WO2015022055A1 - Beschichtung für antimikrobielle oberflächen - Google Patents
Beschichtung für antimikrobielle oberflächen Download PDFInfo
- Publication number
- WO2015022055A1 WO2015022055A1 PCT/EP2014/002108 EP2014002108W WO2015022055A1 WO 2015022055 A1 WO2015022055 A1 WO 2015022055A1 EP 2014002108 W EP2014002108 W EP 2014002108W WO 2015022055 A1 WO2015022055 A1 WO 2015022055A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- coating
- pseudo
- sample
- antimicrobial
- Prior art date
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Classifications
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
Definitions
- the invention relates to the use of a layer as a coating of a surface consisting of an antimicrobial material and to an article having at least partial areas of a surface consisting of an antimicrobial material, the article having such a coating.
- Copper has antimicrobial properties.
- copper is an attractive material for objects that are frequently touched, for example with hands or fingers. These include doorknobs, doorbell buttons or handrails of stair railings.
- copper is an interesting material for use in applications with special hygiene requirements, such as in the medical field or in the field of food processing.
- copper, copper surfaces and copper materials when unprotected, can quickly show tarnish and corrosion by use and especially by contact with sweat. This leads to an unclean appearance.
- a suitable protection against fingerprints and tarnishing by finger perspiration can be achieved by an anti-fingerprint coating, as described, for example, in DE 10 2005 026 359 A1.
- the interferences that occur are expressly desired.
- contamination of the surface can be hidden optically.
- DE 10 353 756 A1 describes an antimicrobial and non-cytotoxic layer material which comprises (a) a biocide layer with a biocidal active substance and (b) a transport control layer covering the biocide layer.
- the transport control layer has a thickness and a porosity which is adjusted so that the biocidal active ingredient is released from the biocide layer through the transport control layer in an antimicrobial and non-cytotoxic amount.
- the transport control layer has a permeability to
- US Pat. No. 6,929,705 describes an increased antimicrobial effect in metallic tapes using particle-containing resin coating. The antimicrobial effect comes about through the addition of additives.
- the invention has for its object to provide improved coatings for antimicrobial materials and objects with an improved coating.
- the coating is said to have the biocidal effect of
- the invention includes the technical teaching of using a layer which has a mean layer thickness s and whose main constituent is amorphous SiO 2 , as a coating of a surface consisting of an antimicrobial material.
- the layer has cracks that allow migration of the antimicrobial material through the layer.
- the cracks are formed so that the measured on a coated sample pseudo-transfer stream is at least 0.1% and at most 1% of the pseudo-transfer stream, which is measurable on an equivalent sample in the uncoated state.
- the invention is based on the consideration that the antimicrobial effect of a material which is coated on its surface, also occurs at the surface facing away from the material of the coating when particles of the material are present in a sufficient amount on the free surface of the coating.
- the layer must have a permeability or permeability to the particles of the material.
- the particles of the material can are present as ions, atoms or in compounds with one or more other elements. It has been found that a layer whose main constituent is amorphous S1O2 can exhibit this property.
- Such layers are deposited on the antimicrobial material by means of a thermal CVD process without the use of a plasma from the gas phase.
- the coating process takes place at substrate temperatures of at least 200 ° C, preferably at least 300 ° C.
- substrate temperatures of at least 200 ° C, preferably at least 300 ° C.
- When cooled to ambient temperature arise in the layer material due to the different thermal expansion coefficients of substrate and layer material compressive stresses that cause fractures, cracks and distortions in the layer material. Individual areas of the layer material shift against each other like plaques and partly over each other. Cracks visible on the surface need not necessarily extend through the entire layer to the substrate.
- the permeability of the layer to particles of both the substrate and the environment can not be sufficiently correlated with purely geometrically detectable parameters such as crack width, crack length, crack depth, or cracked portion of the surface.
- the so-called pseudo-transfer stream is used.
- current density-potential curves are recorded from which the corrosion current is determined.
- electrolytic media particularly preferably sodium sulfate solution of concentration 0.1 mol / l used. Since relatively high voltages are applied to the sample with this method, the measurement becomes the surface the sample changed significantly. This is undesirable.
- the corrosion susceptibility of the sample is derived from readings taken at electrical voltages that do not occur in real life conditions.
- a more suitable way to characterize the corrosion properties of a sample is the determination of a so-called pseudo-transfer stream by means of electrochemical impedance spectroscopy.
- the impedance of the sample is extrapolated to the limiting excitation at vanishing frequency f (ie f-0 Hz), and from this extrapolated impedance and the impressed voltage, the pseudo-transfer current is calculated ,
- the pseudo-transfer current is calculated .
- the pseudo-transfer current which can be determined by this method is at least 0.1% and at most 1% of the pseudo-transfer stream, which can be measured on an equivalent sample in the uncoated state.
- the layer according to the invention thus has a non-zero pseudo-transfer stream. The reason for this is the cracks present in the layer, through which electrically charged particles, such as metal ions, can be transported.
- the detectable pseudo-transfer current is at most 1% of the pseudo-transfer current measurable on an equivalent sample in the uncoated state. This characterizes the corrosion protection effect of the coating according to the invention. If the pseudo-transfer stream for a coated sample is greater than 1% of that measured on an equivalent sample in the uncoated state
- the layer according to the invention is the combination of the corrosion-inhibiting effect with the antimicrobial effect.
- the layer is sufficiently dense to act as a corrosion protection layer, on the other hand it is sufficiently permeable to particles of the coated material to transfer the antimicrobial effect of the base material to the free surface of the coating.
- the coated material may consist of copper or a copper alloy with a copper content of at least 60%.
- the coated material may consist of silver or a silver alloy having a silver content of at least 60%.
- the layer may have on its surface facing away from the antimicrobial material antimicrobial properties, which are characterized in that under incubation conditions analogous to the standard ISO22196: 2007 after an incubation period of 24 h at most 50% of the seeds used are still viable.
- the layer may have on its surface facing away from the antimicrobial material antimicrobial properties, which are characterized in that under incubation conditions analogous to the standard ISO22196: 2007 after an incubation period of 24 h at most 50% of the seeds used are still viable.
- the germs used may still be viable.
- the layer may be used to improve corrosion resistance and / or to improve soil-concealing properties of the surface.
- the coating inhibits or prevents the passage of oxygen or other oxidizing substances to the surface of the base material.
- the layer consisting of amorphous S1O 2 is impermeable to oxygen.
- the corrosion of the material is strongly inhibited until completely prevented.
- the material retains its original appearance. It shows no tarnishes and no color changes.
- the layer can prevent the adhesion of dirt particles or liquids or reduce undesirable effects, in particular unwanted optical effects of adhering dirt particles or liquids. These include, in particular, particles which may be present in the dust, for example, or in the atmosphere for environmental reasons, as well as liquids such as, for example, sweat or other secretions of living beings.
- the layer according to the invention prevents the passage of the particles or of the liquids to the surface of the coated material and thus effectively prevents reactions of the particles or of the liquids with the material or the incorporation of the particles into the surface.
- Another aspect of the invention includes an article which has a surface made of an antimicrobial material at least in some areas, wherein a coating is applied in the area of the surface consisting of the antimicrobial material.
- Coating here comprises at least one layer of average thickness s.
- the main constituent of the layer is amorphous SiO 2 .
- the layer has a structure with cracks that allow migration of the antimicrobial material through the layer.
- the cracks are formed so that the measured on a coated sample pseudo transfer stream is at least 0.1% and at most 1% of the pseudo-transfer stream, which is measurable on an equivalent sample in the uncoated state.
- the invention is based on the consideration that the antimicrobial effect of a material which is coated on its surface, also occurs at the surface facing away from the material of the coating when particles of the material are present in a sufficient amount on the free surface of the coating.
- the coating must have a permeability or permeability for the particles of the material.
- a layer whose main constituent is amorphous SiO 2 can exhibit this property. Due to the structure of such a layer, particles of the coated antimicrobial material may penetrate relatively quickly through the layer to the free surface of the coating. This can be explained by the cracks present in the layer. As described above, such layers are deposited on the antimicrobial material by means of a thermal CVD process without the use of a plasma from the gas phase. The permeability of the layer thus formed to particles of both the substrate and the environment (for example, oxygen or liquids) can not be sufficiently detected with purely geometrical Sizes such as crack width, crack length, crack depth or the crack-covered portion of the surface are correlated.
- the so-called pseudo-transfer current is used.
- this is at least 0.1% and at most 1% of the pseudo-transfer stream, which is measured on an equivalent sample in the uncoated state.
- the coating according to the invention thus has a non-zero pseudo-transfer stream.
- the reason for this is the cracks present in the layer, through which electrically charged particles, such as metal ions, can be transported. The layer is therefore not completely insulating. If the pseudo-transfer stream for a coated sample is less than 0.1% of the pseudo-transfer stream measurable on an equivalent sample in the uncoated state, then insufficient metal ions can be transported from the substrate to the surface through the cracks.
- the coating according to the invention is at most 1% of the pseudo-transfer stream measurable on an equivalent sample in the uncoated state. This characterizes the corrosion protection effect of the coating according to the invention. If the pseudo-transfer current in the case of a coated sample is greater than 1% of the pseudo-transfer current measurable on an equivalent sample in the uncoated state, then the cracks in the layer are formed such that the layer does not have a sufficient anticorrosion effect.
- the coating may be formed as a system of several layers or it may consist only of the layer of amorphous SiO 2 .
- the coating according to the invention greatly inhibits the corrosion of the material until it is completely prevented and the article retains its original appearance. It shows no tarnishing marks and no color changes. Furthermore, the layer may adhere dirt particles or liquids to the surface Prevent the surface of objects or reduce undesirable effects, in particular unwanted optical effects of adhering dirt particles or liquids. As explained above, in the coating of the present invention, the effect manifested by an improvement in the corrosion resistance of the surface can not be phenomenologically separated from the effect manifested by an improvement in dirt-concealing properties of the surface.
- the peculiarity of the coating according to the invention is the combination of the corrosion-inhibiting effect with the antimicrobial effect.
- the coating is sufficiently dense to act as a corrosion protection layer, on the other hand it is sufficiently permeable to particles of the coated material to transfer the antimicrobial effect of the base material to the free surface of the coating.
- This combination of effects makes the coating particularly attractive for articles which are frequently touched, for example with the hands or fingers. These include doorknobs, doorbell buttons, handrails of stair railings, keyboards or housing of mobile phones.
- Particularly preferred applications are found in applications with special hygiene requirements, such as in the medical field, such as handles, trays, stethoscopes or components of hospital beds, or in the field of food processing.
- Objects with the coating according to the invention are both advantageous in terms of hygiene because of their antimicrobial effect and because of their corrosion protection effect optically very attractive.
- the coating according to the invention also makes the coated articles resistant to detergents and disinfectants used in the abovementioned ranges.
- the coating applied to the article may comprise a layer of amorphous SiO 2 , which is applied as a surface layer.
- the amorphous SiO 2 layer is at this Design the layer that represents the outer surface of the coated article.
- the antimicrobial effect of the coated material is not limited by further, overlying layers. Ideally, any intermediate layers between the antimicrobial material and the layer of amorphous SiO 2 will not or only insignificantly reduce the permeability of the particles of the material.
- the coating applied to the article may comprise a layer of amorphous SiO 2 whose thickness on 90% of the coated surface does not deviate by more than +/- 10% from the mean thickness s of the layer.
- the layer is thus characterized by a particular uniformity of the layer thickness.
- the uniformity of the layer thickness is important in order to simultaneously ensure the corrosion-inhibiting effect and the antimicrobial effect in the layer according to the invention. In the case of uneven layer thickness, the corrosion protection effect may be too low at the points of low layer thickness and / or the antimicrobial effect may be too low at the points of large layer thickness.
- Layers of uniform thickness can be deposited by suitable CVD techniques. This is also possible in particular with objects of complex shape such as, for example, with projections, steps, depressions or undercut areas. Coating methods such as plasma polymerization or sputtering are not suitable for this aspect.
- the layer of amorphous SiO 2 deposited on the article may have an average thickness s of at least 10 nm and at most 500 nm, preferably at most 300 nm.
- layer thicknesses of less than 10 nm the improvement in corrosion resistance can no longer be ensured.
- layer thicknesses greater than 500 nm the antimicrobial effect can no longer be ensured since the paths for the permeation and / or diffusion of the particles of the antimicrobial material are too long.
- layer thicknesses of at most 300 nm are particularly preferred.
- the layer of amorphous SiO 2 applied to the article may have an average thickness s of at least 50 nm and at most 100 nm. With layer thicknesses of at least 50 nm, the improvement in corrosion resistance can be ensured in virtually all cases. At layer thicknesses of at most 100 nm, no unwanted intrinsic colors of the layer occur. The layer thus behaves neutral in color.
- the applied to the article layer may consist of at least 90 wt .-% of amorphous SiO 2 .
- the layer may contain impurities that are unavoidable due to the coating process. These include organic radicals from the precursors and hydrogen atoms and OH groups. In particular, the layer is free of carbon, apart from organic radicals from the precursors.
- Carbon incorporated into an amorphous Si0 2 structure makes it chemically unstable and particularly susceptible to oxidation. Further, carbon reduces adhesion to the base material and renders the coating vulnerable to infiltration.
- the layer applied to the article may further contain further ceramic oxides.
- Ceramic oxides such as Al 2 O 3 , ZrO 2 and TiO 2 , can contribute to the improvement of the layer properties and make it possible to functionalize the layer.
- the chemical and mechanical resistance can be improved by Al 2 O 3 and ZrO 2 .
- TiO 2 allows disinfection of the coated articles by UV light.
- tape samples of copper with copper content greater than 99.9% were coated by means of a thermal CVD process with an amorphous layer of S1O2.
- the coating time of Sample 2 was four times longer than the coating time of Sample 1.
- the coated samples were tested for their antimicrobial effect together with an uncoated sample according to IS022196: 2007.
- the test microorganisms used were Staphylococcus aureus DSM 346 / ATCC 6538P. In the uncoated sample, a reduction of the bacterial count to 1 / 100,000 of the initial value was observed already after 30 minutes.
- the layer according to the invention transfers it
- the pseudo-transfer current measured on Sample 1 was at least 2,000 times higher than the pseudo-transfer current on the coated with clear coat sample could still be determined.
- the permeability of the layer for copper ions causes the antimicrobial properties of the substrate to also appear on the outer surface of the coating.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Materials Engineering (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE112014003722.2T DE112014003722A5 (de) | 2013-08-12 | 2014-07-31 | Beschichtung für antimikrobielle Oberflächen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102013013311 | 2013-08-12 | ||
DE102013013311.4 | 2013-08-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015022055A1 true WO2015022055A1 (de) | 2015-02-19 |
Family
ID=51298698
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2014/002108 WO2015022055A1 (de) | 2013-08-12 | 2014-07-31 | Beschichtung für antimikrobielle oberflächen |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE112014003722A5 (de) |
WO (1) | WO2015022055A1 (de) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999022878A2 (de) * | 1997-10-31 | 1999-05-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur korrosionsfesten beschichtung von metallsubstraten mittels plasmapolymerisation |
WO2005049699A2 (de) * | 2003-11-17 | 2005-06-02 | Induflex Robert Morgan | Verwendungen eines schichtmaterials |
-
2014
- 2014-07-31 WO PCT/EP2014/002108 patent/WO2015022055A1/de active Application Filing
- 2014-07-31 DE DE112014003722.2T patent/DE112014003722A5/de not_active Ceased
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999022878A2 (de) * | 1997-10-31 | 1999-05-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur korrosionsfesten beschichtung von metallsubstraten mittels plasmapolymerisation |
WO2005049699A2 (de) * | 2003-11-17 | 2005-06-02 | Induflex Robert Morgan | Verwendungen eines schichtmaterials |
Non-Patent Citations (1)
Title |
---|
PECH D ET AL: "Electrochemical behaviour enhancement of stainless steels by a SiO2 PACVD coating", CORROSION SCIENCE, OXFORD, GB, vol. 50, no. 5, 1 May 2008 (2008-05-01), pages 1492 - 1497, XP022616438, ISSN: 0010-938X, [retrieved on 20080216], DOI: 10.1016/J.CORSCI.2008.01.015 * |
Also Published As
Publication number | Publication date |
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DE112014003722A5 (de) | 2016-04-28 |
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