IE930279A1 - Process for manufacture of a high active detergent¹composition containing succinic acid - Google Patents
Process for manufacture of a high active detergent¹composition containing succinic acidInfo
- Publication number
- IE930279A1 IE930279A1 IE930279A IE930279A IE930279A1 IE 930279 A1 IE930279 A1 IE 930279A1 IE 930279 A IE930279 A IE 930279A IE 930279 A IE930279 A IE 930279A IE 930279 A1 IE930279 A1 IE 930279A1
- Authority
- IE
- Ireland
- Prior art keywords
- water
- succinic acid
- buffer tank
- succinic anhydride
- succinic
- Prior art date
Links
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000001384 succinic acid Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003599 detergent Substances 0.000 claims abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 21
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 18
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000004615 ingredient Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 description 12
- 239000003513 alkali Substances 0.000 description 9
- 238000010924 continuous production Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- MWTDCUHMQIAYDT-UHFFFAOYSA-N 2-tetradecylbutanedioic acid Chemical compound CCCCCCCCCCCCCCC(C(O)=O)CC(O)=O MWTDCUHMQIAYDT-UHFFFAOYSA-N 0.000 description 1
- BZECBEKZECEQRI-UHFFFAOYSA-N 3-tetradecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCC1CC(=O)OC1=O BZECBEKZECEQRI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for making a concentrated liquid detergent composition comprising the steps of : i) mixing succinic anhydride, water and an alkaline catalyst, wherein the ratio of succinic anhydride to water is at least 4:1, ii) allowing an exothermic hydrolysis reaction to take place in a buffer tank ,and iii) mixing the resulting highly active, partly neutralised succinic acid with other detergent ingredients l
Description
A High Active Detergent Composition Containing Succinic Acid
Background
Succinic acid and its salts are known ingredients of detergent compositions. They are used for their surface active and hydrotropic properties as well as calcium and magnesium binding capacity.
They are easily processed directly into a detergent liquid or slurry by in situ hydrolysis of the corresponding succinic anhydride, and subsequent neutralisation.
This hydrolysis typically requires a considerable excess of water and the presence of solvents (eg. lower alcohols), in an alkaline environment in order to make the hydrolysis reaction move rapidly to completion.
There is now a trend to more concentrated detergents containing very little water. As the water level is decreased in the hydrolysis step the rate of reaction decreases and undesirable side reactions between the anhydride and the solvents forming, for example esters, start
IQ to become significant.
Various prior art has dealt with detergent compositions containing succinic acid. These applications are in general, dilute.
GB-A-2 049 723, published December 31, 1980, discloses a 15 composition containing partly neutralised succinic acid with one of its salts such that the pH is in the range from 5.5 to 8.0. It describes liquid compositions containing 3%-50% by weight of the partly neutralised succinic acid.
EP 0 028 850, published May 5, 1981, discloses a liquid 20 detergent composition containing succinates and a low level of alkyl benzene sulphonate, for improved storage stability. The application mentions the neutralisation of the acid or anhydride in situ, but there is no mention of high active compositions.
GB 1 285 582, published August 16, 1972, discloses a composition substantially containing 25-90% succinic acid, which may be derived from the anhydride, and 10-75% nonionic surfactant. There is no disclosure of a suitable process for making such compositions.
3θ However, none of the prior art deals with the problem of making a highly concentrated solution of succinic acid which is suitable for further processing into a concentrated liquid detergent. There is a need for a process of hydrolysis of succinic anhydrides which can be carried out effectively in an environment in which very little water is present.
The present invention provides a new process for hydrolysis of the succinic anhydride to yield a solution of at least 85% by weight of partly neutralised succinic acid. The process can be carried out in situ, continuously or batch-wise, and offers a flexible process for making a concentrated liquid detergent.
Summary of the Invention
A process for making a concentrated liquid detergent composition which comprises (A) succinic acid R - CH - CH2
I 1
COOX COOY where R is an alk(en)yl moity with C10-C20 X,Y are independently H,Na,K, alkanolamine and (B) water, characterised in that succinic anhydride, water and an alkaline catalyst are:
i) mixed in a ratio of succinic anhydride to water (B) of not less than 4:1 in order to start an exothermic hydrolysis reaction 9n ii) held in a buffer tank, and iii) mixed with other detergent ingredients.
Detailed Description of the Invention
The present invention provides a process for the hydrolysis of succinic anhydride to succinic acid in the presence of a small excess of water. The process takes place in the presence of an alkali which catalyses the reaction and partly neutralises the succinic acid.
Firstly the succinic anhydride, water and alkali are intimately mixed, either by passing through static mixers, or, preferably, in a high shear mixer. The mixture is then stored in a buffer tank (which may be in-line in a continuous process) until the exothermic hydrolysis reaction is substantially completed. The resulting high active partly neutralised succinic acid may then be stored or transferred directly into a batch tank or continuous process for further processing to a concentrated liquid detergent.
THE SUCCINIC ANHYDRIDE
Any succinic anhydride of the general formula:
R - CH - CO
I >
ch2- co is suitable for use in the present invention. The choice of R 20 will be made by the detergent formulator.
A particularly preferred chain is when:
R is CH3-(CH2)n-CH=CH-CH2- and n=8-10 or mixtures thereof.
THE ALKALI
Any suitable alkali may be used including sodium 25 hydroxide, potassium hydroxide, monoethanolamine and ammonia.
Preferred are sodium hydroxide and potassium hydroxide. The ratio of hydroxide present : hydroxide needed for stoichiometric neutralisation, should be 0.15 or less.
The alkali may be added to the succinic acid in the form of a solution (typically 50% aqueous solution of either sodium or potassium hydroxide). Extra water may also be added in order to ensure complete hydrolysis by the following reaction:
R - CH - CO R - CH - COOH
I z 0 + h2o -► |
CH2- co CH2 - COOH
However total water which is present (both added and 10 with the aqueous alkali) should be limited in order to avoid diluting the final composition, and to avoid an excessively long reaction time. It has been found that the ratio of succinic anhydride to water should be not less than 4:1 by weight.
THE HYDROLYSIS PROCESS
The reactants are brought together and mixed, preferably in a high shear mixer. Suitable mixers include Pentax (trade name), supplied by Bran and Luebbe, Germany; Dispax (trade name), supplied by Janke and Kunkel, and mixers supplied by
Karg and Fryma. This mixture is then pumped into buffer tank where the hydrolysis reaction will proceed. Preferably the buffer tank already contains an amount of succinic acid which itself promotes rapid hydrolysis of the mixture. In a most preferred embodiment, the buffer tank is in-line in a continuous process and gives a residence time sufficient for hydrolysis to be substantially completed. In this embodiment of the invention the buffer tank contains at all times a mixture of succinic acid, water, alkali and partly neutralised succinic anhydride. The hydrolysis reaction is exothermic, and the temperature rises, preferably to about 90°C.
The buffer tank should be gently stirred or agitated in order to keep the reactants mixed. In the case of a continuous process the buffer tank should be designed to give a residence time of from 2 to 30 minutes, preferably from 5 to 20 minutes.
The high active succinic acid made according to the above ratios and process has a pH of less than 5.5, preferably about pH4.5 when it is diluted to a 0.5% aqueous solution. Furthermore, after hydrolysis the ratio of partly neutralised succinic acid to water will not be less than about 6:1 by weight.
START-UP AND SHUT-DOWN PROCEDURE
When a continuous process is in use as described hereinabove, the process is shut-down by firstly closing the supply of water and alkali to the mixer. The supply of succinic anhydride is allowed to continue until all water and alkali have been flushed through the mixer then this supply
2Q is also shut-down. This procedure ensures that no hydrolysis continues in the mixer whilst not in use.
Preferably not all of the succinic acid is flushed through the buffer tank. This means that when the supplies of succinic anhydride, water and alkali are switched on for start-up, there is still some acid in the buffer tank to seed the hydrolysis reaction.
During the period that the process is not operating, the buffer tank should be maintained at an elevated temperature (typically 60-80°C) in order to prevent solidification of the succinic acid/anhydride mix.
FURTHER PROCESSING
The highly active, partly neutralised succinic acid made by the present invention may subsequently be added to other detergent ingredients including surfactants, builders, 5 chelants, enzymes and softening clays, in order to make a finished liquid detergent composition. An example of this is given hereinbelow.
Preferably the high active succinic acid is mixed with compatible detergent ingredients which allow its temperature to be reduced below 60°C, before it is mixed with lower alcohols. Such short chain alcohols may be present in the final formulation as solvents, examples include ethanol, propanol, propane diol and glycerol. If the succinic acid and such solvents are present at temperatures in excess of 60*C, then undesirable side products such as esters may be formed. An intermediate composition may be formed which is a stable, pumpable liquid at temperatures below 60°C. This intermediate composition preferably consists of at least 40% by weight of partly neutralised succinic acid.
Example 1
Dodecyl/tetradecyl succinic anhydride Potassium hydroxide (50% aq. soln.) Water
300 kg/hour 20 kg/hour 40 kg/hour
Succinic anhydride, potassium hydroxide solution and water are supplied at ambient temperature from metering pumps at the rates described above, into a Pentax KMF8 (Trade Mark) high shear mixer.
This mixture is transferred directly from the outlet port of this mixer into the bottom of a buffer tank. The buffer tank has a diameter of about 0.4m and a height of about 0.8m, giving a residence time of about 17 minutes. The temperature in the buffer tank rises to 92'C as the exothermic hydrolysis reaction takes place.
The reacted material leaving from the top of the buffer tank has a composition of:
Dodecyl/tetradecyl succinic acid (partly neutralised) 90% Water 10% and, when diluted to give a aqueous solution of 0.5% by weight, has a pH of 4.5.
In this example, the high active, partly neutralised succinic acid is mixed with a nonionic surfactant in the ratio of 1:1. The surfactant is supplied at ambient temperature and the
IQ resulting mix has a temperature of 55’C. The resulting mixture is a stable, pumpable intermediate composition at this temperature.
A finished composition is made by mixing the acid/ surfactant mixture with other detergent ingredients as follows (all given as % by weight):
Succinic acid/nonionic surfactant 18
Ethanol & 1,2 propane diol 12
Sodium hydroxide 9*
Alkyl benzene sulphonic acid 12
Sodium alkyl sulphate 2
Citric acid 7
Enzymes and minors 1
Miscellaneous (suds suppressor, perfume etc.)1 Water to balance to 100% *Level of sodium hydroxide may be varied in order to give finished pH8
Claims (6)
1. A process for making a concentrated liquid detergent composition which comprises (A) succinic acid R - CH - CH
2. Coox COOY where R is an alk(en)yl moity with C10-C20 X,Y are independently H,Na,K, alkanolamine and (B) water, characterised in that succinic anhydride, water and an alkaline catalyst are: i) mixed in a ratio of succinic anhydride to water (B) of not less than 4:1 in order to start an exothermic hydrolysis reaction ii) held in a buffer tank, and iii) mixed with other detergent ingredients. A process according to claim 1 which is continuous and in which the reactants have a residence time of at least 5 minutes in the buffer tank.
3. A process according to claim 1 or 2 characterised in that the alkaline catalyst is sodium hydroxide or potassium hydroxide, in a ratio of: hydroxide present : hydroxide needed for stoichiometric neutralisation, of 0.15 or less.
4. A process according to any of claims 1 to 3 where: R is CH3-(CH2)n-CH=CH-CH2- and n=8-10 or mixtures thereof.
5. A process according to claim 1 for making a concentrated liquid detergent composition, substantially as hereinbefore described and exemplified.
6. A concentrated liquid detergent composition, whenever made by a process claimed in a preceding claim.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP19920201034 EP0564719B1 (en) | 1992-04-10 | 1992-04-10 | Process for manufacture of a high active detergent composition containing succinic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IE930279A1 true IE930279A1 (en) | 1993-10-20 |
Family
ID=8210546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE930279A IE930279A1 (en) | 1992-04-10 | 1993-04-08 | Process for manufacture of a high active detergent¹composition containing succinic acid |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0564719B1 (en) |
| JP (1) | JPH07505668A (en) |
| CN (1) | CN1078998A (en) |
| CA (1) | CA2117746C (en) |
| DE (1) | DE69214932T2 (en) |
| ES (1) | ES2093766T3 (en) |
| IE (1) | IE930279A1 (en) |
| MX (1) | MX9302049A (en) |
| WO (1) | WO1993021290A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU130040A1 (en) * | 1959-11-28 | 1959-11-30 | С.В. Леви | The method of obtaining alkenyl succinic acid |
| JPS5850679B2 (en) * | 1979-04-20 | 1983-11-11 | 花王株式会社 | cleaning composition |
| EP0028850B1 (en) * | 1979-11-09 | 1983-04-20 | Unilever N.V. | Liquid detergent composition |
-
1992
- 1992-04-10 EP EP19920201034 patent/EP0564719B1/en not_active Expired - Lifetime
- 1992-04-10 DE DE1992614932 patent/DE69214932T2/en not_active Expired - Fee Related
- 1992-04-10 ES ES92201034T patent/ES2093766T3/en not_active Expired - Lifetime
-
1993
- 1993-03-29 JP JP5518371A patent/JPH07505668A/en active Pending
- 1993-03-29 WO PCT/US1993/002943 patent/WO1993021290A1/en active Application Filing
- 1993-03-29 CA CA002117746A patent/CA2117746C/en not_active Expired - Fee Related
- 1993-04-07 MX MX9302049A patent/MX9302049A/en unknown
- 1993-04-08 IE IE930279A patent/IE930279A1/en not_active Application Discontinuation
- 1993-04-10 CN CN 93104023 patent/CN1078998A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE69214932D1 (en) | 1996-12-05 |
| MX9302049A (en) | 1994-07-29 |
| CA2117746A1 (en) | 1993-10-28 |
| CA2117746C (en) | 1999-04-27 |
| ES2093766T3 (en) | 1997-01-01 |
| EP0564719A1 (en) | 1993-10-13 |
| EP0564719B1 (en) | 1996-10-30 |
| WO1993021290A1 (en) | 1993-10-28 |
| JPH07505668A (en) | 1995-06-22 |
| CN1078998A (en) | 1993-12-01 |
| DE69214932T2 (en) | 1997-05-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FA9A | Application withdrawn section 33(1) |