EP1257416B1 - Structure a surface ultraphobe dotee d'une pluralite de zones hydrophiles - Google Patents

Structure a surface ultraphobe dotee d'une pluralite de zones hydrophiles Download PDF

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Publication number
EP1257416B1
EP1257416B1 EP01909705A EP01909705A EP1257416B1 EP 1257416 B1 EP1257416 B1 EP 1257416B1 EP 01909705 A EP01909705 A EP 01909705A EP 01909705 A EP01909705 A EP 01909705A EP 1257416 B1 EP1257416 B1 EP 1257416B1
Authority
EP
European Patent Office
Prior art keywords
structure according
sheetlike structure
hydrophilic regions
ultraphobic
hydrophilic
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.)
Expired - Lifetime
Application number
EP01909705A
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German (de)
English (en)
Other versions
EP1257416A1 (fr
Inventor
Karsten Reihs
Wolfgang Paffhausen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qiagen GmbH
Original Assignee
Qiagen GmbH
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Filing date
Publication date
Application filed by Qiagen GmbH filed Critical Qiagen GmbH
Publication of EP1257416A1 publication Critical patent/EP1257416A1/fr
Application granted granted Critical
Publication of EP1257416B1 publication Critical patent/EP1257416B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 sheet with an ultraphobic surface, in particular a microtiter plate, and a method for its production, which is structured with a plurality of hydrophilic regions, which are preferably distributed periodically on the surface.
  • the invention also relates to the use of the sheet as a microtiter plate or printing plate.
  • microtiter plates are plates which at regular intervals, for example 2 mm, have a multiplicity of small depressions into which the liquid is introduced. Such microtiter plates are produced by extrusion or injection molding. However, these methods are expensive and have a high scrap. Since microtiter plates are disposables, there is currently a comparatively large amount of waste that has to be disposed of.
  • the object is achieved erfingdungsloom by providing a sheet according to claim 1.
  • the invention relates to a sheet, in particular a plate, particularly preferably a microtiter plate, having a surface with ultraphobic properties, wherein the sheet is structured with a plurality of hydrophilic areas.
  • Such a sheet may be a part of any shaped article.
  • the sheet is a particular flat plate.
  • Hydrophilic areas within the meaning of the invention are areas on which a drop of water with a size of 10 .mu.l assumes a contact angle ⁇ 90.degree. And the rolling angle of the waterdrop with the above-mentioned volume exceeds 10.degree.
  • Ultraphobic regions in the sense of the invention are characterized in that they have an ultraphobic surface on which the contact angle of a drop of a liquid which lies on the surface is significantly more than 120 ° C., in good cases close to 180 °, and the roll-off angle 10 ° does not exceed.
  • the hydrophilic areas on the surface are arranged so that they are enclosed by the ultraphobic areas.
  • the hydrophilic areas represent only a small part of the total surface area.
  • the hydrophilic areas are evenly arranged on the surface, so that a certain pattern results.
  • the hydrophilic regions distributed periodically on the surface have the same surface shape.
  • the surface shape of the individual hydrophilic regions is in a particularly preferred embodiment rectangular or circular.
  • the area size of the individual hydrophilic areas is particularly preferably from 1 nm 2 to 1 ⁇ m 2 .
  • the hydrophilic regions are partially or entirely preferably distributed on the surface of the sheet such that they form a pattern of images and / or characters.
  • Suitable known ultrahydrophobic surfaces are, for example, in the publications WO 98/23549 . WO 96/04123 . WO 96/21523 and WO 96/34697 which are hereby incorporated by reference and thus considered part of the disclosure.
  • the ultraphobic surface of the sheet an aluminum surface, optionally oxidized anodically, treated with hot water or steam, optionally coated with a Haftvermittlenchicht and then provided with a hydrophobic coating agent, as in the unpublished German patent application with the file number 19860138.7 is described.
  • the sheet may in particular be made of aluminum in this case or preferably has an aluminum lining, wherein the surface of the aluminum is 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 subsequently provided with a hydrophobic coating agent, as described in the unpublished German patent application the file number 19860139.5 is described.
  • the Ni (OH) 2 particles have a diameter d 50 of 0.5 to 20 microns.
  • the ultraphobic surface is made of tungsten carbide, which is patterned with a laser, optionally coated with an adhesion promoter and then provided with a hydrophobic coating agent, as in the unpublished German patent application with the file reference 198601352 is described.
  • the sheet is only coated with tungsten carbide, which is then treated as indicated above.
  • the tungsten carbide layer particularly preferably has a layer thickness of from 10 to 500 ⁇ m.
  • the ultraphobic surface of the sheet can be produced by sand blasting the surface of the sheet with a blasting agent, optionally coated with a primer layer and then provided with a hydrophobic coating agent, as in the unpublished German patent application with the file reference 19860140.9 is described.
  • Suitable hydrophobic or oleophobic coating are all surface-active water repellents with any molecular weights.
  • Suitable water repellents are all surface-active substances with arbitrary molecular weights. These compounds are preferably cationic, anionic, amphoteric or nonionic surface-active compounds, as used, for example, in US Pat Directory "Surfactants Europe, A Dictionary of Surface Active Agents available in Europe, Edited by Gordon L. Hollis, Royal Socity of Chemistry, Cambridge, 1995 be listed.
  • anionic water repellents include: alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosuccinates, sulfosuccinamides, paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates, taurates and lignin compounds.
  • cationic hydrophobizing agents examples include quaternary alkylammonium compounds and imidazoles.
  • Amphoteric water repellents are, for example, betaines, glycinates, propionates and imidazoles.
  • Nonionic water repellents are, for example: alkoxylates, alkylamides, esters, amine oxides and alkypolyglycosides. Also suitable are: reaction products of alkylene oxides with alkylatable compounds, e.g. Fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols such as styrene-phenol condensates, carboxylic acid amides and resin acids.
  • alkylatable compounds e.g. Fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols such as styrene-phenol condensates, carboxylic acid amides and resin acids.
  • water repellents in which 1 to 100%, particularly preferably 60 to 95% of the hydrogen atoms are substituted by fluorine atoms.
  • These polymeric water repellents may be nonionic, anionic, cationic or amphoteric compounds.
  • these polymeric water repellents can be homo- and copolymers, graft copolymers and graft copolymers as well as random block polymers.
  • Particularly preferred polymeric water repellents are those of the type AB, BAB and ABC block polymers.
  • the A segment is a hydrophilic homopolymer or copolymer
  • the B block is a hydrophobic homopolymer or copolymer or a salt thereof.
  • anionic, polymeric repellents in particular condensation products of aromatic sulfonic acids with formaldehyde and alkylnaphthalenesulfonic acids or from formaldehyde, naphthalenesulfonic acids and / or benzenesulfonic acids, condensation products of optionally substituted phenol with formaldehyde and sodium bisulfite.
  • condensation products which are obtainable 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 hydrophobizing agent is selected from the group of sulfosuccinic acid esters and alkylbenzenesulfonates.
  • sulfated, alkoxylated fatty acids or salts thereof are C 6 -C 22 -fatty-acid alcohols which are saturated or unsaturated, in particular stearyl alcohol, having from 5 to 120, from 6 to 60, very particularly preferably from 7 to 30, ethylene oxide units. Understood.
  • the sulfated alkoxylated fatty acid alcohols are preferably present as salt, in particular as alkali or amine salts, preferably as diethylamine salt.
  • the fabrics of the invention are advantageously prepared by destroying and hydrophilizing a surface fabric having an ultraphobic surface locally at the locations where the surface is to be hydrophilic.
  • the sheet 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 printing plate or microtiter plate.
  • the ultraphobic surface is selectively destroyed and hydrophilized in the areas in which the ink is to adhere.
  • the ultraphobic layer is destroyed at a variety of locations. These sites have, for example, an area in the order of 1 mm 2 - 1 micron 2 and are, preferably arranged at regular intervals of a few mm to each other.
  • the sheet according to the invention is simple and inexpensive to produce. It can e.g. produced as a film and adhered to any shaped body as a substrate.
  • the film can therefore be sold as a microtiter plate, after use only the film and not the entire molded article on which it was applied, must be disposed of.
  • Another subject of the invention is the use of the sheet according to the invention as a printing plate, in particular for black and white printing or multi-color printing.
  • the invention also provides the use of the invention sheet as a microtiter plate.
  • Another object of the invention is a process for producing a fabric according to the invention, by targeted removal of an ultraphobic surface layer on a hydropilen substrate, at the locations which are hydrophilic To form areas, in particular by mechanical or chemical removal, irradiation or optionally ablation of the surface, in particular by means of laser radiation of suitable intensity.
  • the hydrophilic regions can be kept very small on a microtiter plate and positioned very accurately, so that the surface density of the test volumes can be significantly reduced in comparison to microtiter plates according to the prior art.
  • the layer thickness was 50 ⁇ m. The plate was then flashed for 12 hours at room temperature.
  • the contact angle of a drop of water lying on this surface is 174 °
  • the rolling angle of a drop of water with a volume of 10 ⁇ l is ⁇ 5 °.
  • the ultraphobic coating of the Al test plate was then partially ablated by laser ablation to use the test plate as a microtiter plate.
  • the drops were e.g. be used to carry out a color reaction.
  • the color reaction can either be read out qualitatively (for example color change) or, as in conventional test plates, it is also possible to carry out a quantitative concentration determination by means of an absorption measurement.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Clinical Laboratory Science (AREA)
  • Hematology (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  1. Structure plate, de préférence plaque, et plus préférablement plaque de microtitrage, présentant une surface avec des propriétés ultraphobes, dans laquelle la structure plate est structurée avec une pluralité de zones hydrophiles, qui sont entièrement entourées par des zone ultraphobes, dans laquelle l'angle de contact d'une goutte d'un liquide, qui se trouve sur la surface, vaut plus de 120°, caractérisée en ce que l'angle de roulement ne dépasse pas 10°.
  2. Structure plate selon la revendication 1, caractérisée en ce que les zones hydrophiles sont réparties partiellement ou totalement de manière périodique sur la surface.
  3. Structure plate selon la revendication 2, caractérisée en ce que les zones hydrophiles réparties périodiquement sur la surface ont la même forme de surface.
  4. Structure plate selon la revendication 3, caractérisée en ce que la forme de surface des zones hydrophiles individuelles est rectangulaire ou circulaire.
  5. Structure plate selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la grandeur de surface des zones hydrophiles individuelles vaut de 1 nm2 à 1 µm2.
  6. Structure plate selon la revendication 1, caractérisée en ce que les zones hydrophiles sont réparties partiellement ou totalement sur la surface, de telle manière qu'elles forment des motifs d'image et/ou de signes.
  7. Structure plate selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'elle est un film, qui est de préférence éliminé après son utilisation.
  8. Utilisation d'une structure plate selon l'une quelconque des revendications 1 à 7 comme plaque d'impression, en particulier pour l'impression en noir et blanc ou l'impression polychrome.
  9. Utilisation de la structure plate selon l'une quelconque des revendications 1 à 7 comme plaque de microtitrage.
  10. Procédé de fabrication d'une structure plate selon l'une quelconque des revendications 1 à 7, par enlèvement ciblé d'une couche de surface ultraphobe sur un substrat hydrophile, aux endroits qui forment des zones hydrophiles, en particulier par enlèvement mécanique ou chimique, irradiation et éventuellement ablation de la surface, en particulier au moyen d'un rayonnement laser d'intensité appropriée.
EP01909705A 2000-02-09 2001-01-29 Structure a surface ultraphobe dotee d'une pluralite de zones hydrophiles Expired - Lifetime EP1257416B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10005600 2000-02-09
DE10005600A DE10005600A1 (de) 2000-02-09 2000-02-09 Ultraphobes Flächengebilde mit einer Vielzahl von hydrophilen Bereichen
PCT/EP2001/000906 WO2001058688A1 (fr) 2000-02-09 2001-01-29 Structure a surface ultraphobe dotee d'une pluralite de zones hydrophiles

Publications (2)

Publication Number Publication Date
EP1257416A1 EP1257416A1 (fr) 2002-11-20
EP1257416B1 true EP1257416B1 (fr) 2008-11-05

Family

ID=7630275

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01909705A Expired - Lifetime EP1257416B1 (fr) 2000-02-09 2001-01-29 Structure a surface ultraphobe dotee d'une pluralite de zones hydrophiles

Country Status (7)

Country Link
US (1) US7632466B2 (fr)
EP (1) EP1257416B1 (fr)
AT (1) ATE413273T1 (fr)
AU (1) AU2001237353A1 (fr)
DE (2) DE10005600A1 (fr)
ES (1) ES2316434T3 (fr)
WO (1) WO2001058688A1 (fr)

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DE10164358C2 (de) * 2001-12-28 2003-11-27 Advalytix Ag Charakterisierungsverfahren für funktionalisierte Oberflächen
AU2003210342A1 (en) 2002-02-22 2003-09-09 Scienion Ag Use of ultraphobic surfaces having a multitude of hydrophilic areas for analyzing samples
DE10207614A1 (de) * 2002-02-22 2003-09-04 Sunyx Surface Nanotechnologies Verwendung von ultraphoben Oberflächen miteiner Vielzahl hydrophiler Bereiche zur Analyse von Proben
WO2003070364A1 (fr) * 2002-02-22 2003-08-28 Sunyx Surface Nanotechnologies Gmbh Porte echantillon ultraphobe a zones fonctionnelles hydrophiles et/ou oleophiles
DE10241409A1 (de) * 2002-09-06 2004-03-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Mikroarray-Träger, Verfahren zu dessen Herstellung sowie dessen Verwendung
DE10258674A1 (de) * 2002-12-13 2004-06-24 Sunyx Surface Nanotechnologies Gmbh Verfahren zur Herstellung eines Probenträgers für die MALDI-Massenspektrometrie
US6911276B2 (en) * 2003-04-15 2005-06-28 Entegris, Inc. Fuel cell with ultraphobic surfaces
US6845788B2 (en) * 2003-04-15 2005-01-25 Entegris, Inc. Fluid handling component 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
EP2125220A1 (fr) * 2006-12-13 2009-12-02 Qiagen GmbH Microréseaux de transfection
WO2009073972A1 (fr) * 2007-12-12 2009-06-18 University Health Network Dispositif de cristallisation pour examen visuel à grand débit et diffractométrie de rayons x
US20120103456A1 (en) * 2010-08-25 2012-05-03 Massachusetts Institute Of Technology Articles and methods for reducing hydrate adhesion
EP2948251A1 (fr) 2013-01-24 2015-12-02 SABIC Global Technologies B.V. Plaque de micro-puits fabriquée à partir d'un polyester-polycarbonate
WO2014116979A1 (fr) * 2013-01-24 2014-07-31 Sabic Innovative Plastics Ip B.V. Plaque de micro-puits fabriquée à partir d'un polyester-polycarbonate
CN104955575A (zh) 2013-01-24 2015-09-30 沙特基础全球技术有限公司 由聚酯-聚碳酸酯制成的微流体装置和微孔
WO2014145586A1 (fr) * 2013-03-15 2014-09-18 Jonathan David Smith Procédés et articles destinés à des surfaces imprégnées de liquide pour l'inhibition de la nucléation en phase vapeur ou en phase gazeuse
WO2014145414A1 (fr) * 2013-03-15 2014-09-18 Jonathan David Smith Procédés et articles destinés à des surfaces imprégnées de liquide présentant une plus grande durabilité

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Also Published As

Publication number Publication date
US7632466B2 (en) 2009-12-15
AU2001237353A1 (en) 2001-08-20
US20030108449A1 (en) 2003-06-12
WO2001058688A1 (fr) 2001-08-16
EP1257416A1 (fr) 2002-11-20
ATE413273T1 (de) 2008-11-15
DE10005600A1 (de) 2001-08-16
ES2316434T3 (es) 2009-04-16
DE50114469D1 (de) 2008-12-18

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