EP0618854A1 - Verfahren zur herstellung von span- oder faserplatten - Google Patents
Verfahren zur herstellung von span- oder faserplattenInfo
- Publication number
- EP0618854A1 EP0618854A1 EP93919235A EP93919235A EP0618854A1 EP 0618854 A1 EP0618854 A1 EP 0618854A1 EP 93919235 A EP93919235 A EP 93919235A EP 93919235 A EP93919235 A EP 93919235A EP 0618854 A1 EP0618854 A1 EP 0618854A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- binder
- fiberboard
- chipboard
- nco groups
- 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- Withdrawn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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000835 fiber Substances 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title claims abstract description 8
- 239000002245 particle Substances 0.000 title claims description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 239000011094 fiberboard Substances 0.000 claims abstract description 35
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 239000011093 chipboard Substances 0.000 claims abstract description 21
- 238000003825 pressing Methods 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000001302 tertiary amino group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 150000003512 tertiary amines Chemical class 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010016275 Fear Diseases 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- -1 aliphatic amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
Definitions
- the invention relates to a process for the production of chipboard or fiberboard, in which lignose-cellulose-containing chips or fibers are glued with a binder containing NCO groups, shaped into a mat and pressed under the action of heat to the chipboard or fiberboard.
- a particle board or fiber board bonded with a binder containing NCO groups advantageously has excellent moisture resistance and no formaldehyde emission resulting from binder. It turns out to be disadvantageous, however, that binders containing NCO groups have a lower adhesive effect than other binders, which also has to be activated by comparatively high temperatures and long pressing times when the chipboard or fiberboard is hot-pressed.
- the invention is therefore based on the object of further developing a method of the type described at the outset such that stable chipboard or fiberboard can be obtained with a lower binder content and / or that the pressing times can be shortened and / or that the pressing temperatures can be reduced.
- REPLACEMENT LEAF reactive groups in that they are chemically incorporated into the polyurethane foam and thus inactivated after the polyurethane reaction has been carried out.
- tertiary amines are not known as catalysts which accelerate the hardening of the binder during hot pressing.
- the US-PS 47 72 442 discloses a method of the type described above for the production of chipboard or fiberboard using a binder containing NCO groups, wherein a fatty substance is used as a release agent for the hot-pressed chipboard or fiberboard from the press plates of the hot press becomes.
- the detaching aid is applied in an aqueous emulsion, to which triethanolamine is added as an emulsifier.
- US Pat. No. 4,772,442 does not report any catalytic effects of triethanolamine with regard to the binder.
- a binder additive for the production of aminoplast resin-bound chipboard and fibreboard is known.
- the addition of the binder is said to improve the flame-retardant properties of the particle board or fiberboard without impairing its stability.
- constituents of the binder additive are, for example, a water-soluble amine or polyamine and a further water-soluble compound with at least one organically bound hydroxyl group or a liquid alcohol. It is also possible to add isocyanate as the binder component containing NCO groups to the binder consisting essentially of aminoplast resin.
- a person skilled in the art from DE-OS 34 38 735 cannot infer a catalytic effect of the amines or polyamines as such on the hardening of the binder. In particular, this does not result in a direct link between the amines and binders containing NCO groups, insofar as they are used solely as binders.
- the object of the invention is achieved by adding a catalyst which accelerates a polyurethane reaction to the binder containing NCO groups.
- various known catalysts which accelerate the polyurethane reaction in the production of polyurethane foams are suitable as an additive to the binder containing NCO groups used in the production of chipboard or fiberboard as reactive groups.
- the maintenance of the adhesive effect of the binder during the open storage period of the glued chips or fibers, which was previously regarded as critical, has proven to be largely problem-free.
- the binder can be applied to the chips or fibers in an aqueous suspension and / or emulsion, the catalyst being dissolved in the water.
- a water-soluble catalyst has the particular advantage that it can be distributed finely and uniformly in the binder. Lower amounts of the generally high-priced catalyst are sufficient than if the catalyst is water-insoluble and has to be dispersed in the water.
- the application of the binder containing NCO groups to the chips or fibers in the form of an aqueous suspension or emulsion is a common method in the production of chipboard and fiberboard. Likewise, the use of suspensions or emulsions is up
- the catalyst would have to be added to the binder via the toluene.
- the catalyst can have a hydroxyl group.
- the hydroxyl group of the catalyst is u. a. an indication of the water solubility of the catalyst.
- the catalyst can be chemically incorporated into the particle board or fiberboard during pressing.
- a catalyst firmly integrated after hot pressing is chemically activated. This is of particular importance since the catalysts which accelerate a polyurethane reaction have almost completely irritating, in some cases even toxic, properties in the unbound state. However, this irritating or even toxic effect no longer comes into play after the catalytic converter has been chemically installed in the particle board or fiberboard.
- the catalyst can be a tertiary amine.
- Amines are the best known group of catalysts which accelerate a polyurethane reaction. It is precisely the tertiary amines which are found to be advantageous in the production of particleboard and fiberboard using a binder containing NCO groups. When the glued chips are hot-pressed, they are firmly built into the resulting bonds and thereby chemically inactivated if they have an NCO-reactive group. Secondary and primary amines are always bound in the binder containing NCO groups by means of an NH / NCO reaction.
- the ether and aliphatic amines appear particularly suitable for carrying out the invention.
- binding agents can be eliminated by using a blocked catalyst which can be activated by supplying heat.
- a blocked catalyst which can be activated by supplying heat.
- Such catalysts are also known per se to those skilled in the art for accelerating a polyurethane reaction.
- a blocked catalyst which can be activated by the supply of heat can be achieved particularly simply by masking the catalyst with an acid.
- the resulting reaction product with the catalyst disintegrates above the temperature which is characteristic of the open storage time, but is in the lower range of the temperatures reached during the hot pressing of the chips or fibers.
- the catalyst can be used in a concentration between 2.0 and 0.001% by weight, based on the binder. In particular, concentrations between 0.5 and 0.005% by weight have proven to be suitable in the production of particle board and fiberboard using a binder containing NCO groups.
- concentrations between 0.5 and 0.005% by weight have proven to be suitable in the production of particle board and fiberboard using a binder containing NCO groups.
- the low proportions in which the catalyst accelerating a polyurethane reaction is sufficient to ignite the desired effect make it clear that, although it may be chemically incorporated into the reaction product, it is a true catalyst in the classic sense and is not an actual reaction partner.
- the low concentrations required are also a prerequisite for the production of particle board and fiberboard using the catalyst to have economic advantages. It would be nonsensical if the achievable pressing time reduction of about 30% or the achievable pressing temperature reduction of about 30 K or the binder saving were more or completely offset by an increased financial use for the catalyst.
- the binder can be a polyisocyanate, in particular polymeric 4,4'-methylene diisocyanate (PMDI).
- PMDI polymeric 4,4'-methylene diisocyanate
- NCO group-containing binder is in itself unchanged composition suitable for the production of particle board and fiberboard using a catalyst which accelerates a polyurethane reaction.
- a commercially available catalyst which accelerated a polyurethane reaction was added to the binder.
- the binder a polymeric 4-methylene diisocyanate (PMDI)
- PMDI polymeric 4-methylene diisocyanate
- the ratio of the proportions of water and PMDI was 1: 1.
- the binder was a commercially available, unmodified polyisocyanate (Desmodur 1520 A, Bayer Leverkusen AG).
- the catalyst which accelerated a polyurethane reaction was a water-soluble, tertiary amine (TEXACAT-DPA, Texaco-Chemical GmbH) and was added to the water content of the binder emulsion in a concentration which corresponded to 0.5% by weight of the PMDI content of the emulsion.
- the binder emulsion thus enriched was used to glue chips in the usual way. After the formation of a mat from the chips and the pressing of the mat into a chipboard under the influence of heat, the quality of the resulting chipboard was examined as a function of the pressing time. Even when the pressing time falls below the usual pressing time by approx. 25%, no drops in quality impairing the commercial ability of the particle board have been observed. Instead, there were improved mechanical properties of the chipboard assessed, which still occurred significantly below the usual pressing time. With regard to the open storage time, up to 30
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4229396 | 1992-09-03 | ||
| DE19924229396 DE4229396C2 (de) | 1992-09-03 | 1992-09-03 | Verfahren zur Herstellung von Span- oder Faserplatten |
| PCT/EP1993/002358 WO1994005475A1 (de) | 1992-09-03 | 1993-09-01 | Verfahren zur herstellung von span- oder faserplatten |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0618854A1 true EP0618854A1 (de) | 1994-10-12 |
Family
ID=6467120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93919235A Withdrawn EP0618854A1 (de) | 1992-09-03 | 1993-09-01 | Verfahren zur herstellung von span- oder faserplatten |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0618854A1 (de) |
| CA (1) | CA2122368A1 (de) |
| DE (1) | DE4229396C2 (de) |
| WO (1) | WO1994005475A1 (de) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9417502D0 (en) * | 1994-08-31 | 1994-10-19 | Smith & Nephew | Water curable compositions |
| DE19646879A1 (de) * | 1995-11-23 | 1997-05-28 | Henkel Kgaa | Einkomponenten-Polyurethan-Reaktionsklebstoff |
| DE19603330C1 (de) * | 1996-01-31 | 1997-06-05 | Bayer Ag | Verfahren zur Herstellung von Holzwerkstoffen mit Polyisocyanat-Bindemitteln unter Mitverwendung von latenten, wärmeaktivierbaren Katalysatoren |
| US6124278A (en) * | 1998-04-03 | 2000-09-26 | The Regents Of The University Of California | Acylbenzoxazines for enhancing synaptic response |
| WO2000046306A1 (en) * | 1999-02-08 | 2000-08-10 | Sappi Limited | Timber process and product |
| DE10047485A1 (de) | 2000-09-26 | 2002-04-11 | Bayer Ag | Lagerstabile latente Katalysatoren enthaltende Isocyanat-Bindemittel |
| US9631058B2 (en) | 2013-09-03 | 2017-04-25 | The Willamette Valley Company | Composite wood particulate products with aldehyde-free adhesives and method for making same |
| DE102015210569A1 (de) * | 2015-06-09 | 2016-12-15 | Georg-August-Universität Göttingen Stiftung Öffentlichen Rechts | Erhöhung der Reaktivität von Isocyanatklebstoffen durch Amin-/Ammoniumverbindungen |
| EP4015173B1 (de) | 2020-12-21 | 2023-09-06 | Georg-August-Universität Göttingen | Erhöhung der reaktivität von isocyanatklebstoffen durch ammoniumverbindungen |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA794435A (en) * | 1965-11-27 | 1968-09-10 | A. Sharp John | Particle board prepared with a polyisocyanate-pine resin extract adhesive |
| GB1309075A (en) * | 1969-04-02 | 1973-03-07 | Gen Foam Products | Production of moulded articles and board |
| US4101466A (en) * | 1976-12-01 | 1978-07-18 | Texaco Development Corp. | Bis (dimethylaminopropyl)-amine derivatives as polyurethane catalysts |
| DE2711958B2 (de) * | 1977-03-18 | 1981-08-13 | Bayer Ag, 5090 Leverkusen | Binde- oder Imprägnierungsmittel für lignocellulosehaltige Materialien |
| GB2076414A (en) * | 1980-04-30 | 1981-12-02 | Ici Ltd | Isocyanate reactions |
| DE3328662A1 (de) * | 1983-08-09 | 1985-02-21 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von presswerkstoffen mit polyisocyanat-bindemitteln unter mitverwendung von latenten, waermeaktivierbaren katalysatoren |
| US4609513A (en) * | 1984-08-15 | 1986-09-02 | Jim Walter Research Corp. | Binder composition for manufacture of fiberboard |
| DE4200324A1 (de) * | 1992-01-09 | 1993-07-15 | Bayer Ag | Verwendung eines isocyanatgruppen aufweisenden sumpfprodukts als bindemittel bei der verpressung von substraten zur herstellung von presswerkstoffen |
-
1992
- 1992-09-03 DE DE19924229396 patent/DE4229396C2/de not_active Expired - Lifetime
-
1993
- 1993-09-01 CA CA 2122368 patent/CA2122368A1/en not_active Abandoned
- 1993-09-01 WO PCT/EP1993/002358 patent/WO1994005475A1/de not_active Ceased
- 1993-09-01 EP EP93919235A patent/EP0618854A1/de not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9405475A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2122368A1 (en) | 1994-03-17 |
| WO1994005475A1 (de) | 1994-03-17 |
| DE4229396C2 (de) | 1997-06-05 |
| DE4229396A1 (de) | 1994-03-10 |
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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 |
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