EP0313144A2 - Phosphatfreie Reinigungs- und Bleichmittel - Google Patents

Phosphatfreie Reinigungs- und Bleichmittel Download PDF

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Publication number
EP0313144A2
EP0313144A2 EP19880202244 EP88202244A EP0313144A2 EP 0313144 A2 EP0313144 A2 EP 0313144A2 EP 19880202244 EP19880202244 EP 19880202244 EP 88202244 A EP88202244 A EP 88202244A EP 0313144 A2 EP0313144 A2 EP 0313144A2
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
sodium
acid
composition
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.)
Ceased
Application number
EP19880202244
Other languages
English (en)
French (fr)
Other versions
EP0313144A3 (de
Inventor
William Derek Emery
Stephen George Barnes
Peter Stanford Sims
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
Original Assignee
Unilever PLC
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
Application filed by Unilever PLC filed Critical Unilever PLC
Publication of EP0313144A2 publication Critical patent/EP0313144A2/de
Publication of EP0313144A3 publication Critical patent/EP0313144A3/de
Ceased 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds
    • 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

Definitions

  • This invention relates to non-phosphorus detergent bleach compositions.
  • it relates to aluminosilicate built laundry detergent bleach compositions having improved cleaning and stain-removal performances.
  • zeolites Water-insoluble aluminosilicates, commonly known as zeolites, have been used in detergent compositions as important alternative builders to phosphates (see, for example, GB-A-­1429143; GB-A-1470250; GB-A-1504211; GB-A-1529454 and US-A-­4064062). Bleaching experiments have indicated, however, that the bleach performances of aluminosilicate built formulations are well below those of phosphate built products.
  • aluminosilicate built detergent compositions which contain 0.01-4% by weight of a polyphosphonate sequestering agent and 5-25% by weight of citric acid or citrates as pH-regulating agent. These compositions are unsatisfactory when used for washing at the low wash temperature region of 40°C and below.
  • non-­phosphorus detergent bleach composition comprising at least one detergent-active material and :
  • the detergent composition of the invention necessarily contains a peroxybenzoic acid bleach precursor as the bleach activator, which on perhydrolysis generates a peroxybenzoic acid.
  • a peroxybenzoic acid bleach precursor as the bleach activator, which on perhydrolysis generates a peroxybenzoic acid.
  • Other bleach precursors such as the most commonly used tetraacetylene diamine (TAED), which generates peracetic acid, are much less effective and hence unsuitable for use in the present invention.
  • TAED tetraacetylene diamine
  • Peroxybenzoic acid precursors are known in the art, e.g. from GB-A-836988. Examples thereof are phenylbenzoate; phenyl p-­nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromophenyl benzoate; sodium or potassium benzoyloxybenzenesulphonate; and benzoic anhydride.
  • the compounds have the general formula : wherein R is H or a substituent selected from -NO2 and halogens, and L is a leaving group, the conjugate acid of which has a pKa in the range of from about 6 to about 13.
  • L can be essentially any suitable leaving group that is displaced from the bleach precursor as a consequence of the nucleophilic attack on the bleach precursor by the perhydroxide anion, HOO ⁇ .
  • This perhydrolysis reaction results in the formation of the peroxybenzoic acid.
  • a group to be a suitable leaving group it must exert an electron-attracting effect, which facilitates the nucleophilic attack by the perhydroxide anion.
  • Leaving groups that exhibit such behaviour are those in which their conjugate acid has a pKa in the range of from 6 to 13, preferably from about 7 to about 11, and most preferably from 8 to 11.
  • L examples of suitable L are : wherein R1 is an alkylene chain containing from 1 to 8 carbon atoms; R2 is H or an alkyl chain containing from 1 to 8 carbon atoms; R3 is phenyl or an alkyl chain containing from 5 to 18 carbon atoms; and Y is a solubilizing group, preferably selected from -SO3 ⁇ M+, -COO ⁇ M+ or -SO4 ⁇ M+.
  • a preferred peroxybenzoic acid bleach precursor is sodium p-­benzoyloxybenzene sulphonate of the formula :
  • the inorganic peroxide compounds usable in the present invention can be true persalts or perhydrates, which liberate hydrogen peroxide in aqueous solution.
  • examples or inorganic peroxide compounds are the alkali metal perborates, percarbonates, and persilicates, the perborates, particularly sodium perborate tetra- and monohydrate being preferred because of their commercial availability.
  • the inorganic peroxide compound and the peroxybenzoic acid bleach precursor in the composition of the invention may be present in a molar ratio of between 0.5:1 and about 20:1, preferably from 1:1 to 10:1. Under certain wash conditions a molar ratio of about 2:1 may be of advantage.
  • composition of the invention contains at least one detergent-active material which can be an organic soap or synthetic detergent surfactant material.
  • an organic, anionic, nonionic, amphoteric or zwitterionic detergent compound, soap, or mixtures thereof is included.
  • Many suitable detergent-active compounds are commercially available and are fully described in literature, for example in US-A-4222905 and US-A-4239659 and in "Surface Active Agents and Detergents", Vol. 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 synthetic, anionic detergent compounds are sodium and potassium alkyl sulphates, especia­lly those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those esters 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 (C9-C18) 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
  • Suitable soaps are the alkali metal salts of long chain C8-C22 fatty acids such as the sodium soaps of tallow, coconut oil, palmkernel oil, palm oil or hardened rapeseed oil fatty acids or mixtures thereof.
  • the preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates and sodium (C16-C18) alkyl sulphates.
  • nonionic detergent compounds examples include the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, genera­lly 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic (C8-C18) 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 ethylene diamine.
  • nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • 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 the compositions based on the much more commonly used synthetic anionic and/or nonionic detergent-active compounds.
  • the detergent composition of the invention also contains a water-insoluble aluminosilicate cation-exchange material in an amount of from 15% to about 40% by weight, preferably from 20% to 35% by weight.
  • the aluminosilicate can be crystalline or amorphous in character, preferred materials having the unit cell formula I M z [(AlO2) z (SiO2) y ] xH2O I wherein M is a calcium-exchange cation, z and y are at least 6; the molar ratio of z to y is from about 1.0 to about 0.5 and x is at least 5, preferably from about 7.5 to about 276, more preferably from about 10 to about 264.
  • the aluminosilic­ate materials are in hydrated form and are preferably crystalline containing from about 10% to about 28%, more preferably from about 18% to about 22% water.
  • the aluminosilicate ion-exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns, preferably from about 0.2 micron to about 4 microns.
  • particle size diameter herein represents the average particle size diameter of a given ion-­exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the aluminosilicate ion-exchange materials herein are usually further characteri­zed by their calcium ion-exchange capacity, which is at least about 200 mg.
  • aluminosilicate ion- exchange materials herein are still further characterized by their calcium ion-­exchange rate which is at least about 2 grains Ca++/gallon/­minute/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/­gallon/minute/gram/gallon to about 6 grains/gallon/minute/­gram/gallon, based on calcium ion hardness.
  • Optimum aluminosilicates for builder purposes exhibit a calcium ion-­exchange rate of at least about 4 grains/gallon/minute/gram/­gallon.
  • Aluminosilicate ion-exchange materials useful in the practice of this invention are commercially available and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion-exchange materials is discussed in US-A-3985669.
  • Preferred synthetic crystalline aluminosilicate ion-exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
  • the crystalline aluminosilicate ion-exchange material is Zeolite A and has the formula Na12[AlO2)12 (SiO2)12] xH2O wherein x is from about 20 to about 30, especially about 27.
  • Zeolite X of formula Na86 [(AlO2)86)(SiO2)106] .276 H2O is also suitable, as well as Zeolite HS of formula Na6 [(AlO2)6 (SiO2)6] 7.5 H2O).
  • the detergent composition of the invention further contains an alkali metal citrate or citric acid in an amount of from about 1% to about 15%, preferably from 2 to 10%, by weight of the composition.
  • a preferred alkali metal citrate is sodium citrate, particularly trisodium citrate, i.e. C6H5O7.Na3.2H2O.
  • the detergent composition herein can contain any of the conventional additives and adjuncts in the amounts in which such materials are normally employed in fabric washing compositions.
  • additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel and coconut fatty acids; lather depressants such as alkyl phosphates, silicones and waxes; anti-­redeposition agents such as sodium carboxymethyl cellulose (SCMC), polyvinyl pyrrolidone (PVP) and the cellulose ethers, such as methylcellulose and ethyl hydroxyethyl cellulose; stabilizers such as ethylene diamine tetraacetate; 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, amylases and lipases; germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanol
  • Polycarboxylate polymers though not essential, may also be included as desired in amounts of e.g. from about 0.5% to 6% by weight of the total composition.
  • the polycarboxylate polymers herein are preferably selected from co-polymeric polycarboxylic acids and their salts derived from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid or mesaconic acid as a first monomer and ethylene, methyl vinyl ether, acrylic acid or metacrylic acid as a second monomer, the co-polymer comprising at least about 10 mole%, preferably at least about 20 mole% of polycarboxylic acid units and having weight average molecular weights of at least about 10,000, preferably at least about 30,000; homopolyacrylates and homopolymethacrylates having a weight average molecular weight of from about 1000 to about 10,000, preferably from about 5000 to about 50,000; and mixtures thereof.
  • the detergent bleach compositions of the invention are alkaline and will advantageously have a solution pH (2-10 g/l) of from 8-11, with an optimal pH of between 8 and 9.
  • a wash pH of, say, 8.5 appears to give the best compromise for achieving good bleaching, detergency and enzymatic soil removal.
  • buffering agents such as borax, may be necessary.
  • the detergent compositions of the invention are preferably presented in free-flowing particulate, e.g. powdered or granular form, and can be produced by any of the known techniques commonly employed in the manufacture of such washing compositions, but preferably by spray-drying an aqueous slurry comprising the surfactant(s), the alumino­silicate and the alkali metal citrate to form a detergent base powder, to which the heat-sensitive ingredients, including the peroxybenzoic acid bleach precursor, the inorganic percompound, enzymes and optionally some other ingredients as conveniently desirable are added.
  • the alkali metal citrate can be separately dry-mixed with the spray-dried base powder.
  • the bleach precursor and enzymes are preferably added as granulated particles. It is preferred that the process used to form the compositions should result in a product having a moisture content of up to about 15%, more preferably from about 7% to about 14% by weight.
  • composition A Parts by weight Sodium linear alkylbenzene sulphonate 9.0 Fatty alcohol-7 ethoxylate 1.5
  • Maleic acid/acrylic acid copolymer Sokalan ® CP5 ex BASF
  • 4.0 Sodium aluminosilicate Zeolite A 24.0
  • Sodium sulphate anhydrous
  • EDTA ethylenediamine tetraacetate
  • Na2CO3 Sodium carbonate
  • Composition B Sodium perborate monohydrate 13.0 Anti-foaming agent 2.5
  • Proteolytic enzyme Savinase ® ex NOVO
  • trisodium citrate boosts the bleach performances on tea and wine stains without a negative effect on detergency and enzyme action, i.e. protein soil removal.

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  • 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)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP88202244A 1987-10-23 1988-10-07 Phosphatfreie Reinigungs- und Bleichmittel Ceased EP0313144A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8724900 1987-10-23
GB878724900A GB8724900D0 (en) 1987-10-23 1987-10-23 Detergent bleach compositions

Publications (2)

Publication Number Publication Date
EP0313144A2 true EP0313144A2 (de) 1989-04-26
EP0313144A3 EP0313144A3 (de) 1989-10-18

Family

ID=10625800

Family Applications (1)

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EP88202244A Ceased EP0313144A3 (de) 1987-10-23 1988-10-07 Phosphatfreie Reinigungs- und Bleichmittel

Country Status (8)

Country Link
EP (1) EP0313144A3 (de)
JP (1) JPH01146997A (de)
KR (1) KR920002085B1 (de)
AU (1) AU612711B2 (de)
BR (1) BR8805450A (de)
CA (1) CA1316790C (de)
GB (1) GB8724900D0 (de)
NO (1) NO884700L (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990001535A1 (de) * 1988-08-01 1990-02-22 Henkel Kommanditgesellschaft Auf Aktien Granulares, bleichaktivatoren enthaltendes bleichhilfsmittel
EP0448298A1 (de) * 1990-03-19 1991-09-25 Unilever Plc Detergenszusammensetzungen
EP0448297A1 (de) * 1990-03-19 1991-09-25 Unilever Plc Detergenszusammensetzungen
WO1991015566A1 (en) * 1990-04-03 1991-10-17 The Procter & Gamble Company Fabric cleaning process
EP0504091A1 (de) * 1991-03-15 1992-09-16 Cleantabs A/S Phosphatfreies Maschinengeschirrspülmittel
WO1992018596A1 (en) * 1991-04-19 1992-10-29 The Procter & Gamble Company Granular laundry detergent compositions having improved solubility
EP0520582A1 (de) * 1991-06-28 1992-12-30 Colgate-Palmolive Company Sprühgetrocknete Waschmittelzusammensetzungen auf Zeolithbasis und Verfahren zur deren Herstellung
ES2039191A1 (es) * 1991-03-20 1993-09-01 Sandoz Ag Procedimiento para el pretratamiento de un material textil.
US5583098A (en) * 1993-11-24 1996-12-10 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
US5723428A (en) * 1993-11-24 1998-03-03 Lever Brothers Company Detergent compositions and process for preparing them
WO2001016279A1 (en) * 1999-09-02 2001-03-08 The Procter & Gamble Commpany Bleaching detergent compositions
US6548467B2 (en) 1999-09-02 2003-04-15 The Procter & Gamble Company Sanitizing compositions and methods
WO2003048291A1 (en) * 2001-11-30 2003-06-12 Ecolab, Inc. Stabilized active oxygen compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4087369A (en) * 1976-11-08 1978-05-02 The Procter & Gamble Company Peroxybleach activated detergent composition
EP0028432B1 (de) * 1979-11-03 1984-01-18 THE PROCTER & GAMBLE COMPANY Granulare Waschmittelzusammensetzungen
DE3163946D1 (en) * 1980-03-21 1984-07-12 Unilever Nv Bleaching detergent compositions
JPS6091917A (ja) * 1983-10-22 1985-05-23 井関農機株式会社 コンバインの刈取装置
JPS60221496A (ja) * 1984-04-17 1985-11-06 ライオン株式会社 漂白性洗浄剤組成物

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990001535A1 (de) * 1988-08-01 1990-02-22 Henkel Kommanditgesellschaft Auf Aktien Granulares, bleichaktivatoren enthaltendes bleichhilfsmittel
EP0356700A1 (de) * 1988-08-01 1990-03-07 Henkel Kommanditgesellschaft auf Aktien Granulares, Bleichaktivatoren enthaltendes Bleichhilfsmittel
EP0448298A1 (de) * 1990-03-19 1991-09-25 Unilever Plc Detergenszusammensetzungen
EP0448297A1 (de) * 1990-03-19 1991-09-25 Unilever Plc Detergenszusammensetzungen
WO1991015566A1 (en) * 1990-04-03 1991-10-17 The Procter & Gamble Company Fabric cleaning process
EP0504091A1 (de) * 1991-03-15 1992-09-16 Cleantabs A/S Phosphatfreies Maschinengeschirrspülmittel
ES2039191A1 (es) * 1991-03-20 1993-09-01 Sandoz Ag Procedimiento para el pretratamiento de un material textil.
US5538648A (en) * 1991-03-20 1996-07-23 Sandoz Ltd. Process for pretreating a textile material
WO1992018596A1 (en) * 1991-04-19 1992-10-29 The Procter & Gamble Company Granular laundry detergent compositions having improved solubility
US5338476A (en) * 1991-04-19 1994-08-16 The Procter & Gamble Company Granular laundry detergent compositions having improved solubility
EP0520582A1 (de) * 1991-06-28 1992-12-30 Colgate-Palmolive Company Sprühgetrocknete Waschmittelzusammensetzungen auf Zeolithbasis und Verfahren zur deren Herstellung
US5583098A (en) * 1993-11-24 1996-12-10 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
US5723428A (en) * 1993-11-24 1998-03-03 Lever Brothers Company Detergent compositions and process for preparing them
WO2001016279A1 (en) * 1999-09-02 2001-03-08 The Procter & Gamble Commpany Bleaching detergent compositions
US6548467B2 (en) 1999-09-02 2003-04-15 The Procter & Gamble Company Sanitizing compositions and methods
WO2003048291A1 (en) * 2001-11-30 2003-06-12 Ecolab, Inc. Stabilized active oxygen compositions

Also Published As

Publication number Publication date
AU2400788A (en) 1989-04-27
KR920002085B1 (ko) 1992-03-10
KR890006803A (ko) 1989-06-16
EP0313144A3 (de) 1989-10-18
NO884700D0 (no) 1988-10-21
JPH01146997A (ja) 1989-06-08
AU612711B2 (en) 1991-07-18
GB8724900D0 (en) 1987-11-25
NO884700L (no) 1989-04-24
CA1316790C (en) 1993-04-27
BR8805450A (pt) 1989-06-27

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