EP0395970B1 - Wasch- und Reinigungsmittelzusammensetzungen - Google Patents

Wasch- und Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0395970B1
EP0395970B1 EP90107599A EP90107599A EP0395970B1 EP 0395970 B1 EP0395970 B1 EP 0395970B1 EP 90107599 A EP90107599 A EP 90107599A EP 90107599 A EP90107599 A EP 90107599A EP 0395970 B1 EP0395970 B1 EP 0395970B1
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EP
European Patent Office
Prior art keywords
lactobionic acid
compositions
washing
builder
cleaning
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
EP90107599A
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German (de)
English (en)
French (fr)
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EP0395970A1 (de
Inventor
Klaus-Günter Gerling
Detlef Wilke
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.)
Kali Chemie AG
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Kali Chemie AG
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Publication of EP0395970A1 publication Critical patent/EP0395970A1/de
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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
    • C11D3/046—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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the invention relates to compositions for washing and cleaning applications which contain biodegradable and ecologically compatible builder substances, to the use of these builder substances and to a method for washing and / or cleaning.
  • Builders are of central importance for the course of the washing and cleaning process.
  • the function of the builders is mainly that they are partly from water, partly from dirt or e.g. Eliminate textiles from calcium and magnesium ions by complex formation or ion exchange from the washing or cleaning process and to support the surfactant effect.
  • Modern builders therefore have to meet a number of eligibility criteria.
  • builders should have a certain primary washing or cleaning action. This means, for example, a good specific washing and cleaning action against pigments and fats or, for example, a good washing action against certain textile fibers, the improvement of the surfactant properties and a favorable influence on the foaming behavior.
  • they should make a major contribution to dispersing dirt in washing and cleaning liquors. In this way, for example, graying and yellowing of the textiles to be washed pushed back, which is very important for good washing results.
  • builders should have good dirt-bearing capacity and e.g. prevent incrustation on textiles. In addition, they should also prevent corresponding deposits in washing machines and cheap, i.e. show no correspondence behavior.
  • the builder substances should continue to be chemically stable, technically easy to process, non-hygroscopic, stable in storage and compatible with the other detergents and cleaning agents. They should also have perfect color and smell qualities and be based on a secure raw material base.
  • the builder substances should also be harmless to the environment, be biodegradable and, last but not least, also meet economic requirements.
  • Builder substances known in the prior art are e.g. certain washing alkalis (such as soda, sodium silicate or sodium monophosphate), complexing agents (such as e.g. sodium diphosphate, sodium triphosphate, phosphonic acid derivatives, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), citric acid, O- (carboxymethyl) malic acid) or ionol exchanger (e.g. zeolite exchanger).
  • washing alkalis such as soda, sodium silicate or sodium monophosphate
  • complexing agents such as e.g. sodium diphosphate, sodium triphosphate, phosphonic acid derivatives, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), citric acid, O- (carboxymethyl) malic acid
  • ionol exchanger e.g. zeolite exchanger
  • Alkaline detergents such as soda or monophosphate are now considered technically obsolete, since they form precipitates with the calcium and magnesium salts (so-called hardness formers) of service water, which deposit on laundry and appliances as undesirable and annoying deposits.
  • the builder substances currently used no longer precipitate the hardness formers of the water, but instead eliminate them through complex formation or ion exchange.
  • the phosphates used as complexing agents contribute Eutrophication of standing or slowly flowing waters. The ecological side effect of the phosphates is undesirable and has led to an intensive search worldwide for suitable substitutes.
  • EP-AO 107 159 discloses hair treatment compositions which contain lactic acid as active ingredients in hair cosmetics.
  • the object was therefore to provide washing and cleaning agent compositions which avoid or at least reduce the disadvantages of the prior art with regard to the builder substances contained in the compositions.
  • a further task was to specify builders which can be used in compositions for washing and cleaning purposes or in washing and cleaning processes and which, in addition to having sufficient calcium binding capacity, ecological compatibility and biodegradability, are characterized above all by very good dispersing behavior, which is necessary to achieve a good washing and cleaning effect is required.
  • the invention proposes detergent and cleaning agent compositions which contain surfactants and, if appropriate, further constituents customary in detergents and cleaning agents, and lactobionic acid and / or lactobionic acid salts in the presence of a boron oxygen compound as builder substances.
  • Lactobionic acid (4- (beta-D-galactosido) -D-gluconic acid) is already known as such and can be obtained, for example, by oxidation of lactose. So far, the lactobionic acid in the form of the calcium salt has been used pharmaceutically in the so-called calcium preparations for the prevention and therapy of calcium deficiency states. The use as a builder in washing and cleaning agents, however, has not been described so far.
  • both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substance in the compositions according to the invention.
  • Alkali metal lactobionates, in particular sodium and potassium lactobionate, are preferably used here.
  • lactobionic acid and / or lactobionic acid salts can be present in the compositions according to the invention in amounts which are conventional per se for builder substances.
  • the lactobionic acid and its salts can then be present in the detergent and cleaning agent compositions in an amount based on the total composition of up to 40% by weight.
  • the amount of builder substances contained in the compositions according to the invention is preferably up to 35% by weight.
  • these compositions contain a further component which consists of one or more boron oxygen compounds consists.
  • the builder action of lactobionic acid or its salts is increased in an unexpected and surprising manner by the presence of the boron oxygen compound.
  • the boron oxygen compounds are generally present in the compositions in an amount such that at least 1 mol of boron is contained for 1 mol of lactobionic acid and / or lactobionic acid salt.
  • boron oxygen compounds are suitable for this purpose, for example conventional borates known in the prior art, such as sodium borate, sodium metaborate, borax, pentaborate, etc., or mixtures thereof. Boron oxygen compounds of the aforementioned type are contained in particular in those compositions which contain no bleaching agent or no perborate bleaching agent.
  • Peroxy group-containing boron oxygen compounds i.e. boron-containing peroxygen bleach
  • boron oxygen compounds can also be used as boron oxygen compounds, e.g. those perborates known per se in the prior art, which are usually contained as bleaching agents in detergent and cleaning agent compositions.
  • the perborates are used in the washing and cleaning compositions in amounts customary for bleaching agents and, in this case, no further addition of boron oxygen compounds of the type described above (i.e. borates etc.) is therefore required.
  • lactobionic acid and its salts per se can be used as builders for any detergent and cleaning agent compositions, for example also in liquid detergents and cleaning agents (for example liquid detergents), but the advantages which can be achieved with these builder substances are particularly evident in powdered detergents. and detergent compositions, for example in so-called powdered universal detergents, or in hand and machine dishwashing detergents.
  • lactobionic acid and / or their salts as cobuilders in combination with further organic and / or inorganic builders which have been customary in the prior art in the detergent and cleaning agent compositions.
  • Typical examples of customary builders known in the prior art which may be present in the compositions as builders with the builders used according to the invention are sodium aluminosilicates (e.g. zeolites), sodium citrate or salts of aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid.
  • lactobionic acid and / or its salts can also be present in combination with lactobionic acid and / or its salts in detergent and cleaning agent compositions.
  • lactobionic acid and / or its salts are present as cobuilders in amounts of up to 25% by weight, based on the total composition.
  • compositions of the invention can contain any bleaching agent or bleaching agent mixture customary in the art, for example chlorine bleaching agent or peroxygen bleaching agent.
  • the bleaching agent is a peroxygen bleaching agent, such as persulfate, percarbonate or perborates.
  • perborates such as sodium perborate tetrahydrate or sodium perborate monohydrate are particularly preferred.
  • compositions according to the invention can be formulated in a manner known per se.
  • all the usual materials that are usually used for the formulation of detergent and detergent compositions per se can be used in the compositions according to the invention usual amounts are used.
  • the compositions according to the invention contain surfactants as an essential constituent, and, if appropriate, other customary auxiliaries.
  • compositions according to the invention can contain any surface-active organic compounds, such as anionic, cationic, ampholytic or non-ionic surfactants or mixtures thereof, as surfactants.
  • Anionic surfactants are e.g. synthetic surface-active compounds with one or more functional groups that ionize in aqueous solution to form negatively charged ions.
  • Suitable anionic surfactants are, for example, alkali metal, ammonium or alkanolamine salts of alkylbenzenesulfonates having 10 to 18 carbon atoms in the alkyl group; Alkyl and alkyl ether sulfates with 10 to 24 carbon atoms in the alkyl group and with 1 to 5 ethylene oxide groups; C10- to C12- ⁇ -olefin sulfonates, ⁇ -sulfo fatty acid esters.
  • Cationic surfactants are surfactants with one or more functional groups that ionize in aqueous solution to form positively charged organic ions.
  • cationic surfactants are aliphatic or aromatic higher-alkyl-di-lower-alkyl-ammonium halides, for example dialkyl-dimethylammonium chlorides such as distearyl-dimethylammonium chloride; Alkyl dimethyl benzyl ammonium chloride; Imidazolinium salts.
  • ampholytic (zwitterionic) surfactants include derivatives of straight-chain or branched aliphatic compounds with usually 8 to 24 carbon atoms, which contain aliphatic quaternary ammonium, phosphonium or sulfonium groups and at least one anionic water-soluble group and optionally also other substituents.
  • Examples are C12- to C18-alkyl betaines of the formula R-N+ (CH3) 2CH2-COO ⁇ and C12- to C18-alkyl sulfobetaines of the formula R-N+ (CH3) 2-SO3 ⁇ .
  • Non-ionic surfactants are usually cocondensates of ethylene oxide or propylene oxide with hydrocarbons which carry reactive groups such as hydroxyl, carboxyl or amino groups.
  • Examples are alkylphenol polyglycol ethers with C8-C12 alkyl radicals and 5 to 10 ethylene glycol units; Alkyl polyglycol ethers such as fatty alcohol polyethylene glycol ether and oxo alcohol polyethylene glycol ether; Fatty acid alkanolamides, e.g. of the fatty acid ethanolamide type.
  • non-ionic surfactants are the semi-polar non-ionic surfactants, e.g. water-soluble amine oxides with alkyl or hydroxyalkyl units with 8 to 28 C atoms, it being possible for two of these alkyl or hydroxyalkyl units to be linked to form a ring structure with 1 to 3 C atoms.
  • the detergent and cleaning agent compositions of the present invention can contain further customary auxiliaries for the formulation of detergents and cleaning agents.
  • auxiliaries include enhancers, detergent enzymes, enzyme stabilizers, dirt carriers and / or compatibilizers, complexing agents and chelating agents, soap foam regulators and additives such as optical brighteners, opacifying agents, corrosion inhibitors, Antistatic agents, dyes, bactericides, bleach activators, peracid bleach precursors.
  • the invention also relates to compositions for washing and cleaning purposes or for bleaching purposes in washing and cleaning processes which contain lactobionic acid and / or lactobionic acid salts as builder substances in the presence of a boron oxygen compound, but in themselves are not yet complete washing and cleaning agent compositions in the above described senses, since they contain only a part of the ingredients usually contained in a complete detergent composition suitable for use.
  • Such partial compositions according to the invention can serve on the one hand for the industrial production of complete detergent and cleaning agent compositions.
  • the partial compositions are well suited as components for so-called modular detergent and cleaning agent systems.
  • the constituents are not already mixed with one another as in conventional (complete) detergent and cleaning agent compositions, but instead lie as separate system components, for example as surfactant, bleach and builder components. in front.
  • the individual components are only coordinated by the user depending on the individual requirements (such as the type of material to be washed or cleaned; type of washing or cleaning process, e.g. hot or delicate laundry, etc .; water hardness etc.).
  • the components can either be mixed with one another before use or metered separately into the wash water.
  • the boron oxygen compound contained therein can be a peroxygen bleaching agent, in analogy to that described above in connection with the washing and cleaning compositions.
  • Preferred peroxygen bleaches are perborates.
  • Such partial compositions for example in the form of powders or granules, which contain lactobionic acid and / or lactobionic acid salts in the presence of perborate, are suitable, for example, for use as so-called dry bleach in washing and cleaning processes.
  • the invention further relates to the use of lactobionic acid and / or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes.
  • lactobionic acid and / or lactobionic acid salts as builder substances in compositions for washing and cleaning purposes.
  • Both the free lactobionic acid itself and its salts with environmentally compatible, non-hardness-forming metal cations or mixtures of these substances can be used as builder substances in the manner described above for compositions according to the invention.
  • preference is given in particular to using the sodium or potassium salt of lactobionic acid.
  • the invention further relates to a method for washing and cleaning, which is characterized in that lactobionic acid and / or lactobionic acid salts are used as builder substances in the presence of boron oxygen compounds.
  • compositions according to the invention, the use according to the invention and the method according to the invention offer a surprising and problem-free solution to the widespread desire for suitable environmentally compatible and biodegradable builder substances which, in addition to good calcium binding capacity, in particular show very good dispersing behavior.
  • the very good dispersibility of lactobionic acid and its salts results in the presence a boron oxygen compound to suppress graying and yellowing. This property is of paramount importance for washing and cleaning processes and is excellently fulfilled by lactobionic acid and its salts.
  • incrustations for example on textiles or in washing machines, are prevented to an unexpectedly favorable extent.
  • Lactobionic acid and its salts also show the so-called threshold effect, i.e. they are able to delay, reduce, or at least cause the precipitation of insoluble salts even when using substoichiometric amounts of builders, or at least to cause the insoluble salts to occur predominantly in amorphous form and that Formation of sharp-edged, fiber-damaging crystals (eg calcite crystals) is largely suppressed.
  • the compounds are chemically stable, not hygroscopic, stable in storage and easy to process technically. Furthermore, they are well compatible with common detergent and cleaning agent ingredients.
  • the compounds can be easily obtained from lactose by oxidation on the basis of a secure raw material base and are also economically advantageous.
  • the biological origin and complete biodegradability of the substances guarantee harmlessness to humans and favorable environmental behavior.
  • the lime binding capacity of lactobionic acid in the presence of boron oxygen compounds (2.13 g borax and / or 2 g sodium perborate in 100 ml solution) was determined at pH 10 by mixing 100 ml of an aqueous solution of 1% by weight lactobionic acid, 0.4% by weight % Sodium carbonate and optionally 0.1% by weight TAED as bleach activator with an aqueous 0.1 N calcium chloride solution until occurrence a permanent cloudiness titrated. Under these test conditions, lactobionic acid is present as the sodium salt in the test solution.
  • the measured number for the lime binding capacity is the gram number of calcium ions which can be kept in solution per 100 g of lactobionic acid as builder substance under the aforementioned conditions.
  • aqueous dispersions were prepared from 0.1% by weight of the builder substance to be tested and 4% by weight powder graphite as dispersa by weighing the substances into a 100 ml shaking measuring cylinder, making up to 100 ml with water and shook vigorously for a minute.
  • the sedimentation volume of the graphite particles was determined as a measure of the dispersing capacity and, for additional tests, a sample was additionally taken from the dispersion at the level of the 70 ml measuring mark of the shaking measuring cylinder and sent to a photometric test.
  • the transmission of the samples was measured here in comparison to corresponding blank samples without graphite (transmission 100%), with smaller transmission values indicating better dispersibility.
  • the washing performance was determined by washing tests on test fabrics in two standard washing machines (type: Miele W 180). For this purpose, 2 kg of test fabric was washed with 155 g of detergent in the short program (washing time 1 h). A standardized heavy-duty detergent formulation was used as the detergent, which contained 30% by weight of the builder system to be tested.
  • composition of the standardized heavy-duty detergent formulation 30.0% by weight builder system (see table) 11.9% by weight of dodecylbenzenesulfonate 4.0% by weight of tallow fatty alcohol ethoxylate with 11 moles of ethylene oxide 4.0% by weight of sebum soap 4.0% by weight sodium silicate 32.9% by weight sodium perborate tetrahydrate 11.9% by weight sodium sulfate 1.3 wt% tylose.
  • the experiments were carried out at pH 10 and 18 ° dH at 30 and 60 ° C. The fleet ratio was 1:12.
  • the washing performance was determined by measuring the lightening of soiled test fabrics (cotton fabric and cotton blended fabrics) as the reflectance difference (reflectance of the dry test fabric after the wash test minus the reflectance test fabric before the wash test) at 530 nm. The larger remission difference indicates the better washing performance. Lactobionic acid alone, lactobionic acid with zeolite (in a 1: 1 ratio) and STPP as a comparison were used as builder systems in the heavy-duty detergent formulations. The experiments according to the invention of this example (No.
  • lactobionic acid as builder substance prevents the graying of textiles
  • washing tests were carried out on bleached test fabrics without artificial soiling and without optical brighteners.
  • the test fabrics were allowed to run through a total of 25 washing cycles analogous to the washing conditions specified in Example 4 at 60 ° C. in the normal program (soaking process, 2 h).
  • the graying of the test fabrics was then determined by measuring the reflectance at 530 nm.
  • Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison.
  • the remission is indirectly proportional to the graying.
  • the experiments according to the invention of this example show that when lactobionic acid is used as builder in detergent and cleaning agent compositions, the graying of textiles is also prevented in an excellent manner by the known builders of the prior art (comparative experiments Nos. 37 and 39 ).
  • test fabrics were run through a total of 25 washing cycles analogous to the washing conditions given in Example 4. After completion of the washing cycles, the test fabrics were incinerated according to standard conditions known per se and the remaining ash content in% by weight (based on the test fabric used) was determined as a measure of the inorganic incrustation. Lactobionic acid was used as the builder in the standardized heavy-duty detergent formulation (see Example 4) and STPP as a comparison. The smaller the remaining ash content, the lower the incrustation.
  • the experiments according to the invention of this example Nos.

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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)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP90107599A 1989-04-29 1990-04-21 Wasch- und Reinigungsmittelzusammensetzungen Expired - Lifetime EP0395970B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3914293A DE3914293A1 (de) 1989-04-29 1989-04-29 Wasch- und reinigungsmittelzusammensetzungen
DE3914293 1989-04-29

Publications (2)

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EP0395970A1 EP0395970A1 (de) 1990-11-07
EP0395970B1 true EP0395970B1 (de) 1994-06-15

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EP90107599A Expired - Lifetime EP0395970B1 (de) 1989-04-29 1990-04-21 Wasch- und Reinigungsmittelzusammensetzungen

Country Status (8)

Country Link
US (1) US5069808A (ja)
EP (1) EP0395970B1 (ja)
JP (1) JP2672175B2 (ja)
AT (1) ATE107348T1 (ja)
CA (1) CA2012836C (ja)
DE (2) DE3914293A1 (ja)
DK (1) DK0395970T3 (ja)
ES (1) ES2057245T3 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3156475B1 (de) 2015-10-16 2018-06-06 Hans Georg Hagleitner Flüssiges reinigungskonzentrat

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2659979B1 (fr) * 1990-03-23 1994-04-29 Roquette Freres Produit de lavage a teneur reduite ou nulle en phosphates.
DE4215478A1 (de) * 1992-05-11 1993-11-18 Solvay Deutschland Lactobionsäureamidzusammensetzungen und deren Verwenndung
US5433883A (en) * 1993-11-04 1995-07-18 Lever Brothers Company, Division Of Conopco, Inc. Toilet bar compositions comprising nonionic glycolipid surfactants and polyalkylene glycol structurant
DE4435817A1 (de) * 1993-12-29 1996-04-11 Solvay Interox Gmbh Beschichtete Alkalimetallperoxosalze und Verfahren zu deren Herstellung
WO2006131503A2 (en) * 2005-06-10 2006-12-14 Novozymes A/S Detergents with enzymatic builder and bleach systems
CN106496618B (zh) * 2016-10-18 2022-02-08 浙江伟星实业发展股份有限公司 一种果实纽扣镭射镂空处理液以及镭射镂空的果实纽扣

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GB852958A (en) * 1956-08-07 1960-11-02 Union Starch And Refining Comp Sequestering composition comprising polyhydroxy carboxylic acids and process of making same
US3062878A (en) * 1959-10-05 1962-11-06 Olin Mathieson Sugar sequestering agent
US3256203A (en) * 1963-11-18 1966-06-14 Nalco Chemical Co Cooling water treatment and compositions useful therein
US3634392A (en) * 1969-03-28 1972-01-11 Procter & Gamble Carboxymethylated derivatives of diand tri-saccharide compounds and detergent compositions containing them
GB1355998A (en) * 1970-09-30 1974-06-12 Unilever Ltd Builders for detergent compositions
US4000083A (en) * 1974-05-06 1976-12-28 B°V° Chemie Combinatie Amsterdam C°C°A° Sequestering agents
US4539131B1 (en) * 1982-06-25 1990-09-04 Lever Brothers Ltd Solid detergent composition containing sodium perborate monohydrate having specified surface area
US4938961A (en) * 1989-04-28 1990-07-03 Geoffrey Collins Organ preservation solution containing pokyethylene gycol and method of performing cardioplegia

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3156475B1 (de) 2015-10-16 2018-06-06 Hans Georg Hagleitner Flüssiges reinigungskonzentrat

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CA2012836A1 (en) 1990-10-29
DE3914293A1 (de) 1990-10-31
ES2057245T3 (es) 1994-10-16
US5069808A (en) 1991-12-03
EP0395970A1 (de) 1990-11-07
CA2012836C (en) 1999-06-29
JPH02305899A (ja) 1990-12-19
DK0395970T3 (da) 1994-07-04
ATE107348T1 (de) 1994-07-15
DE59006100D1 (de) 1994-07-21
JP2672175B2 (ja) 1997-11-05

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