EP1257416A1 - Ultraphobic surface structure having a plurality of hydrophilic areas - Google Patents
Ultraphobic surface structure having a plurality of hydrophilic areasInfo
- Publication number
- EP1257416A1 EP1257416A1 EP01909705A EP01909705A EP1257416A1 EP 1257416 A1 EP1257416 A1 EP 1257416A1 EP 01909705 A EP01909705 A EP 01909705A EP 01909705 A EP01909705 A EP 01909705A EP 1257416 A1 EP1257416 A1 EP 1257416A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrophilic
- flat structure
- hydrophilic areas
- areas
- ultraphobic
- 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.)
- Granted
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
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/508—Containers for the purpose of retaining a material to be analysed, e.g. test tubes rigid containers not provided for above
- B01L3/5085—Containers for the purpose of retaining a material to be analysed, e.g. test tubes rigid containers not provided for above for multiple samples, e.g. microtitration plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1033—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials by laser or spark ablation
Definitions
- the invention relates to a flat structure with an ultraphobic surface, in particular a microtiter plate, and to a method for its production which is structured with a multiplicity of hydrophilic regions, which are preferably distributed periodically on the surface.
- the invention also relates to the use of the fabric as a microtiter plate or pressure plate.
- Microtiter plates are plates that e.g. 2 mm one
- microtiter plates are produced by extrusion or by injection molding.
- Microtiter plates are disposable items, a comparatively large amount of waste currently has to be disposed of.
- the object is achieved according to the invention by the provision of a flat structure which at the same time has ultrahydrophobic and specifically hydrophilic areas.
- the invention relates to a flat structure, in particular a plate, particularly preferably a microtiter plate, having a surface with ultraphobic properties.
- shafts characterized in that the fabric is structured with a plurality of hydrophilic areas.
- Such a flat structure can be part of any shaped body.
- the fabric is preferably a particularly flat plate.
- Hydrophilic areas in the sense of the invention are areas on which a water drop with a size of 10 ⁇ l has a contact angle ⁇ 90 ° and the roll angle of the water drop with the above-mentioned volume exceeds 10 °.
- Ultrahydrophobic areas in the sense of the invention are distinguished by the fact that they have an ultrahydrophobic surface on which the contact angle of a drop of a liquid lying on the surface is clearly more than 120 ° C. in good cases close to 180 ° and the roll angle 10 ° does not exceed.
- the hydrophilic regions are advantageously arranged on the surface in such a way that they are enclosed by the ultrahydrophobic regions.
- the hydrophilic regions likewise preferably represent only a small part of the entire surface.
- the hydrophilic regions are advantageously arranged uniformly on the surface, so that a certain pattern results.
- a flat structure is preferred in which the hydrophilic regions are partially or entirely periodically distributed on the surface.
- the periodically distributed hydrophilic regions particularly preferably have the same surface shape.
- the surface shape of the individual hydrophilic regions is rectangular or circular.
- the area size of the individual hydrophilic regions is particularly preferably from 1 nm ⁇ to 1 ⁇ m ⁇ .
- hydrophilic regions are preferably distributed on the surface of the fabric in such a way that they form an image and / or drawing pattern.
- Suitable known ultrahydrophobic surfaces are e.g. in publications WO 98/23549, WO 96/04123, WO 96/21523 and WO 96/34697, which are hereby introduced as a reference and are therefore considered part of the disclosure.
- the ultraphobic surface has a
- the ultraphobic surface of the fabric is an aluminum surface, which optionally oxidizes anodically, with hot
- the fabric can in particular be made entirely of aluminum or preferably has an aluminum lining, the surface of the aluminum being treated as indicated above.
- the ultraphobic surface a surface which is coated with Ni (OH) 2 particles, is optionally coated with an adhesion promoter and is subsequently provided with a hydrophobic coating agent, as described in the unpublished German patent application the file number 19860139.5.
- the Ni (OH) 2 particles preferably have a diameter d 50 of 0.5 to 20 ⁇ m.
- the ultraphobic surface is made of tungsten carbide, which is structured with a laser, optionally coated with an adhesion promoter and then provided with a hydrophobic coating agent, as described in the unpublished German patent application with the file number 19860135.2.
- the fabric is preferably coated only with tungsten carbide, which is then treated as indicated above. Has particularly preferred
- Tungsten carbide layer a layer thickness of 10 to 500 microns.
- the ultraphobic surface of the fabric can be produced by sandblasting the surface of the fabric, optionally coating it with an adhesion promoter layer and then providing it with a hydrophobic coating agent, as described in the unpublished German patent application with the file number 19860140.9 is described.
- All surface-active coatings are suitable as ultra-hydrophobic or oleophobic coatings
- Water repellent with any molecular weight All surface-active substances with any molecular weight are suitable as water repellents. These compounds are preferably cationic, anionic, amophotere or non-ionic surface-active compounds, as described, for example, in the directory "Surfactants Europe, A Dictionary of Surface
- anionic water repellents alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosucinates, sulfosuccinatamides,
- Paraffin sulfonates Paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates, taurates and Lingnine compounds.
- Quaternary alkylammonium compounds and imidazoles may be mentioned as cationic water repellents.
- Amphoteric water repellents are, for example, betaines, glycinates, propionates and imidazoles.
- nonionic water repellents examples include alkoxylates, alkylamides,
- Esters, amine oxides and alkypolyglycosides are also suitable.
- reaction products of alkylene oxides with alkylatable compounds such as e.g. Fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols, such as styrene-phenol condensates, carboxamides and resin acids.
- Hydrophobing agents in which 1 to 100%, particularly preferably 60 to 95%, of the hydrogen atoms are substituted by fluorine atoms are particularly preferred.
- Examples include perfluorinated alkyl sulfate, perfluorinated alkyl sulfonates, perfluorinated alkyl phosphates, perfluorinated alkyl phosphinates and perfluorinated carboxylic acids.
- polymeric hydrophobizing agents are used for the hydrophobic coating or as polymeric hydrophobic material for the surface compounds with a molecular weight M w > 500 to 1,000,000, preferably 1,000 to 500,000 and particularly preferably 1,500 to 20,000.
- polymeric water repellents can be nonionic, anionic, cationic or amphoteric compounds. Furthermore, these polymeric water repellents can be homopolymers and copolymers, graft and graft copolymers and random block polymers.
- Particularly preferred polymeric water repellents are those of the AB-,
- the A segment is a hydrophilic homopolymer or copolymer and the B block is a hydrophobic homopolymer or copolymer or a salt thereof.
- Anionic, polymeric phobicizing aids are also particularly preferred, in particular condensation products of aromatic sulfonic acids with formaldehyde and alkylnaphthalenesulfonic acids or from formaldehyde, naphthalenesulfonic acids and / or benzenesulfonic acids, condensation products from optionally substituted phenol with formaldehyde and sodium bisulfite.
- condensation products which can be obtained by reacting naphthols with alkanols, additions of alkylene oxide and at least partial conversion of the terminal hydroxyl groups into sulfo groups or half esters of maleic acid and phthalic acid or succinic acid.
- the water repellent is from the group of the sulfosuccinic acid esters and alkylbenzenesulfonates.
- Sulfated, alkoxylated fatty acids or their salts are also preferred.
- Alkoxylated fatty acid alcohols include, in particular, those with 5 to 120, with 6 to 60, very particularly preferably with 7 to 30, Cg-C2 2 -
- the sulfated alkoxylated fatty acid alcohols are preferably present as a salt, in particular as alkali or amine salts, preferably as a diethylamine salt.
- the surfaces according to the invention are advantageously produced in that a fabric with an ultraphobic surface is locally destroyed and hydrophilized at the points where the surface is supposed to be hydrophilic.
- the surface according to the invention can be used in all areas in which it is desired that water or water-containing substances only partially wet a surface.
- the sheet can be used particularly advantageously as a pressure plate or microtiter plate.
- the ultrahydrophobic layer of the surface in the areas in which the printing ink is supposed to adhere is deliberately destroyed and hydrophilized.
- the ultrahydrophobic layer is destroyed in a number of places. These places have e.g. an area of the order of 1 nm - 1 ⁇ m and are, preferably in regular
- the volume of the water drops can be easily controlled by measuring the diameter of the spherical drops.
- microtiter plate is simpler than in the prior art.
- the laser structuring can also be very easily integrated into the automatic dispenser.
- the microtiter plates can be sold in the form of simple foils, which the customer can use flexibly in a corresponding grid and field size.
- test volumes are freely accessible drops that can be approached and scanned more easily with detection devices.
- the drop volumes can easily be reduced to the range of lnl. As a result, the areal density of the test volumes can be increased significantly compared to the conventional microtiter plates.
- the material required to produce a microtiter plate is less than in the prior art. There is less waste after using this disposable item.
- the fabric according to the invention is simple and inexpensive to manufacture. For example, produced as a film and glued to any shaped body as a substrate.
- the film can therefore be sold as a microtiter plate, but after its use only the film and not the entire molded article to which it was applied has to be disposed of.
- Another object of the invention is the use of the fabric according to the invention as a printing plate, in particular for black and white printing or multicolor printing.
- the invention also relates to the use of the fabric according to the invention as a microtiter plate.
- a further subject of the invention is a method for producing a flat structure according to the invention by deliberately removing an ultraphobic
- hydrophilic Areas are to be formed, in particular by mechanical or chemical ablation, radiation or optionally ablation of the surface, in particular by means of laser radiation of suitable intensity.
- the hydrophilic areas can be on a
- Microtiter plates are kept very small and positioned very precisely, so that the areal density of the test volumes can be considerably reduced compared to microtiter plates according to the prior art.
- An epoxy-functional resin (KBD7142) was first produced to coat an aluminum plate. For that, a mix was made
- MIBK methyl isobutyl ketone
- the KBD 7142 was then 1:50 dissolved in MIBK (methyl isobutyl ketone, 100 ml) and 1 g of finely divided SiO 2 type Aerosil R 812 (manufacturer Degussa, Hanau) was added.
- MIBK methyl isobutyl ketone, 100 ml
- SiO 2 type Aerosil R 812 manufactured by Degussa, Hanau
- the layer thickness was 50 ⁇ m.
- the plate was then flashed off at room temperature for 12 h.
- the contact angle of a drop of water lying on this surface is 174 °
- the roll angle of a drop of water with a volume of 10 ⁇ l is ⁇ 5 °.
- the ultrahydrophobic coating of the Al test plate was then partially removed by laser ablation in order to use the test plate as a microtiter plate.
- 64x64 4096 areas of the size of 20x20 ⁇ m 2 with a distance of 2mm each on a total area of 126x126 mm 2 were irradiated with the laser in the plate. Water droplets with a volume of 500nl were then positioned on each of the irradiated areas using a pipette. The diameter of the water drops is approx. 1mm. The positioning of the drops was carried out using a
- the drops are fixed to the hydrophilic areas in a vibration-stable manner and serve as sample volumes of the microtitre plates for carrying out sample reactions.
- Defect of the surface (here 5x5 ⁇ m) fixes the drop at the desired position.
- the drops were e.g. be used to carry out a color reaction.
- the color reaction can either be read qualitatively (e.g. color change) or, as in conventional test plates, you can also carry out a quantitative concentration determination by means of an absorption measurement.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10005600 | 2000-02-09 | ||
DE10005600A DE10005600A1 (en) | 2000-02-09 | 2000-02-09 | Ultraphobic fabric with a variety of hydrophilic areas |
PCT/EP2001/000906 WO2001058688A1 (en) | 2000-02-09 | 2001-01-29 | Ultraphobic surface structure having a plurality of hydrophilic areas |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1257416A1 true EP1257416A1 (en) | 2002-11-20 |
EP1257416B1 EP1257416B1 (en) | 2008-11-05 |
Family
ID=7630275
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01909705A Expired - Lifetime EP1257416B1 (en) | 2000-02-09 | 2001-01-29 | Ultraphobic surface structure having a plurality of hydrophilic areas |
Country Status (7)
Country | Link |
---|---|
US (1) | US7632466B2 (en) |
EP (1) | EP1257416B1 (en) |
AT (1) | ATE413273T1 (en) |
AU (1) | AU2001237353A1 (en) |
DE (2) | DE10005600A1 (en) |
ES (1) | ES2316434T3 (en) |
WO (1) | WO2001058688A1 (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10162188A1 (en) * | 2001-12-17 | 2003-06-18 | Sunyx Surface Nanotechnologies | Apparatus to manipulate the smallest droplets has a screen pattern of electrodes, with a control system to apply an individual voltage to selected electrodes for a given time span to set the droplet movement path and speed |
DE10164358C2 (en) * | 2001-12-28 | 2003-11-27 | Advalytix Ag | Characterization process for functionalized surfaces |
EP1478456A1 (en) * | 2002-02-22 | 2004-11-24 | Sunyx Surface Nanotechnologies GmbH | Ultraphobic sample carrier having functional hydrophilic and/or oleophilic areas |
US7456392B2 (en) | 2002-02-22 | 2008-11-25 | Qiagen Gmbh | Use of ultraphobic surfaces having a multitude of hydrophilic areas for analyzing samples |
DE10207614A1 (en) * | 2002-02-22 | 2003-09-04 | Sunyx Surface Nanotechnologies | Precise, contamination-free dosing of liquids onto surface with hydrophilic or oleophilic areas surrounded by ultraphobic areas comprises applying drop of liquid to hydrophilic or oleophilic areas |
DE10241409A1 (en) * | 2002-09-06 | 2004-03-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Microarray carrier, useful for detecting protein or DNA, comprises substrate of hydrophobic polymer with functionalized hydrophilic regions containing silanol groups |
DE10258674A1 (en) * | 2002-12-13 | 2004-06-24 | Sunyx Surface Nanotechnologies Gmbh | Manufacturing sample carrier with points for matrix-assisted laser desorption and ionization, forms MALDI matrix points by gas phase sublimation |
US6845788B2 (en) * | 2003-04-15 | 2005-01-25 | Entegris, Inc. | Fluid handling component with ultraphobic surfaces |
US6911276B2 (en) * | 2003-04-15 | 2005-06-28 | Entegris, Inc. | Fuel cell with ultraphobic surfaces |
US20070062594A1 (en) * | 2005-09-16 | 2007-03-22 | Extrand Charles W | Microfluidic device with anisotropic wetting surfaces |
US20070065637A1 (en) * | 2005-09-16 | 2007-03-22 | Extrand Charles W | Carrier with anisotropic wetting surfaces |
US20070065702A1 (en) * | 2005-09-16 | 2007-03-22 | Extrand Charles W | Fuel cell with anisotropic wetting surfaces |
WO2008071430A1 (en) * | 2006-12-13 | 2008-06-19 | Qiagen Gmbh | Transfection microarrays |
CA2708596A1 (en) * | 2007-12-12 | 2009-06-18 | University Health Network | Crystallization device for high-throughput visual inspection and x-ray diffraction analysis |
US20120103456A1 (en) * | 2010-08-25 | 2012-05-03 | Massachusetts Institute Of Technology | Articles and methods for reducing hydrate adhesion |
WO2014116955A1 (en) * | 2013-01-24 | 2014-07-31 | Sabic Innovative Plastics Ip B.V. | Microwell plate made from a polyester-polycarbonate |
CN104955576A (en) | 2013-01-24 | 2015-09-30 | 沙特基础全球技术有限公司 | Microwell plate made from a polyester-polycarbonate |
WO2014116951A2 (en) | 2013-01-24 | 2014-07-31 | Sabic Innovative Plastics Ip B.V. | Polycarbonate microfluidic articles |
WO2014145586A1 (en) * | 2013-03-15 | 2014-09-18 | Jonathan David Smith | Methods and articles for liquid-impregnated surfaces for the inhibition of vapor or gas nucleation |
CN105408031B (en) * | 2013-03-15 | 2019-07-16 | 利奎格莱股份有限公司 | The surface through liquid infiltration of durability with enhancing |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4802951A (en) * | 1986-03-07 | 1989-02-07 | Trustees Of Boston University | Method for parallel fabrication of nanometer scale multi-device structures |
US4741619A (en) * | 1987-05-05 | 1988-05-03 | Molecular Devices Corporation | Hydrophilic microplates for vertical beam photometry |
US5229163A (en) * | 1989-12-21 | 1993-07-20 | Hoffmann-La Roche Inc. | Process for preparing a microtiter tray for immunometric determinations |
EP0772514B1 (en) | 1994-07-29 | 1998-12-23 | Wilhelm Barthlott | Self-cleaning surfaces of objects and process for producing same |
JPH08246163A (en) | 1995-01-11 | 1996-09-24 | Kao Corp | Method for imparting liquid pepellency to metallic surface |
US5674592A (en) | 1995-05-04 | 1997-10-07 | Minnesota Mining And Manufacturing Company | Functionalized nanostructured films |
DE19628928A1 (en) | 1996-07-18 | 1998-01-22 | Basf Ag | Solid supports for analytical measurement processes, a process for their production and their use |
FR2756276B1 (en) | 1996-11-26 | 1998-12-24 | Saint Gobain Vitrage | SUBSTRATE WITH IMPROVED HYDROPHILIC OR HYDROPHOBIC PROPERTIES, CONTAINING IRREGULARITIES |
BR9714569B1 (en) | 1997-04-09 | 2009-05-05 | process and culture device for recording and detecting or counting microorganisms in microvolumes. | |
US5948591A (en) * | 1997-05-27 | 1999-09-07 | Agfa-Gevaert, N.V. | Heat sensitive imaging element and a method for producing lithographic plates therewith |
DE19754978C2 (en) * | 1997-12-11 | 2000-07-13 | Bruker Daltonik Gmbh | Sample holder for MALDI mass spectrometry along with the process for producing the plates and applying the samples |
DE19860135C2 (en) | 1998-12-24 | 2003-02-06 | Sunyx Surface Nanotechnologies | Ultraphobic surface based on tungsten carbide, a process for its production and its use |
DE19860136C2 (en) | 1998-12-24 | 2002-11-28 | Sunyx Surface Nanotechnologies | Ultraphobic surface, its use and process for its manufacture |
DE19860139C1 (en) | 1998-12-24 | 2000-07-06 | Bayer Ag | Process for producing an ultraphobic surface based on nickel hydroxide, ultraphobic surface and their use |
-
2000
- 2000-02-09 DE DE10005600A patent/DE10005600A1/en not_active Ceased
-
2001
- 2001-01-29 WO PCT/EP2001/000906 patent/WO2001058688A1/en active Application Filing
- 2001-01-29 DE DE50114469T patent/DE50114469D1/en not_active Expired - Lifetime
- 2001-01-29 ES ES01909705T patent/ES2316434T3/en not_active Expired - Lifetime
- 2001-01-29 EP EP01909705A patent/EP1257416B1/en not_active Expired - Lifetime
- 2001-01-29 US US10/182,722 patent/US7632466B2/en not_active Expired - Fee Related
- 2001-01-29 AT AT01909705T patent/ATE413273T1/en active
- 2001-01-29 AU AU2001237353A patent/AU2001237353A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO0158688A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE10005600A1 (en) | 2001-08-16 |
DE50114469D1 (en) | 2008-12-18 |
ES2316434T3 (en) | 2009-04-16 |
US7632466B2 (en) | 2009-12-15 |
ATE413273T1 (en) | 2008-11-15 |
WO2001058688A1 (en) | 2001-08-16 |
EP1257416B1 (en) | 2008-11-05 |
US20030108449A1 (en) | 2003-06-12 |
AU2001237353A1 (en) | 2001-08-20 |
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