CA2116217A1 - Process for treating materials adhesively secured together by an adhesive agent - Google Patents
Process for treating materials adhesively secured together by an adhesive agentInfo
- Publication number
- CA2116217A1 CA2116217A1 CA 2116217 CA2116217A CA2116217A1 CA 2116217 A1 CA2116217 A1 CA 2116217A1 CA 2116217 CA2116217 CA 2116217 CA 2116217 A CA2116217 A CA 2116217A CA 2116217 A1 CA2116217 A1 CA 2116217A1
- Authority
- CA
- Canada
- Prior art keywords
- materials
- another
- separated
- solvent
- 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.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
- B03B9/061—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse the refuse being industrial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B5/00—Washing granular, powdered or lumpy materials; Wet separating
- B03B5/28—Washing granular, powdered or lumpy materials; Wet separating by sink-float separation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Sustainable Development (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
ABSTRACT
The invention relates to a process for treating at least two materials which are secured together by an adhesive agent. Once such materials have served their purpose they are dumped or burned. The proposal is for a process by means of which one reduces the need for dumping and avoids the problems of incineration. This is achieved in that the adhesive is dissolved by a solvent which does not dissolve the materials themselves so that the adhesively secured materials can be separated and recycled on their own.
The invention relates to a process for treating at least two materials which are secured together by an adhesive agent. Once such materials have served their purpose they are dumped or burned. The proposal is for a process by means of which one reduces the need for dumping and avoids the problems of incineration. This is achieved in that the adhesive is dissolved by a solvent which does not dissolve the materials themselves so that the adhesively secured materials can be separated and recycled on their own.
Description
211~2~7 REPLACENENT PAGE
Process for Treatinq ~aterials Joined to One Anothèr By Adhesion Promoter The invention relates to a process for treating at least two materials joined to one another by adhesion promoter. Such materials can be, e.g., cable sheathings or parts of cable sheathings, in which essentially polyethylene and aluminum are ~oined to one another by an adhesion promoter. But, e.g., -aluminum blister packs or toothpaste tubes or similar things can also be involved here, in which, such as, e.g., in the case of aluminum blisters, essentially aluminum and plastics, such as polypropylene or PVC, are joined to one another by an adhesion promoter. The treatment of these materials, once they have fulfilled their purpose, now consists of disposing of them or burning them. If they are disposed of, a considerable need for a disposal site develops, and simultaneously it must be accepted that such materials do not decompose in the foreseeable future but remain intact. But if they are burned, a considerable ;~
expense is required to make harmless the harmful waste gases developing in this case. If the plastic portions are PVC, additional measures must be taken in the incinerator to neutralize the waste gas flows forming hydrochloric acid or to make it harmless in any other way.
Processes for separating compound materials are already known from the prior art. Such a process using a chlorinated organic solvent, e.g., methylene chloride, chloroform or carbon tetrachloride, and subceuqent azeotropic distillation is : : :
, 2 i! ._ 21 16 2 ~ ~
~ REPLACEMENT PAGE ~
: .
described in publication US-PS 4,543,346. A mixture of methanol and methylene chloride is used in the process to separate polyester and/or polyvinyl material disclosed anonymously 24520 in Research Disclosure, Vol. 245, p. 430. JP-A-60 212 434 tChemical Abstract, Vol. 104, No. 14, 111021 t3 also describes organic solvents or mixtures, but which are free of water.
Drawbacks of these previously known mixtures or pure ~;-solvents to be cited are relatively many plastics and dyes -~
dissolve in solvents and thus the solution must be worked up or replaced more often than desired.
Starting from this situation, the invention is based on the object to propose a process of the initially described type, with which the disposal site require~ent is at least reduced and the problems of combustion are avoided and the solvent mixture used is suitable for treating maximum amounts of compound material without being purified or replaced.
This object is achieved in a process of the initially described type in that the adhesion promoter is dissolved by an acetone-water mixture that does not dissolve the materials themselves and as a result the materials joined to one another are separated from one another. If the adhesion promoter is dissolved, the elements of the materials previously joined to one another are present individually and can be easily separated and recycled. But if they can be simply recycled, a disposal site is no longer necessary nor an incineration. Thus, the expenses for ~ ~ ' '! ' ' ~ ~ ` V ~
21~fi2~7 , REPLACEMENT PAGE
¦ a space for a disposal site are saved and the problems with the incinexation are avoided.
In an embodiment of the proce s, it i8 proposed to spray the crushed materials with the solvent or to immerse them in the solvent. Thiis is in each case a very simple method with respect to the course of the process to bring the solvent into contact with the adhesion promoter. Simultan-ously, the already dissolved adhesion promoter ~ 8 separated as a result also in a simple manner, so that the dissolution process is accelerated.
Preferably, the material to be separated is crushed, and the piece size of the crushed material i~ up to 10 cm2. As a result, a large surface is provided at the edges on which the ~olvent can reach the adhesion promoter more quickly. The solvsnt can then quickly penetrate the adhesion promoter from several sides and dissolve the latter. m e penetration depth, in this case, can be relatively small, nevertheless a quick and complete detaching can take place.
If, on the other hand, greater piece sizes are selected, the later separation of the components can possibly be facilitated.
Thus, for example, usual pharmaceutical agent blisters can also be processed without crushi~g.
The materials separated from one another by dissolution of the adhesion promoter can now be separated by material groups.
Thus, it i8 useful to separate,-for example, an aluminum portion from a plastic portion, but also to separate further the plastic ;
. ' ' ~' ~ 4 ; ~.
21~ ~2~ ~
~ REPLACEMENT PAGE
~ , portion once more into a PVC portion and "non-~VC portion." As a result, the further recycling is considera~ly simplified. In thifi case, it can be achieved, for example, in the float-sink process that plastic portions float and aluminum portions sink.
The floating plastic portions can then be skimmed off or screened out.
In addition, it is then also proposed that before the archimedean separation, the materials separated froM one another be removed from the solvent. on the one hand, the separation of plastics and metal is, of course, very easily possible by this above-mentioned archimedean separation. On the other hand, however, the plastic portions can also be separated from one another according to this principle. But in this case, only a separation of the plastics into PVC and non-PVC portions is important. Such a separation is possible problem-free because of the clearly different specific weights of the above-mentioned plastic groups.
Further possibilities of the material separation are, for example, the hydrocyclone technique or air separation.
It is advantageous, of course, to move the crushed materials and the solvent relative to one another. This can take place, for example, by simple stirring, but also by recycling the solvent. As a result, on the-one hand, the washing off of already dissolved portions of the adhesion promoter is - 2 ~ 7 REPLACEMENT PAGE
accelerated and shearing forces are exerted by the mechanical stress, which also support the detaching process.
In addition, it is also proposed that the materials separated from one another be purified by the solvent. This can take place, for example, by drying. The materials separated from one another are then present larg~ly residue-free f'or a further treatment.
The materials separated from one another can exhibit, on their part, still other co~tings, surfac0s or varnishings also on their respective exteriors. The elements of the materials separated from one another can thus be easily subjected to a further treatment to remove such layers.
The most important feature of the acetone-water mixture is that it dissolves out only the adhesion promoter, and plastic as well as aluminum remain largely unchanged.
Depending on the desired quality of the recovered products, it is possible that other chemical components, such as printing inks, varnishes and adhesion promoters, are detached especially from plastic and remain in the solvent to obtain the purest possible substances and thuc to achieve a high value added. The solvent must then be purified again from the dissolved substances by distillation either in the process itself or else by a certain number of process steps. In this case, the remaining low distillation residue is the sole residual substance accumulating in the process, which must be disposed of.
. ~
~::;~:
f, 21 1 6 21 i' REPLACEMENT PAGE
An acetone-water mixture, containing 1-20% by weight of water, has proven itself as a suitable solvent mixture. The solvent mixtures have the advantage that the detachment properties can be set pinpointed and variably depending on the mixing ratio. Acetone-containing ~olvent ~ixtures are further distinguished by rela~ively low toxicity as well as a good drying behavior (high vapor pressure of the acetone) of the PVC swollen with acetone.
It is possible with the process according to the invention, in a very simple way, to separate from one another materials that are especially flexible and joined to one another by an adhesion promoter by dissolving the adhesion promoter and thus to make recycling available. As a result, raw materials are saved, and the burden on incinerators and disposal sit~s is relieved.
. ` ~, 5 ~ ~
~ 7 211~2~7 REPLACEMENT PAGE
: :
Example 1 5 grams of pharmaceutical agent blisters are covered with 40 g of a solvent mixture made of 90% acetone and 10~ water in a 250 ml beaker and allowed to stand. After 80 minutes, the PVC has completely separated from the aluminum and the solvent mixture i~
then decanted. Aluminum and PVC are dried in a forced-air drying oven at 50C and then separated pure grade from one another by alr s aration.
: :~
Process for Treatinq ~aterials Joined to One Anothèr By Adhesion Promoter The invention relates to a process for treating at least two materials joined to one another by adhesion promoter. Such materials can be, e.g., cable sheathings or parts of cable sheathings, in which essentially polyethylene and aluminum are ~oined to one another by an adhesion promoter. But, e.g., -aluminum blister packs or toothpaste tubes or similar things can also be involved here, in which, such as, e.g., in the case of aluminum blisters, essentially aluminum and plastics, such as polypropylene or PVC, are joined to one another by an adhesion promoter. The treatment of these materials, once they have fulfilled their purpose, now consists of disposing of them or burning them. If they are disposed of, a considerable need for a disposal site develops, and simultaneously it must be accepted that such materials do not decompose in the foreseeable future but remain intact. But if they are burned, a considerable ;~
expense is required to make harmless the harmful waste gases developing in this case. If the plastic portions are PVC, additional measures must be taken in the incinerator to neutralize the waste gas flows forming hydrochloric acid or to make it harmless in any other way.
Processes for separating compound materials are already known from the prior art. Such a process using a chlorinated organic solvent, e.g., methylene chloride, chloroform or carbon tetrachloride, and subceuqent azeotropic distillation is : : :
, 2 i! ._ 21 16 2 ~ ~
~ REPLACEMENT PAGE ~
: .
described in publication US-PS 4,543,346. A mixture of methanol and methylene chloride is used in the process to separate polyester and/or polyvinyl material disclosed anonymously 24520 in Research Disclosure, Vol. 245, p. 430. JP-A-60 212 434 tChemical Abstract, Vol. 104, No. 14, 111021 t3 also describes organic solvents or mixtures, but which are free of water.
Drawbacks of these previously known mixtures or pure ~;-solvents to be cited are relatively many plastics and dyes -~
dissolve in solvents and thus the solution must be worked up or replaced more often than desired.
Starting from this situation, the invention is based on the object to propose a process of the initially described type, with which the disposal site require~ent is at least reduced and the problems of combustion are avoided and the solvent mixture used is suitable for treating maximum amounts of compound material without being purified or replaced.
This object is achieved in a process of the initially described type in that the adhesion promoter is dissolved by an acetone-water mixture that does not dissolve the materials themselves and as a result the materials joined to one another are separated from one another. If the adhesion promoter is dissolved, the elements of the materials previously joined to one another are present individually and can be easily separated and recycled. But if they can be simply recycled, a disposal site is no longer necessary nor an incineration. Thus, the expenses for ~ ~ ' '! ' ' ~ ~ ` V ~
21~fi2~7 , REPLACEMENT PAGE
¦ a space for a disposal site are saved and the problems with the incinexation are avoided.
In an embodiment of the proce s, it i8 proposed to spray the crushed materials with the solvent or to immerse them in the solvent. Thiis is in each case a very simple method with respect to the course of the process to bring the solvent into contact with the adhesion promoter. Simultan-ously, the already dissolved adhesion promoter ~ 8 separated as a result also in a simple manner, so that the dissolution process is accelerated.
Preferably, the material to be separated is crushed, and the piece size of the crushed material i~ up to 10 cm2. As a result, a large surface is provided at the edges on which the ~olvent can reach the adhesion promoter more quickly. The solvsnt can then quickly penetrate the adhesion promoter from several sides and dissolve the latter. m e penetration depth, in this case, can be relatively small, nevertheless a quick and complete detaching can take place.
If, on the other hand, greater piece sizes are selected, the later separation of the components can possibly be facilitated.
Thus, for example, usual pharmaceutical agent blisters can also be processed without crushi~g.
The materials separated from one another by dissolution of the adhesion promoter can now be separated by material groups.
Thus, it i8 useful to separate,-for example, an aluminum portion from a plastic portion, but also to separate further the plastic ;
. ' ' ~' ~ 4 ; ~.
21~ ~2~ ~
~ REPLACEMENT PAGE
~ , portion once more into a PVC portion and "non-~VC portion." As a result, the further recycling is considera~ly simplified. In thifi case, it can be achieved, for example, in the float-sink process that plastic portions float and aluminum portions sink.
The floating plastic portions can then be skimmed off or screened out.
In addition, it is then also proposed that before the archimedean separation, the materials separated froM one another be removed from the solvent. on the one hand, the separation of plastics and metal is, of course, very easily possible by this above-mentioned archimedean separation. On the other hand, however, the plastic portions can also be separated from one another according to this principle. But in this case, only a separation of the plastics into PVC and non-PVC portions is important. Such a separation is possible problem-free because of the clearly different specific weights of the above-mentioned plastic groups.
Further possibilities of the material separation are, for example, the hydrocyclone technique or air separation.
It is advantageous, of course, to move the crushed materials and the solvent relative to one another. This can take place, for example, by simple stirring, but also by recycling the solvent. As a result, on the-one hand, the washing off of already dissolved portions of the adhesion promoter is - 2 ~ 7 REPLACEMENT PAGE
accelerated and shearing forces are exerted by the mechanical stress, which also support the detaching process.
In addition, it is also proposed that the materials separated from one another be purified by the solvent. This can take place, for example, by drying. The materials separated from one another are then present larg~ly residue-free f'or a further treatment.
The materials separated from one another can exhibit, on their part, still other co~tings, surfac0s or varnishings also on their respective exteriors. The elements of the materials separated from one another can thus be easily subjected to a further treatment to remove such layers.
The most important feature of the acetone-water mixture is that it dissolves out only the adhesion promoter, and plastic as well as aluminum remain largely unchanged.
Depending on the desired quality of the recovered products, it is possible that other chemical components, such as printing inks, varnishes and adhesion promoters, are detached especially from plastic and remain in the solvent to obtain the purest possible substances and thuc to achieve a high value added. The solvent must then be purified again from the dissolved substances by distillation either in the process itself or else by a certain number of process steps. In this case, the remaining low distillation residue is the sole residual substance accumulating in the process, which must be disposed of.
. ~
~::;~:
f, 21 1 6 21 i' REPLACEMENT PAGE
An acetone-water mixture, containing 1-20% by weight of water, has proven itself as a suitable solvent mixture. The solvent mixtures have the advantage that the detachment properties can be set pinpointed and variably depending on the mixing ratio. Acetone-containing ~olvent ~ixtures are further distinguished by rela~ively low toxicity as well as a good drying behavior (high vapor pressure of the acetone) of the PVC swollen with acetone.
It is possible with the process according to the invention, in a very simple way, to separate from one another materials that are especially flexible and joined to one another by an adhesion promoter by dissolving the adhesion promoter and thus to make recycling available. As a result, raw materials are saved, and the burden on incinerators and disposal sit~s is relieved.
. ` ~, 5 ~ ~
~ 7 211~2~7 REPLACEMENT PAGE
: :
Example 1 5 grams of pharmaceutical agent blisters are covered with 40 g of a solvent mixture made of 90% acetone and 10~ water in a 250 ml beaker and allowed to stand. After 80 minutes, the PVC has completely separated from the aluminum and the solvent mixture i~
then decanted. Aluminum and PVC are dried in a forced-air drying oven at 50C and then separated pure grade from one another by alr s aration.
: :~
Claims (8)
1. Process for treating at least two materials joined to one another by adhesion promoter, characterized in that the adhesion promoter is dissolved by an acetone-water mixture, containing 1-20% water, that does not dissolve the materials themselves, and as a result, the materials joined to one another are separated from one another.
2. Process according to claim 1, wherein the materials are crushed before they are exposed to the solvent.
3. Process according to claims 1 and 2, wherein the crushed materials are sprayed with the solvent or immersed in the solvent.
4. Process according to one of claims 1-3, wherein materials separated from one another by dissolution of the adhesion promoter are separated by material groups.
5. Process according to claim 4, wherein the separation takes place in an archimedean manner.
6. Process according to claim 5, wherein the materials separated from one another are removed from the solvent before the archimedean separation and put in the liquid of suitable density.
7. Process according to one of claims 1-6, wherein the materials separated from one another are purified by the solvent.
REPLACEMENT PAGE
REPLACEMENT PAGE
8. Process according to one of claims 1-7, wherein in further treatments, the materials are separated from coatings or surfaces.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4127705.8 | 1991-08-23 | ||
| DE4127705A DE4127705A1 (en) | 1991-08-23 | 1991-08-23 | METHOD FOR TREATING MATERIALS ASSOCIATED BY ADMINISTRATORS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2116217A1 true CA2116217A1 (en) | 1993-03-04 |
Family
ID=6438779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2116217 Abandoned CA2116217A1 (en) | 1991-08-23 | 1992-08-04 | Process for treating materials adhesively secured together by an adhesive agent |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0599905B1 (en) |
| JP (1) | JPH07501348A (en) |
| AT (1) | ATE186314T1 (en) |
| CA (1) | CA2116217A1 (en) |
| DE (2) | DE4127705A1 (en) |
| ES (1) | ES2141724T3 (en) |
| MX (1) | MX9204850A (en) |
| WO (1) | WO1993004116A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4320000C1 (en) * | 1993-06-11 | 1994-05-11 | Schering Ag | Appts. to break binding of two or more materials - has reactor drum partially and intermittently immersed in solvent, used for recycling waste blister packaging for tablets |
| FR2730847B1 (en) * | 1995-02-16 | 1997-04-30 | Alcatel Cable | METHOD AND DEVICE FOR RECOVERING ELECTRICAL TRANSPORT CABLE COMPONENTS |
| DE10207591A1 (en) * | 2002-02-22 | 2003-09-04 | Kuraray Specialities Europe | Process for recycling coated plastic moldings |
| DE102013006749A1 (en) | 2013-04-10 | 2014-10-16 | Kunststoffrecycling CKT GmbH & Co. KG | Process for separating aluminum-butyl compounds |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4543364A (en) * | 1984-12-13 | 1985-09-24 | The Dow Chemical Company | Recovery of polyethylene terephthalate (PET) |
| DE3831023A1 (en) * | 1988-09-12 | 1990-03-15 | Herbold Gmbh Maschinenfabrik | METHOD FOR PROCESSING AND REUSING POLLUTED PLASTIC PRODUCTS |
-
1991
- 1991-08-23 DE DE4127705A patent/DE4127705A1/en not_active Withdrawn
-
1992
- 1992-08-04 JP JP4511658A patent/JPH07501348A/en active Pending
- 1992-08-04 CA CA 2116217 patent/CA2116217A1/en not_active Abandoned
- 1992-08-04 ES ES92917082T patent/ES2141724T3/en not_active Expired - Lifetime
- 1992-08-04 EP EP19920917082 patent/EP0599905B1/en not_active Expired - Lifetime
- 1992-08-04 AT AT92917082T patent/ATE186314T1/en not_active IP Right Cessation
- 1992-08-04 DE DE59209767T patent/DE59209767D1/en not_active Expired - Fee Related
- 1992-08-04 WO PCT/EP1992/001767 patent/WO1993004116A1/en active IP Right Grant
- 1992-08-21 MX MX9204850A patent/MX9204850A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO1993004116A1 (en) | 1993-03-04 |
| JPH07501348A (en) | 1995-02-09 |
| EP0599905A1 (en) | 1994-06-08 |
| ATE186314T1 (en) | 1999-11-15 |
| DE59209767D1 (en) | 1999-12-09 |
| EP0599905B1 (en) | 1999-11-03 |
| DE4127705A1 (en) | 1993-02-25 |
| MX9204850A (en) | 1993-04-01 |
| ES2141724T3 (en) | 2000-04-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |