WO2003013731A1 - Pointes de pipette a surfaces en partie structurees, aux proprietes de pipettage ameliorees - Google Patents
Pointes de pipette a surfaces en partie structurees, aux proprietes de pipettage ameliorees Download PDFInfo
- Publication number
- WO2003013731A1 WO2003013731A1 PCT/EP2002/006734 EP0206734W WO03013731A1 WO 2003013731 A1 WO2003013731 A1 WO 2003013731A1 EP 0206734 W EP0206734 W EP 0206734W WO 03013731 A1 WO03013731 A1 WO 03013731A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pipette tips
- poly
- particles
- solvent
- elevations
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/02—Burettes; Pipettes
- B01L3/0275—Interchangeable or disposable dispensing tips
Definitions
- the invention relates to pipette tips with improved pipetting properties and a method for their production.
- Pipette tips or similar tools are often used for the defined absorption and distribution of liquids. With the help of these pipette tips, liquids can be removed from a storage container or defined amounts of liquid can be transferred from one container to another. In molecular biology, high throughput screening or combinatorial chemistry, smaller and smaller volumes are pipetted. For technical reasons, the pipette tips currently available on the market cannot pipette arbitrarily small volumes without contact, that is, with the liquid to be pipetted being detached completely and independently from the pipette tip. Technically, therefore, a pipette tip is desired with which volumes ⁇ 500 nl can be pipetted without contact.
- DE 2819440 describes a method in which liquid is conveyed to the dispensing nozzle from a storage container located above the dispensing nozzle via a hose line. Drops created at the opening are torn off by a pressure gas pulse. This method can also be used to tear off a drop of liquid from a pipette tip and has the advantage that the smallest drops can be applied to a surface. Disadvantages of the method are the poor reproducibility of the drop size and the fact that the pressure pulse can also force liquid out of the reaction vessel.
- DE 19742005 describes a method with which volumes of less than 100 nl can also be pressed from a thin capillary.
- the volume pressed out depends on the diameter of the capillary and the applied pressure pulse.
- the disadvantage of this method is, firstly, the very complex printing technology and the poor reproducibility of the drop size.
- DE 19742005 describes a further development of this method.
- the pressure for pressing out is generated electrically.
- the pressure pulse is generated by a piezo modulator mounted on the capillary.
- the advantage of this method is the improved reproducibility of the pulses and thus the drop size as well as the simple electrical control.
- the state of the art for these surfaces is that an aspect ratio of> 1 and a surface energy of less than 20 mN / m are required for such self-cleaning surfaces.
- the aspect ratio is defined as the quotient of the height and the width of the structure.
- the aforementioned criteria are realized in nature, for example in the lotus leaf.
- the surface of the plant formed from a hydrophobic wax-like material has elevations that are a few ⁇ m apart. Water drops essentially only come into contact with these tips. Such water-repellent surfaces have been widely described in the literature.
- CH-PS-268 258 describes a method in which structured surfaces are produced by applying powders such as kaolin, talc, clay or silica gel. The powders are fixed on the surface by oils and resins based on organosilicon compounds (Examples 1 to 6).
- EP 0 909 747 teaches a method for producing a self-cleaning surface.
- the surface has hydrophobic elevations with a height of 5 to 200 ⁇ m.
- Such a surface is produced by applying a dispersion of powder particles and an inert material in a siloxane solution and then curing. The structure-forming particles are thus fixed to the substrate by an auxiliary medium.
- WO 00/58410 comes to the conclusion that it is technically possible to make the surfaces of objects artificially self-cleaning.
- the surface structures of elevations and depressions required for this have a distance between the elevations of the surface structures in the range from 0.1 to 200 ⁇ m and a height of the elevation in the range 0.1 to 100 ⁇ m.
- the materials used for this must consist of hydrophobic polymers or permanently hydrophobized material. Detachment of the particles from the carrier matrix must be prevented.
- hydrophobic materials, such as perfluorinated polymers, for the production of hydrophobic surfaces is known. A further development of these surfaces consists in structuring the surfaces in the ⁇ m range to the nm range. US Pat. No.
- 5,599,489 discloses a method in which a surface can be given a particularly repellent finish by bombardment with particles of a corresponding size and subsequent perfluorination.
- Another method describes H. Saito et al. in "Service Coatings International", 4, 1997, p.168 ff.
- particles of fluoropolymers are applied to metal surfaces, with a greatly reduced wettability of the surfaces thus produced against water with a significantly reduced tendency to icing.
- WO 00/58410 describes the structures and claims the formation thereof by spraying on hydrophobic alcohols, such as nonacosan-10-ol or alkanediols, such as nonacosan-5,10-diol.
- hydrophobic alcohols such as nonacosan-10-ol or alkanediols, such as nonacosan-5,10-diol.
- the disadvantage here is the poor stability of the self-cleaning surfaces, since detergents lead to the dissolution of the structure.
- the object of the present invention was therefore to provide pipette tips with which liquids can be easily taken up and distributed without residue.
- the process should be so simple that the effect is achieved by simply modifying the surface of existing pipette tips.
- the present invention therefore relates to pipette tips, the surfaces of which come into contact with a liquid at least partially have structures from elevations, which are characterized in that the elevations are formed by particles firmly connected to the surface.
- the present invention also relates to a method for producing pipette tips with surfaces that have all or part of the elevations, which is characterized in that a surface of the pipette tips that is dissolved by a solvent is treated with this solvent, the solvent undissolved particles contains, and after removal of the solvent, at least some of the particles are firmly connected to the surface of the pipette tips.
- the present invention also relates to pipettes which are characterized in that they have pipette tips according to at least one of claims 1 to 14.
- the present invention also relates to a pipetting device which has a pipette according to at least one of claims 27 to 29.
- the pipette tips according to the invention are much easier to manufacture than pipette tips with good draining behavior according to the prior art, which also have elevations.
- suitable particles for the production of the elevations it is not necessary to create the superficial elevations by molding. Rather, it is possible to subsequently equip commercially available pipette tips with good draining properties or to produce pipette tips in the usual manner and then to provide them with good draining properties.
- the pipette tips according to the invention also have the advantage that no liquids remain on the pipette tip during the pipetting (depending on the design, neither inside nor outside).
- the pipette tips according to the invention thus achieve the following advantages: can also be used with liquid quantities of less than 1 ⁇ l, no use of pressure pulses - no use of antimicrobial materials, no “carryover” of reaction media when, for example, pipette tips or capillary tips are immersed in liquids due to residues of these liquids, high volume accuracy high reproducibility
- the pipette tips according to the invention are distinguished by the fact that the elevations are formed by particles firmly connected to the surface.
- the at least partially present elevations on the surface of the pipette tip ensure that these surface areas are difficult to wet and that the liquids to be pipetted do not get caught on the pipette tip and thus falsify the pipetted volume.
- the pipette tips preferably have elevations with an average height of 50 nm to 25 ⁇ m and an average distance of 50 nm to 25 ⁇ m, preferably with an average height of 50 nm to 25 ⁇ m and / or an average distance of 50 nm to 25 ⁇ m and very particularly preferably with an average height of 50 nm to 4 ⁇ m and / or an average distance of 50 nm to 4 ⁇ m.
- the pipette tips according to the invention very particularly preferably have elevations with an average height of 0.25 to 1 ⁇ m and an average distance of 0.25 to 1 ⁇ m.
- the mean distance between the elevations is understood to mean the distance between the highest elevation of one elevation and the next highest elevation. If an elevation has the shape of a cone, the tip of the cone represents the highest elevation of the elevation. If the elevation is a cuboid, the top surface of the cuboid represents the highest elevation of the elevation.
- the wetting of solids can be described by the contact angle that a drop of water forms with the surface.
- a contact angle of 0 degrees means complete wetting of the surface.
- the wetting angle on fibers is measured in the
- the thread is wetted by a liquid and the force with which the fiber is pulled into the liquid due to the surface tension.
- the aspect ratio is defined as the quotient of the height to the width of the structure of the surface.
- the pipette tips according to the invention with a self-cleaning and very water-repellent surface have a high aspect ratio of the elevations.
- the elevations of the pipette tips according to the invention preferably have an aspect ratio of 0.5 to 20, preferably 1 to 10.
- the pipette tips have the elevations applied to a superstructure with an average height of 10 ⁇ m to 1 mm and an average distance of 10 ⁇ m to 1 mm.
- the pipette tips can have the elevations on all surfaces or only on certain surfaces.
- the pipette tips according to the invention preferably have the elevations applied to the inner surface of the pipette tips, to the outer surface of the pipette tips and / or to the pipette tip outlet.
- the elevations according to the invention on the outer surfaces of the pipette tips prevent liquid from being transported from the storage vessel in the form of drops on the outer sides of the pipette tip.
- the elevations according to the invention on the inner surfaces of the pipette tips prevent liquid from remaining in the pipette tip when the liquid is ejected.
- the dispensing of the liquid to be pipetted is significantly simplified by the elevations according to the invention on the pipette tip outlet.
- the pipette tips preferably have a material selected from poly (tetrafiuorethylene), poly (trifluoroethylene), poly (vinylidene fluoride), poly (chlorotrifluoroethylene), poly (hexafluoropropylene), poly (perfluoropropylene oxide), poly (2.2, 3,3-tetraflluoroxetane), poly (2,2-bis (trifluoromethyl) -4,5-difluoro-l, 3-dioxole), poly (fluoroalkyl acrylate), poly (fluoroalkyl methacrylate), poly (vinyl perfluoroalkyl ether) or other polymers from perfluoroalkoxy compounds, poly (ethylene), poly (propylene), poly (isobutene), poly (isoprene), poly (4-methyl-1-pentene), polynorbornene, polynorbornadienes, poly (vinyl alkanoates) and poly (vinyl methyl ether)
- the particles firmly attached to the surface, which form the elevations on the surface of the pipette tips, are preferably selected from silicates, minerals, metal oxides, metal powders, silicas, pigments or polymers, very particularly preferably from pyrogenic silicas, precipitated silicas, aluminum oxide, silicon oxide, doped Silicates, pyrogenic silicates or powdered polymers.
- the particles which form the elevations of the structured surface are preferably those which have an irregular fine structure in the nanometer range on the surface. It can also be advantageous if the particles have hydrophobic properties.
- the particles which are firmly bonded to the surface are preferably at least 5 to 90%, particularly preferably 10 to 30, 31 to 60 or 61 to 90% and very particularly preferably 10 to 25% of their surface with the surface of the Pipette tip connected. In this way it is achieved that the firmly connected particles are connected to the pipette tip in a very durable manner and thus there is no contamination of the liquids to be pipetted with the particles.
- the pipette tips are particularly suitable for pipetting small volumes.
- volumes from 10 nl to 10 ml preferably volumes from 10 nl to 10 ⁇ l, particularly preferably from 10 nl to 100 nl, from 100 nl to 1 ⁇ l or from 1 ⁇ l to 10 ⁇ l and very particularly preferably pipette from 100 nl to 500 nl.
- the error in the pipetted volume is very particularly preferably less than 20%, preferably less than 10% and very particularly preferably less than 1%.
- the pipette tips according to the invention are preferably produced in accordance with the method according to the invention for the production of pipette tips with surfaces that have wholly or partially raised areas, which is characterized in that a surface of the pipette tips that is dissolved by a solvent is treated with this solvent, whereby the Solvent contains particles undissolved, and after removal of the solvent, at least some of the particles are firmly connected to the surface of the pipette tips.
- the particles are preferably dispersed or suspended in the solvent.
- the surface which is dissolved by a solvent preferably has polymers based on polycarbonates, poly (meth) acrylates, polyamides, PVC, polyethylenes, polypropylenes, polystyrenes, polyesters, polyether sulfones, aliphatic linear or branched alkenes, cyclic alkenes, polyacrylonitrile or polyalkylene terephthalates, as well as their mixtures or copolymers.
- the surface of the pipette tip made of the polymers mentioned may be inherently present if the pipette tip or the pipette itself was made entirely from this material. However, the polymers can also be applied as a coating to other materials. So z. B. pipette tips made of glass or metal can be equipped with a wholly or partially with a surface made of one of the polymers mentioned, for. B. by dipping into a polymer melt and subsequent solidification of the melt or by applying a reactive polymer adhesive and solidifying the adhesive on the pipette tip or pipette.
- At least one compound suitable as a solvent for the corresponding surface can be selected from the group of alcohols, glycols, ethers, glycol ethers, ketones, esters, amides, nitro compounds, halogenated hydrocarbons, aliphatic and aromatic Hydrocarbons or mixtures thereof are used.
- solvent at least one compound suitable as solvent for the corresponding surface selected from methanol, ethanol, propanol, butanol, octanol, cyclohexanol, phenol, cresol, ethylene glycol, diethylene glycol, diethyl ether, Dibutyl ether, anisole, dioxane, dioxolane, tetrahydrofuran, monoethylene glycol ether, diethylene glycol ether, triethylene glycol ether, polyethylene glycol ether, acetone, butanone, cyclohexanone, ethyl acetate, butyl acetate, iso-amylacetate, ethylhexyl acetate, glycol ester, dimethylolidonyl acetyl, methyl-nitryl, methyl-nitrone, methyl-methyl-nitrone, methyl-methyl-nitrone, methyl-methyl-nitrone, methyl-methyl-nitrone, methyl-
- the solvent which has the particles has a temperature of from -30 ° C. to 300 ° C., preferably 25 to 100 ° C. and very particularly preferably from 25 to 49 ° C., before being applied to the surface 50 to 85 ° C or from 86 to 100 ° C.
- the solvent preferably contains particles which have at least one material selected from silicates, minerals, metal oxides, metal powders, silicas, pigments or polymers.
- particles are used which have a particle diameter of 0.02 to 100 ⁇ m, particularly preferably from 0.1 to 50 ⁇ m and very particularly preferably from 0.1 to 30 ⁇ m. Particles with diameters of less than 500 nm can also be used. However, particles which are composed of primary particles to form agglomerates or aggregates with a size of 0.2-100 ⁇ m are also suitable.
- particles in particular as particles which have an irregular fine structure in the nanometer range on the surface, those particles are used which have at least one compound selected from pyrogenic silicic acid, precipitated silicic acids, aluminum oxide, silicon dioxide, pyrogenic and / or doped silicates or powdery polymers ,
- the particles preferably have hydrophobic properties, the hydrophobic properties relating to the material properties of those present on the surfaces of the particles Materials themselves can decline or can be obtained by treating the particles with a suitable compound.
- the particles can be provided with hydrophobic properties before or after they are connected to the surface.
- the particles can be treated with a compound from the group of the alkylsilanes, the fluoroalkylsilanes or the disilazanes.
- the particles preferably used are explained in more detail below.
- the particles used can come from different areas.
- it can be silicates, doped silicates, minerals, metal oxides, aluminum oxide, silicas or pyrogenic silicates, aerosils or powdered polymers, such as, for. B. spray-dried and agglomerated emulsions or cryomilled PTFE.
- Particularly suitable particle systems are hydrophobicized pyrogenic silicas, so-called aerosils.
- a hydrophobicity is necessary to generate the self-cleaning surfaces.
- the particles used can themselves be hydrophobic, such as PTFE.
- the particles can be made hydrophobic, such as the Aerosil VPR 411 or Aerosil R 8200.
- Such articles to be hydrophobized are, for example, Aeroperl 90/30, Sipemat silica 350, aluminum oxide C, zirconium silicate, vanadium-doped or Aeroperl P 25/20.
- the hydrophobization is expediently carried out by treatment with perfluoroalkylsilane and subsequent tempering.
- the pipette tips are preferably treated according to the invention by immersing the pipette tips in the solvent which has the particles.
- the duration of the immersion of the pipette tips depends on the rate of dissolution of the polymer in the solvent, but is preferably less than 5 minutes, preferably from 1 second to 5 minutes, particularly preferably from 1 to 20 seconds, from 20 seconds to 1.5 minutes or from 1.5 to 2 minutes.
- the immersion of the pipette tip in the solvent is very particularly preferably from 5 to 15 seconds.
- After immersing the Pipette tips in the solvent are removed from the solvent and dried. Drying can be done slowly in air. Drying can also be carried out by thermal treatment at 30 to 70 ° C, preferably at 40 to 60 ° C.
- the method can be applied to all devices with which the smallest amounts of liquid can be taken up.
- the pipette tips according to the invention are outstandingly suitable for use with pipettes.
- the pipettes can have the pipette tips according to the invention as exchangeable tips or can be firmly connected. In the case of pipettes in which the pipette tip is firmly connected to the pipette, it can be advantageous if the pipette and pipette tip are made from one piece.
- Pipettes according to the invention with pipette tips according to the invention can, for. B. also in pipetting devices, e.g. B. in automatic pipetting devices. Depending on the intended use of the pipetting device, these pipettes can have exchangeable tips or with firmly connected tips.
- the structuring i.e. H. the elevations can be applied to the inner (a in FIG. 1) or the outer surface of the pipette tip (b in FIG. 2). It is also possible to place the elevations only on the end of the pipette tip, i.e. H. to apply to the pipette outlet (c in Fig. 3).
- FIG. 4 shows an SEM image which shows a surface modified by the aforementioned method.
- volumes could be pipetted that are at least 10 times smaller.
- FIG. 5 shows an enlargement of the modified surface from FIG. 4.
- a commercial pipette tip from Eppendorf is immersed in a suspension of decalin and 1% by weight Aerosil R8200 (Degussa AG) at 90 ° C. for 5 s and then air-dried.
- a pipette tip with a surface according to the invention is obtained.
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- Health & Medical Sciences (AREA)
- Clinical Laboratory Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Devices For Use In Laboratory Experiments (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10138037.2 | 2001-08-03 | ||
DE2001138037 DE10138037A1 (de) | 2001-08-03 | 2001-08-03 | Pipettenspitzen mit teilweise strukturierten Oberflächen mit verbesserten Pipettiereigenschaften |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003013731A1 true WO2003013731A1 (fr) | 2003-02-20 |
Family
ID=7694216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/006734 WO2003013731A1 (fr) | 2001-08-03 | 2002-06-19 | Pointes de pipette a surfaces en partie structurees, aux proprietes de pipettage ameliorees |
Country Status (2)
Country | Link |
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DE (1) | DE10138037A1 (fr) |
WO (1) | WO2003013731A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120009100A1 (en) * | 2010-07-12 | 2012-01-12 | Hamilton Bonaduz Ag | Pipette tip having a hydrophobic surface texture |
CN115850778A (zh) * | 2022-09-30 | 2023-03-28 | 深圳市皆特生物科技有限公司 | 一种自动化导电移液吸头的表面处理方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102022120212A1 (de) | 2022-08-10 | 2024-02-15 | Hamilton Bonaduz Ag | Pipettierspitze mit sich gekrümmt verjüngendem Aufnahmeraum |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3354022A (en) * | 1964-03-31 | 1967-11-21 | Du Pont | Water-repellant surface |
EP0339622A2 (fr) * | 1988-04-28 | 1989-11-02 | Fuji Photo Film Co., Ltd. | Procédé et dispositif permettant de rendre hydrophobe un élément tubulaire |
EP0423719A2 (fr) * | 1989-10-16 | 1991-04-24 | Fuji Photo Film Co., Ltd. | Embout pour pipette |
WO1996004123A1 (fr) * | 1994-07-29 | 1996-02-15 | Wilhelm Barthlott | Surfaces autonettoyantes d'objets et leur procede de production |
US5516564A (en) * | 1993-04-28 | 1996-05-14 | Costar Corporation | Sterile irradiated hydrophobic pipette tip |
US5674592A (en) * | 1995-05-04 | 1997-10-07 | Minnesota Mining And Manufacturing Company | Functionalized nanostructured films |
WO2000039240A1 (fr) * | 1998-12-24 | 2000-07-06 | Sunyx Surface Nanotechnologies Gmbh | Surface ultraphobe |
DE19913601C1 (de) * | 1999-03-25 | 2000-08-10 | Wilhelm Barthlott | Vorrichtung und Verfahren zum verlustfreien Transport von Flüssigkeiten |
-
2001
- 2001-08-03 DE DE2001138037 patent/DE10138037A1/de not_active Withdrawn
-
2002
- 2002-06-19 WO PCT/EP2002/006734 patent/WO2003013731A1/fr not_active Application Discontinuation
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3354022A (en) * | 1964-03-31 | 1967-11-21 | Du Pont | Water-repellant surface |
EP0339622A2 (fr) * | 1988-04-28 | 1989-11-02 | Fuji Photo Film Co., Ltd. | Procédé et dispositif permettant de rendre hydrophobe un élément tubulaire |
EP0423719A2 (fr) * | 1989-10-16 | 1991-04-24 | Fuji Photo Film Co., Ltd. | Embout pour pipette |
US5516564A (en) * | 1993-04-28 | 1996-05-14 | Costar Corporation | Sterile irradiated hydrophobic pipette tip |
WO1996004123A1 (fr) * | 1994-07-29 | 1996-02-15 | Wilhelm Barthlott | Surfaces autonettoyantes d'objets et leur procede de production |
US5674592A (en) * | 1995-05-04 | 1997-10-07 | Minnesota Mining And Manufacturing Company | Functionalized nanostructured films |
WO2000039240A1 (fr) * | 1998-12-24 | 2000-07-06 | Sunyx Surface Nanotechnologies Gmbh | Surface ultraphobe |
DE19913601C1 (de) * | 1999-03-25 | 2000-08-10 | Wilhelm Barthlott | Vorrichtung und Verfahren zum verlustfreien Transport von Flüssigkeiten |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120009100A1 (en) * | 2010-07-12 | 2012-01-12 | Hamilton Bonaduz Ag | Pipette tip having a hydrophobic surface texture |
DE102010031240A1 (de) | 2010-07-12 | 2012-01-12 | Hamilton Bonaduz Ag | Pipettierspitze mit hydrophober Oberflächenausbildung |
EP2428272A2 (fr) | 2010-07-12 | 2012-03-14 | Hamilton Bonaduz AG | Seringue pour pipette à revêtement hydrophobe |
JP2012073227A (ja) * | 2010-07-12 | 2012-04-12 | Hamilton Bonaduz Ag | 疎水性表面テクスチャを有するピペット先端部 |
US8753715B2 (en) | 2010-07-12 | 2014-06-17 | Hamilton Bonaduz Ag | Process for hydrophobically coating a pipette tip |
US8840957B2 (en) | 2010-07-12 | 2014-09-23 | Hamilton Bonaduz Ag | Process for hydrophobically coating a pipette tip |
EP2428272A3 (fr) * | 2010-07-12 | 2015-04-29 | Hamilton Bonaduz AG | Seringue pour pipette à revêtement hydrophobe |
CN115850778A (zh) * | 2022-09-30 | 2023-03-28 | 深圳市皆特生物科技有限公司 | 一种自动化导电移液吸头的表面处理方法 |
Also Published As
Publication number | Publication date |
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