CN1078998A - A kind of manufacture method that contains the high active detergent composition of succsinic acid - Google Patents
A kind of manufacture method that contains the high active detergent composition of succsinic acid Download PDFInfo
- Publication number
- CN1078998A CN1078998A CN 93104023 CN93104023A CN1078998A CN 1078998 A CN1078998 A CN 1078998A CN 93104023 CN93104023 CN 93104023 CN 93104023 A CN93104023 A CN 93104023A CN 1078998 A CN1078998 A CN 1078998A
- Authority
- CN
- China
- Prior art keywords
- water
- succsinic acid
- succinyl oxide
- composition
- less
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000002253 acid Substances 0.000 title claims abstract description 33
- 239000003599 detergent Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 abstract description 12
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 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
- 238000004140 cleaning Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- -1 tetradecyl succinyl oxide Chemical compound 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
- BAWFJGJZGIEFAR-NNYOXOHSSA-N NAD zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 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
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 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 kind of method of making spissated liquid detergent composition may further comprise the steps:
I) mix succinyl oxide, water and a kind of basic catalyst, wherein the ratio of succinyl oxide and water was not less than 4: 1;
The hydrolysis reaction of heat release is carried out in surge tank;
Iii) mix high reactivity, part neutral succsinic acid and other detergent ingredients.
Description
Succsinic acid and salt thereof are the principal component of cleaning composition, because of it has surfactivity, water-soluble and calcium magnesium adhesive capacity is used.
Succsinic acid can be simply with its corresponding acid anhydrides in-situ hydrolysis then the neutral method directly add in the solution or suspension of washing composition.
Usually, need at alkaline environment, under the existence of quite excessive water and solvent (as lower alcohol), hydrolysis reaction just can carry out fast and fully.
There is a kind of washing composition that makes more concentrated now, makes it to contain the trend of few moisture content.Yet begin it should be noted that along with the minimizing of hydrolysing step moisture content, speed of reaction reduces, acid anhydrides and solvent have produced bad side reaction, for example generate the ester class.
Various prior arts have related to the cleaning composition that contains succsinic acid, and these compositions generally will dilute when using.
049 No. 723 patent disclosures of GB-A-2 of announcing on December 31st, 1980 a kind of composition that contains part neutral succsinic acid and its a kind of salt, its pH value scope is that to contain weight percent be the part neutral succsinic acid of 3%-5% and the composition of its a kind of salt to the described liquid composition of 5.5-8.0.Its pH value scope is 5.5-8.0, and described liquid composition contains the part neutral succsinic acid that weight percent is 3%-5%.
028 No. 850 patents of EPO of announcing on May 5th, 1981 disclose a kind of succinate and a kind of low alkyl group benzene sulfonate of containing to strengthen the cleaning composition of its package stability.The original position neutralization of acid and acid anhydrides has been mentioned in this application, but does not mention its high-activity composition.
No. 1285582 patents of GB that on August 16th, 1972 announced disclose a kind of succsinic acid (can be obtained by acid anhydrides) of 25-90% and composition of 10-75% nonionogenic tenside of containing in fact.But the proper method of any manufacturing said composition is not disclosed.
But relate to manufacturing without any prior art and be applicable to that this problem of the spissated succinic acid solution of the height that further is processed into concentrated liquid detergent, people still need a kind of method that can make succinyl oxide effective hydrolysis under the condition of less water.
The invention provides a kind of hydrolysis succinyl oxide and produce the novel method of weight percent concentration, but this method original position is implemented continuously or off and on greater than 85% part neutral succinic acid solution.The present invention also provides a kind of flexible method of making concentrated liquid detergent.
Making the concentrated liquid detergent method for compositions comprises:
(A) succsinic acid
Wherein R is a kind of alkyl or alkenyl that contains 10-20 carbon
X, Y respectively do for oneself H, Na, K or alkanolamine
(B) water
It is characterized in that succinyl oxide, water and basic catalyst are through following operation:
ⅰ) with succinyl oxide and water to be not less than 4: 1 mixed, to start the hydrolysis reaction of heat release;
ⅱ) be contained in the surge tank;
ⅲ) mix with other composition of washing composition
The invention provides a kind of under the condition of excessive water seldom the hydrolysis succinyl oxide produce the method for succsinic acid.This process takes place in catalyzed reaction and part and in the presence of the alkali of succsinic acid.At first succinyl oxide, water and alkali are mixed available static mixer or the most handy high-shear mixer.Mixture storage is stored in the surge tank (but arranged type is handled continuously) to be finished substantially until the hydrolysis reaction of heat release.Resultant high reactivity, part neutral succsinic acid can be stored or be delivered directly to a dosing chamber or proceed the course of processing of concentrated liquid detergent.
Succinyl oxide:
Any general formula is
Succinyl oxide all be applicable to the present invention.The R base will be selected according to detergent formulation.A kind of suitable especially chain is:
R is CH
3-(CH
2) n-CH=CH-CH
- 2, n=8-10, or be its mixture.
Alkali:
The alkali that is suitable for comprises NaOH, KOH, and monoethanolamine and ammonia, with NaOH, KOH is advisable, and the ratio that oxyhydroxide exists is: should be less than or equal to 0.15 with required oxyhydroxide in the stoichiometric calculation.
Alkali can solution (typically being the aqueous solution of NaOH, KOH50%) form add in the succsinic acid, can add entry in addition and finish to guarantee following hydrolysis reaction:
But should limit the water inventory (comprising adding contained) of adding, to avoid diluting final composition and to avoid the reaction times long with aqueous solution alkali.The ratio that has now found that acid anhydrides and water should be not less than 4: the 1(weight ratio).
Hydrolytic process
Mixed reactant, the most handy high-shear mixer.The mixing tank that is fit to comprises the Pentar(trade name that German Bran and Luebbe provides); The Dispax(trade name that Janke and Kunel provide) and the mixing tank that provides of Karg and Fryma.Mixture is pumped into surge tank, and hydrolysis reaction carries out at this.Surge tank has preferably contained the succsinic acid of some amount, the hydrolytic process that itself also can accelerating mixture.Illustrated embodiments is: surge tank is continuous arranged type, and the mixture residence time therein enough makes hydrolytic process fully finish.Surge tank contains the mixture of succsinic acid, water, alkali and part neutral succinyl oxide always in the device of the present invention.Hydrolysis reaction is heat release, and temperature raises preferably to about 90 ℃.
The best mild stirring of surge tank is mixed to guarantee reactant.With regard to continuous process, surge tank should be designed to give 2-30 minute residence time, is preferably 5-20 minute.
High reactivity succsinic acid pH value according to aforementioned proportion and method manufacturing should be lower than 5.5, and when to be easy to act as dilution most be 0.5% the aqueous solution, pH value was about 4.5.In addition, the weight ratio of hydrolysis rear section neutral succsinic acid and water was not less than 6: 1.
Start and bolt down procedure:
When the above-mentioned continuation method of utilization, closing of process primarily is the supply that stops water and alkali in the mixture.The supply of succinyl oxide should extend to all water and the equal jet flow of alkali and cross mixing tank and just close then.This step is guaranteed no longer do not have hydrolytic action in the time spent mixing tank.The equal jet flow of best not every succsinic acid is crossed cushion dashpot.This means when beginning to supply succinyl oxide, water and alkali, still have small amount of acid " inoculation " hydrolysis reaction in the surge tank with the startup reaction.
During inoperation, cushion dashpot should keep high temperature (being generally 60-80 ℃) to solidify to prevent succsinic acid/acid anhydride mixture.
Further processing:
The high activity partially neutral succsinic acid of manufacturing of the present invention can add other detergent ingredients subsequently, comprises tensio-active agent, additive, and sequestrant, enzyme and softening clay are to finish the manufacturing of liquid detergent compositions.Provide an example below.
Preferably highly active succsinic acid is mixed with compatible detergent ingredients, with make its temperature reduce to 60 ℃ before lower alcohol mixes.Such short chain alcohol can be used in the final preparation for example comprising ethanol, propyl alcohol, propylene glycol and glycerol as solvent.If more than 60 ℃, succsinic acid and this solvent will produce bad by product such as ester.Can make a kind of stablizing below 60 ℃, pumpable intermediate composition, this intermediate composition preferably contain the 40%(weight ratio at least) part neutral succsinic acid.
Embodiment 1
Dodecyl/tetradecyl succinyl oxide 300Kg/ hour
Potassium hydroxide (50% aqueous solution) 20Kg/ hour
Water 40Kg/ hour
The chamber is turbid down to pump into Penttax KMF8(trade name according to top speed with succinyl oxide, potassium hydroxide and water with volume pump) in the high-shear mixer.
Mixture is directly delivered to the bottom of a surge tank from the outlet of mixing tank, the surge tank diameter is about 0.4 meter, and height is about 0.8 meter, and the residence time is about 17 minutes, and the surge tank temperature rises to 92 ℃ when the hydrolysis reaction of heat release carries out.
From the effusive reactant composition in buffering tank top be:
Dodecyl/tetradecyl succsinic acid (part neutralization) 90%
Water 10%
When dilution for 0.5%(weight) the aqueous solution time, pH value is 4.5.
In this example, the blending ratio of high reactivity, part neutral succsinic acid and non-ionic surface active is 1: 1.Tensio-active agent at room temperature adds, and the temperature of gained mixture is 55 ℃.Resulting mixture is a kind of stable, pumpable intermediate composition under this temperature.
Final product composition having is mixed by acid/surface active agent composition and following other washing composition, below all is weight percentage)
Succsinic acid/nonionogenic tenside 18
Ethanol and 1,2-propylene glycol 12
Sodium hydroxide 9
*
Alkylbenzene sulfonate 12
Sodium alkyl sulfate 2
Citric acid 7
Enzyme and DPN diphosphopyridine nucleotide
Other (froth suppressor, essence etc.) 1
Water adds to 100%
* can change concentration sodium hydroxide, so that final pH value is 8.
Claims (4)
1, a kind of manufacturing concentrated liquid detergent method for compositions, it comprises:
(A) succsinic acid
Wherein R is the alkyl or alkenyl that contains 10-20 carbon atom, each H naturally of X, Y, Na, K, alkanolamine
(B) water
It is characterized in that succinyl oxide, water and basic catalyst are through following operation:
I) with succinyl oxide and water to be not less than 4: 1 mixed, to start the hydrolysis reaction of heat release;
Ii) be contained in the surge tank;
Iii) mix with other composition of washing composition.
2, a kind of method of making the concentrated liquid detergent combination, it comprises
(A) succsinic acid
Wherein R is a kind of alkyl or alkenyl that contains 10-20 carbon atom; X, Y respectively do for oneself H, Na, K, alkanolamine
(B) water
It is characterized in that succinyl oxide, water and basic catalyst are through following operation:
ⅰ) with succinyl oxide and water to be not less than 4: 1 mixed, to start the hydrolysis reaction of heat release;
ⅱ) be contained in the surge tank, average retention time is no less than 5 minutes;
ⅲ) mix with other composition of washing composition.
3, claim 1 or 2 method, it is characterized in that: basic catalyst is sodium hydroxide or potassium hydroxide, and ratio is:
This oxyhydroxide: should be less than or equal to 0.15 with required oxyhydroxide in the stoichiometric calculation.
4, claim 1 or 2 method, wherein R is:
CH
3-（CH
2）
n-CH＝CH-CH
2-，n＝8-10
Or its mixture.
Applications Claiming Priority (2)
| 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 |
| EP92201034.3 | 1992-04-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1078998A true CN1078998A (en) | 1993-12-01 |
Family
ID=8210546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93104023 Pending CN1078998A (en) | 1992-04-10 | 1993-04-10 | A kind of manufacture method that contains the high active detergent composition of succsinic 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 |
| IE930279A1 (en) | 1993-10-20 |
| DE69214932T2 (en) | 1997-05-15 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |