EP0051509B1 - Compositions stabilisantes pour produits peroxydes - Google Patents
Compositions stabilisantes pour produits peroxydes Download PDFInfo
- Publication number
- EP0051509B1 EP0051509B1 EP81401577A EP81401577A EP0051509B1 EP 0051509 B1 EP0051509 B1 EP 0051509B1 EP 81401577 A EP81401577 A EP 81401577A EP 81401577 A EP81401577 A EP 81401577A EP 0051509 B1 EP0051509 B1 EP 0051509B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stabilizing
- composition
- compositions
- bleaching
- magnesium silicate
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 36
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 6
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims abstract description 25
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 24
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 18
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 18
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 18
- 229960003330 pentetic acid Drugs 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract 1
- 238000004061 bleaching Methods 0.000 description 19
- 239000004753 textile Substances 0.000 description 13
- 239000003599 detergent Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000003352 sequestering agent Substances 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229960001922 sodium perborate Drugs 0.000 description 4
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920000742 Cotton Polymers 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- UFZOPKFMKMAWLU-UHFFFAOYSA-N ethoxy(methyl)phosphinic acid Chemical compound CCOP(C)(O)=O UFZOPKFMKMAWLU-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- -1 peroxide compound Chemical class 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002087 whitening effect Effects 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
Definitions
- the present invention relates to stabilizing compositions for peroxidized products, in particular when they are used in the bleaching and bleaching of fibers and textile fabrics. These stabilizing compositions are especially intended for household and industrial detergents.
- Most household detergents contain a peroxidized compound, such as sodium perborate or sodium percarbonate, which has the effect of improving the elimination of many stains and restoring the linen to its original whiteness thanks to its whitening effect.
- a peroxidized compound such as sodium perborate or sodium percarbonate
- the textile industry generally uses baths comprising a peroxidized compound, such as hydrogen peroxide or sodium perborate for the bleaching of unbleached textiles.
- This stabilizing effect can be obtained by the addition, to the washing bath, of magnesium silicate which slows down the rate of decomposition of the peroxidized compound.
- the magnesium silicate makes it possible to keep in the bleaching bath the maximum of active oxygen beyond a temperature of the order of 60 ° C., from which the peroxidized compound will reach its full efficiency.
- the magnesium silicate is added to the detergent either preformed or formed "in situ from sodium silicate and a magnesium salt.
- the "in situ” formation process generally gives a rough feel, causes dye reserves due to the lack of hydrophility, and causes deposits in bleaching or bleaching apparatus which can cause mechanical wear of bleached textile fibers.
- French patent 2,420,593 in the name of Kao Soap, which relates to bleaching compositions which do not alter the color of the treated textiles, proposes to add in particular to sodium percarbonate or to the ethane addition product -1,1,2,2 tetracarboxylate tetrasodium and H 2 0 2 , at least one organoacetic and organophosphonic compound.
- French patent 2,140,213 in the name of Monsanto relates to a stabilizing agent for reducing the decomposition of a peroxidized compound contained in an alkaline aqueous solution.
- This agent is formed by a combination of 1-hydroxyethylidene-1,1-diphosphonic acid, called HEDP, nitrilotriacetic acid, called NTA, and water-soluble salts and a water-soluble salt such as sulfate. magnesium.
- French patent 1,420,462 in the name of the applicant, relates to a process for stabilizing compounds peroxidized by magnesium silicate, during their use in the bleaching and bleaching of fibers and textile fabrics, according to which the silicate of magnesium is used preformed in the colloidal state.
- the magnesium silicate preformed in the colloidal state is used in combination with small amounts of dimagnesium salt of ethylenediaminetotetraacetic acid.
- stabilizing compositions based on colloidal magnesium silicate are proposed for peroxidized products, such as sodium perborate, sodium percarbonate, hydrogen peroxide, etc., intended for the stabilization of laundering baths prepared by means of detergents. household or bleaching baths in the textile industry.
- These compositions contain colloidal magnesium silicate associated with diethylenetriaminepentaacetic acid and with diethylenetriaminepentamethylenephosphonic acid.
- the organophosphonic sequestrant diethylenetriaminepentamethylenephosphonic acid (DTPMP) is in acid or water soluble salt form.
- the organoacetic sequestrant: diethylenetriaminepentaacetic acid is designated by (DTPA).
- the stabilizing composition according to the invention makes it possible to obtain a very substantial gain in the degree of polymerization, while the combination proposed in French patent 2,140,213 does not provide any improvement in the protection of the cellulose.
- compositions based on colloidal magnesium silicate were prepared with variable doses of DTPA and DTPMP.
- the doses of DTPA and DTPMP are given as a percentage by weight of pure product.
- Table 1 below indicates the proportions in percent of the different compositions produced.
- Composition No. 1 does not include DTPA or DTPMP: it is a control composition which serves as a reference for measuring the effectiveness of the other compositions.
- the detergent bath is maintained at 90 ° C for 1 hour; the quantity of active oxygen (OA) residual relative to the quantity of active oxygen initially contained in the bath is then measured.
- OA active oxygen
- the residual gain in OA provided by said compositions is defined as the difference in the stabilizing power of one of these said compositions minus the stabilizing power of the composition. witness # 1.
- Table 2 indicates the stabilizing power and the residual OA gain of the various stabilizing compositions.
- compositions no. 5, 6 and 8 have the same stabilizing power and the same gain in OA while the sum of the percentages of DTPA and DTPMP are respectively 10.7%, 11.4% and 23%.
- composition No. 6 The synergistic effect between the two sequestrants is particularly marked under composition No. 6; it is illustrated in Table 3.
- Table 3 shows that the sum of the results of compositions 2 and 4 corresponding to the hypothetical composition (2 + 4)? are significantly lower as stabilizing power and gain of OA, to the results of composition No. 6 which actually contains percentages of DTPA and DTPMP slightly lower than the percentages of DTPA and DTPMP of the hypothetical composition (2 + 4)?
- the synergy of DTPA and DTPMP at relatively low levels is particularly advantageous from an economic point of view because DTPMP is significantly more expensive than DTPA.
- composition No. 6 which contains only 4.4% of DTPMP has the same stabilizing power and the same gain in OA as composition No. 5, for example which contains 10.7% of DTPMP.
- the pieces tested are made of “EMPA 301” fabric: it is a reference fabric, made of cotton, used in the textile and bleaching industry; this fabric is supplied by the Federal Laboratory for Materials Testing of the Research Institute of St Gall in Switzerland.
- the degree of polymerization of the cellulose is determined according to the method described in standard AFNOR T 12005.
- the DP of the fabric “EMPA 301 was, at the start, before the washes, of 1850.
- Example 5 According to Example 5, Table 3 (6), from French patent 2,140,213, a 36.1% stabilizing solution of 1 mole of NTA, 0.47 mole of magnesium (from a soluble salt such as sulfate) is used. magnesium) and 0.3 moles of HEDP. Or a solution which contains by weight 29% of NTA at 90%, 15.8% of MgSO 4 ⁇ 7 H 2 O and 14.1% of HEDP at 60%.
- the stabilizing composition consists of 78% colloidal magnesium silicate, 14.5% DTPA in 40% solution (sodium salt) and 7.5% DTPMP in 50% solution.
- the degradation of the cellulose was evaluated by determining the degree of polymerization DP after a succession of 5 washes in the presence of each stabilizing composition.
- test 5 the sodium perborate is better stabilized than in the other tests.
- the amount of residual active oxygen is 45%, while it is only 5 and 10% in tests n ° 8 and 11.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Golf Clubs (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81401577T ATE6431T1 (de) | 1980-11-04 | 1981-10-13 | Stabilisatorzusammensetzungen fuer peroxide. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8023524A FR2493294A1 (fr) | 1980-11-04 | 1980-11-04 | Compositions stabilisantes pour produits peroxydes |
| FR8023524 | 1980-11-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0051509A1 EP0051509A1 (fr) | 1982-05-12 |
| EP0051509B1 true EP0051509B1 (fr) | 1984-02-29 |
Family
ID=9247659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81401577A Expired EP0051509B1 (fr) | 1980-11-04 | 1981-10-13 | Compositions stabilisantes pour produits peroxydes |
Country Status (12)
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GR76237B (enrdf_load_stackoverflow) * | 1981-08-08 | 1984-08-04 | Procter & Gamble | |
| US4378300A (en) * | 1981-12-10 | 1983-03-29 | Colgate-Palmolive Company | Peroxygen bleaching composition |
| JPS60201388A (ja) * | 1984-03-26 | 1985-10-11 | 日本板硝子株式会社 | Ｃｒｔデイスプレイ装置における点滅制御方法 |
| US4725281A (en) * | 1985-07-19 | 1988-02-16 | Ciba-Geigy Corporation | Aqueous alkaline, silicate-containing composition and the use thereof for bleaching cellulosic fiber materials in the presence of per compounds |
| JPS6236498A (ja) * | 1985-08-09 | 1987-02-17 | ル・エ−ル・リクイツド・ソシエテ・アノニム・プ−ル・ル・エチユド・エ・ル・エクスプルワテシヨン・デ・プロセデ・ジエオルジエ・クロ−ド | セルロ−ス保護剤 |
| GB8904007D0 (en) * | 1989-02-22 | 1989-04-05 | Procter & Gamble | Stabilized,bleach containing,liquid detergent compositions |
| DE4035813A1 (de) * | 1990-11-10 | 1992-05-14 | Akzo Gmbh | Sauerstoffbleichung |
| FI963633A0 (fi) * | 1994-03-14 | 1996-09-13 | Procter & Gamble | Rakeisia valkaisukoostumuksia |
| US5780419A (en) * | 1994-04-20 | 1998-07-14 | The Procter & Gamble Company | Detergent powder compositions comprising metal ion-chelant complex and anionic functional polymer |
| EP0678572A1 (en) * | 1994-04-20 | 1995-10-25 | The Procter & Gamble Company | Detergent powder compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1420462A (fr) | 1964-10-22 | 1965-12-10 | Air Liquide | Procédé de stabilisation de composés peroxygénés |
| US3766078A (en) * | 1971-06-03 | 1973-10-16 | Monsanto Co | Processes for stabilizing peroxy solutions |
| BE795085A (fr) * | 1972-03-10 | 1973-05-29 | Benckiser Knapsack Gmbh | Procede de blanchiment de fibres cellulosiques seules ou en melange avec des fibres synthetiques |
| FR2396114A1 (fr) * | 1977-06-29 | 1979-01-26 | Protex Manuf Prod Chimiq | Perfectionnements aux procedes de blanchiment oxydant |
| US4279769A (en) * | 1978-03-20 | 1981-07-21 | Kao Soap Co., Ltd. | Bleaching composition |
| FI64639C (fi) * | 1978-09-27 | 1983-12-12 | Unilever Nv | Bleknings- och rengoeringskomposition |
| US4259200A (en) * | 1979-04-06 | 1981-03-31 | Lever Brothers Company | Bleaching and cleaning compositions |
-
1980
- 1980-11-04 FR FR8023524A patent/FR2493294A1/fr active Granted
-
1981
- 1981-10-13 AT AT81401577T patent/ATE6431T1/de not_active IP Right Cessation
- 1981-10-13 EP EP81401577A patent/EP0051509B1/fr not_active Expired
- 1981-10-13 DE DE8181401577T patent/DE3162441D1/de not_active Expired
- 1981-10-28 US US06/316,052 patent/US4384970A/en not_active Expired - Lifetime
- 1981-10-29 GR GR66387A patent/GR75357B/el unknown
- 1981-10-29 CA CA000388971A patent/CA1166406A/fr not_active Expired
- 1981-11-03 DK DK485481A patent/DK149338C/da not_active IP Right Cessation
- 1981-11-03 ES ES506799A patent/ES506799A0/es active Granted
- 1981-11-03 NO NO813714A patent/NO154343C/no unknown
- 1981-11-03 FI FI813452A patent/FI66820C/fi not_active IP Right Cessation
- 1981-11-04 JP JP56175869A patent/JPS57105499A/ja active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| ATE6431T1 (de) | 1984-03-15 |
| NO154343B (no) | 1986-05-26 |
| FR2493294A1 (fr) | 1982-05-07 |
| US4384970A (en) | 1983-05-24 |
| DK149338B (da) | 1986-05-05 |
| ES8307660A1 (es) | 1983-07-01 |
| CA1166406A (fr) | 1984-05-01 |
| NO154343C (no) | 1986-09-03 |
| FI66820B (fi) | 1984-08-31 |
| DK149338C (da) | 1987-02-02 |
| FI813452L (fi) | 1982-05-05 |
| JPS57105499A (en) | 1982-06-30 |
| NO813714L (no) | 1982-05-05 |
| ES506799A0 (es) | 1983-07-01 |
| GR75357B (enrdf_load_stackoverflow) | 1984-07-13 |
| DK485481A (da) | 1982-05-05 |
| EP0051509A1 (fr) | 1982-05-12 |
| FR2493294B1 (enrdf_load_stackoverflow) | 1985-02-22 |
| JPH0227399B2 (enrdf_load_stackoverflow) | 1990-06-15 |
| DE3162441D1 (en) | 1984-04-05 |
| FI66820C (fi) | 1984-12-10 |
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Legal Events
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