EP0070079B1 - Composition détergente - Google Patents

Composition détergente Download PDF

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Publication number
EP0070079B1
EP0070079B1 EP19820200887 EP82200887A EP0070079B1 EP 0070079 B1 EP0070079 B1 EP 0070079B1 EP 19820200887 EP19820200887 EP 19820200887 EP 82200887 A EP82200887 A EP 82200887A EP 0070079 B1 EP0070079 B1 EP 0070079B1
Authority
EP
European Patent Office
Prior art keywords
weight
activator
bleach
cleaning composition
compositions
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
Application number
EP19820200887
Other languages
German (de)
English (en)
Other versions
EP0070079A3 (en
EP0070079A2 (fr
Inventor
Francis Geoffrey Foster
Arthur George Leigh
Thomas Stirling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10523251&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0070079(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to AT82200887T priority Critical patent/ATE42335T1/de
Publication of EP0070079A2 publication Critical patent/EP0070079A2/fr
Publication of EP0070079A3 publication Critical patent/EP0070079A3/en
Application granted granted Critical
Publication of EP0070079B1 publication Critical patent/EP0070079B1/fr
Expired legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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

Definitions

  • This invention relates to cleaning compositions which are particularly, but not essentially, adapted for fabric washing, and more particularly to aluminosilicate built cleaning compositions.
  • a bleach system comprising a peroxide bleach such as sodium perborate, together with a peracid bleach precursor, also called an activator, in detergent compositions so as to provide an effective bleaching at lower temperatures.
  • a peroxide bleach such as sodium perborate
  • a peracid bleach precursor also called an activator
  • Such detergent compositions conventionally include a phosphate detergency builder such as sodium triphosphate.
  • phosphate detergency builder such as sodium triphosphate.
  • Water-insoluble alumino-silicate cation exchange materials have been suggested as alternative builders to phosphates (see for example GB-1.429.143, GB-1.470.250, GB-1.504.211, GB-1.529.454 and US ⁇ 4.064.062). However, it has been found that in alumino-silicate built compositions the performance of this bleach system is significantly reduced.
  • Detergent compositions comprising zeolite compounds and a nitrilotriacetic compound have been suggested in e.g. FR-2.335.594, FR-2.335.596, FR-2.335.598 and FR-2.410.074.
  • an alumino-silicate built cleaning composition comprising:
  • the cleaning compositions of the invention will include at least one organic soap or synthetic detergent-active material.
  • at least one organic soap or synthetic detergent-active material Preferably, from about 5% to 40% by weight of an organic, anionic, nonionic, amphoteric or zwitterionic detergent compound, soap or mixtures thereof are included.
  • suitable detergent-active compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • the preferred detergent-active compounds which can be used are synthetic anionic, soap and nonionic compounds.
  • the first-mentioned are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include-the alkyl portion of higher aryl radicals.
  • Suitable anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 ⁇ C 18 ) alcohols produced for example from tallow or coconut oil; sodium and potassium alkyl (C9-CZO) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 ⁇ C 15 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 9 -C, 8 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl
  • nonionic detergent compounds examples include the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C s -C 22 ) phenols, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic (C 8 ⁇ C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • alkylene oxides usually ethylene oxide
  • alkyl (C s -C 22 ) phenols generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule
  • condensation products of aliphatic (C 8 ⁇ C 18 ) primary or secondary linear or branched alcohols with ethylene oxide generally 6 to 30 EO
  • nonionic detergent compounds include long-chain tertiary amine oxides, long-chain tertiary phosphine oxides
  • detergent-active compounds for example mixed anionic or mixed anionic and nonionic compounds
  • Amounts of amphoteric or zwitterionic detergent-active compounds can also be used in the compositions of the invention, but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent-active compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anion and/or nonionic detergent-active compounds.
  • the alumino-silicate cation exchange material is a crystalline or amorphous material having the general formula: wherein Cat is a cation having valency n that is exchangeable with calcium (e.g. Na + or K + ); x is a number from 0.7-1.5; y is a number from 1.3-4; and z is such that the bound water content is from 10% to 28% by weight.
  • a crystalline material which can be described by the unit cell content: wherein x and y are integers of at least 6, the ratio of x to y being in the range of 1:1 to 1:2; and z is such that the bound water content is from 10% to 28% by weight.
  • the alumino-silicate preferably has a particle size of from 0.1 to 100 micrometers, ideally between 0.1 and 10 micrometers, and an ion exchange capacity of at least 200 mg CaC0 3 per gram of alumino-silicate (anhydrous basis).
  • the water insoluble alumino-silicate is a crystalline material having the formula described by the unit cell content: wherein z is from 20 to 30, preferably about 27.
  • Zeolite type A is the commercially available product known as Zeolite type A, which is typically: and is also described by the unit cell content:
  • the bleach system used in the present invention essentially comprises a peroxy bleach compound which is an inorganic persalt, and an activator therefor.
  • the activator makes the bleaching more effective at lower temperatures, i.e. in the range from ambient temperature to about 60°C, so that such bleach systems are commonly known as low-temperature bleach systems and are well known in the art.
  • the inorganic persalt such as sodium perborate, acts to release active oxygen in solution, and the activator therefor is usually an organic compound having one or more reactive acyl residues, which cause the formation of peracids, the latter providing a more effective bleaching action at lower temperatures than the peroxy bleach compound.
  • the ratio by weight of the peroxy bleach compound to the activator in the composition of the invention may vary from about 30:1 to about 1:1, preferably from 15:1 to 2:1.
  • a particularly preferred ratio is from 5:1 to 2:1.
  • the amount of the bleach system i.e. peroxy bleach compound and activator, may be varied between about 3.5% and about 45% by weight of the detergent compositions, it is preferred to use about 5% to about 35% of the ingredients forming the bleach system.
  • Suitable peroxy bleach compounds are alkali metal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred.
  • Activators for peroxy bleach compounds have been amply described in the literature, including British patents 836 988, 855 735, 907 356, 907 358, 970 950, 1 003 310 and 1 246 339, U.S. patents 3 332 882 and 4 128 494, Canadian patent 844 481 and South African patent 68/6 344.
  • Specific suitable activators include:
  • N-diacetylated and N,N'-polyacylated amines mentioned under (a) are of special interest, particularly N,N,N',N' - tetraacetylethylenediamine (TAED).
  • the activator in granular form, preferably wherein the activator is present in finely divided form as described in our GB Patent Specification N° 2 053 998.
  • the sedimentation losses, when using an activator with an average particle size of less than 150 um, are substantially decreased.
  • Even better bleach performance is obtained if the average particle size of the activator is less than 100 um.
  • too small a particle size gives increased decomposition, dust formation and handling problems, and although particle sizes below 100 pm can provide an improved bleaching efficiency, it is desirable that the activator should not have more than 20% by weight of particles with a size of less than 50 pm.
  • the activator may have a certain amount of particles of a size greater than 150 pm, but it should not contain more than 5% by weight of particles >300 ⁇ m, and not more than 20% by weight of particles >150 ⁇ m. If needle-shaped crystalline activator particles are used, these sizes refer to the needle diameter. It is to be understood that these particle sizes refer to the activator present in the granules, and not to the granules themselves. The latter have generally a particle size, the major part of it ranging from 100 to 2000 pm, preferably 250 to 1000 pm. Up to 5% by weight of granules with a particle size of >1600 ⁇ m and up to 10% by weight of granules ⁇ 250 pm is tolerable.
  • the granules incorporating the activator may be obtained by granulating the activator with a suitable carrier material, such as sodium tripolyphosphate and/or potassium tripolyphosphate.
  • a suitable carrier material such as sodium tripolyphosphate and/or potassium tripolyphosphate.
  • Other granulation methods e.g. using organic and/or inorganic granulation aids, can also be usefully applied.
  • the granules can be subsequently dried, if required. Basically, any granulation process is applicable, as long as the granule contains the activator, and as long as the other materials present in the granule do not negatively affect the activator.
  • nitrilotriacetic acid compounds contemplated for use in the present invention may be represented by the following structural formula: wherein X is hydrogen or a water-solubilizing cation, such as sodium, potassium and ammonium cations.
  • Preferred compounds falling within the ambit of the above-described definition and formula are nitrilotriacetic acid, trisodium nitrilotriacetate, tripotassium nitrilotriacetate, disodium nitrilotriacetate and dipotassium nitrilotriacetate.
  • the amount of nitrilotriacetic acid compound (NTA), taken as trisodium nitrilotriacetate, in the compositions of the invention may be varied between 1 and 15% by weight of the composition and will depend on the amount of alumino-silicate cation exchange material.
  • the percentage quantity of nitrilotriacetic acid compound (N) and the percentage quantity of aluminosilicate cation exchange material (A) are such that the sum of A+2N lies between 40 and 55.
  • a preferred range of NTA usable in the present invention is from 2.5 to 10% by weight of the composition.
  • the cleaning compositions of the present invention are preferably substantially free of inorganic phosphate builders.
  • the compositions may contain inorganic phosphate such as the alkali metal (preferably sodium) triphosphate, pyrophosphate, orthophosphate or polymer phosphate, but only at a level of below 12.5% by weight based on the composition.
  • the cleaning compositions of the invention can contain any of the conventional additives in the amounts in which such materials are normally employed in fabric-washing detergent compositions.
  • these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids; lather depressants such as alkyl phosphates and silicones; antiredeposition agents such as sodium carboxymethylcellulose, polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose; stabilizers such as ethylenediamine tetraacetic acid, ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate; fabric-softening agents; inorganic salts such as sodium sulphate and sodium carbonate; and-usually present in very minor amounts-fluorescent agents, perfumes, enzymes such as proteases and amylases; germ
  • antideposition agents in the cleaning compositions of the invention, to decrease a tendency to form inorganic deposits on washed fabrics.
  • the amount of any such antideposition agent is normally from about 0.1 % to about 5% by weight, preferably from about 0.2% to about 2.5% by weight of the composition.
  • the preferred antideposition agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.
  • non-phosphate detergency builders may be incorporated as well if desired, but only in minor amounts, preferably not more than 10% by weight of the cleaning composition.
  • an amount of an alkali metal silicate particularly sodium ortho-, meta- or preferably neutral or alkaline silicate.
  • an alkali metal silicate particularly sodium ortho-, meta- or preferably neutral or alkaline silicate.
  • the presence of such alkali metal silicates at levels of at least about 1 %, and preferably from about 5% to about 15% by weight of the composition, is advantageous in decreasing the corrosion of metal parts in washing machines, besides giving processing benefits and generally improved powder properties.
  • the more highly alkaline ortho- and meta-silicates would normally only be used at lower amounts within this range, in admixture with the neutral or alkaline silicates.
  • compositions of the invention are required to be alkaline, but not too strongly alkaline as this could result in fabric damage and also be hazardous for domestic usage.
  • the compositions should give a pH of from about 8.5 to about 11 in use in aqueous wash solution. It is preferred in particular for domestic products to have a pH of from about 9.0 to about 10.5, as lower pHs tend to be less effective for optimum detergency, and more highly alkaline products can be hazardous if misused.
  • the pH is measured at the lowest normal usage concentration of 0.1% w/v of the product in water of 12°H (Ca) (French permanent. hardness, calcium only) at 50°C so that a satisfactory degree of alkalinity can be assured in use at all normal product concentrations.
  • the cleaning compositions mf the invention are preferably presented in free-flowing particulate e.g. powdered or granular form, and can be produced by any of the techniques commonly employed in the manufacture of such washing compositions, but preferably by slurry-making and spray-drying processes to form a detergent base powder to which the heat-sensitive ingredients, e.g. the bleach system and optionally some other ingredients as desired, are added. It is preferred that the process used to form the compositions should result in a product having a moisture content of not more than about 12%, more preferably from about 4% to about 10% by weight, as the lower moisture levels have been found to be beneficial for stability of the bleach systems employed.
  • the following cleaning powders were prepared by spray-drying a detergent slurry, followed by post-dosing the sensitive ingredients including the bleach system.
  • compositions similar to those used in Examples I ⁇ II with varying builder mixtures were used in the following bleaching tests carried out in the same manner as described in Examples I ⁇ II. The results were as follows:
  • This Example shows the importance of critical NTA level and NTA/alumino-silicate ratio.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Dental Preparations (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Claims (4)

1. Composition détergente à effet de lavage amélioré, à base d'aluminosilicate, à faible teneur en phosphate, qui comprend, outre que moins de 12,5% en poids d'un adjuvant phosphate inorganique,
(a) de 15 à 50% en poids d'un matériau d'aluminosilicate, échangeur de cations, insoluble dans l'eau;
(b) de 3 à 30% en poids d'un agent de blanchiment peroxyde;
(c) de 0,5 à 15% en poids d'un activateur pour ledit agent de blanchiment peroxyde; et
(d) un acide nitrilotriacétique ayant une formule développée N≡(CH2COOX)3 dans laquelle X représente un atome d'hydrogène ou un cation soluble dans l'eau, caractérisée en ce qu'elle comprend de 1 à 15% en poids dudit composé acide nitrilotriacétique, les quantités des pourcentages (a)+2(d) étant comprises entre 40 et 55.
2. Composition détergente selon la revendication 1, caractérisée en ce que le composé acide nitrilotriacétique est présent en une quantité comprise entre 2,5 et 10% en poids.
3. Composition détergente selon la revendication 1 ou 2, caractérisée en ce que le composé acide nitrilotriacétique est le nitrilotriacétate de sodium.
4. Composition détergente selon l'une quelconque des revendications 1 à 3, caractérisée en ce qu'elle est exempte ou pratiquement exempte d'adjuvants phosphate inorganique.
EP19820200887 1981-07-15 1982-07-13 Composition détergente Expired EP0070079B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82200887T ATE42335T1 (de) 1981-07-15 1982-07-13 Reinigungsmittelzusammensetzung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8121755 1981-07-15
GB8121755 1981-07-15

Publications (3)

Publication Number Publication Date
EP0070079A2 EP0070079A2 (fr) 1983-01-19
EP0070079A3 EP0070079A3 (en) 1986-02-05
EP0070079B1 true EP0070079B1 (fr) 1989-04-19

Family

ID=10523251

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19820200887 Expired EP0070079B1 (fr) 1981-07-15 1982-07-13 Composition détergente

Country Status (14)

Country Link
EP (1) EP0070079B1 (fr)
JP (1) JPS5823894A (fr)
AT (1) ATE42335T1 (fr)
AU (1) AU547825B2 (fr)
BR (1) BR8204090A (fr)
CA (1) CA1191067A (fr)
DE (1) DE3279624D1 (fr)
DK (1) DK315082A (fr)
FI (1) FI822428L (fr)
GR (1) GR76168B (fr)
NO (1) NO156755C (fr)
NZ (1) NZ201210A (fr)
PT (1) PT75246B (fr)
ZA (1) ZA825007B (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4539131B1 (en) * 1982-06-25 1990-09-04 Lever Brothers Ltd Solid detergent composition containing sodium perborate monohydrate having specified surface area
US4478733A (en) * 1982-12-17 1984-10-23 Lever Brothers Company Detergent compositions
US4488980A (en) * 1982-12-17 1984-12-18 Lever Brothers Company Detergent compositions
US4525292A (en) * 1983-03-07 1985-06-25 Cushman Mark E Bleaching detergent compositions comprising sulfosuccinate bleach promoters
ZA841401B (en) * 1983-03-15 1985-10-30 Colgate Palmolive Co Bleaching and laundering composition free of water-soluble silicates
ZA841402B (en) * 1983-03-15 1985-10-30 Colgate Palmolive Co Bleaching and laundering composition free of water-soluble silicates
DE3401861A1 (de) * 1983-09-06 1985-03-21 Degussa Ag, 6000 Frankfurt Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate, deren verwendung zur herstellung von phosphatsubstituten fuer wasch- und reinigungsmittel und phosphatsubstitute
GB8334017D0 (en) * 1983-12-21 1984-02-01 Unilever Plc Detergent composition
ZA851897B (en) * 1984-04-02 1986-10-29 Colgate Palmolive Co Non-caking bleaching detergent composition containing a lower hydrate of sodium perborate
US4536183A (en) * 1984-04-09 1985-08-20 Lever Brothers Company Manganese bleach activators
JPH0631415B2 (ja) * 1984-04-17 1994-04-27 ライオン株式会社 洗浄剤組成物
GB8427855D0 (en) * 1984-11-03 1984-12-12 Procter & Gamble Ltd Detergent compositions
US4601845A (en) * 1985-04-02 1986-07-22 Lever Brothers Company Bleaching compositions containing mixed metal cations adsorbed onto aluminosilicate support materials
US4623357A (en) * 1985-04-02 1986-11-18 Lever Brothers Company Bleach compositions
US4711748A (en) * 1985-12-06 1987-12-08 Lever Brothers Company Preparation of bleach catalyst aggregates of manganese cation impregnated aluminosilicates by high velocity granulation
US4655782A (en) * 1985-12-06 1987-04-07 Lever Brothers Company Bleach composition of detergent base powder and agglomerated manganese-alluminosilicate catalyst having phosphate salt distributed therebetween
GB8607387D0 (en) * 1986-03-25 1986-04-30 Unilever Plc Activator compositions
DE3737071A1 (de) * 1987-10-31 1989-05-11 Henkel Kgaa Verwendung von aminethern als netzmittel fuer textilien
GB8728232D0 (en) * 1987-12-02 1988-01-06 Unilever Plc Phosphate-free detergent bleach composition
GB8728386D0 (en) * 1987-12-04 1988-01-13 Unilever Plc Phosphate-free detergent bleach compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120809A (en) * 1973-07-24 1978-10-17 Colgate-Palmolive Company Washing and bleaching with composition containing bleach activator and a nitrilotricarboxylic acid compound
ZA767283B (en) * 1975-12-15 1978-07-26 Colgate Palmolive Co Bleaching compositions
US4064062A (en) * 1975-12-15 1977-12-20 Colgate-Palmolive Stabilized activated percompound bleaching compositions and methods for manufacture thereof
ZA767170B (en) * 1975-12-15 1978-07-26 Colgate Palmolive Co Detergent composition and method for use
JPS608040B2 (ja) * 1977-11-25 1985-02-28 花王株式会社 色，柄物の変，褪色を起さない漂白剤組成物

Also Published As

Publication number Publication date
DK315082A (da) 1983-01-16
JPS5823894A (ja) 1983-02-12
NO822431L (no) 1983-01-17
BR8204090A (pt) 1983-12-20
GR76168B (fr) 1984-08-03
ATE42335T1 (de) 1989-05-15
NO156755C (no) 1987-11-25
FI822428A0 (fi) 1982-07-08
ZA825007B (en) 1984-02-29
NO156755B (no) 1987-08-10
DE3279624D1 (en) 1989-05-24
PT75246A (en) 1982-08-01
EP0070079A3 (en) 1986-02-05
AU547825B2 (en) 1985-11-07
FI822428L (fi) 1983-01-16
EP0070079A2 (fr) 1983-01-19
PT75246B (en) 1985-12-03
NZ201210A (en) 1985-08-16
AU8598182A (en) 1983-01-20
CA1191067A (fr) 1985-07-30

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