EP0269168B1 - Compositions détergentes adoucissantes contenant de la cellulase - Google Patents

Compositions détergentes adoucissantes contenant de la cellulase Download PDF

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Publication number
EP0269168B1
EP0269168B1 EP87202189A EP87202189A EP0269168B1 EP 0269168 B1 EP0269168 B1 EP 0269168B1 EP 87202189 A EP87202189 A EP 87202189A EP 87202189 A EP87202189 A EP 87202189A EP 0269168 B1 EP0269168 B1 EP 0269168B1
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EP
European Patent Office
Prior art keywords
composition
cellulase
softening
compositions
alkyl
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.)
Revoked
Application number
EP87202189A
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German (de)
English (en)
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EP0269168A2 (fr
EP0269168A3 (en
Inventor
Christian Roland Barrat
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.)
Procter and Gamble European Technical Center
Procter and Gamble Co
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Publication of EP0269168A3 publication Critical patent/EP0269168A3/en
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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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

  • the present invention relates to detergent compositions which clean well and at the same time act as textile softeners.
  • European Patent Application 0 026 528 describes the use of water-insoluble long chain tertiary amines in conjunction with a water-soluble cationic quarternary ammonium compound and/or a water-soluble aliphatic amine, optionally with clays, in alkaline detergent compositions to provide fabric softening properties.
  • EP-A 0 120 528 teaches alkaline softening detergent compositions comprising a synergistic mixture of a water-insoluble C10-C26 tertiary amine and cellulase.
  • EP-A 0 177 165 discloses alkaline softening detergent compositions containing a mixture of smectite clay and cellulase.
  • the present invention answers the above need, and provides efficient mild-alkaline softening detergent compositions, which exhibit good fabric-care performance and softeness, and good cleaning properties, especially on cottom fabrics.
  • the present invention also addresses standing prior-art issues by using a cellulase enzyme at a pH range where its activity is optimum, and by the surprising discovery that water-insoluble long chain amines such as described in EPA 0 026 528 or EPA 0 120 528, give softeness negatives in presence of cellulase, upon cumulative washes, under the mild alkaline conditions of the invention.
  • the present invention relates to detergent compositions for the cleaning and softening of fabrics, comprising a surface-active agent, of which at least 50% by weight is a non-soap anionic surface active agent, and a cellulase ;
  • the compositions herein have a pH, 1% solution in distilled water, of from 6.5 to 9.0, and are essentially free of water-insoluble long-chain alkyl amine softening agents, or derivatives thereof.
  • the present compositions include in addition a clay softening material.
  • the surface-active agent is the surface-active agent
  • the surface-active agent useful herein contains at least 50% by weight, preferably 60% to 100% by weight of an anionic surface-active agent (salt form).
  • anionic surface-active agents do not encompass soaps.
  • a wide range of anionic surfactants can be used in the compositions of the present invention.
  • Suitable anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulphocarboxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoxy ether sulphates, 2-acyloxy-alkane-1-sulphonates, and beta-alkyloxy alkane sulphonates.
  • Especially preferred alkyl benzene sulphonates have 9 to 15 carbon atoms in a linear or branched alkyl chain, especially from 11 to 13 carbon atoms.
  • Suitable alkyl sulphates have from 10 to 22 carbon atoms in the alkyl chain, more especially from 12 to 18 carbon atoms.
  • Suitable alkyl polyethoxy ether sulphates have from 10 to 18 carbon atoms in the alkyl chain and have an average of from 1 to 12 - CH2CH2O- groups per molecule, especially from 10 to 16 carbon atoms in the alkyl chain and an average of from 1 to 6 -CH2-CH2O-groups per molecule.
  • Suitable paraffin sulphonates are essentially linear and contain from 8 to 24 carbon atoms, more especially from 14 to 18 carbon atoms.
  • Suitable alpha-olefin sulphonates have from 10 to 24 carbon atoms, more especially from 14 to 16 carbon atoms; alpha-olefin sulphonates can be made by reaction with sulphur trioxide, followed by neutralization under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy alkane sulphonates.
  • Suitable alpha-sulphocarboxylates contain from 6 to 20 carbon atoms; included herein are not only the salts of alpha-sulphonated fatty acids but also their esters made from alcohols containing 1 to 14 carbon atoms.
  • Suitable alkyl glycerly ether sulphates are ethers of alcohols having from 10 to 18 carbon atoms, more especially those derived from coconut oil and tallow.
  • Suitable alkyl phenol polyethoxy ether sulphates have from 8 to 12 carbon atoms in the alkyl chain and an average of from 1 to 6 -CH2CH2O-groups per molecule.
  • Suitable 2-acyloxyalkane-1-sulphonates contain from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety.
  • Suitable beta-alkyloxy alkane sulphonates contain from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
  • the alkyl chains of the foregoing anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example by using the Ziegler or Oxo processes. Water-solubility can be achieved by using alkali metal, ammonium, or alkanol-ammonium cations; sodium is preferred. Mixtures of anionic surfactants are contemplated by this invention; a satisfactory mixture contains alkyl benzene sulphonate having 11-13 carbon atoms in the alkyl group and alkyl sulphate having 12 to 18 carbon atoms in the alkyl group.
  • Nonionic surfactants may be incorporated in the compositions herein, in limited amounts (less than 50%).
  • Suitable nonionics are water-soluble ethoxylated materials of HLB 11.5-17.0 and include (but are not limited to) C10-C20 primary and secondary alcohol ethoxylates and C6-C10 alkylphenol ethoxylates.
  • C14-C18 linear primary alcohols condensed with from seven to thirty moles of ethylene oxide per mole of alcohol are preferred, examples being C14-C15 (EO)7, C16-C18 (EO)25 and especially C16-C18 (EO)11.
  • surfactants can be used in limited amounts, in combination with the anionic surface-active agent. They include zwitterionic amphoteric, as well as cationic surfactants.
  • Cationic co-surfactants which can be used herein, include water-soluble quaternary ammonium compounds of the form R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5, R6 and R7 are each C1 to C7 alkyl preferably methyl; X ⁇ is an anion, e.g. chloride.
  • Examples of such trimethyl ammonium compounds include C12-C14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
  • the cellulase usable in the present invention may be any bacterial or fungal cellulase having a pH optimum of between 5 and 11.5.
  • Suitable cellulase are disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly by the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mullosc (Dolabella Auricula Solander).
  • the cellulase added to the composition of the invention may be in the form of a non-dusting granulate, e.g. "marumes” or “prills”, or in the form of a liquid in which the cellulase is provided as a cellulase concentrate suspended in e.g. a nonionic surfactant or dissolved in an aqueous medium.
  • a non-dusting granulate e.g. "marumes” or "prills”
  • a liquid in which the cellulase is provided as a cellulase concentrate suspended in e.g. a nonionic surfactant or dissolved in an aqueous medium.
  • One CMCase unit is defined as the amount of enzyme which forms per minute an amount of reducing carbohydrate equivalent to 10 ⁇ 6 mole of glucose, in the above-described conditions.
  • a highly preferred range of cellulase activity in the present context is from 5 to 100 CMCase activity units/gram of composition.
  • compositions of the invention are essentially free of water-insoluble long-chain alkyl amine softening agents, and derivatives thereof, since it has surprisingly been discovered that they interact negatively with cellulase, in the pH conditions of the present invention.
  • Derivatives of the amine softening agents include the corresponding amide compounds.
  • Such amine softening agents are disclosed in e.g. EP.A 0.026.528 and EP.A 0.120.528. and include in particular amines of the formula R1R2R3N where R1 and R2 are C6 to C20 alkyl chains, and R3 is C1 to C10 alkyl chain or hydrogen.
  • compositions herein are formulated at a pH in the range of from 6.5 to 9.0, measured as a 1% solution of the composition in distilled water. At this pH-range, the cellulases for use herein have their optimum performance.
  • compositions herein contain a clay softening agent, in combination with the cellulase.
  • clay softening agents ae well-known in the detergency patent literature and are in broad commercial use, both in Europe and in the United States. Included among such clay softeners are various heat-treated kaolins and various multi-layer smectites.
  • Preferred clay softeners are smectite softener clays that are described in German patent document 23 34 899 and in U.K. patent 1,400,898, which can be referred to for details.
  • the most perferred clay fabric softening materials include those materials of bentonitic origin, bentonites being primarly montmorillonite type clays together with various impurities, the level and nature of which depends on the source of the clay material.
  • Softener clays are used in the preferred compositions at levels of at least 1%, generally 1-20%, preferably 2-10%.
  • compositions herein may contain, in addition to the essential ingredients, optional ingredients, which can be highly desirable.
  • through-the-wash detergent compositions contain a detergent builder and/or metal ion sequestrant.
  • detergent builders include the nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, and mixtures thereof
  • Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-polyphosphonates and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here. See U.S. Patent 3.579.454 for typical examples of the use of such materials in various cleaning compositions.
  • Preferred polyfunctional organic acids species for use herein are citric acid, ethylene diamine tetramethylenephosphonic acid, and diethylene triaminepentamethylenephosphonic acid.
  • a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates.
  • the 1-10 micron size zeolite (e.g., zeolite A) builders disclosed in German Parent 24.22.655 are especially preferred for use in low-phosphate or non-phosphate compositions.
  • the builder/sequestrant will comprise from 0.5% to 45% of the composition.
  • compositions herein can also contain fatty acids, saturated or unsaturated, and the corresponding soaps.
  • Suitable fatty acids, saturated or unsaturated have from 10 to 18 carbon atoms in the alkyl chain.
  • Preferred are unsaturated species having from 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid.
  • the corresponding soaps can also be used.
  • the optional fatty acid/soaps are used in levels up to 20%.
  • compositions herein can also contain compounds of the general formula R-CH(COOH)CH2(COOH) i.e. derivatives of succinic acid, wherein R is C10-C20 alkyl or alkenyl, preferalby C12-C16, or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents.
  • the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
  • succinate builders include : lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred) and 2-pentadecenyl succinate.
  • Also useful as builders in the present context are the compounds described in US patent 4.663.071, i.e. mixtures of tartrate monosuccinic acid and tartrate disuccinic acid in a weight ratio of monosuccinic to disuccinic of from 97:3 to 20:80, preferably 95:5 to 40:60.
  • bleaching agent Another optional ingredient is a bleaching agent.
  • peroxygen bleaching agents such as sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate perosyhydrate and urea peroxyhydrate.
  • Bleach activators may be used in combination with the above peroxygen bleaching agents. Classes of bleach activators include esters, imides, imidazoles, oximes, and carbonates.
  • preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-octanoyloxybenzene sulfonate; sodium-4-octanoyloxybenzen sulfonat, and sodium-4-decanoylloxybenzenesulfonate : bisphenol diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.
  • alpho-substituted alkyl or alkenyl esters such as sodium-4(2-chlorooctanoyloxy) benzene sulfonate, sodium 4-(3,5,5-trimethyl hexanoyloxy)benzene sulfonate.
  • Suitable peroxyacids are also peroxygen bleach activators such as described in published European Patent Application 0 166 571, i.e., compounds of the general type RXAOOH and RXAL, wherein R is a hydroxycarbyl group, X is a hetero-atom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.
  • Enzymes other than cellulases such as proteolytic, amylolytic, or lipolytic enzymes can be used in combination with the cellulase herein.
  • All generally known enzyme stabilizing systems can be used in the liquid executions of the compositions herein, at the art established level. Examples of suitable stabilizing systems inlcude short C1 ⁇ 4 chain carboxylic acid, particularly formic acid in combination with a low level of calcium, boric acid and the water-soluble salts thereof possibly in combination with polyols.
  • compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits.
  • Typical ingredients include pH regulants, perfumes, dyes, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach stabilizing agents.
  • the detergent compositions of this invention can be present in any suitable physical state inclusive of granular, liquid, pasty, or sheet-like form.
  • They may be prepared in any way, as appropriate to their physical form, by mixing the components, co-agglomerating them, micro-encapsulating them, dispersing them in a liquid carrier, and releasably adsorbing or coating them onto a non-particulate substrate, such as a non-woven or paper sheet.
  • a non-particulate substrate such as a non-woven or paper sheet.
  • a granular detergent composition was prepared, by using the following ingredients in the stated proportions : ingredients % by weight Sodium Linear C12 alkyl benzene sulfonate 11.0 Sodium Tallow alkyl sulfate 5.0 Tallow alcohol ethoxylate (EO11) 0.3 Sodium tripolyphosphate 24.0 Bentonite clay 8.5 Cellulase 3.0* Proteolytic enzyme 0.9 Sodium Sulfate 40.0 minors and water up to 100 pH, 1% concentration in distilled water 8.7 * represents 40 CMCase units per g of composition
  • composition showed good cleaning performance as well as good softeness benefits, while exhibiting good fabric-care properties (no fabric damage dye fading, or fabric harshening observed)
  • the following granular compositions were also prepared : ingredient % by weight
  • Example II Sodium Linear C12 alkyl benzene sulfonate 7.0 6.5 C13 ⁇ 15 fatty alcohol/11 ethylene oxide condensate 1.0 0.5 Sodium sulfate 15.0 15.0 Sodium tripolyphosphate 24.

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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)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (8)

  1. Composition détergente pour le nettoyage et l'assouplissement du linge, contenant un agent tensioactif et une cellulase détergente, dans laquelle
    - l'agent tensioactif contient au moins 50% en poids d'un agent tensioactif anionique de type non savon;
    - la composition est essentiellement dépourvue d'alkylamines à chaîne longue, insolubles dans l'eau, d'agents assouplissants, ou de leurs dérivés;
    - la composition contient une matière argileuse assouplissant le linge; caractérisée en ce que
    - le pH d'une solution à 1% de la composition détergente dans de l'eau distillée est de 6,5 à 9,0.
  2. Composition selon la revendication 1, dans laquelle la cellulase est une cellulase bactérienne ou fongique ayant un pH optimum compris entre 5 et 11,5.
  3. Composition selon la revendication 1 ou 2, dans laquelle la cellulase est une cellulase alcaline ayant un pH optimum de 6,5 à 9,5.
  4. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition a une activité de cellulase de 5 à 100 unités d'activité CMCase/gramme de composition.
  5. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'agent tensioactif contient de 60% à 100% en poids d'agent tensioactif anionique de type non savon.
  6. Composition selon la revendication 1, dans laquelle la matière argileuse assouplissant le linge est présente dans des proportions de 1% à 20% en poids de la composition.
  7. Composition selon la revendication 6, dans laquelle la matière argileuse assouplissant le linge est une argile bentonite.
  8. Composition selon la revendication 1, dans laquelle ledit pH est de 6,5 à 8,7.
EP87202189A 1986-11-21 1987-11-11 Compositions détergentes adoucissantes contenant de la cellulase Revoked EP0269168B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB868627914A GB8627914D0 (en) 1986-11-21 1986-11-21 Softening detergent compositions
GB8627914 1986-11-21

Publications (3)

Publication Number Publication Date
EP0269168A2 EP0269168A2 (fr) 1988-06-01
EP0269168A3 EP0269168A3 (en) 1989-05-31
EP0269168B1 true EP0269168B1 (fr) 1995-05-17

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EP87202189A Revoked EP0269168B1 (fr) 1986-11-21 1987-11-11 Compositions détergentes adoucissantes contenant de la cellulase

Country Status (13)

Country Link
EP (1) EP0269168B1 (fr)
JP (1) JPS63199297A (fr)
KR (1) KR880006354A (fr)
CN (1) CN87107306A (fr)
AT (1) ATE122713T1 (fr)
AU (1) AU595401B2 (fr)
DE (1) DE3751304T2 (fr)
DK (1) DK611487A (fr)
EG (1) EG18380A (fr)
FI (1) FI91276C (fr)
GB (1) GB8627914D0 (fr)
PH (1) PH25615A (fr)
TR (1) TR24080A (fr)

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Publication number Priority date Publication date Assignee Title
US5120463A (en) * 1989-10-19 1992-06-09 Genencor International, Inc. Degradation resistant detergent compositions based on cellulase enzymes
SG52693A1 (en) * 1991-01-16 1998-09-28 Procter & Gamble Detergent compositions with high activity cellulase and softening clays
US5443750A (en) * 1991-01-16 1995-08-22 The Procter & Gamble Company Detergent compositions with high activity cellulase and softening clays
US5668073A (en) * 1991-11-06 1997-09-16 The Procter & Gamble Company Detergent compounds with high activity cellulase and quaternary ammonium compounds
JP3244700B2 (ja) * 1991-12-04 2002-01-07 ザ、プロクター、エンド、ギャンブル、カンパニー クエン酸，セルラーゼ，およびタンパク質分解酵素を阻害するホウ酸‐ジオール錯体を含有した液体洗濯洗剤
JP2974780B2 (ja) * 1992-02-18 1999-11-10 ザ、プロクター、エンド、ギャンブル、カンパニー 高活性セルラーゼと第四級アンモニウム化合物とを有する洗剤組成物
AU678356B2 (en) * 1992-05-01 1997-05-29 Genencor International, Inc. Methods for treating cotton-containing fabrics with CBH I enriched cellulase
US5599786A (en) * 1993-08-12 1997-02-04 The Procter & Gamble Company Cellulase fabric-conditioning compositions
US5616553A (en) * 1993-08-12 1997-04-01 The Procter & Gamble Company Fabric conditioning compositions
BR9507559A (pt) * 1994-04-29 1997-08-05 Procter & Gamble Composições de condicionamento de pano de celulase
US5445747A (en) * 1994-08-05 1995-08-29 The Procter & Gamble Company Cellulase fabric-conditioning compositions
DE19515072A1 (de) * 1995-04-28 1996-10-31 Cognis Bio Umwelt Cellulasehaltiges Waschmittel
US6187740B1 (en) 1997-07-11 2001-02-13 The Procter & Gamble Company Alkaline detergent compositions comprising a specific cellulase
CA2296559A1 (fr) * 1997-07-11 1999-01-21 The Procter & Gamble Company Compositions detergentes alcalines comportant une cellulase specifique
JP4417608B2 (ja) * 2002-04-25 2010-02-17 花王株式会社 変異アルカリセルラーゼ
CN103897840A (zh) * 2012-12-26 2014-07-02 青岛锦涟鑫商贸有限公司 一种织物用柔性洗涤剂

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Also Published As

Publication number Publication date
FI875137A0 (fi) 1987-11-20
EG18380A (en) 1993-07-30
FI875137A (fi) 1988-05-22
EP0269168A2 (fr) 1988-06-01
AU8143387A (en) 1988-05-26
DE3751304D1 (de) 1995-06-22
EP0269168A3 (en) 1989-05-31
DK611487A (da) 1988-05-22
JPS63199297A (ja) 1988-08-17
DK611487D0 (da) 1987-11-20
CN87107306A (zh) 1988-06-01
TR24080A (tr) 1991-03-04
GB8627914D0 (en) 1986-12-31
KR880006354A (ko) 1988-07-22
FI91276C (fi) 1994-06-10
ATE122713T1 (de) 1995-06-15
FI91276B (fi) 1994-02-28
PH25615A (en) 1991-08-08
DE3751304T2 (de) 1995-11-09
AU595401B2 (en) 1990-03-29

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