such anti-microbial polymer, they be by by secondary amino group at least the aliphatic unsaturated monomer of monofunctional on substrate, carry out graft copolymerization and obtain, also relate to their preparation method and application thereof.
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, then just cause the sharp increase of microbial population, these microorganisms since then will be for a long time, constantly destroy the quality of water, beverage or food, even damage 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 during when needs or 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 need continue following the direction of novel composition and need improve and render a service 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 two or multiple through secondary amino group at least the aliphatic unsaturated monomer of monofunctional carry out copolymerization, perhaps these components graft copolymerization on substrate, generate a kind of polymkeric substance with long-acting microbicidel surface, this polymkeric substance 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.
Therefore, the invention provides anti-microbial polymer, they be by through secondary amino group at least monofunctional aliphatic unsaturated monomer (component I) and another kind of through secondary amino group at least the copolymerization between the aliphatic unsaturated monomer (component I I) of monofunctional obtain, wherein component I and component I I differ from one another.
The present invention also provides a kind of method for preparing anti-microbial polymer, this polymkeric substance by through secondary amino group at least monofunctional aliphatic unsaturated monomer (component I) with another kind of through secondary amino group at least the graft copolymerization of the aliphatic unsaturated monomer (component I I) of monofunctional obtain, wherein component I and component I I differ from one another.
Through secondary amino group at least the aliphatic unsaturated monomer of monofunctional (component I and II) also can under the situation that the aliphatic unsaturated monomer of another kind (component III) participates in, implement according to copolyreaction of the present invention, its function of killing microorganism still keeps substantially.
Suitable comonomer structural unit, except european patent application 0 862 858 and 0 862859 described secondary amino group functionalized propylene acid esters and methacrylic ester, also comprise any aliphatic unsaturated monomer with at least one secondary amino group functional group, 3-phenyl methylamino--2-butylene acetoacetic ester for example, 3-ethylamino-2-butylene acetoacetic ester, 3-methylamino--2-butylene acetoacetic ester, 3-methylamino--1-phenyl-2-propylene-1-ketone, 2-methyl-N-4-methylamino--1-anthraquinonyl (anthrachinoyl) acrylamide, N-9,10-dihydro-4-(4-aminomethyl phenyl amino)-9,10-dioxo-1-anthraquinonyl (anthrachinyl)-2-methyl-acrylamide, 2-hydroxyl-3-(3-triethoxysilyl third amino)-2-propyl acrylate, 1-(1-methyl ethylamino)-3-(2-(2-propenyl) phenoxy group)-2-propyl alcohol hydrogenchloride, 3-phenyl amino-2-butylene acetoacetic ester, 1-(1-methyl ethylamino)-3-(2-(2-propenyloxy group) phenoxy group)-2-propyl alcohol hydrogenchloride, 2-acrylamido-2-methoxy menthyl acetate, 2-acetamidoacrylic acid methyl esters, N tert butyl acrylamide, 2-hydroxy-n-2-propenylbenzene methane amide and N-methyl-2-acrylamide.
That the present invention uses, through the secondary amino group aliphatic unsaturated monomer component I or the II of monofunctional at least, 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 (acrylicradicals) 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, component I that the present invention uses or the monomeric molar mass of II should be less than 900, preferably less than 550g/mol.
In a special embodiment of the present invention, used component I or II can comprise through the aliphatic unsaturated monomer secondary amino group monofunctional and that have following general formula,
R
1NR
2H is R wherein
1Be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group, it has maximum 50 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom, and
R
2Be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group, it has maximum 25 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom.
The monomer of component I and II must differ from one another, thus the molar mass between the two should to differ be 23g/mol at least.The example of component I, II and the randomly combination of III will be described in an embodiment.
Antimicrobial multipolymer of the present invention also can by component I and II or I, II and III respectively the copolymerization on substrate obtain.This will generate a kind of physical adsorption coating that is made of antimicrobial multipolymer 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 not be with the radiation-sensitive group.The inventive method also can be used on body surfaces of metal, glass or timber top coat or other usefulness plastic-coated.
In another embodiment of the present invention, this multipolymer can be by component I and II, perhaps component I, II and III graft copolymerization and making on substrate.Can produce covalent linkage between antimicrobial multipolymer and the substrate in the grafting on the substrate.Spendable substrate can be any polymeric material, plastics for example above-mentioned.
Before the graft copolymerization, 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.This surface is preferably 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 activatory substrate surface like this, be coated with by currently known methods, for example dip-coating, spraying or brush gone up through secondary amino group aliphatic unsaturated monomer (component I) and one or more aliphatic unsaturated monomers (component I I) of monofunctional at least, but having at least a kind of among the component I I is through functionalized and with going up secondary amino group, randomly, apply with the solution form, wherein component I and component I I differ from one another.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.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.
Monomeric graft copolymerization on the paint activating surface can be practicably causes 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.
The graft copolymerization of this comonomer composite of the present invention also can be implemented by european patent application 0,872 512 described method, and this method is based on the graft copolymerization by swelling bonded monomer molecule and initiator molecule.The monomer that this swelling method uses can be a component III.
Even if be not grafted to substrate surface, by through secondary amino group this antimicrobial multipolymer of the present invention of making of the aliphatic unsaturated monomer of monofunctional (component I and II) and randomly another kind of aliphatic unsaturated monomer (component III) at least, wherein component I and component I I differ from one another, and still show microbicidel or antimicrobial behavior.
Another embodiment of the invention is included in and implements component I and II on the substrate, the perhaps copolymerization of I, II and III, and wherein component I and II differ from one another.
Component I, II and III randomly, can solution form paint substrate on.The example of suitable solvent is water, ethanol, methyl alcohol, butanone, Anaesthetie Ether, dioxane, hexane, heptane, benzene, toluene, chloroform, methylene dichloride, tetrahydrofuran (THF) and acetonitrile.Component III also can be used as the solvent of component I and II.
Component III can comprise the aliphatic unsaturated monomer of the copolyreaction of any participation component I and II.Component III also can comprise other through the secondary amino group aliphatic unsaturated monomer of monofunctional at least, and in such cases, component I, II and III should all have nothing in common with each other each other.In addition, component III also can comprise acrylate or methacrylic ester, 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.
The antimicrobial multipolymer of the present invention also can directly use, that is, and not by the polymerization of component on substrate, but as antimicrobial coatings.Suitable coating process is multipolymer is mixed with solution or is coated with melt form.
The solution of polymkeric substance of the present invention can pass through, and for example dip-coating, spraying or brushing come on the paint substrate.
Do not carry out crosslinkedly if polymkeric substance of the present invention directly generates on 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.
Anti-microbial polymer of the present invention also can be used as the composition of preparation lacquer and top coat.
The application of polymer-modified substrate
The application that the present invention also provides anti-microbial polymer of the present invention 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 is preferably based on and adopts polymkeric substance of the present invention to carry out the following material of surface modification: 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.
The present invention also provides a kind of surface to adopt polymkeric substance of the present invention or method to carry out the application of polymeric substrates aspect production health product or field of medical technology article of 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.
Multipolymer of the present invention or graft copolymer can be used for any to surperficial release characteristics special concern or require its surface must not have bacterium, that is, and and can microbicidal occasion.The top coat in the especially following field of the example application of multipolymer of the present invention or graft copolymer, 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 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:
5g 2-acrylamido-2-methoxy menthyl acetate (Aldrich company), 5g 2-acetamidoacrylic acid methyl esters (Aldrich) and 55mL ethanol join in the three-necked flask, and be heated to 65 ℃ under argon gas stream.Subsequently, under agitation slowly drip the 0.14g Diisopropyl azodicarboxylate and be dissolved in the solution of preparing in the 4mL butanone.Mixture heating up to 70 ℃, and stir 72h in this temperature.After this time finished, reaction mixture stirred and joins in the 0.5L normal hexane, and this polymerisate precipitates immediately.After product filtered, filter residue was with the washing of 100mL normal hexane, to remove any residual monomer that still exists.Subsequently, product dry 24h under 50 ℃ of vacuum.
Embodiment 1a:
0.05g put in the 20mL streptococcus aureus test microbial suspension body from the product of embodiment 1 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 30min.After this time finished, microbe number was by 10
7Be reduced to 10
3
Embodiment 1b:
0.05g put in the 20mL Pseudomonas aeruginosa test microbial suspension body from the product of embodiment 1 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 60min.After this time finished, microbe number was by 10
7Be reduced to 10
4
Embodiment 2:
5g 2-acrylamido-2-methoxy menthyl acetate (Aldrich company), 3g N tert butyl acrylamide (Aldrich) and 55mL ethanol join in the three-necked flask, and be heated to 65 ℃ under argon gas stream.Subsequently, under agitation slowly drip the 0.12g Diisopropyl azodicarboxylate and be dissolved in the solution of preparing in the 4mL butanone.Mixture heating up to 70 ℃, and stir 72h in this temperature.After this time finished, reaction mixture stirred and joins in the 0.5L normal hexane, and this polymerisate precipitates immediately.After product filtered, filter residue was with the washing of 100mL normal hexane, to remove any residual monomer that still exists.Subsequently, product dry 24h under 50 ℃ of vacuum.
Embodiment 2a:
0.05g put in the 20mL streptococcus aureus test microbial suspension body from the product of embodiment 2 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 30min.After this time finished, microbe number was by 10
7Be reduced to 10
3
Embodiment 2b:
0.05g put in the 20mL Pseudomonas aeruginosa test microbial suspension body from the product of embodiment 2 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 60min.After this time finished, microbe number was by 10
7Be reduced to 10
3
Embodiment 3:
4g 2-acetamidoacrylic acid methyl esters (Aldrich company), 5g N tert butyl acrylamide (Aldrich) and 65mL ethanol join in the three-necked flask, and be heated to 65 ℃ under argon gas stream.Subsequently, under agitation slowly drip the 0.15g Diisopropyl azodicarboxylate and be dissolved in the solution of preparing in the 5mL butanone.Mixture heating up to 70 ℃, and stir 72h in this temperature.After this time finished, reaction mixture stirred and joins in the 0.5L normal hexane, and this polymerisate precipitates immediately.After product filtered, filter residue was with the washing of 100mL normal hexane, to remove any residual monomer that still exists.Subsequently, product dry 24h under 50 ℃ of vacuum.
Embodiment 3a:
0.05g put in the 20mL streptococcus aureus test microbial suspension body from the product of embodiment 3 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 15min.This time just no longer detects any streptococcus aureus microorganism after finishing.
Embodiment 3b:
0.05g put in the 20mL Pseudomonas aeruginosa test microbial suspension body from the product of embodiment 3 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 60min.After this time finished, microbe number was by 10
7Be reduced to 10
3
Embodiment 4:
1.5g 3-ethylamino-2-butylene acetoacetic ester (Sigma company), 1.5g 3-methylamino--2-butylene acetoacetic ester (Sigma company) and 35mL ethanol join in the three-necked flask, and be heated to 65 ℃ under argon gas stream.Subsequently, under agitation slowly drip the 0.1g Diisopropyl azodicarboxylate and be dissolved in the solution of preparing in the 3mL butanone.Mixture heating up to 70 ℃, and stir 72h in this temperature.After this time finished, reaction mixture stirred and joins in the 0.35L normal hexane, and this polymerisate precipitates immediately.After product filtered, filter residue was with the washing of 70mL normal hexane, to remove any residual monomer that still exists.Subsequently, product dry 24h under 50 ℃ of vacuum.
Embodiment 4a:
0.05g put in the 20mL streptococcus aureus test microbial suspension body from the product of embodiment 4 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 15min.This time just no longer measures any streptococcus aureus microorganism after finishing.
Embodiment 4b:
0.05g put in the 20mL Pseudomonas aeruginosa test microbial suspension body from the product of embodiment 4 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 60min.After this time finished, microbe number was by 10
7Be reduced to 10
2
Embodiment 5:
4g 2-acrylamido-2-methoxy menthyl acetate (Aldrich company), 5g 2-acetamidoacrylic acid methyl esters (Aldrich), 3g methyl methacrylate (Aldrich) and 65mL ethanol, join in the three-necked flask, and under argon gas stream, be heated to 65 ℃.Subsequently, under agitation slowly drip the 0.15g Diisopropyl azodicarboxylate and be dissolved in the solution of preparing in the 4mL butanone.Mixture heating up to 70 ℃, and stir 72h in this temperature.After this time finished, reaction mixture stirred and joins in the 0.5L normal hexane, and this polymerisate precipitates immediately.After product filtered, filter residue was with the washing of 100mL normal hexane, to remove any residual monomer that still exists.Subsequently, product dry 24h under 50 ℃ of vacuum.
Embodiment 5a:
0.05g put in the 20mL streptococcus aureus test microbial suspension body from the product of embodiment 5 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 15min.This time just no longer detects any streptococcus aureus microorganism after finishing.
Embodiment 5b:
0.05g put in the 20mL Pseudomonas aeruginosa test microbial suspension body from the product of embodiment 5 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 60min.After this time finished, microbe number was by 10
7Be reduced to 10
2
Embodiment 6:
4g 2-acrylamido-2-methoxy menthyl acetate (Aldrich company), 4g 2-acetamidoacrylic acid methyl esters (Aldrich), 2.5g butyl methacrylate (Aldrich) and 65mL ethanol, join in the three-necked flask, and under argon gas stream, be heated to 65 ℃.Subsequently, under agitation slowly drip the 0.15g Diisopropyl azodicarboxylate and be dissolved in the solution of preparing in the 4mL butanone.Mixture heating up to 70 ℃, and stir 72h in this temperature.After this time finished, reaction mixture stirred and joins in the 0.5L normal hexane, and this polymerisate precipitates immediately.After product filtered, filter residue was with the washing of 100mL normal hexane, to remove any residual monomer that still exists.Subsequently, product dry 24h under 50 ℃ of vacuum.
Embodiment 6a:
0.05g put in the 20mL streptococcus aureus test microbial suspension body from the product of embodiment 6 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 15min.After this time finished, microbe number was by 10
7Be reduced to 10
3
Embodiment 6b:
0.05g put in the 20mL Pseudomonas aeruginosa test microbial suspension body from the product of embodiment 6 and to shake.After duration of contact, take out 1mL test suspensoid, the microbe number in the confirmed test mixture then through 60min.After this time finished, microbe number was by 10
7Be reduced to 10
4
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 (20)
1. anti-microbial polymer, its can by through secondary amino group at least the aliphatic unsaturated monomer (component I) of monofunctional with another kind of through the secondary amino group copolymerization acquisition between the aliphatic unsaturated monomer (component I I) of monofunctional at least, wherein component I and component I I differ from one another.
2. the anti-microbial polymer of claim 1 is characterized in that, copolyreaction is carried out under other aliphatic unsaturated monomers (component III) participate in.
3. claim 1 and one of 2 anti-microbial polymer is characterized in that, component I and II respectively comprise through secondary amino group aliphatic unsaturated monomer functionalized and that have following general formula,
R
1NR
2H is R wherein
1Be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group, it has maximum 50 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom, and
R
2Be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group, it has maximum 25 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom.
4. the anti-microbial polymer of one of claim 1～3 is characterized in that, there is the difference of 23g/mol at least in the monomer of component I and II on molar mass.
5. the anti-microbial polymer of one of claim 1～4 is characterized in that, copolyreaction is carried out on substrate.
6. the anti-microbial polymer of one of claim 1～4 is characterized in that, copolyreaction is to carry out as the graft polymerization of substrate.
7. the anti-microbial polymer of claim 6 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.
8. the anti-microbial polymer of claim 6 is characterized in that, substrate was realized activation by uv-radiation with light trigger before graft polymerization.
9. method for preparing anti-microbial polymer, comprise will through secondary amino group at least monofunctional aliphatic unsaturated monomer (component I) with another kind of through secondary amino group at least the aliphatic unsaturated monomer (component I I) of monofunctional carry out copolymerization, wherein component I and component I I differ from one another.
10. the method for claim 9 is characterized in that, copolyreaction is carried out under other aliphatic unsaturated monomers (component III) participate in.
11. the method for one of claim 9 and 10 is characterized in that, component I and II respectively comprise through secondary amino group aliphatic unsaturated monomer functionalized and that have following general formula,
R
1NR
2H is R wherein
1Be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group, it has maximum 50 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom, and
R
2Be branching, non-branching or cyclic, saturated or undersaturated hydrocarbyl group, it has maximum 25 carbon atoms, and it can be replaced by Sauerstoffatom, nitrogen-atoms or sulphur atom.
12. the method for one of claim 9～11 is characterized in that, there is the difference of 23g/mol at least in the monomer of component I and II on molar mass.
13. the method for one of claim 9～12 is characterized in that, copolyreaction is carried out on substrate.
14. the method for one of claim 9～12 is characterized in that, copolyreaction is to carry out as the graft polymerization of substrate.
15. the method for claim 14 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.
16. the method for claim 14 is characterized in that, substrate was realized activation by uv-radiation with light trigger before graft polymerization.
17. the anti-microbial polymer of one of claim 1～8 has application in the product of the antimicrobial coatings that is made of this polymkeric substance in production.
18. the anti-microbial polymer of one of claim 1～8 has application in the medical skill articles for use of the antimicrobial coatings that is made of this polymkeric substance in production.
19. the anti-microbial polymer of one of claim 1～8 has application in the sanitary product of the antimicrobial coatings that is made of this polymkeric substance in production.
20. the application of the anti-microbial polymer of one of claim 1～8 in top coat, protective paint or other coatings.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19921899.4 | 1999-05-12 | ||
| DE19921899A DE19921899A1 (en) | 1999-05-12 | 1999-05-12 | Antimicrobial copolymer for medical and hygiene articles, varnishes, paints and coatings comprises monomers with a sec. amino group(s) and monomers having a sec. amino group(s) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1361797A true CN1361797A (en) | 2002-07-31 |
Family
ID=7907834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00810327A Pending CN1361797A (en) | 1999-05-12 | 2000-03-30 | Microbicidal copolymers |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1183293A1 (en) |
| JP (1) | JP2002544347A (en) |
| CN (1) | CN1361797A (en) |
| AU (1) | AU7236300A (en) |
| DE (1) | DE19921899A1 (en) |
| NO (1) | NO20015531L (en) |
| WO (1) | WO2000069934A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10061250A1 (en) * | 2000-12-09 | 2002-06-13 | Creavis Tech & Innovation Gmbh | Process for thermally assisted antimicrobial surface finishing |
| 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 |
| EP2036930A1 (en) * | 2007-09-12 | 2009-03-18 | Institut National De La Recherche Agronomique (Inra) | Copolymer-grafted polyolefin substrate having antimicrobial properties and method for grafting |
| CN102325446B (en) * | 2008-12-29 | 2014-07-09 | 3M创新有限公司 | Antimicrobial copolymer for coating surfaces, obtained by derivatization of a vinylamine-vinylalcohol copolymer |
| WO2015146196A1 (en) * | 2014-03-28 | 2015-10-01 | 株式会社日本触媒 | Novel polymer, resin composition, resin molded article, and method for producing novel polymer |
| JP6809777B2 (en) * | 2015-03-27 | 2021-01-06 | 株式会社日本触媒 | A method for producing a thermoplastic polymer, a resin composition, a resin molded product, an optical member, and a thermoplastic polymer. |
| JP6846105B2 (en) * | 2015-08-20 | 2021-03-24 | 株式会社日本触媒 | Polymers, resin compositions and resin molded products, and methods for producing polymers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19709075A1 (en) * | 1997-03-06 | 1998-09-10 | Huels Chemische Werke Ag | Process for the production of antimicrobial plastics |
| DK0872512T3 (en) * | 1997-04-14 | 2001-08-27 | Degussa | Method of Modifying the Surface of Polymeric Substrates by Graft Polymerization |
-
1999
- 1999-05-12 DE DE19921899A patent/DE19921899A1/en not_active Withdrawn
-
2000
- 2000-03-30 CN CN00810327A patent/CN1361797A/en active Pending
- 2000-03-30 EP EP00929329A patent/EP1183293A1/en not_active Withdrawn
- 2000-03-30 WO PCT/EP2000/002781 patent/WO2000069934A1/en not_active Application Discontinuation
- 2000-03-30 JP JP2000618349A patent/JP2002544347A/en active Pending
- 2000-03-30 AU AU72363/00A patent/AU7236300A/en not_active Abandoned
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2001
- 2001-11-12 NO NO20015531A patent/NO20015531L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP1183293A1 (en) | 2002-03-06 |
| AU7236300A (en) | 2000-12-05 |
| NO20015531D0 (en) | 2001-11-12 |
| DE19921899A1 (en) | 2000-11-16 |
| NO20015531L (en) | 2002-01-11 |
| WO2000069934A1 (en) | 2000-11-23 |
| JP2002544347A (en) | 2002-12-24 |
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