EP0300305B1 - Verwendung von Hydroxyalkylpolyethylenglykolethern in Klarspülmitteln für die maschinelle Geschirreinigung - Google Patents

Verwendung von Hydroxyalkylpolyethylenglykolethern in Klarspülmitteln für die maschinelle Geschirreinigung Download PDF

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Publication number
EP0300305B1
EP0300305B1 EP88111024A EP88111024A EP0300305B1 EP 0300305 B1 EP0300305 B1 EP 0300305B1 EP 88111024 A EP88111024 A EP 88111024A EP 88111024 A EP88111024 A EP 88111024A EP 0300305 B1 EP0300305 B1 EP 0300305B1
Authority
EP
European Patent Office
Prior art keywords
general formula
compounds
alkyl radical
weight
rinse
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 - Lifetime
Application number
EP88111024A
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German (de)
English (en)
French (fr)
Other versions
EP0300305A2 (de
EP0300305A3 (en
Inventor
Horst Prühs
Gilbert Dr. Schenker
Theodor Dr. Altenschöpfer
Robert Dr. Piorr
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
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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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT88111024T priority Critical patent/ATE85642T1/de
Publication of EP0300305A2 publication Critical patent/EP0300305A2/de
Publication of EP0300305A3 publication Critical patent/EP0300305A3/de
Application granted granted Critical
Publication of EP0300305B1 publication Critical patent/EP0300305B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents

Definitions

  • the invention relates to the use of hydroxyalkyl polyethylene glycol ethers in rinse aids for machine dishwashing.
  • the rinse aid must be as low-foaming as possible.
  • Common anionic wetting agents such as higher molecular weight Alkyl sulfates or alkyl or alkyl aryl sulfonates have a strong tendency to foam and are therefore not suitable as rinse aid.
  • agents based on nonionic surfactants for example of ethylene oxide adducts with fatty alcohols, alkylphenols or polypropylene glycols of relatively high molecular weights, are now widely used.
  • Non-ionic alkoxylation products which are sparingly water-soluble at rinse aid temperatures are suitable as such. These include ethylene oxide adducts with higher alcohols, alkylphenols or amines with a low degree of ethoxylation or corresponding adducts of ethylene oxide and propylene oxide or propylene oxide and ethylene oxide in any order and in any ratio. However, such compounds have no wetting action at application temperatures and therefore represent a burden on the rinse aid.
  • rinse aids for machine dishwashing based on nonionic, low-foaming surfactants with an adduct content of 5 to 20 moles of ethylene oxide and 1 to 10 moles of propylene oxide with secondary aliphatic alcohols with a linear alkyl chain with 10 to 20 C atoms.
  • the adducts mentioned show an excellent drainage and clear drying effect.
  • the requirements for biodegradability at that time were met.
  • the compounds mentioned do not meet current legal requirements for the degradability of compounds that get into wastewater.
  • R1 represents a straight-chain alkyl radical having 1 to 16 carbon atoms.
  • alkyl radicals are the radicals methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl , n-Pentadecyl and n-Hexadecyl in question.
  • hydroxyalkyl polyethylene glycol ethers of the general formula (I) are used, in which R 1 represents a linear alkyl radical having 12 to 16 carbon atoms.
  • R 1 represents a linear alkyl radical having 12 to 16 carbon atoms.
  • Such hydroxyalkyl polyethylene glycol ethers of the general formula (I) when used in rinse aids, give the rinsing water a particularly good drainage behavior.
  • R2 represents a straight-chain or branched alkyl radical having 4 to 8 carbon atoms.
  • the residues n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl and the respective branched isomers of the alkyl residues mentioned are thus suitable. Since alcohols are used as starting materials for the preparation of the compounds of the general formula (I), the alkyl radical of which corresponds to the radical R 2 in the abovementioned general formula (I), the linear or branched alcohols with 4 to 8 C are therefore preferred for the preparation Atoms in the alkyl radical in question.
  • R3 is hydrogen or a straight-chain alkyl radical having 1 to 16 carbon atoms.
  • R3 is hydrogen or a straight-chain alkyl radical having 1 to 16 carbon atoms.
  • R3 is hydrogen or a straight-chain alkyl radical having 1 to 16 carbon atoms.
  • R3 is hydrogen or a straight-chain alkyl radical having 1 to 16 carbon atoms.
  • R3 is hydrogen or a straight-chain alkyl radical having 1 to 16 carbon atoms.
  • R3 is hydrogen or a straight-chain alkyl radical having 1 to 16 carbon atoms.
  • hydroxyalkyl polyethylene glycol ethers of the general formula (I) in which R 1 is a linear alkyl radical having 12 to 16 carbon atoms and R 3 is hydrogen.
  • R 1 is a linear alkyl radical having 12 to 16 carbon atoms
  • R 3 is hydrogen.
  • Such compounds result in particularly good rinse aid effects: they are also accessible from corresponding epoxides in which the oxirane ring is terminal and which consequently can be converted particularly well into compounds of the general formula (I).
  • n stands for a number in the range from 7 to 30. This means nothing other than that - in the preparation of the compounds of the general formula (I) - the starting alcohol from the group mentioned above is ethoxylated in a molar ratio of 1: 7 to 1:30 with ethylene oxide. The corresponding number of recurring ethoxy units then also results for the compounds of the general formula (I) used according to the invention.
  • Compounds (I) whose general formula n stands for a number in the range from 8 to 16 are preferably used. Because of the good wetting behavior, particularly good rinse aid effects are achieved with such compounds (I), in the general formula of which n stands for a number in the range from 9 to 14.
  • linear or branched alcohols having 4 to 8 carbon atoms are used as starting material for the preparation of the hydroxyalkyl polyethylene glycol ethers of the general formula (I), it being possible for the alcohols to be present both individually and in a mixture, for example in a mixture of several isomers to use.
  • the reaction partner of the alcohols mentioned is then ethylene oxide, the molar ratio of the reaction partners of the ethoxylation reaction (alcohol: ethylene oxide) being in the range from 1: 7 to 1:30.
  • n in the starting materials for the preparation of the compounds of the general formula (I) used according to the invention is a number in the range from 7 to 30.
  • the alcohol ethoxylates obtained are reacted with epoxides having 10 to 18 carbon atoms to prepare the compounds (I) used according to the invention.
  • epoxides having 10 to 18 carbon atoms
  • Both 1,2-epoxides and compounds with an internal oxirane ring are suitable for this reaction.
  • Epoxides with a terminal oxirane ring and 12 to 16 carbon atoms in the alkyl radical R have proven to be particularly suitable.
  • Mixtures of epoxides of different chain lengths can also be used in the reaction to produce the compounds (I) used according to the invention.
  • the reaction usually takes place in the presence of suitable, usually alkaline, catalysts. These are added to the reaction mixture in an amount of 0.1 to 1% by weight, based on the amount of epoxy used.
  • the molar ratio of alcohol alkoxylate: epoxy is advantageously approximately in the range of 1: 1 for the reaction.
  • the reaction mixture becomes heated to temperatures in the range from 100 to 200 ° C., preferably in the range from 120 to 180 ° C.
  • the degree of conversion can easily be determined by determining the epoxy content of the mixture.
  • a reaction time of 4 to 8 hours at a temperature in the range from 150 to 170 ° C. is generally sufficient.
  • the compounds of the above general formula (I) are used in rinse aids as the sole surfactant component.
  • Rinse aids which contain hydroxyalkyl polyethylene glycol ethers of the general formula (I) as the sole surfactant component, not only have the advantage of a pronounced lack of foam compared to the prior art, but also ensure that there are no problems with the requirements of biodegradability with regard to this surfactant component.
  • rinse aids show excellent wetting behavior; Even glasses whose rinsing was always considered problematic according to the state of the art are rinsed perfectly and can therefore be cleaned with good results even with dishwashers commonly used in commercial companies, i.e. rinse without stains and streaks.
  • hydroxyalkyl polyethylene glycol ethers of the general formula (I) with small amounts of other nonionic surfactants.
  • Suitable other nonionic surfactants are, for example, sufficiently degradable Ethylene oxide adducts with fatty alcohols or adducts of propylene oxide or butylene oxide with fatty alcohol ethoxylates.
  • the quality of the rinse aid using the hydroxyalkyl polyethylene glycol ethers of the general formula (I) to be used according to the invention does not undergo any significant change, in particular no deterioration.
  • the compounds (I) used according to the invention are used in the rinse aid in a concentration of 5 to 65% by weight, based on the total weight of the rinse aid.
  • aqueous solutions are preferably used which enable the compounds (I) to be rapidly distributed or dissolved in the rinsing liquid.
  • the preferred concentration range for the use of the compounds (I) is 15 to 50% by weight, based on the total weight of the rinse aid.
  • the use according to the invention of the compounds of the general formula (I) also corresponds to adding further substances to the rinse aid which are normally used in such rinse aid.
  • the rinse aid which are normally used in such rinse aid.
  • solubilizing substances into the recipes.
  • Monohydric or polyhydric alcohols are to be mentioned as such, of which ethanol, n-propanol, i-propanol, ethylene glycol and propylene glycol are preferred.
  • alkali metal salts of low molecular weight alkylbenzenesulfonic acids such as sodium cumene sulfonate, sodium xylene sulfonate or sodium toluenesulfonate, which are known from the prior art, are also suitable for this purpose.
  • the amounts of the solvent-imparting substances mentioned can be in the range between 0 and 40% by weight, based on the total rinse aid. The exact amount depends - among other parameters - on the cloud point of the surfactant used and the desired storage stability and can be varied within the limits mentioned without the excellent rinse effects achieved by the use of the compounds of the general formula (I) in any way influence.
  • complexing agents should be mentioned in particular, which are intended to prevent limescale deposits on the dishes when non-softened water is used in the rinse cycle.
  • Such complexing agents can be added in amounts of 0 to 40% by weight, based on the total rinse aid, preferably in amounts of 10 to 35% by weight.
  • Complexing agents which have proven themselves in this connection are, for example, citric acid, tartaric acid, glycolic acid, nitrilotriacetic acid or commercially available technical mixtures of succinic acid, glutaric acid and adipic acid (available under the name "Sokalan DCS” ®) from the company BASF).
  • Complexing agents which have threshold-effective properties can also be used, provided they are physiologically harmless and can therefore be used in the area of machine washing of objects which come into contact with food.
  • Examples of such complexing agents are 2-phosphonobutane-1.2.4-tricarboxylic acid and comparable compounds.
  • the former is available, for example, under the name "Bayhibit AM” ®.
  • the use concentrations can be lower than those for the above-mentioned complexing agents and can be 0 to 10% by weight, preferably 2 to 7% by weight, based on the total rinse aid.
  • the analytically determined hydroxyl number of the product was 80.
  • Alkalinity and temperature correspond to the conditions in a commercial dishwasher.
  • Foam height in ml without fresh egg Foam height in ml with fresh egg after 10 sec after 30 sec after 60 sec after 10 sec after 30 sec after 60 sec 1 10th 10th 10th 15-20 15 15 2nd 5 5 0-5 20th 15 15 3rd 0-5 0-5 0-5 10th 5-10 5-10 4th 10th 10th 10th 15 15 15 5 10th 5 5 10th 5-10 5-10 6 7 7 5 15 10th 8th 7 10th 9 7 22 18th 15 8th 43 40 35 60 50 45 without surfactant 0 0 0 160 160 160 160
  • the biodegradability of the adducts used was checked in the OECD Screening Test (RVO on the Detergent Act) and stated in the BiAS acceptance after 19 days.
  • Degradability was also measured according to the GF test method specified in the Chemicals Act "Ready biodegradability” according to the GF / BSB test regulation (COD / Chemical Oxygen Demand).
  • a rinse aid of the following composition was tested in a household dishwasher. 15% Compound from example 5 8th % Na cumene sulfonate 10% Citric acid (anhydrous) 0.3% Lemon Perfume Oil 66.7% Water (fully desalinated)
  • this recipe did not cause any disruptive foaming in all zones (65 ° C cleaning zone, 43 ° C pre-clearing zone with heavy contamination).
  • the clear dry effect was good in the entire dosage range 0.1 to 1.3 g / l.
  • Example 8 which foams more strongly above 40 ° C., but has better wetting properties, was combined with the low-foam compound from Example 1 from 30 ° C., resulting in a low-foaming rinse aid from 40 ° C., plastic parts with good wetting properties.
  • the test was carried out at 0.8 g / l in a commercial multi-tank dishwasher, with good rinse aid results.
  • a hydroxyalkyl polyethylene glycol ether (I) was blended with a fatty alcohol ethylene glycol propylene glycol ether and checked in a commercial refueling machine. 15% Compound from example 3 10% Fatty alcohol (C12 ⁇ 14) + 5 EO + 4 PO 4% Na cumene sulfonate 10% citric acid 5% Sokalan DCS® (dicarboxylic acid mixture, see page 11, line 34) 56% water
  • the rinse aid was low-foaming from 30 ° C and, with 0.1 to 1.0 g / l, had a good clear-dry effect without disruptive foaming when cleaning soiled lunch dishes.
  • the rinse aid was low in foam in the application liquor from 43 ° C. A good clear drying effect was achieved in both a household and a commercial dishwasher with 0.1 to 1.0 g / l.
  • the clear dry effect of two of the surfactants used according to the invention was compared to that of a less readily degradable surfactant (sec.-C11 ⁇ 15 alcohol + 8 EO + 5 PO).
  • the tests were carried out in a household dishwasher (softened water; 300 mg salt load) with one cleaning and one rinse cycle, with grades from 1 (very poor) to 10 (optimal rinse; highest possible grade).
  • the dosage of the surfactants in the rinse aid was 0.02 to 0.1 g / l.
  • Drinking glasses served as items to be washed, as they are most sensitive to stains, streaks and streaks. That grade 10 was not achieved here is due to the very critical grading and the fact that the water used was softened but not desalinated.

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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)
  • Detergent Compositions (AREA)
EP88111024A 1987-07-18 1988-07-11 Verwendung von Hydroxyalkylpolyethylenglykolethern in Klarspülmitteln für die maschinelle Geschirreinigung Expired - Lifetime EP0300305B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88111024T ATE85642T1 (de) 1987-07-18 1988-07-11 Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3723873 1987-07-18
DE19873723873 DE3723873A1 (de) 1987-07-18 1987-07-18 Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung

Publications (3)

Publication Number Publication Date
EP0300305A2 EP0300305A2 (de) 1989-01-25
EP0300305A3 EP0300305A3 (en) 1989-11-15
EP0300305B1 true EP0300305B1 (de) 1993-02-10

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EP88111024A Expired - Lifetime EP0300305B1 (de) 1987-07-18 1988-07-11 Verwendung von Hydroxyalkylpolyethylenglykolethern in Klarspülmitteln für die maschinelle Geschirreinigung

Country Status (7)

Country Link
US (1) US4898621A (es)
EP (1) EP0300305B1 (es)
JP (1) JP2536904B2 (es)
AT (1) ATE85642T1 (es)
DE (2) DE3723873A1 (es)
ES (1) ES2051802T3 (es)
GR (1) GR3007459T3 (es)

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US7947087B2 (en) 2006-03-14 2011-05-24 Henkel Ag & Co. Kgaa Color transfer inhibitors, detergent compositions containing the same and uses therefor
US8263541B2 (en) 2005-08-19 2012-09-11 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor

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DE102008038479A1 (de) 2008-08-20 2010-02-25 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit gesteigerter Waschkraft
BRPI0913700A2 (pt) * 2008-09-24 2015-10-13 Dow Brasil Sudeste Ind Ltda agente de controle de espuma e método para controlar espuma em um processo de fermentação
DE102008059447A1 (de) * 2008-11-27 2010-06-02 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel enthaltend Proteasen aus Bacillus pumilus
DE102008059446A1 (de) 2008-11-27 2010-06-02 Henkel Ag & Co. Kgaa Neue Proteasen und Mittel enthaltend diese Proteasen
DE102008062772A1 (de) 2008-12-18 2010-06-24 Henkel Ag & Co. Kgaa Desinfektion von Viren an Textilien und harten Oberflächen
DE102009001114A1 (de) 2009-02-24 2010-08-26 Henkel Ag & Co. Kgaa Schonendes Entfärben von Farbschmutz auf harten und/oder weichen Oberflächen
DE102009016313A1 (de) * 2009-04-06 2010-12-02 Miele & Cie. Kg Verfahren zur Durchführung eines Spülprogramms in einer Haushaltsgeschirrspülmaschine und Klarspülmittel
DE102009027045A1 (de) 2009-06-19 2010-12-30 Henkel Ag & Co. Kgaa Neue Proteasen und Mittel enthaltend diese Proteasen
DE102009027158A1 (de) 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
DE102009027540A1 (de) 2009-07-08 2010-05-06 Henkel Ag & Co. Kgaa Neue Proteasen und Mittel enthaltend diese Proteasen
DE102009028507A1 (de) 2009-08-13 2011-02-17 Henkel Ag & Co. Kgaa Niotensidhaltiges Sprühtrocknungsprodukt
DE102009045064A1 (de) 2009-09-28 2011-03-31 Henkel Ag & Co. Kgaa Stabilisierte enzymatische Zusammensetzung
DE102010040564A1 (de) 2010-09-10 2012-03-15 Henkel Ag & Co. Kgaa Mikrokapselhaltiges Wasch- oder Reinigungsmittel
DE102011083942A1 (de) 2011-10-04 2013-04-04 Henkel Ag & Co. Kgaa Hydrogelbildner enthaltende Wasch- oder Reinigungsmittel
WO2013120816A1 (de) 2012-02-13 2013-08-22 Basf Se Farbschützendes wasch- oder reinigungsmittel
ES2575802T3 (es) 2012-02-13 2016-07-01 Henkel Ag & Co. Kgaa Agente de lavado o de limpieza protector del color
DE102014206068A1 (de) 2014-03-31 2015-10-01 Henkel Ag & Co. Kgaa Toilettenreiniger
DE102014223296A1 (de) 2014-11-14 2016-05-19 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel, enthaltend mindestens zwei Proteasen
DE102014223969A1 (de) 2014-11-25 2016-05-25 Henkel Ag & Co. Kgaa Verwendung von Molkenproteinisolat in enzymhaltigen Wasch- oder Reinigungsmitteln zur Erhöhung der Stabilität von Enzymen
DE102014226251A1 (de) 2014-12-17 2016-06-23 Henkel Ag & Co. Kgaa Verwendung anorganischer Oxide, Hydroxide oder Oxidhydroxide in enzymhaltigen Wasch- oder Reinigungsmitteln zur Erhöhung der Stabilität von Enzymen
DE102015217816A1 (de) 2015-09-17 2017-03-23 Henkel Ag & Co. Kgaa Verwendung hochkonzentrierter Enzymgranulate zur Erhöhung der Lagerstabilität von Enzymen
DE102015223269A1 (de) 2015-11-25 2017-06-01 Henkel Ag & Co. Kgaa Verwendung von Polyoxyalkylenaminen in enzymhaltigen Wasch- oder Reinigungsmitteln zur Erhöhung der Stabilität von Enzymen
WO2018035131A1 (en) 2016-08-16 2018-02-22 Diversey, Inc. A composition for aesthetic improvement of food and beverage containers and methods thereof
JP6498734B2 (ja) * 2017-08-24 2019-04-10 攝津製油株式会社 洗浄剤組成物、洗浄剤、及び洗浄方法

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AU2373767A (en) * 1966-08-12 1969-01-09 W. R. Grace & Co Rinse and compositions
DE2106819C3 (de) * 1971-02-12 1978-11-16 Henkel Kgaa, 4000 Duesseldorf Klarspülmittel für die maschinelle Geschirreinigung
DE2432757C2 (de) * 1974-07-08 1984-02-16 Henkel KGaA, 4000 Düsseldorf Als Schauminhibitoren geeignete, Hydroxylgruppen enthaltende Polyäthylenglykol-diäther sowie deren Herstellung
JPH0227398B2 (ja) * 1982-04-23 1990-06-15 Asahi Denka Kogyo Kk Senjozaisoseibutsu
DE3345349A1 (de) * 1983-12-15 1985-06-27 Henkel KGaA, 4000 Düsseldorf Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8263541B2 (en) 2005-08-19 2012-09-11 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor
US8785362B2 (en) 2005-08-19 2014-07-22 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor
US7947087B2 (en) 2006-03-14 2011-05-24 Henkel Ag & Co. Kgaa Color transfer inhibitors, detergent compositions containing the same and uses therefor

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DE3878330D1 (de) 1993-03-25
JP2536904B2 (ja) 1996-09-25
EP0300305A2 (de) 1989-01-25
ES2051802T3 (es) 1994-07-01
GR3007459T3 (es) 1993-07-30
JPS6438497A (en) 1989-02-08
US4898621A (en) 1990-02-06
EP0300305A3 (en) 1989-11-15
DE3723873A1 (de) 1989-01-26
ATE85642T1 (de) 1993-02-15

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