EP0484363A1 - Composition de blanchiment liquide. - Google Patents

Composition de blanchiment liquide.

Info

Publication number
EP0484363A1
EP0484363A1 EP90910739A EP90910739A EP0484363A1 EP 0484363 A1 EP0484363 A1 EP 0484363A1 EP 90910739 A EP90910739 A EP 90910739A EP 90910739 A EP90910739 A EP 90910739A EP 0484363 A1 EP0484363 A1 EP 0484363A1
Authority
EP
European Patent Office
Prior art keywords
bleach
electrolyte
metaborate
weight
liquid detergent
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.)
Granted
Application number
EP90910739A
Other languages
German (de)
English (en)
Other versions
EP0484363B1 (fr
Inventor
Theresia Maria Olsthoorn
De Pas Johannes Cornelis Van
Ton Swarthoff
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
Priority claimed from EP90200290A external-priority patent/EP0385522B1/fr
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0484363A1 publication Critical patent/EP0484363A1/fr
Application granted granted Critical
Publication of EP0484363B1 publication Critical patent/EP0484363B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/046—Salts
    • 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
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising an aqueous base, detergent active materials and a bleach material.
  • the present invention relates a liquid detergent composition
  • a liquid detergent composition comprising an aqueous base, a bleach material and from 2-60 % by weight of detergent active materials, wherein the composition also comprises a metaborate electrolyte or a boron electrolyte
  • compositions according to the present invention are provided.
  • bleach material which is preferably a peroxygen bleach.
  • This bleach component may be present in the system in dissolved form, but preferred is that only part of the peroxygen bleach is solubilized, the remaining part preferably being present as solid
  • bleach compounds include hydrogen peroxide, the perborates, persulfates, peroxy
  • peroxyhydrates formed by reacting hydrogen peroxide with urea or alkali metal carbonate are also encapsulated bleaches may be used. Preferred bleaches are only partially soluble in the system. Especially preferred is the use of perborate or percarbonate bleaches.
  • the bleach component is preferably added in an amount corresponding to 0.1 to 15% by weight of active oxygen, more preferred from 0.5 to 10% active oxygen, typically from 1.0 to 5.0% active oxygen. Typical amounts of bleach will be between 1 and 40 % by weight of the aqueous composition, more preferred from 7 to 30%, especially preferred from 10 to 25 % by weight of the composition.
  • Compositions of the invention also comprise a metaborate electrolyte or a boron electrolyte obtainable by using metaborate.
  • Suitable metaboric compounds include for example netaboric acid, alkali metal metaborates and alkali earth metal metaborates.
  • metaborate electrolyte can have two functions, firstly it prevents the solubilisation of the bleach material, therewith minimizing the amount of instable dissolved bleach and secondly it retards the decomposition of the dissolved bleach materials.
  • the level of metaborate electrolyte is preferably more than 0.1 % by weight of the compositions, especially preferred more than 0.2 % by weight of the composition, most preferred more than 0.4 %. Generally the level of metaborate electrolyte is less than 10%, more preferred less than 7 %, especially preferred less than 5 %.
  • Typical levels of metaborate electrolytes are from 0.5 to 5 %.
  • the percentages for the metaborate electrolyte are calculated on the basis of the anhydrous metaborate equivalent of the electrolyte.
  • the metaborate level is preferably determined by measuring the boron content of the formulation and subsequently calculating the
  • the calculated level of the metaborate at the standard pH is then defined as the metaborate level in the composition.
  • the molar ratio of metaborate or boron equivalent thereof to hydrogen peroxide (if any) in the ready to use composition is more than 1 : 1, preferably more than 2 : 1, most preferred more than 5 : 1. detergent active materials
  • compositions of the present invention also comprise detergent active materials. Surprisingly it has been found that a combination of bleach materials and
  • metaborate electrolytes or boron derivatives thereof is suitable for use in ready to use aqueous liquid
  • the detergent active materials in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and ⁇ provided mutually compatible) mixtures thereof.
  • surfactants may be selected from any of the classes, sub-classes and specific materials described in "Surface Active Agents" Vol. I, by Schwartz & Perry, Interscience 1949 and
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example
  • nonionic detergent compounds are alkyl (C 6 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and
  • nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phospine oxides and dialkyl sulphoxides.
  • salting out resistant active materials such as for example described in EP 328 177, especially the use of alkyl poly glycoside surfactants, such as for example disclosed in EP 70 074.
  • Suitable anionic surfactants 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 acyl radicals.
  • Suitable synthetic 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 (C 9 -C 20 ) benzene sulphonates,
  • sulphonates sodium and potassium salts of sulphuric acid esters of higher (C 8 -C 18 ) 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
  • alkane monosulphonates such as those derived by reacting alpha- olefins (C 8 -C 20 ) with sodium bisulphite and those derived from reacting paraffins with SO 2 and Cl 2 and then hydrolysing with a base to produce a random
  • olefin sulphonates which term is used to describe the material made by reacting olefins
  • the preferred anionic detergent compounds are sodium (C 11 - C 15 ) alkyl benzene sulphonates and sodium or potassium primary (C 10 -C 18 ) alkyl sulphates.
  • an alkali metal soap of a fatty acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, alkylsuccinic acid, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • the total detergent active material may be present at from 2% to 60% by weight of the total composition, for example from 5% to 40% and typically from 10% to 30% by weight.
  • one preferred class of compositions comprises at least 20%, most preferably at least 25% and especially at least 30% of detergent active material based on the weight of the total composition.
  • compositions of the invention may be un-structured
  • Structured liquids of the invention may be internally structured whereby the structure is formed by the detergent active materials in the composition or externally structured, whereby the structure is provided by an external structurant.
  • compositions of the invention are internally structured.
  • the presence and identity of a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, x-ray or neutron diffraction, and sometimes, electron microscopy.
  • the aqueous continuous phase contains dissolved electrolyte.
  • electrolyte means any ionic water soluble material. However, in lamellar dispersions, not all the electrolyte is necessarily dissolved but may be
  • electrolytes suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte.
  • Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase.
  • Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g. the order of addition of components.
  • salts includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water soluble materials) .
  • compositions where the detergent active material comprises blends of different surfactant types.
  • Typical blends usefu- for fabric washing compositions include those where the primary surfactant(s) comprise nonionic and/or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
  • compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • the builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material.
  • the salting-out electrolyte comprises citrate.
  • phosphorous-containing inorganic detergency. builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and
  • Phosphonate sequestrant builders may also be used. Examples of non-phosphorus-containing inorganic
  • detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and
  • potassium bicarbonates silicates and zeolites.
  • electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts.
  • electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts.
  • organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
  • ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, CMOS, TMS, TDS, melitic acid, benzene polycarboxylic acids and citric acid.
  • the level of non-soap builder material is from 0-50% by weight of the composition, more preferred from 5-40%, most preferred 10-35%.
  • organic builders it is also desirable to incorporate polymers which are only partly dissolved, in the aqueous continuous phase as described in EP
  • compositions of the present invention alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100ml of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal to or less than the vapour pressure of a reference 2% by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000.
  • Use of such polymers is generally described in our EP 301,883. Typical levels are from 0.5 to 4.5% by weight.
  • compositions according to the present is preferably less than 1500 mPas, more preferred less than 1000 mPas, especially preferred between 30 and 900 mPas at 21 s -1 .
  • One way of regulating the viscosity and stability of compositions according to the present invention is to include viscosity regulating polymeric materials.
  • Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are for instance described in our copending European application EP 89201530.6
  • formulations according to the present invention may be of anionic, nonionic or cationic nature.
  • deflocculating polymers are preferred.
  • the hydrophilic backbone of the polymer is typically a homo-, co- or ter-polymer containing carboxylic acid groups (or more preferably) salt forms thereof), e.g. maleate or acrylate polymers or co-polymers of these together or with other monomer units such as vinyl ethers, styrene etc.
  • the hydrophobic chain or chains typically are selected from saturated and unsaturated alkyl chains, e.g. having from 5 to 24 carbon atoms and are optionally bonded to the backbone via an alkoxylene or polyalkoxylene linkage, for example a polyethoxy, polypropoxy or butyloxy (or mixtures of same) linkage having from 1 to 50 alkoxylene groups.
  • the side chain(s) will essentially have the character of a nonionic surfactant.
  • Preferred anionic polymers are disclosed in our copending European patent application EP 89201530.6 (EP 346 995).
  • the amount of viscosity regulating polymer is from 0.1 to 5% by weight of the total composition, more preferred from 0.2 to 2%.
  • C 1-5 alcohols are di- or tri- alcohols comprising three or four carbon atoms per molecule.
  • propylene glycol and glycerol is especially preferred.
  • the level of C 1-5 poly-hydric alcohols is more than 1 % by weight of the composition, preferably more than 2 %, especially preferred more than 3 %.
  • compositions of the invention will comprise less than 30 % by weight of the polyhydric alcohol, more preferred less than 20 %, especially preferred less than 15 %. Typical levels are from 4 to 10 % by weight of the composition. Compositions of the invention may also comprise
  • compositions of the invention contain enzymes such as amylases, proteases and lipolases.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, germicides colourants and enzymes such as proteases, cellulases, amylases and lipases (including Lipolase (Trade Mark) ex Novo).
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • fabric softeners such as clays, amines and amine oxides
  • lather depressants such as inorganic salts such as sodium sulphate
  • fluorescent agents such as fluorescent agents, perfumes, germicides colourants and enzymes such as proteases, cellulases, amylases and lipases (including Lipolase (Trade Mark) ex
  • protease enzymes are Savinase (ex Novo), Maxatal (gist-brocades), Opticlean (ex MKC) or AP122 (ex Showa Denko), Alcalase, Maxatase, Esperase, Optimase, proteinase K and
  • subtilisin BPN subtilisin BPN.
  • Suitable lipolases are for example
  • Lipolase (ex Novo), Amano lipases, Meito lipases,
  • Suitable amylases are for example Termamyl (TM of Novo) and
  • Suitable cellulases include Celluzym (ex Novo). Amongst these optional ingredients, as mentioned
  • compositions of the invention preferably comprise from 10 -80 %% by weight of water, more preferably from 15-60%, most preferably from 20-50 %.
  • Liquid detergent compositions according to the invention are preferably physically stable in that they show less than 2% by volume phase separation upon storage for 21 days after preparation at 25°C.
  • Liquid detergent compositions according to the invention are preferably volume stable in that they show less than 25% preferably less than 10%, more preferably less than 5% volume increase during storage at a temperature between 20 and 37°C for a period of three months after preparation.
  • compositions according to the present invention also comprise a second stabilising agent for the bleach component.
  • Suitable stabilisers are well-known in art and include EDTA, Magnesium silicates and phosphonates such as for instance the Dequest range ex Monsanto and Naphthol ex Merck.
  • the amount of these stabilising agents is from 0.05 to 5 % by weight of the composition, more preferred from 0.05 to 1% of the composition.
  • Compositions of the present invention may comprise one or more bleach precursor agents.
  • a well-known example of such an agent is TAED.
  • the bleach precursor agent is present in the system in at least partly undissolved form.
  • One way of ensuring that the precursor is present in undissolved form is to increase the amount of electrolyte in the composition, therewith reducing the solubility of the precursor in the system.
  • Suitable electrolytes for this purpose are for instance the at least partially water soluble carbonate, sulphate and halogenide salts.
  • the detergent compositions of the inventention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
  • concentration of liquid detergent composition in the wash liquor is preferably from 0.05 to 10 %, more preferred from 0.1 to 3% by weight.
  • liquid detergent compositions preferably are alkaline, and it is
  • the undiluted liquid composition should preferably be of a pH above 7, for example about pH 8.0 to about 12.5. It should be noted that an excessively high pH, e. g. over about pH 13 , is less desirable for domestic safety. If hydrogen peroxide is present in the liquid composition, then the pH is generally from 7.5 to 10.5, preferably 8 to 10, and especially 8.5 to 10, to ensure the combined effect of good detergency and good physical and chemical stability.
  • the ingredients in any such highly alkaline detergent composition should, of course, be chosen for alkaline stability, especially for pH-sensitive
  • the pH may be adjusted by addition of a suitable alkaline or acid material.
  • compositions according to the invention may be prepared by any method for the preparation of liquid detergent compositions.
  • a preferred method involves the addition of metaborate to water, which optionally comprises one or more of the other ingredients of the formulation.
  • the bleach materials are preferably added as a pre-dispersion .
  • composition A comprises 20 parts of bleach materials and 40 parts of water; a corresponding liquid detergent composition would comprise 20 parts of bleach, 40 parts of water and 40 (up to 100) parts of detergent active materials in combination with other ingredients.
  • absolute stability of the bleach in the compositions without the detergent active materials can differ from the absolute stability of the bleach in the
  • compositions A-D were prepared by adding the ingredients to water in the listed order under stirring. The result is a physically instable perborate dispersion from which the undissolved bleach materials will sediment. The continuous electrolyte phase containing the dissolved ingredients was isolated and assessed for bleach content and bleach stability. Since only the dissolved amount of bleach will contribute to the decomposition of the bleach, the results obtained for the separated
  • electrolyte phase are representative for the stability of the total bleach stability in the system.
  • electrolyte phase was measured by iodometric titiations, the half-life time was determined on the basis of measurements of the amount of solubilised bleach in the-separated electrolyte phase as a function of time.
  • composition A comprising the bleach material in water in the absence of
  • composition D containing glycerol and bleach in water in the absence of metaborate also provides a high level of dissolved bleach which decomposes in less than 1 day.
  • Composition B contains metaborate in combination with bleach
  • composition C which additionally comprises Glycerol has the advantage of a lower pH; this is especially preferred for enzyme containing liquid detergent compositions. Also this composition is more stable than the corresponding composition without metaborate.
  • compositions were prepared and the amount of dissolved bleach and its stability was measured as in example 1.
  • Tests F-G and J show that the pH of a bleach and metaborate composition can advantageously be decreased by using citric acid; the obtained compositions are of acceptable stability. Lowering the pH of the compositions with sulphuric acid (tests H-I) leads to instability of th bleach especially at low pH values.
  • compositions were prepared and assessed for bleach stability as in example 1. The following results were obtained
  • liquid detergent compositions may be formulated by adding the ingredients to water in the listed order:
  • Example 5 the following formulations may be prepared as in example 4:
  • detergent compositions may be prepared as in example 4.
  • ICI approximate 65% perborate dispersion in water with an average perborate particle size of 40 micrometer).
  • composition of example 7 was prepared, while CaCl 2 was used at a level of 1% in combination with 0.8% of enzymes, whereby the following types of enzymes were used.
  • Savinase slurry (Savinase 16.0 SL ex Novo).
  • Alcalase liquid Alcalase 2.34 LDX ex Novo

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  • 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)
  • Cosmetics (AREA)

Abstract

Composition détergente liquide et prête à l'emploi comportant une base aqueuse, un matériau de blanchiment, entre 2 % et 60 % en poids de matières détergentes actives ainsi qu'un électrolyte de métaborate ou un électrolyte boré pouvant être obtenu au moyen d'un métaborate.
EP90910739A 1989-07-13 1990-06-27 Composition de blanchiment liquide Expired - Lifetime EP0484363B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB898916094A GB8916094D0 (en) 1989-07-13 1989-07-13 Liquid bleach composition
GB8916094 1989-07-13
EP90200290A EP0385522B1 (fr) 1989-02-27 1990-02-08 Composition détergente liquide
PCT/EP1990/001046 WO1991000902A1 (fr) 1989-07-13 1990-06-27 Composition de blanchiment liquide

Publications (2)

Publication Number Publication Date
EP0484363A1 true EP0484363A1 (fr) 1992-05-13
EP0484363B1 EP0484363B1 (fr) 1993-09-29

Family

ID=26125738

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90910739A Expired - Lifetime EP0484363B1 (fr) 1989-07-13 1990-06-27 Composition de blanchiment liquide

Country Status (11)

Country Link
EP (1) EP0484363B1 (fr)
JP (1) JPH0768549B2 (fr)
AU (1) AU636629B2 (fr)
BR (1) BR9007519A (fr)
CA (1) CA2062781C (fr)
DE (1) DE69003683T2 (fr)
ES (1) ES2060186T3 (fr)
GB (1) GB8916094D0 (fr)
TR (1) TR25827A (fr)
WO (1) WO1991000902A1 (fr)
ZA (1) ZA905510B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69109273T2 (de) * 1990-02-08 1995-08-24 Unilever Nv Flüssiges bleichmittel.
DE4123142A1 (de) * 1991-07-12 1993-01-14 Henkel Kgaa Fluessigwaschmittel
WO1996033258A1 (fr) * 1995-04-20 1996-10-24 Albright & Wilson Uk Limited Suspensions aqueuses stabilisees d'agent de blanchiment contenant des particules de perborate
ES2373300B1 (es) * 2011-12-14 2012-12-20 Soro Internacional, S.A. Detergente para lavavajillas.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2140822A5 (en) * 1971-06-09 1973-01-19 Air Liquide Bleaching liquids - contg hydrogen peroxide or persalts in alkaline medium with stabilisers
DE3007796C2 (de) * 1980-02-29 1982-07-15 Hoffmann's Stärkefabriken AG, 4902 Bad Salzuflen Verfahren zur Erhöhung des Weißgrades, zur Verhinderung der Vergrauung sowie zur Entgrauung von Geweben und Gewirken aus Chemiefasern oder Mischungen aus Chemiefasern und Naturfasern
GB8424812D0 (en) * 1984-10-02 1984-11-07 Unilever Plc Enzymatic detergent composition
GB8712430D0 (en) * 1987-05-27 1987-07-01 Procter & Gamble Liquid detergent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9100902A1 *

Also Published As

Publication number Publication date
CA2062781A1 (fr) 1991-01-14
AU5954190A (en) 1991-02-06
ES2060186T3 (es) 1994-11-16
JPH04506535A (ja) 1992-11-12
BR9007519A (pt) 1992-06-23
EP0484363B1 (fr) 1993-09-29
JPH0768549B2 (ja) 1995-07-26
GB8916094D0 (en) 1989-08-31
CA2062781C (fr) 1997-11-25
DE69003683D1 (de) 1993-11-04
DE69003683T2 (de) 1994-01-27
ZA905510B (en) 1992-03-25
WO1991000902A1 (fr) 1991-01-24
AU636629B2 (en) 1993-05-06
TR25827A (tr) 1993-09-01

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