CA2004895A1 - Liquid non-phosphate detergent of high alkalinity - Google Patents

Liquid non-phosphate detergent of high alkalinity

Info

Publication number
CA2004895A1
CA2004895A1 CA002004895A CA2004895A CA2004895A1 CA 2004895 A1 CA2004895 A1 CA 2004895A1 CA 002004895 A CA002004895 A CA 002004895A CA 2004895 A CA2004895 A CA 2004895A CA 2004895 A1 CA2004895 A1 CA 2004895A1
Authority
CA
Canada
Prior art keywords
weight
detergent
component
alkyl
sodium
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.)
Abandoned
Application number
CA002004895A
Other languages
French (fr)
Inventor
Uwe Trabitzsch
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 DE3841129A external-priority patent/DE3841129A1/en
Priority claimed from DE19893906766 external-priority patent/DE3906766A1/en
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of CA2004895A1 publication Critical patent/CA2004895A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE
A detergent concentrate suitable for the preparation of liquid, concentrated stock solutions comprising (A) 5 to 20% by weight nonionic surfactants, of which (A1) 4 to 20%
by weight comprises alkyl glucosides corresponding to the formula R-O-Gx and (A2) 0 to 2% by weight C12-18 alkyl polyglycol ethers containing 5 to 9 ethylene oxide groups, (B1) 4 to 20% by weight sodium hydroxide, (B2) 0.5 to 12%
by weight sodium silicate Na2O : SiO2 = 1:1 to 1:3.4, (B3) 2 to 12% by weight sodium nitrilotriacetate and 0 to 3% by weight of at least one phosphonic acid in the form of the sodium salt, in the formula R-O-GX, R is a C8-14 alkyl radical, G is a glucose residue and the index x is a number of 1.2 to 5. The sum of the constituents (B3) and (B4) is 3 to 12% by weight.

Description

PATENT
Case D 7813-I CA

A ~IQUID NON-PHOSP~IATE DETERGENT OF HIGH ALKALINITY
BACKGROUND OF THE INVENTION
Field of the Invention:
Laundry detergents for institutional laundries differ considerably in their composition from those typically used in the home. On the one hand, softened water, i.e. Ca- and Mg-free water, is generally used in institutional laun-dries. On the other hand, institutional laundry deter-gents often contain highly alkaline builder salts and alkalis, such as sodium metasilicate and sodium hydroxide, which - although they can be safely handled by the expert -are unadvisable in the home for safety reasons. These highly alkaline constituents can in turn interact with the surfactants typically present, particularly nonionics of the alkyl polyglycol ether type, and can decompose them to a greater or lesser extent in the event of prolonged storage together. These problems exist in particular in the case of liquid concentrates and products which are intended for the preparation of concentrated stock solu-tions and in whose case the decomposing effect is particu-larly intensive through lack of spatial separation between the surfactant and alkali component. Highly alkaline liquid products and stock solutions have the advantage over powder-form preparations of the same composition in that they are dust free and, in particular, can be automatically dispensed and hence pose no operating problems.
Another aspect is the almost exclusive use of surfac-tants which can be obtained from natural, i.e. renewable, raw materials and which are distinguished by complete and rapid biodegradability in the wastewater.
In addition, detergents of the type in question should not produce troublesome quantities of foam either in the ~ . ~

.
~ ;:
- 2~

main wash cycle or in the final rinse cycle. Since stan-dard foam inhibitors, such as polysiloxanes and paraffin hydrocarbons, undergo losses of effect when dispersed in liquid detergents or, in the case of polysiloxanes, are decomposed by alkali, the surfactant component must i$self be low-~oaming.
DESCRIPTION OF THE_INVENTION
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".
The present invention, by which these problems are solved, relates to a liquid, aqueous, non-phosphate deter-gent concentrate comprising 5 to 20% by weight of a non-ionic surfactant component (A), 15 to 40% by weight of a builder component (B), up to 3% by weight of other non-surfactant and non-builder detergent constituents and the balance, water wherein said components have the following composition, based on the weight of the detergent:
~1) 4 to 20% by weight of an alkyl glucoside corresponding to formula ~
R-0-GX (I) where R = a C814 alkyl radical, G = a glucose residue and x = a number of 1.2 to 5, A2) o to 2~ by weight of at least one nonionic surfactant selected from the group consisting of alkyl polyglycol ethers containing C1218 alkyl groups and 5 to 9 ethylene oxide groups, B1) 4 to 20% by weight sodium hydroxide, B2) 0.5 to 12% by weight sodium silicate having the composition ratio Na20 : sio2 = 1:1 to 1:3.4, B3) 2 to 12% by weight sodium nitrilotriacetate, and B4) 0 to 3% by weight of the sodium salt of at least one phosphoric acid, with the proviso that the content of constituents B3) + B4) is from 3 to 12% by weight.
3 ~

., The detergent preferably contains the individual components in the following quantities:
A1) 5 to 12 ~ by weight A2) 0.5 to 1.5 % by weight B1) 6 to 15 % by weight B2) 0.5 to 3 % by weight B3) 3 to 10 % by weight B4) 0.2 to 2 ~ by weight Component (Al) comprises alkyl glucosides or alkyl oligoglucosides of the type described, for example, in US
Patents 3,5~7,828, 3,772,269 and 3,839,318. They are obtainable by reaction of glucose or depolymeriæed starch and alcohols containing C814 alkyl groups in the presence or absence of lower alcohols or glycols, such as butanol or propylene glycol, and acidic acetalization catalysts.
Alcohols or mixtures of alcohols obtained from natural fats, such as coconut oil or palm kernel oil, are preferably used as the fatty alcohols. Examples include octyl, decyl, lauryl and myristyl alcohol and also mixtures thereof. Alternatively, it is also possible to use alkyl glucosides which are derived from oxoalcohols and which, in addition to linear alcohols, also contain alcohols which are methyl-branched in the 2-position in admixture or an even or odd number of C atoms in the alkyl chain.
Examples are octyl, nonyl, decyl, undecyl, dodecyl and tridecyl alcohol and also mixtures thereof. R is prefer-ably a C812 alkyl group and more especially a C810 alkyl groupO In the reaction of the glucose or glucose~contain-ing starch degradation products with the alcohols, the glucose is partly oligomerized in the presence of acidic acetalization catalysts, resulting in the formation of mixtures of alkyl monoglucosides and alkylol oligogluco-sides. The parameter x in formula I thus represents an average degree of oligomerization and is preferably from 1.3 to 3. Mixtures such as these are meant where alkyl glucosides are mentioned generally in the context of the :
.

2~

invention.
From their production, the alkyl glucosides still contain small quantities of free fatty alcohol and glucose.
Alkyl glucosides containing less than 5% by weight and, more especially, less than 2% by weight fatty alcohols (based on alkyl glucoside) are preferably used.
In addition to the alkyl glucosides, the detergents may optionally contain nonionic surfactants of the ethoxy-lated fatty alcohol and oxoalcohol type containing 12 to 18 C atoms and 5 to 9 ethylene oxide groups (E0) as component (A2). Suitable nonionic surfactants of this type are, for example, ethoxylates derived from coconut oil, tallow or palm kernel oil fatty alcohols having an HLB value of more than 12, for example from 13 to 18, and corresponding ethoxylates of oxoalcohols containing 12 to 16 C atoms and 6 to 8 E0 groups.
The builder component comprises sodium hydroxide (constituent Bl), sodium silicate (constituent B2) and sequestering polyanionic salts derived from nitrilotriace-tic acid (NTA) and, optionally, phosphonic acids (constitu-ents B3 and B4).
In the sodium silicate, the ratio of Na20 to sio2 may be from 1:1 (metasilicate) to 1:3.4 (waterglass). In detergents containing relatively small amounts of sodium hydroxide, metasilicate is preferably used in the interests of high alkalinity whereas, in detergents having relatively high contents of sodium hydroxide, the sodium silicate may consist predominantly or completely of waterg].ass.
The NTA is present in the form of the trisodium salt, the quantitative calculation also being based on this form.
The NTA content is preferably from 5 to 10% by weight.
The phosphonate is primarily the sodium salt of 1-hydroxyethane~ -diphosphonic acid (HED~). The quantita-tive calculation is based on the tetrasodium salt. It is also possible to use the sodium salts of aminotrimethylene phosphonic aci~ (ATMP), ethylenediamine tetramethylene rj phosphonic acid ~EDTMP), diethylenetriamine pentamethylene phosphonic acid (DTPMP) and higher homologs thereof, al-though EDTMP is less preferred on account of its as yet unclear property in the wastewater. Their quantitative calculation is based on neutrally reacting sodium salts (Na3 salt in the case of ATMP, Nas salt in the case of ~DTMP, Na6 salt in the case of DTPMP). The sum of components B3 + B4 is from 3 to 12% by weight and preferably from 6 to 11% by weight.
In addition to the constituents mentioned above, the detergents may contain other non-surfactant and non-builder constituents, including optical brighteners in a quantity of up to 1% by weight and preferably from 0.05 to 0.3% by weight. Examples of optical brighteners are derivatives of bis-(triazinylamino)-stilbene disulfonic acid, for example the sodium salt of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazin-6-ylamino)-stilbene-2,2'-disulfonic acid and of the chlorinated diphenyl distyryl sulfonic acids.
Other optional constituents are enzymes, fragrances, dyes, hydrotropes and water-miscible solvents. Suitable hydrotropes are, for example, toluenesulfonate, xylenesul fonate and cumenesulfonate, in each case in the form of the sodium salts. Suitable solvents are, for example, ethanol, propanol, isopropanol and also ether alcohols, such as di-glycol, and C13 monoalkyl ethers of C24 diols. The hydro-tropes may be present in quantities of up to 6% by weight while the alcohols or ether alcohols may be present in quantities of up to 10% by weight. The detergents may also contain neutral salts, such as sodium sulfate and sodium chloride, in small quantities as impurities of the raw materials used. The balance to 100% by weight consists essentially of water.
The detergents are storable, pourable liquids which are suitable both for automatic dispensing and also for the preparation of stock solutions. The concentrates remain liquid and are stable to separation at temperatures of down to -10 D C. Their in-use concentration is generally from 2 to 10 g/l and preferably from 3 to 7 g/l.

r~

EXAMPLES

Detergents were prepared from the following constitu~
ents. In the alkyl glucoside, R was a mixture of C810 groups and X - 1.8, prepared by the direct synthesis method.

Table 1 Example Constituent 1 2 3 4 5 (quantities in % by weight) Alkyl glucoside 6 6 8 6 7 C121s alcohol ~ 7 EO 1 1 - 1 1 NaOH 10 12.5 15 6 13 Na2-SiO3 (1:3-3) 2 2 2 0.7 2.5 NTA (Na3 salt) 8 8 8 6 5 HEDP (Na salt) 2 _ 1 1 2.5 EDTMP (Na salt) DTPMP (Na salt) - - 1 _ 1 Optical brightener 0.1 0.1 0.1 0.1 0.1 Na cumenesulfonate - - - 4 Isopropanol - - - 5 Water bal- bal bal- bal- bal-ance ance ance ance ance .. . _ _ . _ .. . _ A washing machine (of the Frista~R) type) was loaded with lightly soiled laundry (bed and table linen which had been used once) and test cloths soiled as follows:
Al dust-wool grease on cotton A2 blood-milk-indian ink on cotton A3 blood on cotton A4 milk cocoa on cotton A5 dust-sebum on crease-resistant cotton o~

A6 dust-sebum on crease-resistant cotton/polyester blend A7 dust-wool grease on blended fabric ~as A6).
The quantity of laundry amounted to 7.5 kg, the water hardness was 0Gh, normal program (no prewash), detergent concentration 4 g/1, 5 minutes at 40C and 15 minutes at 90C, three rinses, low foaming.
The percentage remission (against a white standard) was photometrically evaluated. The values represent averages of three parallel determinations (scattering 2%).
The results are shown in Table 2 below. A commercially available detergent of similar composition (without gluco-side) was used for comparison (C). Equally good washing results were also obtained when alkyl glucosides in which x = 1.4 and x = 2.2 were used instead of the alkyl gluco-side in which x = 1.8.
Table 2 . . ~
% Remission Soil 1 2 3 5 C
_ _ ___ Al 75.9 73.2 73.1 73.8 71.5 A2 40.2 37.8 37.6 39.2 35.2 A3 83.5 82.4 82.6 82.7 78.2 A4 75.7 72.5 77.9 78.1 74.4 A5 58.6 54.6 52.0 53.8 48.1 A6 72.0 69.1 69.7 71.0 64.5 A7 58.9 56.0 53.6 58.1 49.3 . . ~

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A liquid, aqueous, non-phosphate detergent concen-trate comprising about 5 to about 20% by weight of a non-ionic surfactant component (A), about 15 to about 40% by weight of a builder component (B), up to about 3% by weight of other non-surfactant and non-builder detergent constituents and the balance, water wherein said components have the following composition, based on the weight of said detergent:
A1) about 4 to about 20% by weight of an alkyl glucoside corresponding to formula I
R-0-Gx (I) where R represents a C8-14 alkyl radical, G represents a glucose residue and x represents a number of about 1.2 to about 5, A2) 0 to about 2% by weight of at least one nonionic surfactant selected from the group consisting of alkyl polyglycol ethers containing C12-18 alkyl groups and about 5 to about 9 ethylene oxide groups, B1) about 4 to about 20% by weight sodium hydroxide, B2) about 0.5 to about 12% by weight sodium silicate having the composition ratio Na2O : sioz = 1: 1 to 1:3.4, B3) about 2 to about 12% by weight sodium nitrilotriacetate, and B4) 0 to about 3% by weight of the sodium salt of at least one phosphoric acid, with the proviso that the content of constituents B3) + B4) is from about 3 to about 12%
by weight.
2. A detergent in claim 1, wherein said components are present in the following quantities:
A1) about 5 to about 12 % by weight, A2) about 0.5 to about 1.5 % by weight, Bl) about 6 to about 15 % by weight, B2) about 0.5 to about 3 % by weight, B3) about 3 to about 10 % by weight, and B4) about 0.2 to about 2 % by weight.
A detergent as in claim 1, wherein in formula (I), R
is a C8-12 alkyl radical and x is a number from about 1.3 to about 3.
4. A detergent as in claim 1 wherein said nonionic surfactant of component A2) has an HLB value of about 12 to about 18.
5. A detergent as in claim 1 wherein said component B4) comprises the sodium salt of 1-hydroxyethane-1,1-diphosphonic acid.
6. A detergent as in claim 5, wherein said component B4) includes the sodium salt of diethylenetriamine pentamethylene phosphonic acid.
7. A detergent as in claim 1 wherein the amount of component B3) is from about 5 to about 10% by weight.
8. A detergent as in claim 1 wherein the sum of components B3) + B4) is from about 6 to about 11% by weight.
9. A detergent as in claim 1 wherein said non-surfactant and non-builder constituents are selected from an optical brightener, enzyme, fragrance, dye, hydrotrope and water-miscible solvent.
CA002004895A 1988-12-07 1989-12-07 Liquid non-phosphate detergent of high alkalinity Abandoned CA2004895A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3841129A DE3841129A1 (en) 1988-12-07 1988-12-07 Phosphate-free, liquid detergent with high alkalinity
DEP3841129.6 1988-12-07
DE19893906766 DE3906766A1 (en) 1989-03-03 1989-03-03 Phosphate-free liquid detergent of high alkalinity
DEP3906766.1 1989-03-03

Publications (1)

Publication Number Publication Date
CA2004895A1 true CA2004895A1 (en) 1990-06-07

Family

ID=25874879

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002004895A Abandoned CA2004895A1 (en) 1988-12-07 1989-12-07 Liquid non-phosphate detergent of high alkalinity

Country Status (9)

Country Link
EP (2) EP0377807B1 (en)
JP (1) JPH04502337A (en)
AU (1) AU626954B2 (en)
CA (1) CA2004895A1 (en)
DE (1) DE58906948D1 (en)
DK (1) DK101291D0 (en)
ES (1) ES2061894T3 (en)
PT (1) PT92396A (en)
WO (1) WO1990006353A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995013400A1 (en) * 1993-11-10 1995-05-18 Henkel Corporation Wet treatment of leather hides
US5542950A (en) * 1994-11-10 1996-08-06 Henkel Corporation Alkyl polyglycosides in textile scour/bleach processing
US6194371B1 (en) 1998-05-01 2001-02-27 Ecolab Inc. Stable alkaline emulsion cleaners
US7041177B2 (en) 2002-08-16 2006-05-09 Ecolab Inc. High temperature rapid soil removal method
WO2018005457A1 (en) * 2016-06-27 2018-01-04 The Procter & Gamble Company Improved removal of hydrophilic body soils

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4009533A1 (en) * 1990-03-24 1991-09-26 Henkel Kgaa LOW-EFFICIENT NON-ionic surfactant mix
DE4225224A1 (en) * 1992-07-30 1994-02-03 Henkel Kgaa Process for the production of storage-stable nonionic surfactants
US5525256A (en) * 1995-02-16 1996-06-11 Henkel Corporation Industrial and institutional liquid cleaning compositions containing alkyl polyglycoside surfactants
FR2744132B1 (en) 1996-01-31 1998-04-24 Rhone Poulenc Chimie BASIC SYSTEM OF A NON-IONIC SURFACTANT AND AN ALKALINE METAL SILICATE, IN THE FORM OF A DISPERSION OR PELLETS AND ITS USE IN DETERGENCE
US6369021B1 (en) * 1999-05-07 2002-04-09 Ecolab Inc. Detergent composition and method for removing soil

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772259A (en) 1965-07-12 1973-11-13 American Cyanamid Co 2-vinyl-1-cycloamidinepropionamide polymers
US3547828A (en) 1968-09-03 1970-12-15 Rohm & Haas Alkyl oligosaccharides and their mixtures with alkyl glucosides and alkanols
US3721633A (en) * 1969-10-06 1973-03-20 Atlas Chem Ind Aqueous built liquid detergents containing alkyl glycosides
US3839318A (en) 1970-09-27 1974-10-01 Rohm & Haas Process for preparation of alkyl glucosides and alkyl oligosaccharides
GR76286B (en) * 1981-09-28 1984-08-04 Procter & Gamble
FR2540511B1 (en) * 1983-02-04 1985-08-09 Henkel France LIQUID CLEANING COMPOSITION AND METHOD FOR CLEANING USING THE SAME
DE3518672A1 (en) * 1985-05-24 1986-11-27 Basf Ag, 6700 Ludwigshafen LIQUID CLEANING CONCENTRATE FOR STRONG ALKALINE CLEANING FORMULAS
JPS63503389A (en) * 1986-05-06 1988-12-08 エー・イー・ステーレイ・マニフアクチユアリング・コムパニー Liquid laundry detergent with builder containing alkyl glycoside surfactants
DE3708330A1 (en) * 1987-03-14 1988-09-22 Henkel Kgaa LIQUID, ALKALINE CLEANER CONCENTRATES

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995013400A1 (en) * 1993-11-10 1995-05-18 Henkel Corporation Wet treatment of leather hides
US5503754A (en) * 1993-11-10 1996-04-02 Henkel Corporation Wet treatment of leather hides
US5985167A (en) * 1993-11-10 1999-11-16 Hodgson Process Chemicals Inc. Wet treatment of leather hides
US5542950A (en) * 1994-11-10 1996-08-06 Henkel Corporation Alkyl polyglycosides in textile scour/bleach processing
US6194371B1 (en) 1998-05-01 2001-02-27 Ecolab Inc. Stable alkaline emulsion cleaners
US7041177B2 (en) 2002-08-16 2006-05-09 Ecolab Inc. High temperature rapid soil removal method
WO2018005457A1 (en) * 2016-06-27 2018-01-04 The Procter & Gamble Company Improved removal of hydrophilic body soils

Also Published As

Publication number Publication date
EP0377807B1 (en) 1994-02-09
DE58906948D1 (en) 1994-03-24
AU4626089A (en) 1990-06-26
DK101291A (en) 1991-05-28
EP0447413A1 (en) 1991-09-25
JPH04502337A (en) 1992-04-23
ES2061894T3 (en) 1994-12-16
AU626954B2 (en) 1992-08-13
WO1990006353A1 (en) 1990-06-14
EP0377807A1 (en) 1990-07-18
DK101291D0 (en) 1991-05-28
PT92396A (en) 1990-06-29

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