EP1296913A2 - Photostructured paste - Google Patents
Photostructured pasteInfo
- Publication number
- EP1296913A2 EP1296913A2 EP01921161A EP01921161A EP1296913A2 EP 1296913 A2 EP1296913 A2 EP 1296913A2 EP 01921161 A EP01921161 A EP 01921161A EP 01921161 A EP01921161 A EP 01921161A EP 1296913 A2 EP1296913 A2 EP 1296913A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder
- photostructurable
- polymer
- paste according
- paste
- 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.)
- Withdrawn
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5122—Pd or Pt
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
- G01K7/18—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a linear resistance, e.g. platinum resistance thermometer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
- H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
- H01C17/0654—Oxides of the platinum group
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
- H01C17/06553—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of a combination of metals and oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
- H05K1/167—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed resistors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
Definitions
- the invention relates to a photostructurable paste, in particular for the production of structured resistance layers or conductor tracks on ceramic green cores, according to the preamble of the main claim.
- Paste printed which is then structured by exposure to UV rays and using a photomask. After this structuring, the paste then develops in the exposed areas.
- a disadvantage of this technique is that a yellow space is always required, since the pastes are sensitive to daylight.
- known pastes based on the "fodel technique” are only suitable for temperatures of a maximum of 900 ° C, ie the ceramic green sheets provided with the applied and structured pastes may then be fired at a maximum of 900 ° C or sintered. In many cases, however, these temperatures are not sufficient.
- the "fodel technique” it is not possible to simultaneously produce coarse and very fine structures on the green foils.
- Fine structuring down to lateral dimensions of approx. 10 ⁇ m is possible, while only structures with lateral dimensions above 100 ⁇ m can be produced using conventional screen printing technology.
- Multi-layer hybrids are built up and then sintered into a temperature sensor using co-firing technology.
- the object of the present invention was, based on the application LT-97 161, to modify the photostructurable paste proposed therein in such a way that it is also suitable for direct application to ceramic green sheets. At the same time, it was an object of the present invention to provide a photostructurable paste which significantly increases the
- the photostructurable paste according to the invention has the advantage over the prior art that it can be used to provide ceramic green films directly with functional layers, which are then photostructured, for example in the form of conductor tracks or
- Resistance tracks can be structured. Lateral resolutions of less than 50 ⁇ m, in particular between 5 ⁇ m and 25 ⁇ m, are achieved.
- the paste according to the invention has the further advantage that after the photostructuring on the ceramic green bodies remaining structures have only a small standard deviation of the lateral extent of the structures produced in at least one dimension from a predetermined desired value.
- structures wider than 50 ⁇ m can also be produced, but then have a very precisely defined width, for example.
- the standard deviation from the target value is usually less than 10 ⁇ m, in particular less than 5 ⁇ m.
- the paste according to the invention is thus advantageously suitable for producing multilayer structures on a ceramic basis, ceramic green bodies first being provided with a structured functional layer, which are then processed further to form hybrid components.
- the paste according to the invention can thus also be used to produce the temperature sensor known from application DE 199 34 109.5 with considerably improved properties with regard to the resistance tracks produced.
- the platinum-containing paste according to the invention has the further advantage that, despite the addition of the catalytically very active platinum, it is stable over time and does not disintegrate even in daylight.
- a mixture of platinum powder with aluminum oxide powder and / or zirconium dioxide powder can also be used with the filler used in the photopatternable paste instead of pure platinum powder.
- This mixture leads to an improvement in the adhesion of the Pt conductor track produced on the green body (“green tape”) and / or serves, for example by mixing Pt and Al 2 O 3 powder particles, to increase the electrical resistance of the conductor tracks produced in this way.
- the photosensitive paste can be developed by an aqueous solution and that it has a low sensitivity to visible light and the influence of oxygen.
- the significantly improved resolution that can be achieved with the paste according to the invention can now be used to produce, for example, resistance tracks in a maander structure on ceramic green bodies and thus also on the fired ceramic substrates obtained after the sintering of these green bodies, compared to comparable resistance tracks that have been produced using conventional thick-film technology , Have resistance increases of more than 400%.
- Resistance conductor tracks therefore mean a significantly smaller area requirement when used in temperature sensors or heating elements, with better accuracy of temperature measurement and higher measuring resistance, i.e. a better accuracy of the measurement voltage evaluation.
- the invention is initially based on a photostructurable paste, as is already known in a similar form from the application LT-97 161.
- the photostructurable paste described there is only suitable for application to ceramic substrates that have already been fired and must therefore be modified for application to ceramic green sheets. This modification is based essentially on the fact that in the paste composition known from LT-97 161, the glass components required there in the form of glass powder particles are removed or are not added when the paste is mixed together.
- LT-97 161 known photosensitive paste for direct application on ceramic green cores is suitable if the paste composition described there is modified such that the glass powder components are not added. It was also found that a photosensitive paste modified in this way allows the production of structured functional layers on ceramic green sheets, the lateral extent of the structures produced in these functional layers by the photostructuring at least in one dimension, for example in width, below 50 ⁇ m, in particular between 5 ⁇ m and 25 ⁇ m. At the same time, it was found that even if one wanted to produce wider structures, these can be produced with significantly increased accuracy. A measure of this accuracy is the standard deviation of the lateral extent of the structures produced in at least one dimension from a predetermined target value. This standard deviation is typically less than 10 ⁇ m, in particular less than 5 ⁇ m.
- a platinum powder with an average particle size of 10 nm to 20 ⁇ m, in particular of 50 nm to 2 ⁇ m, is particularly suitable as a filler for the photostructurable paste according to the invention.
- the specific surface area of the inorganic filler or of the platinum powder is preferably 0.5 m 2 / g to 20 m 2 / g.
- the weight fraction of the inorganic filler in the photostructurable paste is between 30% and 90% based on the total weight of the paste. A weight fraction of 50% -60% is preferred.
- the ceramic powder also has an average particle size or specific surface area, comparable to that of the platinum powder, of 10 nm to 20 ⁇ m or 0.5 m 2 / g to 20 m 2 / g.
- aluminum oxide powder, zirconium dioxide powder, yttrium-stabilized zirconium dioxide powder, yttrium oxide powder, titanium dioxide powder, silicon oxide powder or a mixture of these powders are used as the ceramic powder.
- platinum-coated, non-conductive ceramic particles can also be used as the filler.
- platinum compounds in particular platinum precursor compounds such as platinum (II) acetylacetonate, platinum (II) diamine-cyclobatane-1, 1- dicarboxylate, platinum (0) -1, 3-divinyl-l, 1,3,3-tetramethyldisiloxane or platinum (II) tetraammine nitrate in question.
- platinum precursor compounds such as platinum (II) acetylacetonate, platinum (II) diamine-cyclobatane-1, 1- dicarboxylate, platinum (0) -1, 3-divinyl-l, 1,3,3-tetramethyldisiloxane or platinum (II) tetraammine nitrate in question.
- these fillers are not preferred for cost reasons.
- ceramic precursor materials in particular organic precursor materials based on Si, Al, Zr, Ti and Y, can also be used instead of the ceramic powder. Precursor materials of this type are known to the person skilled in the art.
- the ceramic green bodies or ceramic foils to which the photostructurable paste is applied as a functional layer are, moreover, conventional ceramic green foils with ceramic particles embedded in a polymer matrix, for example yttrium-stabilized zirconium dioxide particles or aluminum oxide particles.
- an intermediate layer is first applied to the ceramic green cores before the photostructurable paste can be applied to them.
- This intermediate layer is, for example, an Al 2 O 3 layer or TiO 2 layer which is known per se.
- the ceramic green sheets pretreated in this way are further processed, for example to form multilayer hybrid components.
- the paste according to the invention can also be processed using the known thick-film technology.
- the polymer used in the organic binder is particularly important for the paste.
- This polymer must be a photochemically active polymer, i.e. it not only has the role of a layer-forming and dissolving component in the binder, but is also supposed to initiate the photopolymerization effectively by the initiator, which is insensitive to the visible spectrum of the light. For this purpose, it is designed as a large molecular, polyfunctional monomer.
- the side chains of the polymer with their allyl groups and the organic disulfide additionally used in the organic binder neutralize the inhibitory effect of oxygen.
- no special precautions are required to avoid the contact of the photo-structurable paste with the oxygen present in the air.
- the line-like macromolecules of the polymer used in the binder which have side chains with alkyl and allyl groups, form a dense spatial structure, so that the polymer is perfect in the area of the exposed areas becomes insoluble in water-based solvents.
- the added photoinitiator from the class of the azylphosphines also results in a particularly short exposure time.
- the photostructurable paste has the following composition in mass fractions based on the mass of the inorganic filler:
- Thermal polymerization inhibitor 0.01 to 0.35 organic solvent: 5.50 to 21.50
- the polymer contained in the organic binder should first be soluble in water-soluble base solutions, form a non-sticky skin or a membrane at room temperature, make the viscosity of the photostructurable paste adjustable and actively participate in photoinitiating, radical polymerization in an oxygen-containing environment. Finally, the thermal cleavage of the polymer should also take place at the lowest possible temperatures.
- the polymers that can be used have side chains with acrylic and allyl groups, they reduce the sensitivity of the organic binder against the inhibitory oxygen effect, but do not completely eliminate them. It is therefore also necessary to add an organic disulfide, the general formula R ⁇ -CH 2 -SS-CH 2 -R 2 for the same or different alkyl,
- Isodecyl disulfide is particularly suitable as an organic disulfide.
- a photoinitiator from the acylphosphine class is added to the photostructurable paste as a photoinitiator.
- the compound 2, 6-dimethoxybenzoyldiphenylphosphine is preferred.
- the solvent added to adjust the viscosity of the photostructurable paste should initially dissolve all organic components very well, at the same time not be volatile at room temperature and volatilize relatively quickly at temperatures of 80 ° C - 100 ° C, since such temperatures are typically used when drying green ceramic films especially after the application of the photostructurable paste.
- Preferred solvents are terpenes, carbitol acetate, butyl carbitol acetate or higher alcohol esters. Benzyl alcohol is particularly preferred.
- the compound 2, 6-di-tert-butyl-1,4-cresol has proven to be a particularly suitable inhibitor.
- the processing of the individual components of the photostructurable paste was carried out essentially as already known from LT-97 161.
- the Components of the organic binder are mixed with the filler, for example in a three-roll chair, in order to ensure an even distribution of the filler particles in the organic binder.
- the photostructurable paste prepared in this way is then applied in a manner known per se in the form of a functional layer with a typical thickness of 1 ⁇ m to 10 ⁇ m to a ceramic green sheet with aluminum oxide as the ceramic component.
- the green films provided with the functional layer were then dried at a temperature of 80 ° C. to 100 ° C. for a period of typically 5 minutes to 20 minutes and finally exposed to UV light using a photomask.
- the photomask is structured, for example, in the form of meandering resistance conductor tracks.
- the UV light during the exposure preferably has a wavelength of 320 nm - 400 nm.
- the photostructurable paste was then developed.
- an aerosol of an aqueous, 0.5% monoethanolamine solution is dripped onto a substrate which rotates at a speed of typically 3000 rpm, on which the exposed ceramic green sheets are arranged. This method is generally referred to as “spin development” and is explained in more detail in LT-97 161.
- the unexposed areas are finally washed off again using a water-soluble basic solution.
- the further processing of the ceramic green sheets with the developed, photostructurable paste on them then takes place in the manner known from application DE 199 34 109.5.
- the ceramic green foils provided with the structured functional layers are optionally stacked with further ceramic green foils, provided with vias and electrical connections and finally sintered at temperatures of typically 1050 ° C. to 1650 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a photostructured paste that is particularly suitable for producing structured resistive coats or strip conductors on ceramic green foils. The paste is provided with a light-sensitive organic binder and a filler. The binder is provided with a polymer, a photoinitiator, an inhibitor for thermal polarisation, an organic disulphide and an organic solvent. The filler is a platinum powder, a platinum compound or a mixture of a platinum powder or a platinum compound with a ceramic powder or a ceramic precursor compound.
Description
Photostrukturierbare PastePhotostructurable paste
Die Erfindung betrifft eine photostrukturierbare Paste, insbesondere zur Herstellung von strukturierten Widerstandsschichten oder Leiterbahnen auf keramischen Grunkorpern, nach der Gattung des Hauptanspruches.The invention relates to a photostructurable paste, in particular for the production of structured resistance layers or conductor tracks on ceramic green cores, according to the preamble of the main claim.
Stand der TechnikState of the art
Zur Herstellung von strukturierten Widerstandsschichten oder Leiterbahnen auf keramischen Grunkorpern, die beispielsweise bereichsweise zickzackformig oder maanderformig ausgebildet sind, ist bereits die sog. „Fodel-Technik" bekannt, die von der Firma DuPont entwickelt wurde.The so-called “fodel technique”, which was developed by the DuPont company, is already known for the production of structured resistance layers or conductor tracks on ceramic green cores, which are, for example, zigzag or meandering in some areas.
Im einzelnen wird dabei auf keramischen Grunfolien eineIn detail, one is made on ceramic green foils
Paste aufgedruckt, die anschließend durch Belichtung mit UV- Strahlen und unter Einsatz einer Photomaske strukturiert wird. Nach dieser Strukturierung folgt dann ein Entwickeln der Paste in den belichteten Bereichen. Bei dieser Technik ist jedoch nachteilig, daß stets ein Gelbraum erforderlich, da die Pasten empfindlich gegenüber Tageslicht sind. Zudem eignen sich bekannte Pasten auf Grundlage der „Fodel- Technik" nur für Temperaturen von maximal 900 °C, d.h. die mit den aufgebrachten und strukturierten Pasten versehenen keramischen Grunfolien dürfen danach bei max. 900 °C gebrannt
bzw. gesintert werden. Diese Temperaturen sind vielfach jedoch nicht ausreichend. Zudem ist es mit Hilfe der „Fodel- Technik" nicht möglich, gleichzeitig grobe und sehr feine Strukturierungen auf den Grunfolien zu erzeugen.Paste printed, which is then structured by exposure to UV rays and using a photomask. After this structuring, the paste then develops in the exposed areas. A disadvantage of this technique, however, is that a yellow space is always required, since the pastes are sensitive to daylight. In addition, known pastes based on the "fodel technique" are only suitable for temperatures of a maximum of 900 ° C, ie the ceramic green sheets provided with the applied and structured pastes may then be fired at a maximum of 900 ° C or sintered. In many cases, however, these temperatures are not sufficient. In addition, with the help of the "fodel technique" it is not possible to simultaneously produce coarse and very fine structures on the green foils.
Daruberhinaus ist weiter bekannt, platinhaltige Pasten auf bereits gebrannte keramische Substrate anstelle von keramischen Grunfolien aufzutragen, und diese dann mittels Photostrukturierung mit strukturierten Funktionsschichten zu versehen. Mit Hilfe dieser Technik ist eineFurthermore, it is also known to apply platinum-containing pastes to already fired ceramic substrates instead of green ceramic foils, and then to provide them with structured functional layers by means of photostructuring. Using this technique is one
Feinstrukturierung bis zu lateralen Dimensionen von ca. 10 μm möglich, wahrend mittels herkömmlicher Siebdrucktechnik lediglich Strukturen mit lateralen Ausdehnungen oberhalb von 100 μm erzeugbar sind.Fine structuring down to lateral dimensions of approx. 10 μm is possible, while only structures with lateral dimensions above 100 μm can be produced using conventional screen printing technology.
In der Anmeldung DE 199 34 109.5 ist vorgeschlagen worden, einen Temperaturfühler herzustellen, bei dem zunächst auf keramischen Grunfolien maanderformige Leiterbahnen oder Widerstandsbahnen aus Platin aufgedruckt sind, die danach mit weiteren keramischen Grunfolien in Form einesIn the application DE 199 34 109.5 it has been proposed to produce a temperature sensor in which meandering conductor tracks or resistance tracks made of platinum are first printed on ceramic green sheets, which are then coated with further ceramic green sheets in the form of a
Mehrlagenhybrids aufgebaut und dann in Co-Firing-Technik zu einem Temperaturfühler gesintert werden. Aufgrund der dort eingesetzten, üblichen Dickschichttechnik sind jedoch lediglich Leiterbahnbreiten und -abstände von ca. 0,2 mm realisierbar.Multi-layer hybrids are built up and then sintered into a temperature sensor using co-firing technology. However, due to the usual thick-film technology used there, only track widths and spacing of approx. 0.2 mm can be realized.
Dadurch, daß die bekannten platinhaltigen photostrukturierbaren Pasten nur auf bereits gebrannte Keramiken aufgebracht werden können, lassen sich derartige Prozesse bzw. Pasten nicht in bestehende Fertigungsverfahren integrieren, bei denen bisher stets keramische Grunfolien, beispielsweise mit Hilfe der Siebdrucktechnik, bedruckt werden. Zudem ist die erreichbare Auflosung bei Siebdrucktechnik, wie erläutert, auf ca. 100 μm beschrankt.
In der litauischen Anmeldung LT-97 161 wurde in diesem Zusammenhang bereits eine photostrukturierbare, platinhaltige Paste vorgeschlagen, die sich zum Auftragen auf bereits gebrannten keramischen Folien eignet, und die nach dem Auftragen durch Photostrukturierung strukturiert werden kann. Damit sind laterale Strukturauflosungen von typischerweise 10 μm - 30 μm erreichbar.Because the known platinum-containing photostructurable pastes can only be applied to already fired ceramics, such processes or pastes cannot be integrated into existing manufacturing processes in which ceramic green foils have always been printed, for example with the aid of screen printing technology. In addition, the achievable resolution in screen printing technology, as explained, is limited to approx. 100 μm. In this connection, the Lithuanian application LT-97 161 already proposed a photostructurable, platinum-containing paste which is suitable for application to ceramic films which have already been fired and which can be structured by photostructuring after application. This enables lateral structure resolutions of typically 10 μm - 30 μm to be achieved.
Aufgabe der vorliegenden Erfindung war, ausgehend von der Anmeldung LT-97 161, die darin vorgeschlagene photostrukturierbare Paste derart zu modifizieren, daß sie sich auch zum unmittelbaren Auftrag auf keramische Grunfolien eignet. Gleichzeitig war es Aufgabe der vorliegenden Erfindung, eine photostrukturierbare Paste bereitzustellen, die eine deutliche Erhöhung derThe object of the present invention was, based on the application LT-97 161, to modify the photostructurable paste proposed therein in such a way that it is also suitable for direct application to ceramic green sheets. At the same time, it was an object of the present invention to provide a photostructurable paste which significantly increases the
Strukturauflosung bei gleichzeitiger Beibehaltung der Co- Firing-Technologie zur Herstellung von Multilagenstrukturen bzw. Mehrlagenhybriden ermöglicht. Auf diese Weise soll eine möglichst einfache Integration in bestehende Produktionslinien gewahrleistet werden.Structure resolution while maintaining the co-firing technology for the production of multi-layer structures or multi-layer hybrids possible. In this way, the simplest possible integration into existing production lines is to be ensured.
Vorteile der ErfindungAdvantages of the invention
Die erfindungsgemaße photostrukturierbare Paste hat gegenüber dem Stand der Technik den Vorteil, daß damit keramische Grunfolien unmittelbar mit Funktionsschichten versehen werden können, die danach durch Photostrukturierung beispielsweise in Form von Leiterbahnen oderThe photostructurable paste according to the invention has the advantage over the prior art that it can be used to provide ceramic green films directly with functional layers, which are then photostructured, for example in the form of conductor tracks or
Widerstandsbahnen strukturierbar sind. Dabei werden laterale Auflosungen von weniger als 50 μm, insbesondere zwischen 5 μm und 25 μm erreicht.Resistance tracks can be structured. Lateral resolutions of less than 50 μm, in particular between 5 μm and 25 μm, are achieved.
Neben einer derartigen absoluten lateralen Auflosung der erzeugten Strukturen hat die erfindungsgemaße Paste weiter den Vorteil, daß die nach der Photostrukturierung auf dem
keramischen Grunkorper verbleibenden Strukturen nur eine geringe Standardabweichung der lateralen Ausdehnung der erzeugten Strukturen in mindestens einer Dimension von einem vorgegebenen Sollwert aufweisen. Insofern können auch breitere Strukturen als 50 μm erzeugt werden, die dann jedoch beispielsweise eine sehr genau definierte Breite aufweisen. Die Standarabweichung vom Sollwert liegt dabei üblicherweise unter 10 μm, insbesondere unter 5 μm.In addition to such an absolute lateral resolution of the structures produced, the paste according to the invention has the further advantage that after the photostructuring on the ceramic green bodies remaining structures have only a small standard deviation of the lateral extent of the structures produced in at least one dimension from a predetermined desired value. In this respect, structures wider than 50 μm can also be produced, but then have a very precisely defined width, for example. The standard deviation from the target value is usually less than 10 μm, in particular less than 5 μm.
Die erfindungsgemaße Paste eignet sich somit vorteilhaft zur Erzeugung von Mehrlagenstrukturen auf Keramikbasis, wobei zunächst keramische Grunkorper mit einer strukturierten Funktionsschicht versehen worden sind, die dann zu Hybridbauelementen weiterverarbeitet werden.The paste according to the invention is thus advantageously suitable for producing multilayer structures on a ceramic basis, ceramic green bodies first being provided with a structured functional layer, which are then processed further to form hybrid components.
Mit der erfindungsgemaßen Paste laßt sich somit auch der aus der Anmeldung DE 199 34 109.5 bekannte Temperaturfühler mit erheblich verbesserten Eigenschaften hinsichtlich der erzeugten Widerstandsbahnen herstellen.The paste according to the invention can thus also be used to produce the temperature sensor known from application DE 199 34 109.5 with considerably improved properties with regard to the resistance tracks produced.
Die erfindungsgemaße platinhaltige Paste hat weiter den Vorteil, daß sie trotz des Zusatzes des katalytisch sehr aktiven Platins zeitlich stabil ist und auch unter Tageslichteinfall nicht zerfallt.The platinum-containing paste according to the invention has the further advantage that, despite the addition of the catalytically very active platinum, it is stable over time and does not disintegrate even in daylight.
Weiterhin ist vorteilhaft, daß bei dem in der photo- strukturierbaren Paste eingesetzten Füllstoff anstelle von reinem Platinpulver auch eine Mischung von Platinpulver mit Aluminiumoxidpulver und/oder Zirkoniumdioxidpulver verwendbar ist. Diese Mischung fuhrt zu einer Verbesserung der Haftung der erzeugten Pt-Leiterbahn auf dem Grunkorper („Greentape") und/oder dient, beispielsweise durch Mischung von Pt- und Al203-Pulverpartikeln, der Erhöhung des elektrischen Widerstandes der derart erzeugten Leiterbahnen.
Vorteilhafte Weiterbildungen der Erfindung ergeben sich aus den in den Unteranspruchen genannten Maßnahmen.It is also advantageous that a mixture of platinum powder with aluminum oxide powder and / or zirconium dioxide powder can also be used with the filler used in the photopatternable paste instead of pure platinum powder. This mixture leads to an improvement in the adhesion of the Pt conductor track produced on the green body (“green tape”) and / or serves, for example by mixing Pt and Al 2 O 3 powder particles, to increase the electrical resistance of the conductor tracks produced in this way. Advantageous developments of the invention result from the measures mentioned in the subclaims.
So ist vorteilhaft, daß die photosensitive Paste durch eine wäßrige Losung entwickelt werden kann, und daß sie eine geringe Empfindlichkeit gegenüber sichtbarem Licht und dem Einfluß von Sauerstoff hat. Diese Eigenschaften bedeuten eine erhebliche Vereinfachung der Verfahrenstechnik beim Verarbeiten und Strukturieren der Paste, da beispielsweise nicht in Gelblichtraumen oder unter Sauerstoffausschluß gearbeitet werden muß.It is advantageous that the photosensitive paste can be developed by an aqueous solution and that it has a low sensitivity to visible light and the influence of oxygen. These properties mean a considerable simplification of the process engineering when processing and structuring the paste, since, for example, there is no need to work in yellow light dreams or in the absence of oxygen.
Durch die mit der erfindungsgemaßen Paste erreichbare, wesentlich verbesserte Auflosung können nunmehr auf keramischen Grunkorpern und damit auch auf den nach Abschluß des Sinterns dieser Grunkorper erhaltenen gebrannten keramischen Substraten beispielsweise Widerstandsbahnen in Maanderstruktur erzeugt werden, die gegenüber vergleichbaren Widerstandsbahnen, die über herkömmliche Dickschichttechnik erzeugt worden sind, Widerstandssteigerungen von mehr als 400 % aufweisen. Die derart erzeugtenThe significantly improved resolution that can be achieved with the paste according to the invention can now be used to produce, for example, resistance tracks in a maander structure on ceramic green bodies and thus also on the fired ceramic substrates obtained after the sintering of these green bodies, compared to comparable resistance tracks that have been produced using conventional thick-film technology , Have resistance increases of more than 400%. The so generated
Widerstandsleiterbahnen bedeuten somit beim Einsatz in Temperatursensoren oder Heizelementen einen deutlich kleineren Flachenbedarf bei gleichzeitig besserer Genauigkeit der Temperaturmessung und höherem Meßwiderstand, d.h. einer besseren Genauigkeit der Meßspannungsauswertung.Resistance conductor tracks therefore mean a significantly smaller area requirement when used in temperature sensors or heating elements, with better accuracy of temperature measurement and higher measuring resistance, i.e. a better accuracy of the measurement voltage evaluation.
Aufgrund der erhöhten Auflosung beim Photostrukturieren der erfindungsgemaßen Paste ergeben sich zudem deutlich verringerte Schwankungen in den Widerstanden der erzeugten Widerstandsleiterbahnen, so daß insgesamt eine höhere Fertigungsqualitat, weniger Ausschuß und geringere Abweichungen der erzielten Widerstände von einem vorgegebenen Sollwert erzielt werden.
AusfuhrungsbeipieleDue to the increased resolution during the photostructuring of the paste according to the invention, there are also significantly reduced fluctuations in the resistances of the resistive conductor tracks produced, so that overall a higher manufacturing quality, fewer rejects and fewer deviations of the resistances achieved from a predetermined desired value are achieved. Ausfuhrungsbeipiele
Die Erfindung geht zunächst von einer photostrukturierbaren Paste aus, wie sie in ahnlicher Form bereits aus der Anmeldung LT-97 161 bekannt ist. Die dort beschriebene photostrukturierbare Paste ist jedoch lediglich zum Auftragen auf bereits gebrannten keramischen Substraten geeignet und muß daher zum Auftrag auf keramische Grunfolien modifiziert werden. Diese Modifikation beruht im wesentlichen darauf, daß bei der aus LT-97 161 bekannten Pastenzusammensetzung die dort erforderlichen Glasbestandteile in Form von Glaspulverteilchen entfernt bzw. beim Zusammenmischen der Paste nicht zugesetzt werden.The invention is initially based on a photostructurable paste, as is already known in a similar form from the application LT-97 161. However, the photostructurable paste described there is only suitable for application to ceramic substrates that have already been fired and must therefore be modified for application to ceramic green sheets. This modification is based essentially on the fact that in the paste composition known from LT-97 161, the glass components required there in the form of glass powder particles are removed or are not added when the paste is mixed together.
So wurde überraschend festgestellt, daß sich die ausIt was surprisingly found that the
LT-97 161 bekannte photosensitive Paste zum unmittelbaren Auftragen auf keramischen Grunkorpern dann eignet, wenn man die dort beschriebene Pastenzusammensetzung dahingehend modifiziert, daß die Glaspulverbestandteile nicht zugegeben werden. Weiter wurde festgestellt, daß eine derart modifizierte photosensitive Paste unmittelbar das Erzeugen von strukturierten Funktionsschichten auf keramischen Grunfolien erlaubt, wobei die laterale Ausdehnung der in diesen Funktionsschichten durch die Photostrukturierung erzeugten Strukturen zumindest in einer Dimension, beispielsweise in der Breite, unter 50 μm, insbesondere zwischen 5 μm und 25 μm, liegen. Gleichzeitig wurde festgestellt, daß selbst dann, wenn man breitere Strukturen erzeugen mochte, diese mit deutlich erhöhter Genauigkeit hergestellt werden können. Ein Maß für diese Genauigkeit ist die Standardabweichung der lateralen Ausdehnung der erzeugten Strukturen m mindestens einer Dimension von einem vorgegebenen Sollwert. Diese Standardabweichung liegt typischerweise unter 10 μm, insbesondere unter 5 μm.
Als Füllstoff für die erfindungsgemaße photostrukturierbare Paste eignet sich besonders ein Platinpulver mit einer mittleren Teilchengroße von 10 nm bis 20 μm, insbesondere von 50 nm bis 2 μm. Weiter betragt die spezifische Oberflache des anorganischen Füllstoffes bzw. des Platinpulvers bevorzugt 0,5 m2/g bis 20 m2/g.LT-97 161 known photosensitive paste for direct application on ceramic green cores is suitable if the paste composition described there is modified such that the glass powder components are not added. It was also found that a photosensitive paste modified in this way allows the production of structured functional layers on ceramic green sheets, the lateral extent of the structures produced in these functional layers by the photostructuring at least in one dimension, for example in width, below 50 μm, in particular between 5 μm and 25 μm. At the same time, it was found that even if one wanted to produce wider structures, these can be produced with significantly increased accuracy. A measure of this accuracy is the standard deviation of the lateral extent of the structures produced in at least one dimension from a predetermined target value. This standard deviation is typically less than 10 μm, in particular less than 5 μm. A platinum powder with an average particle size of 10 nm to 20 μm, in particular of 50 nm to 2 μm, is particularly suitable as a filler for the photostructurable paste according to the invention. Furthermore, the specific surface area of the inorganic filler or of the platinum powder is preferably 0.5 m 2 / g to 20 m 2 / g.
Insgesamt liegt der Gewichtsanteil des anorganischen Füllstoffes in der photostrukturierbaren Paste zwischen 30% bis 90% bezogen auf das Gesamtgewicht der Paste. Bevorzugt ist ein Gewichtsanteil von 50% - 60%.Overall, the weight fraction of the inorganic filler in the photostructurable paste is between 30% and 90% based on the total weight of the paste. A weight fraction of 50% -60% is preferred.
Besonders bevorzugt ist der Zusatz eines Gemisches von Platinpulver mit einem keramischen Pulver als anorganischer Füllstoff in der photostrukturierbaren Paste. Dazu weist auch das keramische Pulver eine zu dem Platinpulver vergleichbare mittlere Teilchengroße bzw. spezifische Oberfläche von 10 nm bis 20 μm bzw. 0,5 m2/g bis 20 m2/g auf. Als keramisches Pulver werden insbesondere Aluminiumoxid-Pulver, Zirkoniumdioxid-Pulver, Yttriumstabilisierte Zirkoniumdioxid-Pulver, Yttriumoxid-Pulver, Titandioxid-Pulver, Siliziumoxid-Pulver oder eine Mischung dieser Pulver eingesetzt. Daneben können als Füllstoff jedoch auch platinummantelte, nichtleitende Keramikteilchen eingesetzt werden. Durch den Zusatz des keramischen Pulvers zu dem Platinpulver ergeben sich bei der Herstellung von Widerstandsleiterbahnen mit Hilfe der photostrukturierbaren Paste deutlich höhere Flachenwiderstande . Hinsichtlich näherer Details zu diesem prinzipiell bekannten Sachverhalt sei auf die Anmeldung DE 199 34 109.5 verwiesen.The addition of a mixture of platinum powder with a ceramic powder as an inorganic filler in the photostructurable paste is particularly preferred. For this purpose, the ceramic powder also has an average particle size or specific surface area, comparable to that of the platinum powder, of 10 nm to 20 μm or 0.5 m 2 / g to 20 m 2 / g. In particular, aluminum oxide powder, zirconium dioxide powder, yttrium-stabilized zirconium dioxide powder, yttrium oxide powder, titanium dioxide powder, silicon oxide powder or a mixture of these powders are used as the ceramic powder. In addition, platinum-coated, non-conductive ceramic particles can also be used as the filler. The addition of the ceramic powder to the platinum powder results in significantly higher surface resistances in the production of resistance conductor tracks with the aid of the photostructurable paste. With regard to further details on this fact, which is known in principle, reference is made to the application DE 199 34 109.5.
Neben dem Zusatz von reinem Platin als Füllstoff kommt prinzipiell auch der Zusatz von Platinverbindungen, insbesondere Platinprecursorverbindungen wie Platin (II) acetylacetonat, Platin (II ) diamin-cyclobatan-1, 1-
dicarboxylat, Platin (0) -1, 3-divinyl-l, 1,3,3- tetramethyldisiloxan oder Platin (II) tetraammin-nitrat in Frage. Diese Füllstoffe sind jedoch aus Kostengrunden nicht bevorzugt. Zudem können anstelle des keramischen Pulvers auch keramische Precursormaterialien, insbesondere organische Precursormaterialien auf Basis von Si, AI, Zr, Ti und Y eingesetzt werden. Derartige Precursormaterialien sind dem Fachmann bekannt.In addition to the addition of pure platinum as a filler, there is in principle also the addition of platinum compounds, in particular platinum precursor compounds such as platinum (II) acetylacetonate, platinum (II) diamine-cyclobatane-1, 1- dicarboxylate, platinum (0) -1, 3-divinyl-l, 1,3,3-tetramethyldisiloxane or platinum (II) tetraammine nitrate in question. However, these fillers are not preferred for cost reasons. In addition, ceramic precursor materials, in particular organic precursor materials based on Si, Al, Zr, Ti and Y, can also be used instead of the ceramic powder. Precursor materials of this type are known to the person skilled in the art.
Bei den keramischen Grunkorpern bzw. keramischen Folien, auf die die photostrukturierbare Paste als Funktionsschicht aufgebracht wird, handelt es sich im übrigen um übliche keramische Grunfolien mit in einer Polymermatrix eingebetteten Keramikpartikeln, beispielsweise Yttrium- stabilisierten Zirkoniumdioxidpartikeln oder Aluminiumoxidpartikeln.The ceramic green bodies or ceramic foils to which the photostructurable paste is applied as a functional layer are, moreover, conventional ceramic green foils with ceramic particles embedded in a polymer matrix, for example yttrium-stabilized zirconium dioxide particles or aluminum oxide particles.
Zudem kann auch vorgesehen sein, daß vor dem Aufbringen der photostrukturierbaren Paste auf den keramischen Grunkorpern auf diesen zunächst eine Zwischenschicht aufgebracht wird. Diese Zwischenschicht ist beispielsweise eine an sich bekannte Al203-Schicht oder Ti02-Schicht .In addition, it can also be provided that an intermediate layer is first applied to the ceramic green cores before the photostructurable paste can be applied to them. This intermediate layer is, for example, an Al 2 O 3 layer or TiO 2 layer which is known per se.
Weiter sei betont, daß nach dem Aufbringen der photo- strukturierbaren Paste auf die keramische Grunfolie und deren Strukturierung durch Belichtung und nachfolgende Entwicklung, eine Weiterverarbeitung der derart vorbehandelten keramischen Grunfolien, beispielsweise zu Mehrlagenhybridbauteilen erfolgt .It should also be emphasized that after the photo-structurable paste has been applied to the ceramic green sheet and structured by exposure and subsequent development, the ceramic green sheets pretreated in this way are further processed, for example to form multilayer hybrid components.
Insgesamt ist es somit mit der im nachfolgenden naher beschriebenen photostrukturierbaren Paste möglich, strukturierte Funktionsschichten auf keramischen Grunfolien zu erzeugen, die unempfindlich gegen das sichtbare Spektrum des Lichtes und die inhibitierende Wirkung von Sauerstoff
sind, und die sich durch eine großeOverall, it is thus possible with the photostructurable paste described in more detail below to produce structured functional layers on ceramic green sheets that are insensitive to the visible spectrum of light and the inhibiting effect of oxygen are, and which are characterized by a large
Photopolymerisationsgeschwindigkeit und eine ausgezeichnete Linienauflosung auszeichnen. Weiter laßt sich die erfindungsgemaße Paste auch mit Hilfe der bekannten Dickschichttechnologie verarbeiten.Characterize photopolymerization speed and an excellent line resolution. Furthermore, the paste according to the invention can also be processed using the known thick-film technology.
Besonders wichtig für die Paste ist das in den organischen Binder eingesetzte Polymer. Dieses Polymer muß ein photochemisch aktives Polymer sein, d.h. es hat nicht nur die Rolle einer schichtbildenden und die Losungsfahigkeit vermittelnden Komponente in den Binder, sondern soll gleichzeitig die Photopolymerisation effektiv durch den gegenüber dem sichtbaren Spektrum des Lichtes unempfindlichen Initiator initiieren. Dazu ist es als großmolekulares, polyfunktionales Monomer ausgebildet.The polymer used in the organic binder is particularly important for the paste. This polymer must be a photochemically active polymer, i.e. it not only has the role of a layer-forming and dissolving component in the binder, but is also supposed to initiate the photopolymerization effectively by the initiator, which is insensitive to the visible spectrum of the light. For this purpose, it is designed as a large molecular, polyfunctional monomer.
Gleichzeitig neutralisieren die Seitenketten des Polymers mit deren Allylgruppen und das zusatzlich in den organischen Binder eingesetzte organische Disulfid die inhibitierende Wirkung von Sauerstoff. Auf diese Weise ist gewahrleistet, daß alle technologischen Operationen, d.h. die Vorbereitung des lichtempfindlichen organischen Binders, dessen Vermischung mit dem Füllstoff, das Auftragen der erhaltenen Paste auf eine keramische Grunfolie, das nachfolgende Trocknen, Photostrukturieren und Entwickeln unter Tageslicht oder bei gewohnlicher kunstlicher Beleuchtung ausgeführt werden können. Zudem benotigt man keine speziellen Vorkehrungen, um den Kontakt der photo-strukturierbaren Paste mit dem in der Luft vorhandenen Sauerstoff zu vermeiden.At the same time, the side chains of the polymer with their allyl groups and the organic disulfide additionally used in the organic binder neutralize the inhibitory effect of oxygen. This ensures that all technological operations, i.e. the preparation of the light-sensitive organic binder, the mixing of which with the filler, the application of the paste obtained on a ceramic green sheet, the subsequent drying, photostructuring and development under daylight or under conventional artificial lighting. In addition, no special precautions are required to avoid the contact of the photo-structurable paste with the oxygen present in the air.
Beim Vorgang der Polymerisation bilden im übrigen die linienartigen Makromoleküle des in den Binder eingesetzten Polymers, die Seitenketten mit Alkyl- und Allylgruppen aufweisen, eine dichte raumliche Struktur, so daß das Polymer im Bereich der belichteten Stellen vollkommen
unlösbar in Losungsmitteln auf Wasserbasis wird. Durch den zugesetzten Photoinitiator aus der Klasse der Azylphosphine ergibt sich im übrigen eine besonders kurze Belichtungszeit. Insgesamt weist die photostrukturierbare Paste folgende Zusammensetzung in Massenanteilen bezogen auf die Masse des anorganischen Füllstoffes auf:In the course of the polymerization, moreover, the line-like macromolecules of the polymer used in the binder, which have side chains with alkyl and allyl groups, form a dense spatial structure, so that the polymer is perfect in the area of the exposed areas becomes insoluble in water-based solvents. The added photoinitiator from the class of the azylphosphines also results in a particularly short exposure time. Overall, the photostructurable paste has the following composition in mass fractions based on the mass of the inorganic filler:
Füllstoff: 100,00Filler: 100.00
Polymer: 9,00 bis 36,00 Photoinitiator: 0,50 bis 3,50 organisches Disulfid: 0,20 bis 2,00Polymer: 9.00 to 36.00 Photoinitiator: 0.50 to 3.50 organic disulfide: 0.20 to 2.00
Inhibitor der thermischen Polymerisation: 0,01 bis 0,35 organisches Losungsmittel: 5,50 bis 21,50Thermal polymerization inhibitor: 0.01 to 0.35 organic solvent: 5.50 to 21.50
An das im organischen Binder enthaltene Polymer wird eine Reihe von Anforderungen gestellt. So soll es zunächst in wasserlöslichen Basislosungen loslich sein, ein nicht- haftendes Hautchen bzw. eine Membran bei Zimmertemperatur bilden, die Viskosität der photostrukturierbaren Paste einstellbar machen und aktiv an der photoinitiierenden, Radikalen-Polymerisation in sauerstoffhaltiger Umgebung teilnehmen. Schließlich soll die thermische Spaltung des Polymers auch bei möglichst niedrigen Temperaturen erfolgen.A number of requirements are imposed on the polymer contained in the organic binder. For example, it should first be soluble in water-soluble base solutions, form a non-sticky skin or a membrane at room temperature, make the viscosity of the photostructurable paste adjustable and actively participate in photoinitiating, radical polymerization in an oxygen-containing environment. Finally, the thermal cleavage of the polymer should also take place at the lowest possible temperatures.
Diese Anforderungen werden am besten von Acryl- oder Vinyl- Monomeren und ungesättigten Carbonsaure-Copolymeren erfüllt, wobei deren Molekulmasse bevorzugt zwischen 10.000 und 20.000 liegt und die Masse der ungesättigten Carbonsaure im Copolymer zwischen 15 und 30 Massen% betragt. Hinsichtlich weiterer Details an die Anforderungen und die Möglichkeiten für die verschiedenen einsetzbaren Polymere sei auf die Anmeldung LT- 97-161 verwiesen.These requirements are best met by acrylic or vinyl monomers and unsaturated carboxylic acid copolymers, the molecular weight of which is preferably between 10,000 and 20,000 and the mass of the unsaturated carboxylic acid in the copolymer is between 15 and 30% by mass. For further details on the requirements and the possibilities for the various polymers that can be used, reference is made to the application LT-97-161.
Da die verwendbaren Polymere Seitenketten mit Acryl- und Allylgruppen besitzen, verringern sie die Empfindlichkeit
des organischen Binders gegen die inhibitorische Sauerstoffwirkung deutlich, eliminieren sie jedoch nicht vollständig. Daher ist es weiter erforderlich, ein organisches Disulfid zuzusetzen, dessen allgemeine Formel Rι-CH2-S-S-CH2-R2 f r gleiche oder verschiedene Alkyl-,Since the polymers that can be used have side chains with acrylic and allyl groups, they reduce the sensitivity of the organic binder against the inhibitory oxygen effect, but do not completely eliminate them. It is therefore also necessary to add an organic disulfide, the general formula R ι -CH 2 -SS-CH 2 -R 2 for the same or different alkyl,
Cycloalkyl-, Aryl-, Arylalkyl- oder Carboxylalkyl-Radikale . Besonders geeignet ist als organisches Disulfid Didodecyl- disulfid.Cycloalkyl, aryl, arylalkyl or carboxylalkyl radicals. Isodecyl disulfide is particularly suitable as an organic disulfide.
Als Photoinitiator wird der photostrukturierbaren Paste ein Photoinitiator aus der Acylphosphinklasse zugesetzt. Bevorzugt ist die Verbindung 2, 6-Dimethoxybenzoyldiphenyl- Phosphin.A photoinitiator from the acylphosphine class is added to the photostructurable paste as a photoinitiator. The compound 2, 6-dimethoxybenzoyldiphenylphosphine is preferred.
Das zur Einstellung der Viskosität der photostrukturierbaren Paste zugesetzte Losungsmittel soll zunächst alle organischen Komponenten sehr gut auflosen, gleichzeitig bei Zimmertemperatur wenig fluchtig sein und sich relativ schnell bei Temperaturen von 80°C - 100°C verfluchtigen, da derartige Temperaturen typischerweise beim Trocknen von keramischen Grunfolien insbesondere nach dem Auftragen der photostrukturierbaren Paste eingesetzt werden.The solvent added to adjust the viscosity of the photostructurable paste should initially dissolve all organic components very well, at the same time not be volatile at room temperature and volatilize relatively quickly at temperatures of 80 ° C - 100 ° C, since such temperatures are typically used when drying green ceramic films especially after the application of the photostructurable paste.
Bevorzugt sind als Losungsmittel Terpene, Karbitolacetat, Butylkarbitolacetat oder höhere Alkoholester. Besonders bevorzugt ist Benzylalkohol . Um wahrend desPreferred solvents are terpenes, carbitol acetate, butyl carbitol acetate or higher alcohol esters. Benzyl alcohol is particularly preferred. To during the
Trocknungsvorgangs die Stabilität der photostrukturierbaren Paste sicherzustellen, ist es zudem erforderlich, einen Inhibitor für eine thermische Polymerisation zuzusetzen. Als besonders geeigneter Inhibitor hat sich die Verbindung 2, 6-di-tert-Butyl-l, 4-Kresol erwiesen.To ensure the stability of the photostructurable paste during the drying process, it is also necessary to add an inhibitor for thermal polymerization. The compound 2, 6-di-tert-butyl-1,4-cresol has proven to be a particularly suitable inhibitor.
Die Verarbeitung der einzelnen Komponenten der photostrukturierbaren Paste erfolgte im wesentlichen wie bereits aus LT-97 161 bekannt. Dabei wurden zunächst die
Bestandteile des organischen Binders mit dem Füllstoff beispielsweise in einem Drei-Walzen-Stuhl verrührt, um damit eine gleichmaßige Verteilung der Fullstoffteilchen im organischen Binder zu gewahrleisten. Die auf diese Weise vorbereitete photostrukturierbare Paste wird dann in an sich bekannter Weise in Form einer Funktionsschicht mit einer typischen Dicke von 1 μm bis 10 μm auf eine keramische Grunfolie mit Aluminiumoxid als keramischem Bestandteil aufgetragen.The processing of the individual components of the photostructurable paste was carried out essentially as already known from LT-97 161. Initially, the Components of the organic binder are mixed with the filler, for example in a three-roll chair, in order to ensure an even distribution of the filler particles in the organic binder. The photostructurable paste prepared in this way is then applied in a manner known per se in the form of a functional layer with a typical thickness of 1 μm to 10 μm to a ceramic green sheet with aluminum oxide as the ceramic component.
Danach wurden die mit der Funktionsschicht versehenen Grunfolien bei einer Temperatur von 80°C bis 100°C über eine Zeit von typischerweise 5 min bis 20 min getrocknet und schließlich mit einer Photomaske mit UV-Licht belichtet. Die Photomaske ist dazu beispielsweise in Form von maanderformigen Widerstandsleiterbahnen strukturiert.The green films provided with the functional layer were then dried at a temperature of 80 ° C. to 100 ° C. for a period of typically 5 minutes to 20 minutes and finally exposed to UV light using a photomask. For this purpose, the photomask is structured, for example, in the form of meandering resistance conductor tracks.
Das UV-Licht bei der Belichtung weist bevorzugt eine Wellenlange von 320 nm - 400 nm auf.The UV light during the exposure preferably has a wavelength of 320 nm - 400 nm.
Nach dem Belichten der nicht mit Hilfe der Photomaske abgedeckten Bereiche der Funktionsschicht auf der keramischen Grunfolie erfolgte dann das Entwickeln der photostrukturierbaren Paste. Dazu wird beispielsweise ein Aerosol einer wäßrigen, 0,5%-igen Monoethanolaminlosung auf eine sich mit einer Geschwindigkeit von typischerweise 3000 U/min drehende Unterlage, auf der die belichteten keramischen Grunfolien angeordnet sind, aufgetropft. Dieses Verfahren wird allgemein als „spin-development" bezeichnet und ist in LT-97 161 naher erläutert.After the areas of the functional layer on the ceramic green sheet which were not covered with the aid of the photomask were exposed, the photostructurable paste was then developed. For this purpose, for example, an aerosol of an aqueous, 0.5% monoethanolamine solution is dripped onto a substrate which rotates at a speed of typically 3000 rpm, on which the exposed ceramic green sheets are arranged. This method is generally referred to as “spin development” and is explained in more detail in LT-97 161.
Nach dem Entwickeln der photostrukturierbaren Paste werden schließlich die nicht belichteten Bereiche mit Hilfe einer wasserlöslichen Basislosung wieder abgewaschen.
Die weitere Verarbeitung der keramischen Grünfolien mit der darauf befindlichen, entwickelten, photostrukturierbaren Paste erfolgt dann mittels der aus der Anmeldung DE 199 34 109.5 bekannten Weise. So werden die mit den strukturierten Funktionsschichten versehenen keramischen Grünfolien gegebenenfalls mit weiteren keramischen Grünfolien gestapelt, mit Durchkontaktierungen und elektrischen Anschlüssen versehen und schließlich bei Temperaturen von typischerweise 1050°C bis 1650°C gesintert.
After developing the photostructurable paste, the unexposed areas are finally washed off again using a water-soluble basic solution. The further processing of the ceramic green sheets with the developed, photostructurable paste on them then takes place in the manner known from application DE 199 34 109.5. The ceramic green foils provided with the structured functional layers are optionally stacked with further ceramic green foils, provided with vias and electrical connections and finally sintered at temperatures of typically 1050 ° C. to 1650 ° C.
Claims
1. Photostrukturierbare Paste, insbesondere zur Herstellung von strukturierten Widerstandsschichten oder Leiterbahnen auf keramischen Grunkorpern, mit einem Füllstoff und einem lichtempfindlichen organischen Binder, der ein Polymer, einen Photoinitiator, einen Inhibitor für eine thermische Polymerisation, ein organisches Disulfid und ein organisches Losungsmittel aufweist, wobei der Füllstoff ein Platinpulver, eine Platinverbindung oder eine Mischung eines Platinpulvers oder einer Platinverbindung mit einem keramischen Pulver oder einer keramischen Precursor- Verbindung ist.1. Photostructurable paste, in particular for the production of structured resistance layers or conductor tracks on ceramic green cores, with a filler and a light-sensitive organic binder which comprises a polymer, a photoinitiator, an inhibitor for thermal polymerization, an organic disulfide and an organic solvent, where the filler is a platinum powder, a platinum compound or a mixture of a platinum powder or a platinum compound with a ceramic powder or a ceramic precursor compound.
2. Photostrukturierbare Paste nach Anspruch 1, dadurch gekennzeichnet, daß das Polymer ein membranbildendes Polymer ist.2. Photostructurable paste according to claim 1, characterized in that the polymer is a membrane-forming polymer.
3. Photostrukturierbare Paste nach Anspruch 1, dadurch gekennzeichnet, daß der organische Binder frei von polyfunktionalen Monomeren und das Polymer photochemisch aktiv ist.3. Photostructurable paste according to claim 1, characterized in that the organic binder is free of polyfunctional monomers and the polymer is photochemically active.
4. Photostrukturierbare Paste nach Anspruch 1, dadurch gekennzeichnet, daß der Füllstoff frei von Glaspulver ist. 4. Photostructurable paste according to claim 1, characterized in that the filler is free of glass powder.
5. Photostrukturierbare Paste nach Anspruch 1, dadurch gekennzeichnet, daß das Platinpulver und/oder das keramische Pulver eine mittlere Teilchengroße von 10 nm bis 20 μm, insbesondere 20 nm bis 5 μm, und eine spezifische Oberflache von 0,5 m2/g bis 20 m2/g aufweist.5. Photostructurable paste according to claim 1, characterized in that the platinum powder and / or the ceramic powder have an average particle size of 10 nm to 20 μm, in particular 20 nm to 5 μm, and a specific surface area of 0.5 m 2 / g to 20 m 2 / g.
6. Photostrukturierbare Paste nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß der Füllstoff in einem Gewichtsanteil von 30% bis 90% bezogen auf das Gesamtgewicht der Paste zugesetzt ist.6. Photostructurable paste according to at least one of the preceding claims, characterized in that the filler is added in a weight fraction of 30% to 90% based on the total weight of the paste.
7. Photostrukturierbare Paste nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das keramische Pulver ein Al203-Pulver , ein insbesondere Yttrium-stabilisiertes Zr02-Pulver, ein Y203-Pulver, ein Ti02-Pulver, ein Si02-Pulver oder eine Mischung dieser Pulver ist.7. Photostructurable paste according to at least one of the preceding claims, characterized in that the ceramic powder is an Al 2 0 3 powder, in particular an yttrium-stabilized Zr0 2 powder, a Y 2 0 3 powder, a Ti0 2 powder, is a Si0 2 powder or a mixture of these powders.
8. Photostrukturierbare Paste nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die8. Photostructurable paste according to at least one of the preceding claims, characterized in that the
Bestandteile der Paste in folgenden Massenanteilen, bezogen auf die Masse des anorganischen Füllstoffes, eingesetzt sind: Füllstoff 100,00 Polymer 9,00 bis 36,00Components of the paste in the following mass fractions, based on the mass of the inorganic filler, are used: filler 100.00 polymer 9.00 to 36.00
Photoinitiator 0,50 bis 3,50 organisches Disulfid 0,20 bis 2,00Photoinitiator 0.50 to 3.50 organic disulfide 0.20 to 2.00
Inhibitor 0,01 bis 0,35 organisches Losungsmittel 5,50 bis 21,50Inhibitor 0.01 to 0.35 organic solvent 5.50 to 21.50
9. Photostrukturierbare Paste nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Paste nach einer Belichtung mit einer wasserlöslichen Basislosung entwickelbar ist. 9. Photostructurable paste according to at least one of the preceding claims, characterized in that the paste can be developed after exposure to a water-soluble base solution.
10. Photostrukturierbare Paste nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß der anorganische Füllstoff und der organische Binder in der Paste dispergiert ist.10. Photostructurable paste according to at least one of the preceding claims, characterized in that the inorganic filler and the organic binder is dispersed in the paste.
11. Photostrukturierbare Paste nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das Polymer ein Copolymer von Alkylacrylaten und Alkylmetha- crylaten ist, deren Alkylreste 1 bis 12 Kohlenstoffatome aufweisen, und/oder daß das Polymer ein Copolymer von Cycloalkyl (meth) acrylaten, Arylalkyl (meth) acrylaten, Styrol, Acrylnitril oder deren Mischungen und ungesättigten Carbonsauren ist, deren freie Carboxylgruppen mit 2,3- Epoxypropyl (meth) acrylat und/oder Allylglycidylether verestert sind.11. Photostructurable paste according to at least one of the preceding claims, characterized in that the polymer is a copolymer of alkyl acrylates and alkyl methacrylates, the alkyl radicals of which have 1 to 12 carbon atoms, and / or that the polymer is a copolymer of cycloalkyl (meth) acrylates, Arylalkyl (meth) acrylates, styrene, acrylonitrile or their mixtures and unsaturated carboxylic acids, the free carboxyl groups of which are esterified with 2,3-epoxypropyl (meth) acrylate and / or allyl glycidyl ether.
12. Photostrukturierbare Paste nach Anspruch 1 oder 11, dadurch gekennzeichnet, daß das Polymer ein Copolymer von Styrol und Acrylsaure ist, und insbesondere 15 Massen% nicht veresterter Acrylsaure, 15 Massen! Acrylsaure, verestert mit 2, 3-Epoxypropylmethacrylat, und 6 Massen% Allylglycidylether aufweist, oder daß das Polymer ein Copolymer von Butylmethacrylat und Methacrylsaure ist, und insbesondere 15 Massen% nicht veresterte Methacrylsaure, 20 Massen!12. Photostructurable paste according to claim 1 or 11, characterized in that the polymer is a copolymer of styrene and acrylic acid, and in particular 15 mass% of non-esterified acrylic acid, 15 masses! Acrylic acid, esterified with 2,3-epoxypropyl methacrylate, and 6 mass% allyl glycidyl ether, or that the polymer is a copolymer of butyl methacrylate and methacrylic acid, and in particular 15 mass% unesterified methacrylic acid, 20 masses!
Methacrylsaure, verestert mit 2, 3-Epoxypropylmethacrylat, und 7,5 Massen Allylgliycidylether, aufweist.Methacrylic acid, esterified with 2, 3-epoxypropyl methacrylate, and 7.5 masses of allyl glycidyl ether.
13. Photostrukturierbare Paste nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß der13. Photostructurable paste according to at least one of the preceding claims, characterized in that the
Photoinitiator 2, 6-Dimethoxybenzoyldiphenylphosphin, das organische Losungsmittel Benzylalkohol, das organische Disulfid Didodecyldisulfid und der Inhibitor der thermischen Polymerisation 2, 6-dι-tert-Butyl-l, 4-Kresol ist. Photoinitiator 2, 6-dimethoxybenzoyldiphenylphosphine, the organic solvent benzyl alcohol, the organic disulfide didodecyl disulfide and the thermal polymerization inhibitor 2, 6-di-tert-butyl-1,4-cresol.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10015502 | 2000-03-14 | ||
DE10015502A DE10015502A1 (en) | 2000-03-14 | 2000-03-14 | Photostructurizable paste, for producing structurized resistance film or wiring trace on green ceramic substrate, contains platinum (compound) powder and optionally ceramic (precursor) as filler in light-sensitive organic binder |
PCT/DE2001/000867 WO2001068567A2 (en) | 2000-03-14 | 2001-03-08 | Photostructured paste |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1296913A2 true EP1296913A2 (en) | 2003-04-02 |
Family
ID=7636773
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01921161A Withdrawn EP1296913A2 (en) | 2000-03-14 | 2001-03-08 | Photostructured paste |
Country Status (6)
Country | Link |
---|---|
US (1) | US20030152863A1 (en) |
EP (1) | EP1296913A2 (en) |
JP (1) | JP2003531456A (en) |
KR (1) | KR20030051415A (en) |
DE (1) | DE10015502A1 (en) |
WO (1) | WO2001068567A2 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7864322B2 (en) | 2006-03-23 | 2011-01-04 | The Research Foundation Of State University Of New York | Optical methods and systems for detecting a constituent in a gas containing oxygen in harsh environments |
DE102009029490B4 (en) * | 2009-09-16 | 2023-09-28 | Endress+Hauser SE+Co. KG | Level measuring device |
JP4834170B1 (en) | 2010-07-12 | 2011-12-14 | 田中貴金属工業株式会社 | Conductive fine particles and metal paste for electrode formation and electrode |
TWI499775B (en) * | 2013-01-28 | 2015-09-11 | Tanaka Precious Metal Ind | Metal paste for forming gas sensor electrodes |
KR102432033B1 (en) * | 2018-07-05 | 2022-08-12 | 도레이 카부시키가이샤 | Resin composition, light-shielding film, manufacturing method of light-shielding film, and substrate with barrier ribs |
CA3134212A1 (en) * | 2019-06-10 | 2020-12-17 | Ferro Corporation | High adhesion resistive composition |
DE102022115912A1 (en) | 2022-06-27 | 2023-12-28 | Universität Stuttgart, Körperschaft Des Öffentlichen Rechts | Method for producing an electrical component by successive printing and sintering of particle-containing ink |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2944866A1 (en) * | 1979-11-07 | 1981-05-21 | Hoechst Ag, 6000 Frankfurt | PHOTOPOLYMERIZABLE MIXTURE AND PHOTOPOLYMERIZABLE COPY MATERIAL MADE THEREOF |
JP3405199B2 (en) * | 1992-01-24 | 2003-05-12 | 東レ株式会社 | Photoconductive paste |
TW367504B (en) * | 1996-05-21 | 1999-08-21 | Du Pont | Photosensitive aqueous developable thick film composition employing vinylpyrrolidone polymer |
-
2000
- 2000-03-14 DE DE10015502A patent/DE10015502A1/en not_active Ceased
-
2001
- 2001-03-08 US US10/221,995 patent/US20030152863A1/en not_active Abandoned
- 2001-03-08 JP JP2001567668A patent/JP2003531456A/en active Pending
- 2001-03-08 WO PCT/DE2001/000867 patent/WO2001068567A2/en not_active Application Discontinuation
- 2001-03-08 EP EP01921161A patent/EP1296913A2/en not_active Withdrawn
- 2001-03-08 KR KR1020027012001A patent/KR20030051415A/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO0168567A2 * |
Also Published As
Publication number | Publication date |
---|---|
KR20030051415A (en) | 2003-06-25 |
JP2003531456A (en) | 2003-10-21 |
WO2001068567A3 (en) | 2003-01-09 |
WO2001068567A2 (en) | 2001-09-20 |
US20030152863A1 (en) | 2003-08-14 |
DE10015502A1 (en) | 2001-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE68912212T2 (en) | Photosensitive, water-developable, ceramic coating composition. | |
DE69320092T2 (en) | Diffusion structuring of organic polymer substrates increased by light | |
DE69925512T2 (en) | METHOD FOR THE PRECISION CASTING AND ALIGNMENT OF STRUCTURES ON A SUBSTRATE USING A DEVICABLE CASTING FORM | |
DE2610014C2 (en) | ||
DE69733745T2 (en) | ROLL COATED ELECTROLUMINESCENT PANEL | |
DE60220539T2 (en) | METHOD FOR FORMING MICROSTRUCTURES ON A SUBSTRATE USING A FORM | |
DE3115556C2 (en) | Paste for forming an electrically conductive, solid filler in a cavity of a substrate made of ceramic material and method for filling the cavity | |
DE69230575T2 (en) | Thick film paste composition suitable for screen printing | |
DE1291674B (en) | Precious metal paste for the production of ceramic multiple capacitors | |
DE69607569T3 (en) | USE OF A PHOTO SENSITIVE PASTE, METHOD FOR PRODUCING A PLASMA DISPLAY PANEL, AND PLASMA DISPLAY PANEL WHICH CAN BE PRODUCED BY THIS METHOD | |
DE102009000642A1 (en) | Process for producing microstructured components by means of photolithography | |
EP1296913A2 (en) | Photostructured paste | |
DE68913082T2 (en) | Photosensitive, semi-aqueous developable, ceramic coating composition. | |
KR100527805B1 (en) | Process for thick film circuit patterning | |
DE10237489A1 (en) | Photoreactive resin composition and method of manufacturing a circuit board and a ceramic multilayer substrate using the resin composition | |
DE69910335T2 (en) | Composition for a photosensitive conductive tape containing silver and the tape treated therewith | |
EP1194815B1 (en) | Ceramic blank with a photostructurable functional layer containing platinum and method for production thereof | |
DE69702571T2 (en) | Photosensitive, aqueous developable thick film composition using polyvinylpyrrolidone | |
DE69329329T2 (en) | CERAMIC GREEN FILM | |
EP1342760A1 (en) | Water soluble paste and its use | |
EP0750597B1 (en) | Method of producing ceramic composite bodies | |
DE69417170T2 (en) | Diffusion patterning method and screen therefor | |
DE4113483C2 (en) | Process for producing fine conductor tracks on a ceramic carrier | |
DE2427656A1 (en) | PHOTOHARDABLE PASTE COMPOSITIONS WITH HIGH GRID SHARPNESS | |
DE69431173T2 (en) | Water-cleanable thick film paste composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
17P | Request for examination filed |
Effective date: 20030709 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): CH DE FR GB IT LI |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20041001 |