CA2231120A1 - Process for the preparation of antimicrobial plastics - Google Patents
Process for the preparation of antimicrobial plastics Download PDFInfo
- Publication number
- CA2231120A1 CA2231120A1 CA002231120A CA2231120A CA2231120A1 CA 2231120 A1 CA2231120 A1 CA 2231120A1 CA 002231120 A CA002231120 A CA 002231120A CA 2231120 A CA2231120 A CA 2231120A CA 2231120 A1 CA2231120 A1 CA 2231120A1
- Authority
- CA
- Canada
- Prior art keywords
- antimicrobial
- tert
- substrate
- butylaminoethyl methacrylate
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- A01N25/08—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 containing solids as carriers or diluents
- A01N25/10—Macromolecular 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
- A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
Abstract
Disclosed are a process for the preparation of an antimicrobial polymer by polymerizing tert-butylaminoethyl methacrylate and an article (such as a medical or hygiene article) having a surface coating layer of the antimicrobial polymer. The polymerization may be conducted by grafting polymerization of tert-butylaminoethyl methacrylate on a polymeric surface of a substrate of the article.
Description
CA 0223ll20 l998-03-04 Process for the preparation of antimicrobial plastics The invention relates to a process for the preparation of antimicrobial polymers by polymerization of tert-butylaminoethyl methacrylate, and the use of the antirnicrobial polymers.
s The invention furthermore relates to a process for the preparation of antimicrobial polymers by grafting polymerization of tert-butylaminoethyl methacrylate on a substrate, and the use of the antimicrobial polymers.
Colonizations and spreads of bacteria on surfaces of pipelines, containers or packaging are highly undesirable. Layers of slime often form, which allow the 10 microbe populations to rise to extreme levels, lastingly impair the quality of water, drinks and foodstuffs, and can even lead to decay of the goods and damage to the health of consumers.
8acteria are to be kept away from all areas of life where hygiene is of importance. This affects textiles for direct contact with the body, in particular 15 for the genital area, and for care of the sick and elderly. Bacteria are also to be kept away from the surfaces of furniture and equipment in nursing wards, in particular in the intensive care and infant care sector, in hospitals, especially in rooms for medical operations, and in isolation wards for critical cases of infection, as well as in toilets.
20 Equipment. surfaces of furniture and textiles are currently treated against bacteria as required or also preventively with chemicals or solutions and mixtures thereof which act as disinfectants with a more or less broad and powerful antimicrobial action. Such chemical compositions have a non-specific action are often themselves toxic or irritating, or form de~radation 25 products which are unacceptable to health. Intolerances are often also found in appropriately sensitized persons.
Another procedure against spreads of bacteria on surfac~s is incorPoration of antimicrobially acting sub~tances into a matrix.
O.Z. 5161 Tert-butylaminoethyl methacrylal:e is a commercially available monomer of methacrylate chemistry and is employed in particular as a hydrophilic constituent in copolymerizations. l-hus, EP-B 0 290 676 describes the use of various polyacrylates and polymethacrylates as a matrix for immobilization of 5 bactericidal quaternary ammonium compounds.
US-A 3 592 805 discloses the preparation of systemic fungicides in which perhalogenated acetone derivatives are reacted with methacrylate esters, such as, for example, tert-butylaminoethyl methacrylate.
US-A 4 515 910 describes the use of polymers of hydrogen fluoride salts of 10 aminometh.acrylates in dental medicine. The hydrogen fluoride bonded in the polymers emerges slowly from the polymer matrix and is said to be effective against caries.
From another technical field, US-A 4 532 269 discloses a terpolymer of butyl methacrylal:e, tributyltin methacrylate and tert-butylaminoethyl methacrylate.
15 This polymer is used as an antimicrobial paint for ships, the hydrophilic tert-butylaminoethyl methacrylate promoting slow erosion of the polymer and in this way liberating the highly toxic tributyltin methacrylate as an antimicrobial active compound.
In these applications, the copolyrner prepared with amino-methacrylates is 20 only a matrix or carrier substance for added microbicidal active compounds, which can cliffuse or migrate out of the carrier. Poiymers of this type lose their action at a faster or slower rate when the necessary "minimum inhibitory concentration" (MIC) is no longer achieved on the surface.
EP-B 0 20~1312 describes a proc,ess for the preparation of antimicrobially 25 treated acrylonitrile fibers. The antimicrobial action is based on a protonated amine as <3 comonomer unit. dimethyiaminoethyl methacrylate and tert-butylaminoethyl methacrJIate. inter alia, being used as prrltonated species.
s The invention furthermore relates to a process for the preparation of antimicrobial polymers by grafting polymerization of tert-butylaminoethyl methacrylate on a substrate, and the use of the antimicrobial polymers.
Colonizations and spreads of bacteria on surfaces of pipelines, containers or packaging are highly undesirable. Layers of slime often form, which allow the 10 microbe populations to rise to extreme levels, lastingly impair the quality of water, drinks and foodstuffs, and can even lead to decay of the goods and damage to the health of consumers.
8acteria are to be kept away from all areas of life where hygiene is of importance. This affects textiles for direct contact with the body, in particular 15 for the genital area, and for care of the sick and elderly. Bacteria are also to be kept away from the surfaces of furniture and equipment in nursing wards, in particular in the intensive care and infant care sector, in hospitals, especially in rooms for medical operations, and in isolation wards for critical cases of infection, as well as in toilets.
20 Equipment. surfaces of furniture and textiles are currently treated against bacteria as required or also preventively with chemicals or solutions and mixtures thereof which act as disinfectants with a more or less broad and powerful antimicrobial action. Such chemical compositions have a non-specific action are often themselves toxic or irritating, or form de~radation 25 products which are unacceptable to health. Intolerances are often also found in appropriately sensitized persons.
Another procedure against spreads of bacteria on surfac~s is incorPoration of antimicrobially acting sub~tances into a matrix.
O.Z. 5161 Tert-butylaminoethyl methacrylal:e is a commercially available monomer of methacrylate chemistry and is employed in particular as a hydrophilic constituent in copolymerizations. l-hus, EP-B 0 290 676 describes the use of various polyacrylates and polymethacrylates as a matrix for immobilization of 5 bactericidal quaternary ammonium compounds.
US-A 3 592 805 discloses the preparation of systemic fungicides in which perhalogenated acetone derivatives are reacted with methacrylate esters, such as, for example, tert-butylaminoethyl methacrylate.
US-A 4 515 910 describes the use of polymers of hydrogen fluoride salts of 10 aminometh.acrylates in dental medicine. The hydrogen fluoride bonded in the polymers emerges slowly from the polymer matrix and is said to be effective against caries.
From another technical field, US-A 4 532 269 discloses a terpolymer of butyl methacrylal:e, tributyltin methacrylate and tert-butylaminoethyl methacrylate.
15 This polymer is used as an antimicrobial paint for ships, the hydrophilic tert-butylaminoethyl methacrylate promoting slow erosion of the polymer and in this way liberating the highly toxic tributyltin methacrylate as an antimicrobial active compound.
In these applications, the copolyrner prepared with amino-methacrylates is 20 only a matrix or carrier substance for added microbicidal active compounds, which can cliffuse or migrate out of the carrier. Poiymers of this type lose their action at a faster or slower rate when the necessary "minimum inhibitory concentration" (MIC) is no longer achieved on the surface.
EP-B 0 20~1312 describes a proc,ess for the preparation of antimicrobially 25 treated acrylonitrile fibers. The antimicrobial action is based on a protonated amine as <3 comonomer unit. dimethyiaminoethyl methacrylate and tert-butylaminoethyl methacrJIate. inter alia, being used as prrltonated species.
O.Z. 5161 However, the antlmlcrobla:l actlon of protonated surfaces ls severely reduced after loss of the H~ lons.
A ma~or ob~ect of the present lnventlon ls to develop materlals whlch hc~ve antiml/roblal propertles, whlch contaln no actlve compounds whlch can be washed out, and ln whlch the antlmlcroblal actlon ls pH-lndependent.
It has now been found, surprlslngly, that polymers whlch have a surface whlch ls permanently mlcroblcldal, ls not attacked by solvents and physlcal slresses and shows no mlgratlon are obtalned by polymerlzatlon of tert-butyl-aminoethyl methacrylate or by grafting polymerlzatlon of tert-butylamlnoethyl methacrylate on a substrate. It ls not necessary here to employ i-urther blocldal actlve compounds.
The present lnvention thus provldes a process for the preparatlon of antlmlcroblal po:Lymer, whlch comprlses polymerlzlng tert-butylam:Lnoethyl methacrylate.
The present lnvention fur1hermore provides a process for the preparatlon of ant;lmlcroblal articles, whlch comprlses sub~ectlng tert-butylamlnoethyl met}-acrylate to grafting 2G polymerlz:atlon on a substrate.
The present lnventlon furthermore provldes use of the antlmlcrobial polymers for the production of products wlth an antlmi.croblal coatlng 1-rom the polymer.
The present lnventlo:n moreover provldes the products having an antlmlcroblal coatlng of the polymer.
The antimicroblal polymers can be obtalned by graftlng polymerlzatlon ol- tert-butylamlnoethyl methacrylate on a substrate.
O.Z. 5161 CA 0223ll20 l998-03-04 Suitable substraLte materlals are, above all, any polymeric plastics, such as, for example, polyurethanes, polyamides, polyester, polyethers, polyether-block amldes, polystyrene, polyvlnyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroeth~lene (PTFE), correspondlng copolymers and blends, as well as natural and synthetic rubbers, wlth or wlthout radiation-3ensitive groups. The process according to the :Lnvention can also be applied on the surfaces of metal, glass or wooden bodles whlch are painted or are otherwise coated wlth polymeric plastics.
The surfaces of the substrates are preferably activatecl by a number of methods before the grafting polymerlzation. They are preferably freed from olls, greases or other impurltles beforehand ln a known manner by means of a solvent.
The standard po:Lymers may be actlvated by UV
radlatlon. A sultable source of radiation ls, for example, a UV-exclmer apparatus HERAE~US* NobleLlght, Hanau, Germany.
However, mercury vapor larnps are also suitable for actlvatlon of the substrate if they emit conslderable proportlons of radlatlon ln the ranges mentloned. The exposure time ls ln general from 0.1 second to 20 minutes, preferably from 1 second to 10 minutes.
The activatlon of the standard polymers wlth UV
radlatlon may furthermore be carrled out with an additional photosensitlzer. For thls" the phot;osensltizer, such as, for *Trade-mark O.Z. 5161 example, benzophenone, ls applled to the surface of the substrate and lrradlated. Thls may llkewlse be carrled out wlth a mercury vapor lamp uslng exposure tlmes of from 0.1 second to 20 mlnutes, preEerably from l second to 10 mlnutes.
The actlvatlon may also be achleved by a hlgh-frequency or mlcrowave pl~sma (Hexagon*, Technlcs Plasma, 85551 Klrchheim, Germany) ln alr or a nltrogen or argon atmosphere. The exposure tlmes are ln general from 30 seconds to 30 mlnutes, preferably from 2 to 10 mlnutes.
1() The energy OUtpllt of laboratory apparatus ls between 100 and 500 W, preferably between 230 and 300 W.
Corona apparatus (SOFTAL, Hamburg, Germany) may furthermore be used for the actlvatlon. In this case, the exposure tlmes are ln general from 1 to 10 mlnutes, preferably from 1 to 60 seconds.
The actlvatlon by electron beams or y-rays (for example i-rom a cobalt-60 source) and the ozonlzatlon allow short ex~osure tlmes whlch are ln general 0.1 to 60 seconds.
Flamlng of surfaces llkewlse leads to actlvatlon thereof. Sultable apparatus, ln partlcular those havlng a barrler flame front, can be constructed in a slmple manner or obtained for example, from ARCOTEC, 71297 Monshelm, Germany.
They can be operated wlth hydrocarbons or hydrogen as the combustible gas. In all cases, harmful overheating of the substrates must be avoided, which is easily achleved by lntlmate contact wlth a cooled metal surface on the substrate surface faclng away from the flamlng slde. Actlvatlon by *Trade-mark O.~. 5161 flaming :Ls accordlngly llmlted to relatlvely thln, flat substrates. The exposure tlmes are in general from 0.1 second to 1 mlnute, preferably f:rom 0.5 to 2 seconds. The flames without exceptlon are nonlumlnous and the dlstances between the subst;rate surfaces and the outer flame front are usually from 0.2 to 5 cm, preferably from 0.5 to 2 cm.
The substrate surfaces actlvated ln thls way are coated w:Lth tert-butylamlnoethyl methacrylate, lf approprlate ln solut:Lon, by known methods, such as dipplng, spraying or brushing Suitable solvents have proved to be water and water/ethanol mlxtures although other solvents may also be used lf t;hey have a sufflclent dlssolvlng power for tert-butylamlnoethyl methacryl'~te and wet the substrate surfaces thorough:Ly. Solutions havlng monomer contents of 1 to 10% by weight, i-or example about 5% by welg;ht, have proved particularly suitable in practice and ln general give continuolls coatings which cover the substrate surface and have coating t:hicknesses whlch can be more than 0.1 ~m ln one pass.
The graft polymerizatlon of the monomer applied to the actlvated surfaces ls preferably caused by rays in the short wavelength segment of the vlslble range or in the long wavelengt;h segment of the UV range of electromagnetic radiation. The radiatlon of a UV-e.xcimer of wavelengths of from 250 to 500 nm, preferably from 290 to 320 nm, for example, ls particularly suitable. Mercury vapor lamps are also suit:able here lf they emit conslderable proportlons of radiation in the ranges mentioned. The exposure times are ln general f-rom lO seconds to 30 mlnutes, preferably from 2 to 15 O.Z. 5161 minutes.
Poly-tert-butyl~mlnoethyl methacrylate also shows intrinsic microbicldal properties wlthout graftlng to a substrate surface.
An antimicroblal polymer may furthermore be prepared by polymerlzation of tert-butylamlnoethyl methacrylate by known processes.
In the process ~ccording to the inventlon, the polymer ll.e., homopolymer) of tert-butylamlnoethyl methacry:Late may also be ~pplied to the substrate ln a solution Sultable solvents are, for example, water, ethanol, methanol, methyl ethyl ketone, dlethyl ether, dloxane, hexane, heptane, benzlne, toluene, chloroform, methylene chlorlde, tetrahydrofuran and acetonltrlle.
The solution of the polymer obtained by polymerlzatlon of tert-bul:ylaminoethyl methacrylate ls applled to the st;andard polymers, for example, by dlpplng, spraylng or painting If the polymer ls produced directly on the substrate surface wlthout graftlng, sultable inltlators are added.
Initiators whlch can be used are, inter alia, azonltrl:Les, alkyl peroxides, hydroperoxides, acyl peroxldes, peroxoket;ones, peresters, peroxocarbonates, peroxodlsulfate, persulfat;e and all the customary photolnitiators, such as, for example, acetophenones and benzophenone.
The inltiation of the polymerlzatlon can be carried out by means of heat or by electromagnetic radiation, such as, O.Z. 5161 for example, UV light or ~-radlation.
The ant imicrobial polymers so prepared may be used for the production of art:Lcles such as medical articles or hygiene art icles .
The medical art :Lcles produced with the process accordlng to the lnventlon may be, for example, catheters, blood bags, drainages, gu:Lde wires and surgical instruments.
The process according to the lnvent ion may furthermore be employed for the prot~uct lon of hygiene artlcles, such as, for example, toothbrushes, tollet seats, combs ancl packaglng mater:Lals.
The followlng examples are lntended to illustrate the lnvent ion .
Examp le 1 27 g of tert-but;ylaminoethyl methacrylate and 150 ml of ethanol are heated to 65~C under an inert gas. When the temperature ls reached, 0 37 g of azobisisobutyronltrlle, dlssolvecl ln 10 ml of methyl ethyl ketone, ls added. At the end of 24 hours, the react: ion ls ended by st irrlng the mlxture lnto 1 l of a water~lce m:Lxture. The reaction product is filtered off and washed w:Lth 300 ml of n-hexane. The product is then cllstrlbuted over ç,everal Soxhlets and extracted with water for 24 hours, and i'3 then drled at 50~C in vacuo for 12 - 7a -O. Z . 5161 hours.
Example 2 4 g of poly-tert-butylaminoethyl rnethacrylate from Example 1 are dissolved in 40 ml of tetrahydrofuran. A polyamide 12 film is immersed in this solution 5 for 5 seconds, removed from the solution for 10 seconds and them immersed again for 5 seconds, so that al uniform film of poly-tert-butylaminoethyl methacrylate has formed on the polyamide film after subsequent drying at room temperature under normal pressure. The film is then dried at 50~C in vacuo for 24 hours. The film is subsequently extracted in water at 30~C 5 times for 6 hours and then dried at 50~C for 12 hours.
E-xample 3 49 of poly-tert-butylaminoethyl me~hacrylate from Example 1 are dissolved in 40 ml of tetrahydrofuran. A polyvinyl chloride film is immersed in this solutionfor 2 seconds, removed from the solution for 10 seconds and then immersed 15 again for 2 seconds, so that a uniform film of poly-tert-butylaminoethyl methacrylate has formed on the polyvinyl chloride film after subsequent drying at room temperature under normal pressure. The film is then dried at 50~C in vacuo for 24 hours. The film is subsequently extracted in water at 30~C 5 times for 6 hours and then dried at 50~C for 12 hours.
Example 4:
A polyamide 12 film is exposed to the 172 nm radiation of an excimer radiation source from Heraeus for 2 minutes under a pressure of 1 mbar. The film activated in this way is laid and fixed in an irradiation reactor under an inert gas. rhe film is then covered with a layer of 20 ml of a mixture of 3 g oftert-butylaminoethyl methacrylate and 97 9 of methanol in a countercurrent of inert gas. The irradiation chamber is closed and placed at a distance of 10 cm underneath an excimer irradiation unit from Heraeus, w~lich ha~i an o z 5161 CA 0223ll20 l998-03-04 emission of wavelength 308 nm. Tine irradiation is started, and the exposure time is 15 minutes. The film is then removed and rinsed off with 30 ml of methanol. The film is then dried at 50~C in vacuo for 12 hours. The film is subsequently extracted in water at 30~C 5 times for 6 hours and then dried 5 at 50~C for 12 hours.
Measurement of the bactericidal action The bactericidal action of coated plastics was measured as follows:
100 lul of a cell suspension of Klebsiella pneumoniae were placed on a piece of film 2 x 2 cm in size. The bacteria were suspended in PBS buffer lO (phosphate-buffered saline); the c:ell concentration was 105 cells per ml of buffer solution. This drop was incubated for up to 3 hours. So that any drying out is prevented, the piece of film was laid in a polystyrene Petri dish wetted with 1 ml of water. After the end of the contact time, the 100 ,ul were taken upwith an Eppendorf tip and diluted in 1.9 ml of sterile PBS. 0.2 ml of this 15 solution was plated out on nutrient agar. The rate of inactivation was calculated from the number of colonies which had grown.
Checking the resistance of the coatings:
Before the measurement of the bactericidai action, the coated films were subjected to the following pretreatrnents:
20 A: Washing in boiling water for 10 minutes 13: Washing in 96% strength ethanolic solution for 10 minutes C: Washing in warm water at 25~C under ultrasonic treatment for 10 minutes D: No pretreatment 2S The results of the measurements. taking into account the particular pretreatmenl: are listed in Table 1.
O.Z. 5161 ~3443-645 .~a~e of in~c~iv~tfon J
Exampl e: A B C D
2 4% < 10% 56 % 99.9%
A ma~or ob~ect of the present lnventlon ls to develop materlals whlch hc~ve antiml/roblal propertles, whlch contaln no actlve compounds whlch can be washed out, and ln whlch the antlmlcroblal actlon ls pH-lndependent.
It has now been found, surprlslngly, that polymers whlch have a surface whlch ls permanently mlcroblcldal, ls not attacked by solvents and physlcal slresses and shows no mlgratlon are obtalned by polymerlzatlon of tert-butyl-aminoethyl methacrylate or by grafting polymerlzatlon of tert-butylamlnoethyl methacrylate on a substrate. It ls not necessary here to employ i-urther blocldal actlve compounds.
The present lnvention thus provldes a process for the preparatlon of antlmlcroblal po:Lymer, whlch comprlses polymerlzlng tert-butylam:Lnoethyl methacrylate.
The present lnvention fur1hermore provides a process for the preparatlon of ant;lmlcroblal articles, whlch comprlses sub~ectlng tert-butylamlnoethyl met}-acrylate to grafting 2G polymerlz:atlon on a substrate.
The present lnventlon furthermore provldes use of the antlmlcrobial polymers for the production of products wlth an antlmi.croblal coatlng 1-rom the polymer.
The present lnventlo:n moreover provldes the products having an antlmlcroblal coatlng of the polymer.
The antimicroblal polymers can be obtalned by graftlng polymerlzatlon ol- tert-butylamlnoethyl methacrylate on a substrate.
O.Z. 5161 CA 0223ll20 l998-03-04 Suitable substraLte materlals are, above all, any polymeric plastics, such as, for example, polyurethanes, polyamides, polyester, polyethers, polyether-block amldes, polystyrene, polyvlnyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroeth~lene (PTFE), correspondlng copolymers and blends, as well as natural and synthetic rubbers, wlth or wlthout radiation-3ensitive groups. The process according to the :Lnvention can also be applied on the surfaces of metal, glass or wooden bodles whlch are painted or are otherwise coated wlth polymeric plastics.
The surfaces of the substrates are preferably activatecl by a number of methods before the grafting polymerlzation. They are preferably freed from olls, greases or other impurltles beforehand ln a known manner by means of a solvent.
The standard po:Lymers may be actlvated by UV
radlatlon. A sultable source of radiation ls, for example, a UV-exclmer apparatus HERAE~US* NobleLlght, Hanau, Germany.
However, mercury vapor larnps are also suitable for actlvatlon of the substrate if they emit conslderable proportlons of radlatlon ln the ranges mentloned. The exposure time ls ln general from 0.1 second to 20 minutes, preferably from 1 second to 10 minutes.
The activatlon of the standard polymers wlth UV
radlatlon may furthermore be carrled out with an additional photosensitlzer. For thls" the phot;osensltizer, such as, for *Trade-mark O.Z. 5161 example, benzophenone, ls applled to the surface of the substrate and lrradlated. Thls may llkewlse be carrled out wlth a mercury vapor lamp uslng exposure tlmes of from 0.1 second to 20 mlnutes, preEerably from l second to 10 mlnutes.
The actlvatlon may also be achleved by a hlgh-frequency or mlcrowave pl~sma (Hexagon*, Technlcs Plasma, 85551 Klrchheim, Germany) ln alr or a nltrogen or argon atmosphere. The exposure tlmes are ln general from 30 seconds to 30 mlnutes, preferably from 2 to 10 mlnutes.
1() The energy OUtpllt of laboratory apparatus ls between 100 and 500 W, preferably between 230 and 300 W.
Corona apparatus (SOFTAL, Hamburg, Germany) may furthermore be used for the actlvatlon. In this case, the exposure tlmes are ln general from 1 to 10 mlnutes, preferably from 1 to 60 seconds.
The actlvatlon by electron beams or y-rays (for example i-rom a cobalt-60 source) and the ozonlzatlon allow short ex~osure tlmes whlch are ln general 0.1 to 60 seconds.
Flamlng of surfaces llkewlse leads to actlvatlon thereof. Sultable apparatus, ln partlcular those havlng a barrler flame front, can be constructed in a slmple manner or obtained for example, from ARCOTEC, 71297 Monshelm, Germany.
They can be operated wlth hydrocarbons or hydrogen as the combustible gas. In all cases, harmful overheating of the substrates must be avoided, which is easily achleved by lntlmate contact wlth a cooled metal surface on the substrate surface faclng away from the flamlng slde. Actlvatlon by *Trade-mark O.~. 5161 flaming :Ls accordlngly llmlted to relatlvely thln, flat substrates. The exposure tlmes are in general from 0.1 second to 1 mlnute, preferably f:rom 0.5 to 2 seconds. The flames without exceptlon are nonlumlnous and the dlstances between the subst;rate surfaces and the outer flame front are usually from 0.2 to 5 cm, preferably from 0.5 to 2 cm.
The substrate surfaces actlvated ln thls way are coated w:Lth tert-butylamlnoethyl methacrylate, lf approprlate ln solut:Lon, by known methods, such as dipplng, spraying or brushing Suitable solvents have proved to be water and water/ethanol mlxtures although other solvents may also be used lf t;hey have a sufflclent dlssolvlng power for tert-butylamlnoethyl methacryl'~te and wet the substrate surfaces thorough:Ly. Solutions havlng monomer contents of 1 to 10% by weight, i-or example about 5% by welg;ht, have proved particularly suitable in practice and ln general give continuolls coatings which cover the substrate surface and have coating t:hicknesses whlch can be more than 0.1 ~m ln one pass.
The graft polymerizatlon of the monomer applied to the actlvated surfaces ls preferably caused by rays in the short wavelength segment of the vlslble range or in the long wavelengt;h segment of the UV range of electromagnetic radiation. The radiatlon of a UV-e.xcimer of wavelengths of from 250 to 500 nm, preferably from 290 to 320 nm, for example, ls particularly suitable. Mercury vapor lamps are also suit:able here lf they emit conslderable proportlons of radiation in the ranges mentioned. The exposure times are ln general f-rom lO seconds to 30 mlnutes, preferably from 2 to 15 O.Z. 5161 minutes.
Poly-tert-butyl~mlnoethyl methacrylate also shows intrinsic microbicldal properties wlthout graftlng to a substrate surface.
An antimicroblal polymer may furthermore be prepared by polymerlzation of tert-butylamlnoethyl methacrylate by known processes.
In the process ~ccording to the inventlon, the polymer ll.e., homopolymer) of tert-butylamlnoethyl methacry:Late may also be ~pplied to the substrate ln a solution Sultable solvents are, for example, water, ethanol, methanol, methyl ethyl ketone, dlethyl ether, dloxane, hexane, heptane, benzlne, toluene, chloroform, methylene chlorlde, tetrahydrofuran and acetonltrlle.
The solution of the polymer obtained by polymerlzatlon of tert-bul:ylaminoethyl methacrylate ls applled to the st;andard polymers, for example, by dlpplng, spraylng or painting If the polymer ls produced directly on the substrate surface wlthout graftlng, sultable inltlators are added.
Initiators whlch can be used are, inter alia, azonltrl:Les, alkyl peroxides, hydroperoxides, acyl peroxldes, peroxoket;ones, peresters, peroxocarbonates, peroxodlsulfate, persulfat;e and all the customary photolnitiators, such as, for example, acetophenones and benzophenone.
The inltiation of the polymerlzatlon can be carried out by means of heat or by electromagnetic radiation, such as, O.Z. 5161 for example, UV light or ~-radlation.
The ant imicrobial polymers so prepared may be used for the production of art:Lcles such as medical articles or hygiene art icles .
The medical art :Lcles produced with the process accordlng to the lnventlon may be, for example, catheters, blood bags, drainages, gu:Lde wires and surgical instruments.
The process according to the lnvent ion may furthermore be employed for the prot~uct lon of hygiene artlcles, such as, for example, toothbrushes, tollet seats, combs ancl packaglng mater:Lals.
The followlng examples are lntended to illustrate the lnvent ion .
Examp le 1 27 g of tert-but;ylaminoethyl methacrylate and 150 ml of ethanol are heated to 65~C under an inert gas. When the temperature ls reached, 0 37 g of azobisisobutyronltrlle, dlssolvecl ln 10 ml of methyl ethyl ketone, ls added. At the end of 24 hours, the react: ion ls ended by st irrlng the mlxture lnto 1 l of a water~lce m:Lxture. The reaction product is filtered off and washed w:Lth 300 ml of n-hexane. The product is then cllstrlbuted over ç,everal Soxhlets and extracted with water for 24 hours, and i'3 then drled at 50~C in vacuo for 12 - 7a -O. Z . 5161 hours.
Example 2 4 g of poly-tert-butylaminoethyl rnethacrylate from Example 1 are dissolved in 40 ml of tetrahydrofuran. A polyamide 12 film is immersed in this solution 5 for 5 seconds, removed from the solution for 10 seconds and them immersed again for 5 seconds, so that al uniform film of poly-tert-butylaminoethyl methacrylate has formed on the polyamide film after subsequent drying at room temperature under normal pressure. The film is then dried at 50~C in vacuo for 24 hours. The film is subsequently extracted in water at 30~C 5 times for 6 hours and then dried at 50~C for 12 hours.
E-xample 3 49 of poly-tert-butylaminoethyl me~hacrylate from Example 1 are dissolved in 40 ml of tetrahydrofuran. A polyvinyl chloride film is immersed in this solutionfor 2 seconds, removed from the solution for 10 seconds and then immersed 15 again for 2 seconds, so that a uniform film of poly-tert-butylaminoethyl methacrylate has formed on the polyvinyl chloride film after subsequent drying at room temperature under normal pressure. The film is then dried at 50~C in vacuo for 24 hours. The film is subsequently extracted in water at 30~C 5 times for 6 hours and then dried at 50~C for 12 hours.
Example 4:
A polyamide 12 film is exposed to the 172 nm radiation of an excimer radiation source from Heraeus for 2 minutes under a pressure of 1 mbar. The film activated in this way is laid and fixed in an irradiation reactor under an inert gas. rhe film is then covered with a layer of 20 ml of a mixture of 3 g oftert-butylaminoethyl methacrylate and 97 9 of methanol in a countercurrent of inert gas. The irradiation chamber is closed and placed at a distance of 10 cm underneath an excimer irradiation unit from Heraeus, w~lich ha~i an o z 5161 CA 0223ll20 l998-03-04 emission of wavelength 308 nm. Tine irradiation is started, and the exposure time is 15 minutes. The film is then removed and rinsed off with 30 ml of methanol. The film is then dried at 50~C in vacuo for 12 hours. The film is subsequently extracted in water at 30~C 5 times for 6 hours and then dried 5 at 50~C for 12 hours.
Measurement of the bactericidal action The bactericidal action of coated plastics was measured as follows:
100 lul of a cell suspension of Klebsiella pneumoniae were placed on a piece of film 2 x 2 cm in size. The bacteria were suspended in PBS buffer lO (phosphate-buffered saline); the c:ell concentration was 105 cells per ml of buffer solution. This drop was incubated for up to 3 hours. So that any drying out is prevented, the piece of film was laid in a polystyrene Petri dish wetted with 1 ml of water. After the end of the contact time, the 100 ,ul were taken upwith an Eppendorf tip and diluted in 1.9 ml of sterile PBS. 0.2 ml of this 15 solution was plated out on nutrient agar. The rate of inactivation was calculated from the number of colonies which had grown.
Checking the resistance of the coatings:
Before the measurement of the bactericidai action, the coated films were subjected to the following pretreatrnents:
20 A: Washing in boiling water for 10 minutes 13: Washing in 96% strength ethanolic solution for 10 minutes C: Washing in warm water at 25~C under ultrasonic treatment for 10 minutes D: No pretreatment 2S The results of the measurements. taking into account the particular pretreatmenl: are listed in Table 1.
O.Z. 5161 ~3443-645 .~a~e of in~c~iv~tfon J
Exampl e: A B C D
2 4% < 10% 56 % 99.9%
3 ~% < 10% 54 % 99.9%
4 99. 9% 99. 9% 99. 9% 99. 9%
Table 1 After thermal, chemical or mechanical pretreatment, the antimicrobial layers produced by grafting of a substrate surface continue to show virtually complete inactivation of the bacteria applied. The physically adhered layers are less stable to the pretreatment according to methods A, B and C.
10 In addition ~:o the microbicidal activity against cells of Klebsiella pneumoniae which has been described above, all the coated films also showed a microbicidal action against cells of Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli, Rhizopus oryzae Candida tropicalis and Tetrahymena pyriforrnis. The rate of inactivation after treatment15 method D was also more than 99"/0 in these cases.
--- 1 o
Table 1 After thermal, chemical or mechanical pretreatment, the antimicrobial layers produced by grafting of a substrate surface continue to show virtually complete inactivation of the bacteria applied. The physically adhered layers are less stable to the pretreatment according to methods A, B and C.
10 In addition ~:o the microbicidal activity against cells of Klebsiella pneumoniae which has been described above, all the coated films also showed a microbicidal action against cells of Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli, Rhizopus oryzae Candida tropicalis and Tetrahymena pyriforrnis. The rate of inactivation after treatment15 method D was also more than 99"/0 in these cases.
--- 1 o
Claims (18)
1. A process for the preparation of an antimicrobial poly-tert-butylaminoethyl methacrylate coating layer on a surface of a substrate, which comprises subjecting tert-butylaminoethyl methacrylate to grafting polymerization on a surface of a substrate which is made of a polymeric plastic or is made of a metal, glass or wooden body coated with a polymeric plastic.
2. The process as claimed in claim 1, wherein the surface of the substrate is activated before the grafting polymerization.
3. The process as claimed in claim 2, wherein the activation of the surface of the substrate is carried out by (1) UV radiation with or without an additional photosensitizer, (2) plasma treatment, (3) corona treatment, (4) flaming, ozonization, (5) electrical discharge or (6) .gamma.-radiation.
4. The process as claimed in any one of claims 1 to 3, wherein the graft polymerization is caused by radiation of UV
rays having a wavelength of from 250 to 500 nm.
rays having a wavelength of from 250 to 500 nm.
5. A process as claimed in any one of claims 1 to 4, which produces a medical article.
6. A process as claimed in any one of claims 1 to 5, wherein the substrate is made of a polymeric plastic.
7. A process for the preparation of a medical or hygiene article having an antimicrobial poly-tert-butylaminoethyl methacrylate coating layer on a surface of a substrate, which comprises:
polymerizing tert-butylaminoethyl methacrylate using a polymerization initiator to produce poly-tert-butylaminoethyl methacrylate; and coating a surface of a substrate with the so-produced poly-tert-butylaminoethyl methacrylate, wherein the substrate is made of a polymeric plastic or is made of a metal, glass or wooden body coated with a polymeric plastic.
polymerizing tert-butylaminoethyl methacrylate using a polymerization initiator to produce poly-tert-butylaminoethyl methacrylate; and coating a surface of a substrate with the so-produced poly-tert-butylaminoethyl methacrylate, wherein the substrate is made of a polymeric plastic or is made of a metal, glass or wooden body coated with a polymeric plastic.
8. A medical or hygiene article comprising:
a substrate which is made of a polymeric plastic or is made of a metal, glass or wooden body coated with a polymeric plastic; and an antimicrobial poly-tert-butylaminoethyl methacrylate coating layer on a surface of the substrate.
a substrate which is made of a polymeric plastic or is made of a metal, glass or wooden body coated with a polymeric plastic; and an antimicrobial poly-tert-butylaminoethyl methacrylate coating layer on a surface of the substrate.
9. The article as claimed in claim 8, wherein the antimicrobial poly-tert-butylaminoethyl methacrylate layer is coated onto the surface of the substrate by graft polymerization of tert-butylaminoethyl methacrylate.
10. The article as claimed in claim 8 or 9, which is a medical article selected from the group consisting of catheters, blood bags, drainages, guide wires and surgical instruments.
11. A process for the preparation of an antimicrobial polymer, which comprises polymerizing tert-butylaminoethyl methacrylate.
12. The process as claimed in claim 11, wherein the polymerization of tert-butylaminoethyl methacrylate is carried out on a substrate.
13. The use of the antimicrobial polymer prepared by the process of claim 11 or 12 for the production of a product having an antimicrobial coating of the polymer.
14. The use of the antimicrobial polymer prepared by the process of claim 11 or 12 for the production of a medical article having an antimicrobial coating of the polymer.
15. The use of the antimicrobial polymer prepared by the process of claim 11 or 12 for the production of a hygiene article having an antimicrobial coating of the polymer.
16. The use of the antimicrobial polymer prepared by the process of any one of claims 1 to 6 for the production of a product having a antimicrobial coating of the polymer.
17. The use of the antimicrobial polymer prepared by the process of any one of claims 1 to 6 for the production of a medical article having an antimicrobial coating of the polymer.
18. The use of the antimicrobial polymer prepared by the process of any one of claims 1 to 6 for the production of a hygiene article having an antimicrobial coating of the polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19709076A DE19709076A1 (en) | 1997-03-06 | 1997-03-06 | Process for the production of antimicrobial plastics |
| DE19709076.1 | 1997-03-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2231120A1 true CA2231120A1 (en) | 1998-09-06 |
Family
ID=7822384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002231120A Abandoned CA2231120A1 (en) | 1997-03-06 | 1998-03-04 | Process for the preparation of antimicrobial plastics |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US6096800A (en) |
| EP (1) | EP0862859B1 (en) |
| JP (1) | JPH10251340A (en) |
| AT (1) | ATE220291T1 (en) |
| CA (1) | CA2231120A1 (en) |
| DE (2) | DE19709076A1 (en) |
| DK (1) | DK0862859T3 (en) |
| NO (1) | NO980980L (en) |
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| DE19921897A1 (en) * | 1999-05-12 | 2000-11-16 | Creavis Tech & Innovation Gmbh | 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 |
| DE19921900A1 (en) * | 1999-05-12 | 2000-11-16 | Creavis Tech & Innovation Gmbh | Preparation of antimicrobial polymer for medical and hygiene articles, varnishes, paints and coatings comprises polymerizing monomers that have been functionalized by a sec. amino group |
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| EP0663409B1 (en) * | 1993-07-14 | 1998-10-07 | Nippon Chemical Industrial Company Limited | Antimicrobial polymer, contact lens, and contact lens care products |
-
1997
- 1997-03-06 DE DE19709076A patent/DE19709076A1/en not_active Withdrawn
-
1998
- 1998-01-13 EP EP98100443A patent/EP0862859B1/en not_active Expired - Lifetime
- 1998-01-13 DE DE59804706T patent/DE59804706D1/en not_active Expired - Fee Related
- 1998-01-13 DK DK98100443T patent/DK0862859T3/en active
- 1998-01-13 AT AT98100443T patent/ATE220291T1/en not_active IP Right Cessation
- 1998-03-03 JP JP10050600A patent/JPH10251340A/en active Pending
- 1998-03-04 CA CA002231120A patent/CA2231120A1/en not_active Abandoned
- 1998-03-06 NO NO980980A patent/NO980980L/en not_active Application Discontinuation
- 1998-03-06 US US09/036,194 patent/US6096800A/en not_active Expired - Fee Related
-
2000
- 2000-03-17 US US09/527,829 patent/US6316044B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10251340A (en) | 1998-09-22 |
| ATE220291T1 (en) | 2002-07-15 |
| DE19709076A1 (en) | 1998-09-10 |
| EP0862859B1 (en) | 2002-07-10 |
| NO980980L (en) | 1998-09-07 |
| NO980980D0 (en) | 1998-03-06 |
| US20010007694A1 (en) | 2001-07-12 |
| EP0862859A1 (en) | 1998-09-09 |
| US6316044B2 (en) | 2001-11-13 |
| US6096800A (en) | 2000-08-01 |
| DK0862859T3 (en) | 2002-10-28 |
| DE59804706D1 (en) | 2002-08-14 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |