EP0340371B1 - Bleaching composition containing alkaline hypochlorite and process for its manufacture - Google Patents
Bleaching composition containing alkaline hypochlorite and process for its manufacture Download PDFInfo
- Publication number
- EP0340371B1 EP0340371B1 EP88500116A EP88500116A EP0340371B1 EP 0340371 B1 EP0340371 B1 EP 0340371B1 EP 88500116 A EP88500116 A EP 88500116A EP 88500116 A EP88500116 A EP 88500116A EP 0340371 B1 EP0340371 B1 EP 0340371B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- bleaching composition
- alkaline metal
- composition according
- total weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 7
- 238000004061 bleaching Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- -1 alkylether sulphate Chemical class 0.000 claims abstract description 12
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 11
- 239000002304 perfume Substances 0.000 claims abstract description 8
- 125000000129 anionic group Chemical group 0.000 claims abstract description 7
- 230000003287 optical effect Effects 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 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 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 238000010908 decantation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 claims description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 238000007046 ethoxylation reaction Methods 0.000 claims 1
- 238000013019 agitation Methods 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- 230000002087 whitening effect Effects 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QTDIEDOANJISNP-UHFFFAOYSA-N 2-dodecoxyethyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOCCOS(O)(=O)=O QTDIEDOANJISNP-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 239000010865 sewage Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019093 NaOCl Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
Definitions
- bleaching compositions including alkaline metal hypochlorites have been acreditted due to the fact that they are remarkably viscous and, therefore, are appropriate for the treatment of not only horizontal and slanted surfaces but also for vertical surfaces since the viscosity of these compositions causes that the contact time between them and the surfaces to be treated is of much longer duration than that of fluid compositions which rapidly "run" from these surfaces.
- the principal surface active agent used to date has been an amine oxide, mixed with other surface active agents, which are generally anionic.
- compositions of the prior art have the disadvantage of giving viscosity levels of 200 centipoises only where their ionic strength is in the region of 4, this being achieved when the alkaline hypochlorite concentration is in the region of 8 to 9 % by weight.
- said compositions have a very high decomposition power on organic products such as surface active agents and hydrotopes, thereby noticeably reducing the stability of the product in relation to its content of active chlorine.
- AOX adsorbable organic halogens
- viscosity levels in the region of 700 to 800 centipoises are achieved, with chlorine concentrations lower than those of the compositions of the prior art, specifically in the region of 3 to 5% by weight, corresponding to an ionic strength of 1 to 2.
- compositions according to the invention are more stable in relation to hypochlorite than those of the prior art and thereby the finished product is more stable and has less inherent risk of accidents.
- the viscosity level remains stable with the passing of time.
- compositions according to the invention are that there is no nitrogen in the molecular structure of the surface active agents, thereby avoiding the risk of the formation of chloramines.
- the bleaching composition including an alkaline hypochlorite comprises:
- the anionic surface active agent used in the bleaching compositions including an alkaline hypochlorite according to the invention is an alkylether sulphate of an alkaline cation, which specifically has 2 to 4 units of ethylene oxide and, preferably, 2 to 3 units of ethylene oxide.
- the alkyl chain of the alkylether sulphate of the alkaline metal is linear and has 6 to 20, preferably 12 to 18 and, more particularly 12 to 14, carbon atoms, the alkaline cation being selected preferably from sodium, potassium and lithium.
- the neutral salt which forms a part of the bleaching composition based in an alkaline hypochlorite is sodium chloride.
- these can contain an alkaline metal compound, such as a caustic hydroxide like sodium hydroxide or potassium hydroxide, preferably, however, sodium hydroxide, in such quantities that the pH value of the final composition is between 12.5 and 14 approximately.
- an alkaline metal compound such as a caustic hydroxide like sodium hydroxide or potassium hydroxide, preferably, however, sodium hydroxide, in such quantities that the pH value of the final composition is between 12.5 and 14 approximately.
- the optical whitener can be of the phorwhite BHC 766 type, which is a derivate of the 4,4'-bis-(1,2,3-triazolyl)-(2)-stilbene-2,2-sulphonic acid, in the form of potassium salt.
- the bleaching composition comprising an alkaline hypochlorite is prepared by mixing a solution of alkalinic metal hypochlorite with an alkaline metal alkylether sulphate, with a neutral salt, together with the additives and auxilliary agents which are usual in this type of mixes, such as perfumes, which can be chosen from a great variety of useable perfumes such as monoterpenic, monocyclic and bicyclic alcohols and their esters with alkanoic acids having 2 to 3 carbon atoms such as isoborneol, dihydroterpineol and isobornyl and dihydroterpinyl acetates or similar, as indicated in Spanish patent 554,709, in the name of the same applicant.
- perfumes which can be chosen from a great variety of useable perfumes such as monoterpenic, monocyclic and bicyclic alcohols and their esters with alkanoic acids having 2 to 3 carbon atoms such as isoborneol, dihydroterpineol and isoborn
- optical whiteners can be added, together with perfumes and pigments such as copper phthalocyaninas and ultramarine which are stable in these mixes, and opcionally an alkalinising agent to regulate the pH value, such as sodium or potassium hydroxide, giving a final pH value of between 12.5 and 14 in the mix, with agitation, decantation and filtration to obtain a product which is viscous and free of foreign particles and/or any type of aglomerate.
- perfumes and pigments such as copper phthalocyaninas and ultramarine which are stable in these mixes
- an alkalinising agent to regulate the pH value, such as sodium or potassium hydroxide, giving a final pH value of between 12.5 and 14 in the mix, with agitation, decantation and filtration to obtain a product which is viscous and free of foreign particles and/or any type of aglomerate.
- the order in which the components are mixed is arbitrary, however, it is preferable to add the rest of the components to the alkaline hypochlorite solution, either separately or in any combination, under an eventual agitation, followed by an eventual decantation operation and/or filtration and final packaging.
- the installations used to carry out this process according to the invention are of the usual type used for this kind of operations, which are usually carried out at room temperature.
- an aqueous solution of sodium hypochlorite is placed, with an active chlorine content which varies between 3 and 7 % by weight and a pH value of between 13.0 and 13.5, and to this solution is added an alkaline metal alkylether sulphate, specifically Pulcra's Montosol PL 18, which is a natural alcohol with a linear chain of 12 to 14 carbon atoms in a proportion of 70:30, and an average ethylene oxide content of 2.3 mols per mol of alcohol, sulphated and neutralised with sodium salt, followed by the addition of the other components and, optionally, decantation and filtration.
- an alkaline metal alkylether sulphate specifically Pulcra's Montosol PL 18, which is a natural alcohol with a linear chain of 12 to 14 carbon atoms in a proportion of 70:30, and an average ethylene oxide content of 2.3 mols per mol of alcohol, sulphated and neutralised with sodium salt
- compositions are prepared in accordance with the general formulation and the components and proportions are as shown in table I below.
- Viscosity at 20 o after 8 weeks I-1 3.0 1.0 16 16 I-2 3.5 1.0 24 24 I-3 4.0 1.0 36 36 I-4 4.5 1.0 100 95 I-5 5.0 1.0 182 175 I-6 5.0 1.5 470 450 I-7 5.0 2.0 790 730 I-8 5.5 1.0 230 225 I-9 5.5 1.5 480 460 I-10 5.5 2.0 680 645 I-11 6.0 1.0 160 155 I-12 6.0 1.5 190 182 I-13 6.0 2.0 260 250
- an aqueous solution of sodium hypochlorite is placed, with an active chlorine content which varies between 3 and 7% by weight and a pH value of between 13.0 and 13.5, and to this solution is added an alkaline metal alkylether sulphate, specifically Henkel KGaA's Texapon N-70, which is a natural alcohol with a linear chain of 12 to 14 carbon atoms in a proportion of 70:30, and an average ethylene oxide content of 2.0 mols per mol of alcohol, sulphated and neutralised with a sodium salt, followed by the addition of the other components and, optionally, decantation and filtration.
- an alkaline metal alkylether sulphate specifically Henkel KGaA's Texapon N-70, which is a natural alcohol with a linear chain of 12 to 14 carbon atoms in a proportion of 70:30, and an average ethylene oxide content of 2.0 mols per mol of alcohol, sulphated and neutralised with a sodium salt, followed
- compositions are prepared in accordance with the general formulation and the components and proportions are as shown in tabla II below.
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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT8888500116T ATE104697T1 (de) | 1988-05-05 | 1988-11-28 | Alkalisches hypochlorit enthaltendes bleichmittel und verfahren zu dessen herstellung. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES8801389A ES2007221A6 (es) | 1988-05-05 | 1988-05-05 | Composicion blanqueante a base de hipocloritos alcalinos y procedimiento para su obtencion. |
| ES8801389 | 1988-05-05 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0340371A2 EP0340371A2 (en) | 1989-11-08 |
| EP0340371A3 EP0340371A3 (en) | 1990-04-04 |
| EP0340371B1 true EP0340371B1 (en) | 1994-04-20 |
Family
ID=8256170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88500116A Expired - Lifetime EP0340371B1 (en) | 1988-05-05 | 1988-11-28 | Bleaching composition containing alkaline hypochlorite and process for its manufacture |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0340371B1 (da) |
| AT (1) | ATE104697T1 (da) |
| DE (1) | DE3889217T2 (da) |
| DK (1) | DK219189A (da) |
| ES (1) | ES2007221A6 (da) |
| PT (1) | PT90455B (da) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5034150A (en) * | 1989-05-03 | 1991-07-23 | The Clorox Company | Thickened hypochlorite bleach solution and method of use |
| ES2040620B1 (es) * | 1991-07-24 | 1994-06-01 | Pulcra Sa | Composicion de limpieza a base de tensioactivos e hipoclorito. |
| DE4333100C1 (de) * | 1993-09-29 | 1994-10-06 | Henkel Kgaa | Bleich- und Desinfektionsmittel |
| ES2285726T5 (es) † | 1997-09-19 | 2011-09-05 | THE PROCTER & GAMBLE COMPANY | Composiciones blanqueadoras autoespesadas. |
| US6448215B1 (en) | 1998-01-16 | 2002-09-10 | The Procter & Gamble Company | Stable colored thickened bleaching compositions |
| ATE283342T1 (de) * | 1998-01-16 | 2004-12-15 | Procter & Gamble | Stabile gefärbte verdickte bleichmittelzusammensetzungen |
| DE19803054A1 (de) * | 1998-01-28 | 1999-07-29 | Henkel Kgaa | Bleich- und Desinfektionsmittel |
| EP0942064A1 (en) * | 1998-03-09 | 1999-09-15 | The Procter & Gamble Company | Liquid hypohalite bleach-based cleaning compositions |
| US6506718B1 (en) | 1998-09-01 | 2003-01-14 | The Procter & Gamble Company | Bleaching compositions |
| EP0984059A1 (en) * | 1998-09-01 | 2000-03-08 | The Procter & Gamble Company | Bleaching compositions |
| EP0992576A1 (en) * | 1998-10-01 | 2000-04-12 | The Procter & Gamble Company | Stable bleaching compositions |
| EP0990696B1 (en) * | 1998-10-01 | 2005-04-27 | The Procter & Gamble Company | Stable bleaching compositions |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA674667B (da) * | 1966-08-11 | |||
| US3655566A (en) * | 1970-03-05 | 1972-04-11 | Purex Corp Ltd | Bleach having stable brighteners |
| US4526700A (en) * | 1983-11-04 | 1985-07-02 | The Procter & Gamble Company | Hypochlorite bleach compositions containing optical brighteners |
| EP0206718B1 (en) * | 1984-01-27 | 1990-08-08 | The Clorox Company | Bleaching and brightening composition and method |
| DE3527910A1 (de) * | 1985-08-03 | 1987-02-12 | Basf Ag | Fluessiges bleichmittel |
| NZ224700A (en) * | 1987-05-26 | 1991-09-25 | Bristol Myers Co | Aqueous cleaner comprising alkali metal halogenite, perfume and an anionic surfactant stabiliser |
-
1988
- 1988-05-05 ES ES8801389A patent/ES2007221A6/es not_active Expired
- 1988-11-28 DE DE3889217T patent/DE3889217T2/de not_active Expired - Lifetime
- 1988-11-28 EP EP88500116A patent/EP0340371B1/en not_active Expired - Lifetime
- 1988-11-28 AT AT8888500116T patent/ATE104697T1/de not_active IP Right Cessation
-
1989
- 1989-05-03 PT PT90455A patent/PT90455B/pt not_active IP Right Cessation
- 1989-05-03 DK DK219189A patent/DK219189A/da not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DK219189A (da) | 1989-11-06 |
| DK219189D0 (da) | 1989-05-03 |
| DE3889217T2 (de) | 1994-10-20 |
| EP0340371A3 (en) | 1990-04-04 |
| DE3889217D1 (de) | 1994-05-26 |
| ES2007221A6 (es) | 1989-06-01 |
| PT90455B (pt) | 1994-08-31 |
| PT90455A (pt) | 1989-11-30 |
| EP0340371A2 (en) | 1989-11-08 |
| ATE104697T1 (de) | 1994-05-15 |
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