EP0563148B1 - Beschichtungsverfahren - Google Patents
Beschichtungsverfahren Download PDFInfo
- Publication number
- EP0563148B1 EP0563148B1 EP92901417A EP92901417A EP0563148B1 EP 0563148 B1 EP0563148 B1 EP 0563148B1 EP 92901417 A EP92901417 A EP 92901417A EP 92901417 A EP92901417 A EP 92901417A EP 0563148 B1 EP0563148 B1 EP 0563148B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- layer
- curtain
- liquid material
- bottom layer
- 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
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/007—Slide-hopper coaters, i.e. apparatus in which the liquid or other fluent material flows freely on an inclined surface before contacting the work
- B05C5/008—Slide-hopper curtain coaters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
- B05D1/305—Curtain coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
- B05C9/06—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying two different liquids or other fluent materials, or the same liquid or other fluent material twice, to the same side of the work
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2451/00—Type of carrier, type of coating (Multilayers)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/548—No curing step for the last layer
- B05D7/5483—No curing step for any layer
- B05D7/5485—No curing step for any layer the two layers being applied simultaneously
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/588—No curing step for the last layer
- B05D7/5883—No curing step for any layer
- B05D7/5885—No curing step for any layer all layers being applied simultaneously
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
- G03C2001/7433—Curtain coating
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
- G03C2001/7462—Flowing conditions in slots prior to coating
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
- G03C2001/7481—Coating simultaneously multiple layers
Definitions
- This invention relates to coating processes and is more particularly concerned with curtain coating processes.
- curtain coating as described in US-A-3867901 and US-A-3508947, one or more liquid layers are applied to a moving support as a freely-falling curtain. Under properly controlled conditions, uniform coatings are achieved in which each layer retains its separate identity.
- the curtain can be formed using a conventional multilayer slide hopper fitted with a suitable lip. Edging rods may be used to maintain the width of the curtain, and surface active agents are frequently added to the outer layers to improve curtain stability and promote uniform deposition.
- coating speed One important variable which affects the "coating window” is coating speed. For economic reasons, high coating speeds are desirable provided they can be achieved with low waste and without loss of product quality. However, a major problem with high speed coating is that if the speed is too high, the liquid fails to wet the support in a complete and steady manner. When this occurs, air is entrained at the wetting line and causes patchy or uneven deposition of the coating.
- Air-entrainment is believed to occur whenever the dynamic contact angle formed between the liquid and the support at the wetting line approaches its limiting value of 180°.
- the coating speed at which this happens depends on many factors such as the method of coating and the physical properties of the liquid.
- the viscosity of the liquid being brought into contact with the support at the wetting line is of particular importance.
- a liquid having a relatively low viscosity (typically 3 to 5mPas) is sometimes used to provide a bottom layer for higher viscosity liquids.
- the bottom layer is added to the higher viscosity liquids out of the bottom slot of the hopper (that is, the slot nearest the bead).
- a non-uniform coating is often produced, particularly when the bottom layer is relatively thin, for example, less than about 30 ⁇ m.
- US-A-4569863 discloses a curtain coating process for applying a multiple coating on to a moving support.
- the process enables a plurality of comparatively, high viscosity layers (having viscosities greater than 20mPas) to be applied to the support at coating speeds of 400mmin ⁇ 1 or more.
- This is achieved by the use of a thin bottom layer (otherwise called an accelerating layer) of lower viscosity.
- the thickness of this layer is between 2 and 30 ⁇ m, and its viscosity between 1 and 20mPas.
- the thickness is between 2.5 and 5 ⁇ m, and the viscosity between 2 and 3mPas.
- the use of an upper spreading layer is also disclosed.
- the bottom or accelerating layer is applied directly to the back of the curtain either by discharging the layer from the bottom slot of a conventional slide hopper, or from a slot which flows on to a separate slide which joins at the hopper lip the main hopper slide on which are flowing the other layer compositions. Hoppers designed for this purpose are sometimes known as V-hoppers.
- the freely-falling curtain impinges on to the moving support at an application angle of 0°.
- the application angle may be defined as the slope angle of the support at the point of impingement of the freely-falling and substantially vertical curtain measured as a declination from the horizontal in the direction of coating.
- the height of the curtain is restricted within the range of 10 to 100mm, preferably 15 to 50mm.
- US-A-4569863 may also increase the undesirable tendency of the plane of the curtain to deviate from the vertical, and bend backwards towards the hopper.
- the low viscosity layer which wets the support is delivered using a V-hopper, it faces in a downward direction.
- the establishment of flow on such a slide can be difficult in practice, and dripping of composition off the slide surface may occur.
- there is a component of gravity normal to the slide surface which is de-stabilizing and promotes the growth of waves on the layer as it travels down the slide.
- a low viscosity bottom layer also promotes "puddling" at the point where the freely-falling liquid curtain impinges on the moving support.
- a "heel” appears at the foot of the curtain. If the heel is sufficiently large, it may contain an eddy in which air bubbles and debris may become trapped, thereby generating a line or streak in the coating. A large heel can also oscillate, producing non-uniformities in the coating along and across the direction of web motion.
- the low viscosity bottom layer may have to be kept thin, even though a functional bottom layer may not be thin, and the curtain height low, though this adversely affects curtain stability and restricts the room beneath the hopper for other equipment, such as a start pan.
- a curtain coating process in which liquid material comprising two or more layers is coated on to a moving support, characterized in that the layer of liquid material adjacent the support has a viscosity which is less than 1mPas.
- the bottom layer of low viscosity liquid readily wets the support at high coating speeds and is applied with the curtain as the bottom layer of the liquid material being coated.
- the liquid material to comprise one or more layers of much higher viscosity, which, in the absence of the bottom layer, would not wet the support so readily and which would, therefore, be more difficult to coat without air-entrainment except at much lower speeds.
- the bottom layer may be any low viscosity liquid or solution compatible with the remainder of the liquid material. If the latter comprises aqueous coating compositions, as in the manufacture of photographic products, then the preferred liquid for the bottom layer is water to which small amounts of other substances, such as surfactants, hardeners, dyes etc., may be added as necessary.
- the advantages of high viscosity coating are combined with low viscosity wetting.
- High coating speeds are possible, and the coating speed at which air-entrainment occurs is less seriously affected by the total flow rate.
- the viscosities of the layers comprising the main bulk of the curtain may be chosen to suit factors other than wetting such as uniformity, product specification and the drying capacity of the coating track.
- the low viscosity bottom layer may also be very thin (between 0.5 and 10 ⁇ m, preferably between 1 and 5 ⁇ m). This minimizes the tendency towards puddling and lessens the necessity for the incorporation of non-functional materials.
- a further advantage of using a thin bottom layer is that diffusion into other layers occurs very rapidly, hence flow after coating is minimized.
- application angles greater than 0° may be used, preferably angles between 20° and 60°. This permits the beneficial use of high curtains whilst again minimizing the tendency towards puddling.
- a conventional multilayer curtain-coating slide hopper 10 is shown in Figure 1.
- One method of applying a freely-falling curtain 12 to a moving support 14 is shown, although the support is preferably backed by a precision roller (not shown).
- the hopper 10 is oriented relative to the moving support 14 so that the liquid layers flow down the slide surface 28 in a direction opposite to the coating direction.
- Layer 16 (which wets the support 14), although discharged from slot 18 uppermost on the slide surface 28, becomes the bottom layer of the coating as the curtain 12 impinges on the support 14.
- the other layers are discharged from respective slots 20, 22, 24 and 26, and are inverted in sequence from that of conventional curtain- or bead-coating.
- the support 14 is inclined to the horizontal so that the angle of application of the curtain to the support, ⁇ , is not 0°, that is, the curtain 12 is applied at a forward application angle.
- an exit slot arrangement is shown in which the bottom layer 16 is directly applied to the upstream side of the curtain as it leaves the hopper lip 36.
- the bottom layer 16 is discharged from an additional slot 30.
- This slot 30 is formed by inserting a sub-lip element 32 beneath the overhang 34 at the front of the hopper slide 28.
- the slot exit is positioned exactly at the hopper lip 36 as shown.
- the slot 38 can be recessed to form a short slide 40 (of 1cm or less) on the underside of the hopper lip 36.
- the hopper slide 28 is oriented conventionally in the coating direction as shown in Figure 4 so that the liquid leaving the slots 30, 38 becomes the bottom layer of the liquid material being coated.
- the curtain forming hopper is usually oriented in the direction of web travel and the bottom layer is discharged from the bottom slot (i.e. the slot nearest the lip). If this is used for a low viscosity bottom layer such as water, then the coatings are subject to longitudinal and transverse lines and streaks which are just as unacceptable as those seen in bead coating with the same arrangement. But, by reversing the orientation of the hopper and the order of the other layers, and discharging the bottom layer from the top slot (as discussed with reference to Figure 1), this problem may be removed.
- the hopper slide is inclined at an angle of less than 30° to the horizontal, and the flow rate of the low viscosity liquid layer discharged from the top slot is restricted to not more than one third of the sum of the flow rates of that layer and the high viscosity layer immediately beneath it.
- the slide surface 28 promotes levelling of any unevenness in the water layer, and the flow on the slide surface is sufficiently stable against waves and other manifestations of slide instability.
- curtain processes according to the present invention it is possible, therefore, by using curtain processes according to the present invention, to provide uniform multilayer coatings at higher speeds than previously attainable.
- curtain coating is employed, there is flexibility in the choice of flow rate and the viscosities for the layers forming the bulk of the coating.
- the coating method according to the invention is both product tolerant and easy to engineer with minimum changes in current technology.
- the high viscosity layers comprised an aqueous solution of gelatin having a viscosity of 74mPas at 44°C.
- the maximum coating speed of the gelatin layers alone was typically 324mmin ⁇ 1 at a total wet thickness of 100 ⁇ m, and 372mmin ⁇ 1 at a thickness of 27 ⁇ m. Higher coating speeds produced severe air-entrainment.
- a low viscosity bottom layer 1.1 ⁇ m in thickness, comprising water containing suitable surfactants, and having a surface tension of 21mNm ⁇ 1 and a viscosity of 0.61mPas at 44°C
- uniform coatings were achieved at speeds up to 596mmin ⁇ 1 with gelatin layers having a combined thickness of 45 ⁇ m.
- the thickness of the gelatin layers could be substantially increased by coating at a forward application angle. For example, at an application angle of +20°, uniform coatings of gelatin layers having a combined thickness of 9 ⁇ m were made at speeds of up to 600mmin ⁇ 1 with a low viscosity bottom layer of 4.3 ⁇ m.
- uniform coatings were obtainable with low viscosity bottom layers having thicknesses in the range 1 to 8 ⁇ m, although some successful coatings were made with bottom layers of only 0.5 ⁇ m.
- Table 1 Maximum coating speed (mmin ⁇ 1) Gelatin thickness ( ⁇ m) Bottom layer thickness ( ⁇ m) Curtain height (cm) Application angle (°) 324 100 none 10.2 0 372 27 none 10.2 0 596 45 1.1 10.2 0 600 96 4.3 10.2 20
- the high viscosity layers comprised an aqueous solution of gelatin having a viscosity of 64mPas at 45°C.
- the maximum coating speed of the gelatin layers alone was typically 376mmin ⁇ 1 at a total wet thickness of 44.3 ⁇ m. Higher coating speeds produced severe air-entrainment.
- the high viscosity layers comprised aqueous solutions of gelatin having viscosities of 67.1mPas and 63.2mPas at 42°C.
- the maximum practical coating speed of the gelatin layers alone was typically 313mmin ⁇ 1 at a total wet thickness of 179 ⁇ m. Higher coating speeds were prone to air-entrainment.
- a low viscosity bottom layer comprising water containing suitable surfactants, and having a surface tension of 19.3mNm ⁇ 1 and a viscosity of 0.63mPas at 42°C
- uniform coatings were achieved at speeds up to 738mmin ⁇ 1 with gelatin layers having a combined thickness of 76 ⁇ m and a bottom layer thickness of 2.6 ⁇ m.
- Coating speeds of up to 600mmin ⁇ 1 were achieved with a bottom layer thickness of 1.1 ⁇ m and gelatin layers having a total thickness of 93 ⁇ m.
- Table 3 Maximum coating speed (mmin ⁇ 1) Gelatin thickness ( ⁇ m) Bottom layer thickness ( ⁇ m) Curtain height (cm) Application angle (°) 313 179 none 25.4 45 738 76 2.6 25.4 45 600 93 1.1 25.4 45
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Claims (9)
- Vorhangbeschichtungsverfahren, wobei aus zwei oder mehreren Schichten bestehendes flüssiges Material (12, 16) auf einen bewegten Träger (14) aufgetragen wird, dadurch gekennzeichnet, daß die unmittelbar auf den Träger (14) aufzubringende flüssige Materialschicht (16) eine Viskosität aufweist, die geringer als 1 mPas. ist.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die unmittelbar auf den Träger (14) aufzubringende flüssige Materialschicht (16) in feuchtem Zustand eine Dicke zwischen 0,5 und 10 µm hat.
- Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Dicke des flüssigen Materials zwischen 1 und 5 µm liegt.
- Verfahren nach einem der Ansprüche 1 - 3, dadurch gekennzeichnet, daß das flüssige Material auf den bewegten Träger (14) unter einem Auftragswinkel (α) von über 0° aufgebracht wird.
- Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der Auftragswinkel (α) zwischen +20 und +60° liegt.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Schicht geringer Viskosität (16) als oberste Schicht auf einer Gleitfläche (28), die gegenüber der Horizontalen unter einem Winkel von weniger als 30° geneigt ist, aufgebracht wird, wobei die Fließgeschwindigkeit dieser obersten Schicht (16) nicht mehr als ein Drittel der Summe der Fließgeschwindigkeiten dieser obersten Schicht und der unmittelbar darunter befindlichen Schicht hoher Viskosität beträgt.
- Verfahren nach einem der Ansprüche 1 - 5, dadurch gekennzeichnet, daß die Schicht geringer Viskosität (16) direkt mit dem aus einem an der Gießkante (36) befindlichen Auslaßschlitz austretenden flüssigen Material in Kontakt gebracht wird.
- Verfahren nach einem der Ansprüche 1 - 5, dadurch gekennzeichnet, daß die Schicht von geringer Viskosität (16) direkt mit dem aus einem Auslaßschlitz (38) austretenden flüssigen Material in Kontakt gebracht wird, wobei der Auslaßschlitz so angeordnet ist, daß er an der Unterseite der Gießkante (36) eine kurze Gleitfläche (40) bildet.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die unmittelbar auf dem Träger (14) befindliche Schicht (16) aus flüssigem Material mit oberflächenaktiven Substanzen versetztes Wasser enthält.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9027675 | 1990-12-20 | ||
GB909027675A GB9027675D0 (en) | 1990-12-20 | 1990-12-20 | Coating processes |
PCT/EP1991/002416 WO1992011095A1 (en) | 1990-12-20 | 1991-12-16 | Coating processes |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0563148A1 EP0563148A1 (de) | 1993-10-06 |
EP0563148B1 true EP0563148B1 (de) | 1994-10-26 |
Family
ID=10687354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92901417A Expired - Lifetime EP0563148B1 (de) | 1990-12-20 | 1991-12-16 | Beschichtungsverfahren |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0563148B1 (de) |
JP (1) | JPH06503753A (de) |
DE (1) | DE69104850T2 (de) |
GB (1) | GB9027675D0 (de) |
WO (1) | WO1992011095A1 (de) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0807279B1 (de) * | 1995-02-02 | 1998-10-07 | Minnesota Mining And Manufacturing Company | Methode und vorrichtung zum auftragen einer dünnen,flüssigen,gestreiften beschichtung |
FR2734178B1 (fr) * | 1995-05-19 | 1997-06-20 | Kodak Pathe | Procede et appareil pour ameliorer l'uniformite d'un rideau liquide dans un systeme d'enduction au rideau |
US6368675B1 (en) | 2000-04-06 | 2002-04-09 | 3M Innovative Properties Company | Electrostatically assisted coating method and apparatus with focused electrode field |
US6475572B2 (en) | 2000-04-06 | 2002-11-05 | 3M Innovative Properties Company | Electrostatically assisted coating method with focused web-borne charges |
US6579569B2 (en) * | 2001-02-28 | 2003-06-17 | Eastman Kodak Company | Slide bead coating with a low viscosity carrier layer |
US7473333B2 (en) | 2002-04-12 | 2009-01-06 | Dow Global Technologies Inc. | Process for making coated paper or paperboard |
US7364774B2 (en) * | 2002-04-12 | 2008-04-29 | Dow Global Technologies Inc. | Method of producing a multilayer coated substrate having improved barrier properties |
DE102008014863A1 (de) * | 2008-03-18 | 2009-09-24 | Polytype Converting S.A. | Vorhangbeschichten mit Bend-Back-Reduzierung |
US20110014391A1 (en) * | 2008-03-26 | 2011-01-20 | Yapel Robert A | Methods of slide coating two or more fluids |
EP2268418A1 (de) * | 2008-03-26 | 2011-01-05 | 3M Innovative Properties Company | Verfahren zur gleitbeschichtung mit zwei oder mehr fluiden |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4569893A (en) * | 1983-08-29 | 1986-02-11 | Canon Kabushiki Kaisha | Amorphous matrix of silicon and germanium having controlled conductivity |
-
1990
- 1990-12-20 GB GB909027675A patent/GB9027675D0/en active Pending
-
1991
- 1991-12-16 WO PCT/EP1991/002416 patent/WO1992011095A1/en active IP Right Grant
- 1991-12-16 EP EP92901417A patent/EP0563148B1/de not_active Expired - Lifetime
- 1991-12-16 JP JP4501386A patent/JPH06503753A/ja active Pending
- 1991-12-16 DE DE69104850T patent/DE69104850T2/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE69104850D1 (de) | 1994-12-01 |
DE69104850T2 (de) | 1995-05-24 |
JPH06503753A (ja) | 1994-04-28 |
EP0563148A1 (de) | 1993-10-06 |
GB9027675D0 (en) | 1991-02-13 |
WO1992011095A1 (en) | 1992-07-09 |
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