EP0285734B1 - Process for impregnating hydrophilic paper sheets which can swell - Google Patents
Process for impregnating hydrophilic paper sheets which can swell Download PDFInfo
- Publication number
- EP0285734B1 EP0285734B1 EP87710008A EP87710008A EP0285734B1 EP 0285734 B1 EP0285734 B1 EP 0285734B1 EP 87710008 A EP87710008 A EP 87710008A EP 87710008 A EP87710008 A EP 87710008A EP 0285734 B1 EP0285734 B1 EP 0285734B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- resin
- impregnating
- application
- resin solution
- process according
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 229920002678 cellulose Polymers 0.000 claims abstract description 4
- 239000001913 cellulose Substances 0.000 claims abstract description 4
- -1 for example Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000013067 intermediate product Substances 0.000 claims abstract 2
- 238000010030 laminating Methods 0.000 claims abstract 2
- 239000000123 paper Substances 0.000 claims description 35
- 239000000835 fiber Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000011093 chipboard Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 239000002657 fibrous material Substances 0.000 abstract description 6
- 229920003002 synthetic resin Polymers 0.000 abstract description 3
- 239000000057 synthetic resin Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 9
- 229920000877 Melamine resin Polymers 0.000 description 6
- 206010042674 Swelling Diseases 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004640 Melamine resin Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004924 electrostatic deposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/51—Triazines, e.g. melamine
Definitions
- the invention relates to a method for impregnating hydrophilic swellable paper webs according to the preamble of claim 1.
- the plate-like component used as the base material is provided with an abrasion-resistant surface layer.
- the base materials used in this connection then only have to meet the requirement of sufficient strength and resistance; these can be fiberboard, plywood panels or multilayer paper arrangements.
- Such base materials are provided with decorative laminations in such a way that the outer surface is not only given an attractive appearance, but also the characteristic surface properties, such as high resistance to chemical influences, but also to mechanical stress, heat, light radiation and the like are imparted to it.
- cover layers of interest here to start from cellulose paper webs, which may be printed or unprinted, and to impregnate this starting material with heat-resistant synthetic resin.
- synthetic resin aminoplasts, phenolic resins, Polyester resins, but also melamine resins and the like.
- a further surface layer as a protective layer, such as, for example, a thin plastic film or a further translucent and heat-resistant plastic lacquer.
- Another known method for producing suitably impregnated paper webs is aimed at ensuring a particularly high abrasion resistance and serves to specify a surface layer which is to be connected to a plate-like component, hard paper materials being added to the paper web using an electrostatic deposition process ( DE-B-21 24 432).
- This known method is characterized in that the paper web is impregnated with heat-resistant plastic in an aqueous impregnation bath, then the abrasion-resistant material in the impregnated paper web is introduced and then the impregnated and provided with abrasion-resistant material paper web is dried.
- a paper layer is soaked with a solution which contains approximately 50% melamine resin and 50% water with the addition of a small amount of a wetting agent.
- the impregnated paper web is passed through a drying press, whereby the moisture content can be significantly reduced.
- thermosetting decorative films In another known method (DD-A-217 252), the production of rollable thermosetting decorative films is described with the aim of achieving an improved appearance. This is to be achieved by applying a highly viscous solution of an unsaturated polyester resin in organic solvents as a surface film to the side of the paper web to be printed. The impregnation is then triggered by subsequent heating of the paper webs loaded with resin to temperatures of 60 to 110 ° C. The partially impregnated webs are then cured at an elevated temperature (160 ° C.) and the paper webs prepared in this way are printed.
- impregnation solutions are used in the form of highly concentrated resin solutions free of organic solvents, the disadvantages which occur in the abovementioned known processes can be avoided in an extremely satisfactory manner.
- the proportion of water can be reduced to approximately 1/5 of the comparable impregnating solutions known to date.
- the highly concentrated resin solution is applied evenly to the paper web at room temperature and thus in a relatively viscous state, which at the same time offers advantageous precise dosing options for the resin proportion in relation to the paper portion to be impregnated by the known use of wire doctor blades or the like more.
- the low fiber swelling means that the elasticity of the cellulose fibers, in the case of the use of paper cellulose, gives the impregnate a considerably more favorable flexibility and deformability than was possible with the previous procedures.
- the high quality The surface smoothness achieved guarantees a more uniform coating application, if such an additional coating is desired, with improved drying properties for this coating film. Paint consumption can be significantly reduced thanks to the specified smooth surface.
- a flat fibrous material wound on this roll here a paper tape 3
- a resin application station 5 which is fed from a storage container 4, in which has a highly concentrated resin with a solids content of approx. 70 to 98%.
- the highly concentrated resin such as melamine resin, has a viscosity of approx. 200 to 2000 mPa at room temperature.
- the application station 5 can consist of wire squeegees, roller pairs, a casting head arrangement, air knives, an application apron or the like which are known per se.
- the highly concentrated resin is applied to the paper web 3 within the application station 5 at room temperature and distributed by means of one or more of the above-mentioned devices with a high degree of homogenization and with exact metering, without it being able to penetrate appreciably into or from the pulp given the high viscosity would even be sucked in.
- the paper web 3 passes through a heating station 6, in which the resin application is briefly heated together with the paper to temperatures between 50 and 100 ° C. for a short time.
- Suitable heat sources within the heating station 6 can be infrared radiators, microwave heat sources, hot air arrangements or the like.
- the duration and degree of heating within the heating station 6 are such that the viscosity of the highly concentrated resin is suddenly reduced to such an extent that it can penetrate completely into the paper web or is absorbed by it.
- the duration of the heat application is dimensioned such that the impregnating agent used is not yet appreciably condensed out or polymerized.
- a melamine resin was applied to a paper web with a maximum absorbency of 200 ml, 200 g / m 2 in the form of a 75% resin solution, which corresponds to approximately 150 g resin / m 3 and 50 g solvent / m 3, whereby the end product a density> 1 g / cm3 resulted. No or only a negligible fiber swelling could be observed. The elasticity of the cellulose fibers of the paper used was retained. The end product was characterized by high flexibility and formability. With regard to the drying of the impregnate, it was found that the required evaporation rate was 140% lower compared to conventional impregnation processes or when using a 40% resin solution.
- FIG. 2 differs from that according to FIG. 1 in that another, but known application mechanism is used here.
Landscapes
- Paper (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
Die Erfindung bezieht sich auf ein Verfahren zum Imprägnieren von hydrophilen quellfähigen Papierbahnen gemäß Oberbegriff des Anspruchs 1.The invention relates to a method for impregnating hydrophilic swellable paper webs according to the preamble of claim 1.
Es ist für unterschiedlichste Anwendungsgebiete und Zwecke bekannt, verschiedenartige Basismaterialien dergestalt oberflächenzubeschichten, daß die Oberfläche möglichst optimal die gewünschten Eigenschaften garantiert. Beispielsweise wird für Wandverkleidungen, Möbel aller Art die einer erhöhten Abriebbelastung ausgesetzt sind, das als Basismaterial eingesetzte plattenartige Bauelement mit einer abriebfesten Oberflächenschicht versehen. Die in diesem Zusammenhang verwendeten Basismaterialien müssen dann nur der Anforderung einer ausreichenden Festigkeit und Widerstandskraft genügen, es kann sich hierbei um Faserplatten, Sperrholzplatten oder Vielschichtpapieranordnungen handeln. Solche Basismaterialien werden mit dekorativen Kaschierungen versehen, dergestalt, daß der Außenfläche nicht nur ein attraktives Aussehen verliehen wird, sondern ihr auch die charakteristischen Oberflächeneigenschaften vermittelt werden, wie hohe Widerstandsfähigkeit gegen chemische Einflüsse, aber auch gegen mechanische Belastung, Hitze, Lichteinstrahlung und dergleichen mehr.It is known for a wide variety of applications and purposes to surface-coat different types of base materials in such a way that the surface guarantees the desired properties as optimally as possible. For example, for wall cladding, furniture of all kinds that are exposed to increased abrasion, the plate-like component used as the base material is provided with an abrasion-resistant surface layer. The base materials used in this connection then only have to meet the requirement of sufficient strength and resistance; these can be fiberboard, plywood panels or multilayer paper arrangements. Such base materials are provided with decorative laminations in such a way that the outer surface is not only given an attractive appearance, but also the characteristic surface properties, such as high resistance to chemical influences, but also to mechanical stress, heat, light radiation and the like are imparted to it.
Es ist allgemeiner Stand der Technik für die hier interessierenden Deckschichten, von Zellulosepapierbahnen auszugehen, wobei diese bedruckt oder unbedruckt sein können, und dieses Ausgangsmaterial mit hitzebeständigem Kunstharz zu imprägnieren. In diesem Zusammenhang finden Anwendung Aminoplaste, Phenolharze, Polyesterharze, aber auch Melaminharze und dergleichen mehr. Es ist auch bekannt, derartige Imprägnate zusätzlich mit einer weiteren Oberflächenschicht als Schutzschicht zu beaufschlagen, wie beispielsweise einer dünnen Kunststofffolie oder einem weiteren lichtdurchlässigen und hitzebeständigen Kunststofflack.It is general state of the art for the cover layers of interest here to start from cellulose paper webs, which may be printed or unprinted, and to impregnate this starting material with heat-resistant synthetic resin. In this context, aminoplasts, phenolic resins, Polyester resins, but also melamine resins and the like. It is also known to additionally impregnate such impregnates with a further surface layer as a protective layer, such as, for example, a thin plastic film or a further translucent and heat-resistant plastic lacquer.
Bei einem bekannten Verfahren zum Imprägnieren von Vlies- oder Papiermaterialien mit härtbaren Harzen und deren Aushärtung (DE-C-29 33 998) geht est um die Herstellung von Filtermaterialien, wobei zu Imprägnierung des Vliessubstrates mit Harz und/oder Monomeren das Substrat mit einer Lösung oder Dispersion von mindestens einem durch Elektronenstrahlen härtbaren Flüssigharz getränkt wird, wobei die Konzentration der Harzlösung 1 bis 50 Gew. % bezogen auf das Gewicht der Lösung oder Dispersion enthält. Nach dem erfolgten Durchtränkungsvorgang des Vliesmaterials wird das Lösungsmittel durch Wärmezufuhr entfernt und die Härtung desselben durch Elektronenbestrahlung ausgeführt. Die in diesem Zusammenhang verwendeten Harze und/oder Monomere sind auf der Basis von Acrylsäure- und/oder Metacrylsäureestern mit Polyolen hergestellt.In a known method for impregnating nonwoven or paper materials with curable resins and curing them (DE-C-29 33 998), it is a matter of producing filter materials, with the substrate being impregnated with a resin and / or monomers to impregnate the nonwoven substrate or dispersion of at least one liquid resin curable by electron beams, the concentration of the resin solution containing 1 to 50% by weight based on the weight of the solution or dispersion. After the impregnation process of the nonwoven material has taken place, the solvent is removed by the application of heat and the hardening thereof is carried out by electron radiation. The resins and / or monomers used in this connection are produced on the basis of acrylic acid and / or metacrylic acid esters with polyols.
Ein weiteres bekanntes Verfahren zur Herstellung von geeignet imprägnierten Papierbahnen hat die Gewährleistung einer besonders hohen Abriebfestigkeit zum Ziel und dient der Vorgabe einer Oberflächenschicht, die mit einem plattenartigen Bauelement zu verbinden ist, wobei der Papierbahn unter Verwendung eines elektrostatischen Abscheidungsverfahrens harte, pulverförmige Materialien zugegeben werden (DE-B-21 24 432). Dieses bekannte Verfahren kennzeichnet sich dadurch, daß die Papierbahn in einem wässrigen Imprägnierbad mit hitzebeständigem Kunststoff imprägniert wird, anschließend das abriebfeste Material in die imprägnierte Papierbahn eingebracht wird und dann die imprägnierte und mit abriebfestem Material versehene Papierbahn getrocknet wird. Hierfür wird zunächst zur Herstellung einer imprägnierten Papierbahn ohne abriebfestes Material eine Papierschicht mit einer Lösung getränkt, die ca. 50% Melaminharz und 50% Wasser unter Zugabe einer geringen Menge eines Netzmittels enthält. Um für den Trocknungsvorgang, also die Verdampfung des hohen Wasseranteils, nicht mit zu hohem Energieaufwand arbeiten zu müssen, wird die getränkte Papierbahn durch eine Trockenpresse gegeben, womit der Feuchtigkeitsgehalt erheblich reduziert werden kann.Another known method for producing suitably impregnated paper webs is aimed at ensuring a particularly high abrasion resistance and serves to specify a surface layer which is to be connected to a plate-like component, hard paper materials being added to the paper web using an electrostatic deposition process ( DE-B-21 24 432). This known method is characterized in that the paper web is impregnated with heat-resistant plastic in an aqueous impregnation bath, then the abrasion-resistant material in the impregnated paper web is introduced and then the impregnated and provided with abrasion-resistant material paper web is dried. For this purpose, to produce an impregnated paper web without abrasion-resistant material, a paper layer is soaked with a solution which contains approximately 50% melamine resin and 50% water with the addition of a small amount of a wetting agent. In order not to have to work with too much energy for the drying process, i.e. the evaporation of the high water content, the impregnated paper web is passed through a drying press, whereby the moisture content can be significantly reduced.
Bei einem weiteren bekannten Verfahren (DD-A-217 252) wird die Herstellung rollfähiger duroplastischer Dekorfolien beschrieben mit dem Ziel, ein verbessertes Erscheinungsbild zu erzielen. Dies soll dadurch erreicht werden, daß auf der zu bedruckenden Seite der Papierbahn eine hochviskose Lösung eines ungesättigten Polyesterharzes in organischen Lösungsmitteln als oberflächlicher Film aufgebracht wird. Die Imprägnierung wird dann durch anschließendes Erwärmen der mit Harz beaufschlagten Papierbahnen auf Temperaturen von 60 bis 110°C ausgelöst. Die teilweise imprägnierten Bahnen werden dann noch bei erhöhter Temperatur (160°C) ausgehärtet und die so vorbereiteten Papierbahnen bedruckt.In another known method (DD-A-217 252), the production of rollable thermosetting decorative films is described with the aim of achieving an improved appearance. This is to be achieved by applying a highly viscous solution of an unsaturated polyester resin in organic solvents as a surface film to the side of the paper web to be printed. The impregnation is then triggered by subsequent heating of the paper webs loaded with resin to temperatures of 60 to 110 ° C. The partially impregnated webs are then cured at an elevated temperature (160 ° C.) and the paper webs prepared in this way are printed.
Dennoch leiden die bekannten Verfahren zum Imprägnieren von Papierbahnen oder dergleichen erheblich darunter, daß hohe Flüssigkeitsmengen nach dem Durchlaufen des zu imprägnierenden Materials durch eine entsprechende Imprägnierwanne für den anschließenden Trockenvorgang verdampft werden müssen, was gleichbedeutend mit einem ganz erheblichen Kostenaufwand ist. Insbesondere bei der Einbringung von Kunstharzen in hydrophile Faserwerkstoffe wurde bisher stets davon ausgegangen, daß solche Harze in beispielsweise eine Wirrfaserschicht wie Papier nur mittels des hohen Wasser- oder organischen Lösungsmittelanteils in der Harzlösung als Transportmittel in und zwischen die Fasern eindringen können, so daß bisher kaum Imprägnierlösungen Anwendung fanden, deren Lösungsmittelanteil wesentlich unter 50% oder höchstens 40% liegt.Nevertheless, the known methods for impregnating paper webs or the like suffer considerably from the fact that large amounts of liquid after passing through the material to be impregnated through a corresponding impregnation trough for the subsequent one Drying process must be evaporated, which is synonymous with a very significant cost. In particular, when synthetic resins have been introduced into hydrophilic fiber materials, it has always been assumed that such resins can penetrate into and between the fibers, for example, in a tangled fiber layer such as paper only by means of the high water or organic solvent content in the resin solution, so that hardly any Impregnation solutions were used, the solvent content of which is significantly below 50% or at most 40%.
Für das Imprägnieren von hydrophilen quellfähigen Faserbahnen ergibt sich als nachteilig bei dieser Verfahrensweise neben dem hohen Energieverbrauch für das im Trockenvorgang zu verdampfende Wasser damit noch ein oft unerwünschtes Aufquellen der Zellulosefaser oder dergleichen, wodurch sich Veränderungen in der Oberflächenstruktur des Imprägnats kaum vermeiden lassen.For the impregnation of hydrophilic swellable fiber webs, the disadvantage of this procedure, in addition to the high energy consumption for the water to be evaporated in the drying process, is that there is often an undesirable swelling of the cellulose fiber or the like, which results in changes can hardly be avoided in the surface structure of the impregnate.
Hier setzt die vorliegende Erfindung ein, der die Aufgabe zugrunde liegt, ein Verfahren der gattungsgemäßen Art dahingehend zu verbessern, daß der für die Trocknung der Imprägnierlösung erforderliche Energieaufwand minimiert werden kann bei gleichzeitiger Verhinderung der Gefahr des Aufquellens von Fasermaterialien durch das Lösungsmittel.This is where the present invention comes in, which is based on the object of improving a method of the generic type in such a way that the energy expenditure required for drying the impregnation solution can be minimized while at the same time preventing the risk of swelling of fiber materials by the solvent.
Die Lösung dieser Aufgabe wird erfindungsgemäß durch ein Verfahren erreicht, wie es im Kennzeichen des Anspruchs 1 angegeben ist.This object is achieved according to the invention by a method as specified in the characterizing part of claim 1.
Vorteilhafte Ausgestaltungen und Weiterbildungen dieser Aufgabenlösung ergeben sich aus den Unteransprüchen.Advantageous refinements and developments of this task solution result from the subclaims.
Kommen Imprägnierlösungen in Form hochkonzentrierter, von organischen Lösungsmitteln freien Harzlösungen zur Anwendung, sind die bei den vorgenannten bekannten Verfahren auftretenden Nachteile in außerordentlich befriedigender Weise vermeidbar. Besonders vorteilhaft wirkt sich in diesem Zusammenhang aus, daß auf die Zugabe jeglicher organischer Lösungsmittel verzichtet wird. In einer bevorzugten Ausführungsform, bei der von Melaminharz als Imprägnierungsmittel ausgegangen wird, kann der Anteil des Wassers auf ca. 1/5 der vergleichbaren bisher bekannten Imprägnierlösungen reduziert werden. Die hoch konzentrierte Harzlösung wird bei Zimmertemperatur und damit in einem relativ zähflüssigem Zustand auf die Papierbahn gleichmäßig aufgebracht, was gleichzeitig vorteilhafte genaue Dosierungsmöglichkeiten für den Harzanteil im Verhältnis zu dem zu tränkenden Papieranteil durch die an sich bekannte Verwendung von Drahtrakeln oder dergleichen mehr bietet. Erst nach dieser Auftragung, exakten Homogenisierung und genauen Dosierung des Imprägniermittels auf die Papierbahn oder dergleichen erfolgt dann eine kurzzeitige Wärmebeaufschlagung für eine möglichst schlargartige und drastische Verringerung der Viskosität der Harzlösung, so daß diese in der Lage ist, in kürzester Zeit in die Papierbahn einzudringen, und zwar in einer Zeit, die klein ist gegenüber der für die Aushärtung des Harzes benötigten Zeit.If impregnation solutions are used in the form of highly concentrated resin solutions free of organic solvents, the disadvantages which occur in the abovementioned known processes can be avoided in an extremely satisfactory manner. In this context, it is particularly advantageous that the addition of any organic solvents is dispensed with. In a preferred embodiment, in which melamine resin is used as the impregnating agent, the proportion of water can be reduced to approximately 1/5 of the comparable impregnating solutions known to date. The highly concentrated resin solution is applied evenly to the paper web at room temperature and thus in a relatively viscous state, which at the same time offers advantageous precise dosing options for the resin proportion in relation to the paper portion to be impregnated by the known use of wire doctor blades or the like more. Only after this application, exact homogenization and precise metering of the impregnating agent onto the paper web or the like is there then a brief heat application for a sluggish and drastic reduction in the viscosity of the resin solution, so that it is able to penetrate the paper web in the shortest possible time, in a time that is small compared to the time required for the resin to harden.
Der außerordentlich geringe Wasseranteil der verwendeten konzentrierten Harzlösungen, der bei Raumtemperatur durchgeführte Beschichtungsvorgang und die schockartige Erwärmung nach erfolgter Beschichtung mit der damit verbundenen kurzzeitigen Penetration garantiert eine optimale Papierdurchtränkung ohne oder mit vernachlässigbar geringer chemischer Reaktion der Harzlösung selbst. Die durch die bisher erforderlich gewesenen hohen Wasseranteile hervorgerufenen Faserquellungen werden gänzlich vermieden. Es zeigen sich geringste Beeinträchtigungen der anfänglichen hochqualitativen Rohpapierglätte. Die verzeichnete höhere Harzeinbringung bei gleichzeitiger Vermeidung jeglicher Faserquellung führt zu einem Endprodukt mit besonders hoher Dichte.The extraordinarily low water content of the concentrated resin solutions used, the coating process carried out at room temperature and the shock-like heating after coating with the associated short-term penetration guarantee optimal paper soaking without or with a negligible chemical reaction of the resin solution itself caused fiber swellings are completely avoided. The slightest impairment of the initial high-quality raw paper smoothness can be seen. The higher resin input, while avoiding any fiber swelling, leads to an end product with a particularly high density.
In diesem Zusammenhang ist auch noch als besonders vorteilhaft zu erwähnen, daß durch die geringe Faserquellung die Elastizität der Zellulosefasern für den Fall der Verwendung von Papierzellulose dem Imprägnat eine wesentlich günstigere Flexibilität und Verformbarkeit verleiht als das mit den bisherigen Verfahrensweisen möglich war. Die hohe Qualität der erzielten Oberflächenglätte garantiert einen gleichmäßigeren Lackauftrag, falls eine solche Zusatzbeschichtung gewünscht ist, mit verbesserten Trocknungseigenschaften für diesen Lackfilm. Der Lackverbrauch kann durch die vorgegebene glatte Oberfläche erheblich reduziert werden.In this context it should also be mentioned as particularly advantageous that the low fiber swelling means that the elasticity of the cellulose fibers, in the case of the use of paper cellulose, gives the impregnate a considerably more favorable flexibility and deformability than was possible with the previous procedures. The high quality The surface smoothness achieved guarantees a more uniform coating application, if such an additional coating is desired, with improved drying properties for this coating film. Paint consumption can be significantly reduced thanks to the specified smooth surface.
Schließlich soll noch als besonders vorteilhaft, bedingt durch den niedrigen Lösungsmittelantiel hervorgehoben werden, daß nicht nur der für seine Entfernung erforderliche Energiebedarf im Vergleich zu den bekannten Verfahren erheblich reduziert werden kann, sondern darüberhinaus noch die Trocknungsstrecke sich beträchtlich verkürzen läßt, so daß auch der apparative Aufbau vereinfacht werden kann und insbesondere der bisher für die Trocknungsstrecke benötigte erhebliche Raumbedarf sich entsprechend verringert.Finally, it should be emphasized as particularly advantageous, due to the low solvent content, that not only the energy required for its removal can be considerably reduced compared to the known methods, but also the drying distance can be shortened considerably, so that the apparatus can also be shortened Structure can be simplified and in particular the considerable space required previously for the drying section is reduced accordingly.
Anhand der beiliegenden Zeichnungen, die schematisiert zwei beispielsweise Ausführungsformen einer Einrichtung zur Durchführung des Verfahrens zeigt, sollen nähere Einzelheiten des Verfahrensablaufes verdeutlicht werden, ohne daß jedoch der beschriebene Verfahrensablauf auf die Anwendung dieser Einrichtung beschränkt wäre.The attached drawings, which schematically show two exemplary embodiments of a device for carrying out the method, are intended to clarify further details of the process sequence, but without the process sequence described being restricted to the use of this device.
Wie dargestellt, wird von einer Vorratsrolle 1, die sich in Richtung des Pfeiles 2 dreht, ein auf diese Rolle aufgewickeltes flächiges Fasermaterial, hier ein Papierband 3, abgewickelt und in Pfeilrichtung zunächst einer Harzauftragestation 5 zugeführt, die aus einem Vorratsbehälter 4 gespeist wird, in dem ein Hochkonzentriertes Harz mit einem Feststoffanteil von ca 70 bis 98 % vorhanden ist.As shown, from a supply roll 1, which rotates in the direction of
Das hochkonzentrierte Harz, wie beispielsweise Melaminharz, besitzt bei Zimmertemperatur eine Viskosität von ca. 200 bis 2000 mPa. Die Auftragsstation 5 kann aus an sich bekannten Drahtrakeln, Walzenpaaren, einer Gießkopfanordnung, Luftmessern, einer Auftragschürze oder dergleichen bestehen.The highly concentrated resin, such as melamine resin, has a viscosity of approx. 200 to 2000 mPa at room temperature. The application station 5 can consist of wire squeegees, roller pairs, a casting head arrangement, air knives, an application apron or the like which are known per se.
Das hochkonzentrierte Harz wird innerhalb der Auftragsstation 5 bei Zimmertemperatur auf die Papierbahn 3 aufgebracht und mittels einer oder mehrerer der vorstehend genannten Vorrichtungen mit hohem Homogenisierungsgrad und bei exakter Dosierung verteilt, ohne daß es bei der gegebenen hohen Viskosität bereits nennenswert in Faserstoff eindringen könnte oder von diesen gar eingesaugt würde.The highly concentrated resin is applied to the
Nach dosierter Auftragung des Imprägniermittels durchläuft die Papierbahn 3 eine Heizstation 6, in der eine kurzfristige schockartige Erhitzung des Harzauftrages zusammen mit dem Papier auf Temperaturen zwischen 50 und 100° C erfolgt. Geeignete Wärmequellen innerhalb der Heizstation 6 können Infrarotstrahler, Mikrowellenheizquellen, Heißluftanordnungen oder dergleichen mehr sein. Dauer und Grad der Erwärmung innerhalb der Heizstation 6 sind so bemessen, daß die Viskosität des hochkonzentrierten Harzes schlagartig soweit erniedrigt wird, daß es vollständig in die Papierbahn einzudringen vermag bzw. von dieser aufgesogen wird. Die Dauer der Wärmebeaufschlagung ist dabei so bemessen, daß eine merkliche Auskondensation bzw. Polymerisation des verwendeten Imprägniermittels noch nicht erfolgt. Dies erfolgt dann erst in dem nachgeschalteten Trockner 7, wofür für die Einleitung der Kondensation des Harzes diesem in dem Behälter 4 Katalysatoren oder andere geeignete Beimischungen zugegeben werden können. Solche Beimischungen können auch das Viskositätsverhalten des Imprägniermittels für die gewünschte optimale Penetration innerhalb der Heizvorrichtung 6 vorteilhaft beeinflussen.After metered application of the impregnating agent, the
Im Ausführungsbeispiel wurde ein Melaminharz auf eine Papierbahn mit einer maximalen Aufnahmefähigkeit von 200 ml, 200 g/m² in Form einer 75 %igen Harzlösung, was etwa 150 g Harz/m³ und 50 g Lösungsmittel/m³ entspricht, aufgebracht, wodurch sich für das Endprodukt eine Dicht >1 g/cm³ ergab.
Es konnte keine bzw. nur eine vernachlässigbar geringe Faserquellung beobachtet werden. Die Elastizität der Zellulosefasern des verwendeten Papieres blieb erhalten. Das Endprodukt zeichnete sich durch hohe Flexibilität und Verformbarkeit aus. Hinsichtlich der Trocknung des Imprägnats wurde festgestellt, daß gegenüber herkömmlichen Imprägnierverfahren bzw. bei Verwendung einer 40 %igen Harzlösung die erforderliche Verdampfungsleistung um 140 % geringer lag. Die für bisher bekannte Imprägnierungen verwendeten Imprägnierwannen und die in diesen teilsweise relativ langen Imprägnierstrecken entfallen gänzlich. Anstelle des im Ausführungsbeispiel verwendeten Melaminharzes zeigen auch Polyester-, Epoxid-, Alkydharze vergleichbar vorteilhafte Ergebnisse. Neben Katalysatoren erwies sich als vorteilhaft, Harzen, Netzmittel, Reaktionsbeschleuniger und ähnliche Zusätze in geringem Umfang beizugeben.In the exemplary embodiment, a melamine resin was applied to a paper web with a maximum absorbency of 200 ml, 200 g /
No or only a negligible fiber swelling could be observed. The elasticity of the cellulose fibers of the paper used was retained. The end product was characterized by high flexibility and formability. With regard to the drying of the impregnate, it was found that the required evaporation rate was 140% lower compared to conventional impregnation processes or when using a 40% resin solution. The impregnation troughs used for previously known impregnations and the impregnation paths, which are sometimes relatively long, are completely eliminated. Instead of the melamine resin used in the exemplary embodiment, polyester, epoxy and alkyd resins also show comparably advantageous results. In addition to catalysts, it proved advantageous to add resins, wetting agents, reaction accelerators and similar additives to a small extent.
Die Ausführungsform gemäß Fig. 2 unterscheidet sich dadurch von derjenigen nach Fig. 1, daß hier ein anderer, jedoch an sich bekannter Auftragungsmechanismus zum Einsatz kommt.The embodiment according to FIG. 2 differs from that according to FIG. 1 in that another, but known application mechanism is used here.
Claims (5)
- Process fur impregnating swellable hydrophilic paper sheets, preferably those containing cellulose, for obtaining laminating materials of high surface rigidity for coating plateshaped base materials of all kinds, for example chipboards for use in the furniture industry, wherein condensible or polymerisable resins are at least partially incorporated in the fibre material and the impregnated material is dispatched and/or stored after curing as an intermediate product for future permanent bonding to the surface of a plateshaped base material in the form of rolls, characterised in that the impregnating medium is a high concentration aqueous resin solution which has 70̸ weight-% of solids and is free of organic solvents, that this resin solution is applied (5) continuously with apportioned comparative moderation at room temperature with a viscosity of 20̸0̸ to 20̸0̸0̸ mPA s to the paper sheet (3), that by way of application (5) the resin solution is homogenously dispersed within narrow tolerance limits over the entire application surface, and that after application (5) a shock-like temperature charge on the bonded resin, which is short relative to the curing period for resin bondage, is carried out on the paper sheet (3) at temperatures between 50̸ and 10̸0̸°C (6).
- Process according to claim 1, characterised in that urea- melamine-, polyester-, acryl-, epoxide- and/or alkyd resins are used for producing the resin solution.
- Process according to one of claims 1 or 2, characterised in that additives, such a netting media, reactive catalysers, catalysers or the like, are mixed into the impregnating medium.
- Process according to at least one of claims 1 to 3, characterized in that the homogenizing dispersion of the resin solution over the surface of the fibre material is carried out by means of wire-wound rods, roller-application methods, pouring head, air knife or the like.
- Process according to at least one of claims 1 to 4, characterised in that shocklike short-term heating of a homogeneously dispersed impregnating medium is carried out by using infrared radiators, microwave techniques or hot-air application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87710008T ATE83018T1 (en) | 1987-04-08 | 1987-06-24 | PROCESS FOR IMPREGNATION OF HYDROPHILIC SWELLING PAPER WEBS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873711807 DE3711807A1 (en) | 1987-04-08 | 1987-04-08 | METHOD FOR IMPREGNATING FLAT FIBERS |
| DE3711807 | 1987-04-08 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0285734A2 EP0285734A2 (en) | 1988-10-12 |
| EP0285734A3 EP0285734A3 (en) | 1989-02-01 |
| EP0285734B1 true EP0285734B1 (en) | 1992-12-02 |
Family
ID=6325112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87710008A Expired - Lifetime EP0285734B1 (en) | 1987-04-08 | 1987-06-24 | Process for impregnating hydrophilic paper sheets which can swell |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0285734B1 (en) |
| AT (1) | ATE83018T1 (en) |
| DE (2) | DE3711807A1 (en) |
| ES (1) | ES2036596T3 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19915002A1 (en) * | 1999-04-01 | 2000-10-05 | Basf Ag | Aqueous resin composition for production of composites or stable impregnating resin dispersions has a high content of melamine-formaldehyde resin |
| DE19956665A1 (en) * | 1999-11-25 | 2001-05-31 | Rudolf Ohlinger Gmbh & Co Kg | Production of filter layers comprises forming an aqueous suspension containing natural fibers, applying to a carrier belt to form a strip, adjusting the thickness of the strip, drying using microwaves and cutting into lengths |
| DE50014206D1 (en) * | 2000-10-05 | 2007-05-10 | Basf Ag | CONCENTRATED STABLE AQUEOUS MELAMINE RESIN COMPOSITION |
| DE10200793B4 (en) * | 2002-01-11 | 2005-02-24 | Bausch Gmbh | Flooring element and method for its production |
| DE102008032053A1 (en) * | 2008-07-08 | 2010-01-14 | Kaindl Decor Gmbh | Method and apparatus for drying and precondensing impregnates formed from resin impregnated sheet-like sheet material; Melamine resin-free impregnate |
| CN107988847B (en) * | 2017-12-11 | 2020-08-04 | 浙江海洋大学 | Horizontal dipping dryer for decorative paper production |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2744047A (en) * | 1952-06-02 | 1956-05-01 | Masonite Corp | Process of preparing decorative laminates |
| NL275244A (en) * | 1961-02-28 | |||
| GB1146432A (en) * | 1965-07-20 | 1969-03-26 | Dunlop Co Ltd | Resin impregnated fibrous sheets |
| FR2104707B1 (en) * | 1970-08-07 | 1973-11-23 | Arjomari Prioux | |
| JPS6054179B2 (en) * | 1977-07-07 | 1985-11-29 | 松下電工株式会社 | Decorative board manufacturing method |
| DE2933998C2 (en) * | 1979-08-22 | 1987-05-27 | Otto Dürr Anlagenbau GmbH, 7000 Stuttgart | Method and device for the production of an impregnated paper or non-woven substrate |
| DE3140715A1 (en) * | 1981-10-14 | 1983-04-21 | Cassella Ag, 6000 Frankfurt | AQUEOUS SOLUTION OF A MELAMINE FORMALDEHYDE RESIN AND METHOD FOR THE PRODUCTION THEREOF |
| DE3208728A1 (en) * | 1982-03-11 | 1983-09-22 | Cassella Ag, 6000 Frankfurt | CARRIER MATERIALS COATED WITH AMINO PLASTIC DISPERSIONS AND THEIR PROCESSING OF LAYER MATERIALS |
| US4458062A (en) * | 1983-02-14 | 1984-07-03 | American Cyanamid Company | Continuously produced melt reacted melamine-formaldehyde resins |
| DD217252A1 (en) * | 1983-08-22 | 1985-01-09 | Wtz Holzverarbeitende Ind | METHOD FOR PRODUCING ROLL-ABLE DUROPLASTIC DECOR FILMS WITH IMPROVED APPEARANCE |
| JPS60259443A (en) * | 1984-06-06 | 1985-12-21 | アイカ工業株式会社 | Decorative board |
| US4713138A (en) * | 1984-12-26 | 1987-12-15 | Nevamar Corporation | Method of producing abrasion-resistant decorative laminate |
| DE3700344A1 (en) * | 1986-10-24 | 1988-04-28 | Cassella Ag | METHOD FOR PRODUCING MELAMINE RESIN FILMS |
-
1987
- 1987-04-08 DE DE19873711807 patent/DE3711807A1/en not_active Ceased
- 1987-06-24 DE DE8787710008T patent/DE3782934D1/en not_active Expired - Fee Related
- 1987-06-24 ES ES198787710008T patent/ES2036596T3/en not_active Expired - Lifetime
- 1987-06-24 EP EP87710008A patent/EP0285734B1/en not_active Expired - Lifetime
- 1987-06-24 AT AT87710008T patent/ATE83018T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ES2036596T3 (en) | 1993-06-01 |
| DE3711807A1 (en) | 1988-10-27 |
| DE3782934D1 (en) | 1993-01-14 |
| EP0285734A2 (en) | 1988-10-12 |
| ATE83018T1 (en) | 1992-12-15 |
| EP0285734A3 (en) | 1989-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE60005077T2 (en) | Laminate and its manufacture | |
| DE3137098C2 (en) | ||
| DE69302484T2 (en) | CONNECTIVE FILM | |
| WO1990006232A1 (en) | Decorative high-pressure laminate and a process for producing a surface layer thereon | |
| EP0285734B1 (en) | Process for impregnating hydrophilic paper sheets which can swell | |
| DD259885A5 (en) | METHOD FOR THE PRODUCTION OF PAPER WEBS IMPREGNATED WITH RESIN RESINS IN THE METHOD OF SOLUTIONS AND DISPERSIONS | |
| DE2727312C3 (en) | Process for the production of gap-proof synthetic resin that has hardened on the decor side! Compensation sheets based on papers with | |
| DE2927746C2 (en) | Process for the production of a decorative finished effect film | |
| DE10035924B4 (en) | Impregnate and method of making and using the impregnate | |
| DE10307966C5 (en) | Preimpregnate and process for its preparation | |
| CH641408A5 (en) | METHOD FOR PRODUCING A MELAMINE RESIN-COATED PAPER. | |
| AT397387B (en) | METHOD FOR IMPREGNATING A SURFACE, FIBROUS SUPPORT MATERIAL WITH SYNTHETIC RESIN, DEVICES FOR IMPLEMENTING THIS METHOD, PRODUCTS PRODUCED BY THIS METHOD AND THE USE THEREOF | |
| EP0763387B1 (en) | Process for making a protection sheet for a profile member | |
| DE2316289B2 (en) | Process for producing fast-curing coatings | |
| EP0283651B1 (en) | Method of making coating layers and films | |
| DE1287040C2 (en) | PLASTIC VENEER | |
| DE2238919C2 (en) | Process for the production of a decorative laminated body and intermediate layer product | |
| DE2949306A1 (en) | Synthetic veneer of paper fibre compsn. impregnated with resin - contg. equal wt. of long and short fibres, can be made on paper machine | |
| DE2657973A1 (en) | PROCESS FOR MANUFACTURING AN IMPRAEGNATED CARRIER MATERIAL FOR SURFACE FINISHING | |
| DE2232847A1 (en) | PROCESS FOR THE MANUFACTURING OF CARRIER SHEETS IMPROVED WITH AMINOPLASTIC RESIN AND DECORATED WITH LACQUERED RESIN | |
| DE2013301A1 (en) | Process for coating the surfaces of panels | |
| EP0013267A1 (en) | Method of making laminated products | |
| DE1932528C3 (en) | Process for the production of carrier webs impregnated with aminoplast resin precondensates | |
| AT356390B (en) | METHOD FOR PRODUCING A MELAMINE RESIN-COATED PAPER | |
| DE2558200B2 (en) | PROCESS FOR THE CONTINUOUS MANUFACTURING OF PREPREGS ON THE BASIS OF SOLVENT-FREE, PREFERABLY DUROPLASTIC SYNTHETIC RESINS |
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 |
|
| 17P | Request for examination filed |
Effective date: 19870724 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: BAUSCH AKTIENGESELLSCHAFT |
|
| 17Q | First examination report despatched |
Effective date: 19910305 |
|
| RTI1 | Title (correction) | ||
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19921202 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19921202 Ref country code: FR Effective date: 19921202 |
|
| REF | Corresponds to: |
Ref document number: 83018 Country of ref document: AT Date of ref document: 19921215 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 3782934 Country of ref document: DE Date of ref document: 19930114 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19930107 |
|
| ITF | It: translation for a ep patent filed | ||
| EN | Fr: translation not filed | ||
| NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2036596 Country of ref document: ES Kind code of ref document: T3 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19930630 Ref country code: LI Effective date: 19930630 Ref country code: CH Effective date: 19930630 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| EAL | Se: european patent in force in sweden |
Ref document number: 87710008.1 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19950613 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19950616 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19950619 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19950620 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19950626 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19950727 Year of fee payment: 9 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19960624 Ref country code: AT Effective date: 19960624 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19960625 Ref country code: ES Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES Effective date: 19960625 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19960630 |
|
| BERE | Be: lapsed |
Owner name: BAUSCH A.G. Effective date: 19960630 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19960624 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19970301 |
|
| EUG | Se: european patent has lapsed |
Ref document number: 87710008.1 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 19991007 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050624 |