EP0854908B1 - Kesselstein entfernende reinigungsformulierungen auf basis mikrofibrillierter cellulose - Google Patents

Kesselstein entfernende reinigungsformulierungen auf basis mikrofibrillierter cellulose Download PDF

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Publication number
EP0854908B1
EP0854908B1 EP96927113A EP96927113A EP0854908B1 EP 0854908 B1 EP0854908 B1 EP 0854908B1 EP 96927113 A EP96927113 A EP 96927113A EP 96927113 A EP96927113 A EP 96927113A EP 0854908 B1 EP0854908 B1 EP 0854908B1
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EP
European Patent Office
Prior art keywords
formulation according
acid
microfibrils
less
range
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Expired - Lifetime
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EP96927113A
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English (en)
French (fr)
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EP0854908A1 (de
Inventor
Véronique Guillou
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • the present invention relates to descaling and cleaning formulations with base of cellulose microfibrils.
  • the detergent formulations used for descaling have very specific characteristics.
  • the products used in its composition must be able to remain stable and maintain their properties at very acidic pH, the most of the time less than 2 and very often less than 1.
  • the rheology of the formulations be of the pseudo-plastic type. Indeed, these formulations, for optimal use, must have a low viscosity when they are subjected to a significant shear as it is the case during the application of the product, then a high viscosity when the shear stresses are weak, so as to allow a slow flow along the walls to be descaled.
  • the object of the present invention is to propose a descaling formulation presenting a pseudo-plastic rheological profile, stable over time.
  • the subject of the invention is a descaling formulation comprising cellulose microfibrils, of which at least 80%, preferably at least 85% of the cells are with primary walls and at most 20%, preferably at most 15% of the cells are secondary walls, having a degree of crystallinity of at most 50%, preferably at least plus 40%.
  • microfibrils give the formulation a pseudo-plastic rheology, moreover and that these microfibrils, surprisingly, remained stable and retained their properties in very acidic media, i.e. with a pH between 0 and 1.
  • microfibrils used in the composition of the formulations according to the invention therefore consist of cellulose.
  • Cellulose represents the essential element of the walls of plant cells.
  • the latter consist of primary walls (parenchyma cells) and secondary walls, in different proportions depending on the nature of the plant from which they come.
  • the primary walls mainly comprise certain pectins and proteins and little cellulose, generally around 5%, and depend on the development of the cell.
  • the fibrils of the secondary walls constitute networks forming lamellae in which there is a layer S 1 (thickness of 0.2 to 0.35 ⁇ m) comprising very entangled and spiraled microfibrils, a layer S 2 (thickness of 1.8 to 3.8 ⁇ m) essentially based on cellulose in a very compact, oriented form, with slightly tangled microfibrils forming concentric lamellae, and finally a layer S 3 (thickness of 0.1 to 0.15 ⁇ m) based on cellulose fibers entangled and spiraled.
  • microfibrils used as an additive in the formulations according to the invention have at least 80%, preferably at least 85% of cells with primary walls and at most 20%, preferably at most 15% of cells with secondary walls.
  • the cellulose microfibrils have an average diameter included between 20 and 40 ⁇ , preferably between 30 and 40 ⁇ .
  • the crystallinity of the microfibrils is at most 50%, preferably at most 40%.
  • the rate of crystallinity is between 20 and 38%.
  • microfibrils The length of these microfibrils is of the order of 10 ⁇ m, and less. We can more particularly, use microfibrils with a length less than or equal to 2 ⁇ m.
  • the cellulose microfibrils are obtained from the beet, bran from cereals or any other vegetable.
  • the cellulose microfibrils have a high purity of the order of 90%.
  • the remaining 10% consists in particular of residual compounds such as water, pectins, such as galacturonic acid, rhamnose or ferulic acid, hemicelluloses, such as arabinose, galactose, mannose, xylose as well as mineral salts.
  • step (a) the term “pulp” means moist, dehydrated pulp, preserved by silage or partially defected.
  • the extraction step (a) can be carried out in an acid medium or in a basic medium.
  • the pulp is suspended in a solution of water for a few minutes so as to homogenize the acidified suspension to a pH between 1 and 3, preferably between 1.5 and 2.5.
  • This operation is carried out with a concentrated solution of an acid such than hydrochloric acid or sulfuric acid.
  • This step can be advantageous to remove the calcium oxalate crystals which may be present in the pulp, and which, due to their abrasive nature important, can cause difficulties in the homogenization step.
  • the pulp is added to an alkaline solution of base, for example soda or potash, with a concentration of less than 9% weight, more particularly less than 6% by weight.
  • concentration of the base is between 1 and 2% by weight.
  • a small amount of a water-soluble antioxidant may be added, such as sodium sulfite Na 2 SO 3 , in order to limit the cellulose oxidation reactions.
  • Stage (a) is generally carried out at a temperature of between approximately 60 ° C and 100 ° C, preferably between about 70 ° C and 95 ° C.
  • step (a) is between approximately 1 hour and approximately 4 hours.
  • step (a) partial hydrolysis takes place with release and solubilization of most pectins and hemicelluloses, while preserving the molecular weight of cellulose.
  • the solid residue is recovered from the suspension from step (a) in using known methods. So it is possible to separate the residue solid by centrifugation, by vacuum or pressure filtration, with fabrics filters, or filter presses for example, or by evaporation.
  • the first solid residue obtained is optionally subjected to a second step extraction, carried out under alkaline conditions.
  • a second extraction step is implemented when the first has been driving under acidic conditions. If the first extraction was carried out in alkaline conditions, the second step is only optional.
  • this second extraction is carried out with a base of preference chosen from soda and potash, the concentration of which is less than about 9% by weight, preferably between about 1% and about 6% by weight.
  • the duration of the alkaline extraction step is between approximately 1 and approximately 4 hours. It is preferably equal to approximately 2 hours.
  • step (c) the residue from step (a) or (b) is washed thoroughly with water to recover the residue of cellulosic material.
  • step (c) The cellulosic material of step (c) is then optionally bleached, in step (d), according to conventional methods.
  • Different concentrations of bleach can be used, at temperatures between about 18 ° C and 80 ° C, preferably between about 50 ° C and 70 ° C.
  • the duration of this stage (c) is between approximately 1 hour and approximately 4 hours, preferably between about 1 and about 2 hours.
  • a cellulosic material is then obtained containing between 85 and 95% by weight of cellulose.
  • this bleaching step it may be preferable to wash abundantly cellulose with water.
  • the resulting suspension is then rediluted in water at a rate of 2 to 10% dry matter.
  • the homogenization stage corresponds to mixing, grinding or any operation high mechanical shear, followed by one or more passes of the suspension cells through a small diameter orifice, subjecting the suspension to a drop of pressure of at least 20 MPa and a high speed shearing action followed by a deceleration impact at high speed.
  • Mixing or grinding is, for example, carried out by passage (s) in the mixer or grinder for a period ranging from a few minutes to about an hour, in a type device such as a WARING BLENDOR equipped with a four-blade propeller or wheel mill or any other type of mill, such as a colloid mill.
  • a type device such as a WARING BLENDOR equipped with a four-blade propeller or wheel mill or any other type of mill, such as a colloid mill.
  • the actual homogenization will advantageously be carried out in a homogenizer of the MANTON GAULIN type in which the suspension is subjected to a shear action at high speed and pressure in a narrow passage and against a shock ring.
  • a homogenizer of the MANTON GAULIN type in which the suspension is subjected to a shear action at high speed and pressure in a narrow passage and against a shock ring.
  • the MICRO FLUIDIZER which is a homogenizer mainly consisting of a compressed air motor which will create very strong pressures, an interaction chamber in which the operation will take place homogenization (elongational shear, shock and cavitation) and a chamber low pressure which allows the depressurization of the dispersion.
  • the suspension is preferably introduced into the homogenizer after preheating at a temperature between 40 and 120 ° C, preferably between between 85 and 95 ° C.
  • the temperature of the homogenization operation is maintained between 95 and 120 ° C, preferably greater than 100 ° C.
  • the suspension is subjected in the homogenizer to pressures included between 20 and 100 MPa, and preferably greater than 50 MPa.
  • the homogenization of the cellulosic suspension is obtained by a number of passages can vary between 1 and 20, preferably between 2 and 5, until obtaining of a stable suspension.
  • the homogenization operation can advantageously be followed by an operation high mechanical shear, for example in a device such as the ULTRA TURRAX from SYLVERSON.
  • the amount of microfibrils used in the composition of the formulation according to the invention is between 0.05 and 1.5% by weight. Preferably, this amount is between 0.1 and 1% by weight.
  • the percentages by weight are expressed by weight of material (for example the microfibrils) relative to the total weight of the formulation.
  • the formulation according to the invention also comprises an acidic compound.
  • This the latter can be organic or mineral.
  • organic acids are suitable as long as their pKa is lower or equal to 6. More particularly, mention may be made of mono- or polycarboxylic acids aliphatics comprising 1 to 12 carbon atoms.
  • acids of this type mention may be made of formic acids, acetic, maleic, citric, sulfamic, oxalic, adipic, succinic, glutaric.
  • the amount of acid used in the composition of the formulation is such that the pH of the final formulation is less than or equal to 2, more particularly less than 1.5.
  • the amount of acid used is such that the pH of the formulation is less than or equal to 1, and more particularly less than or equal to 0.5.
  • the skilled person given what has just been written, is able to adapt the quantity of acid to be used, according to the characteristics of the acid or acids envisaged.
  • the acid content in the formulation is between 1 and 20% by weight. More particularly it is between 3 and 15% by weight.
  • the formulation according to the invention also comprises at least one surfactant detergent.
  • this compound is chosen from nonionic surfactants, cationic or amphoteric.
  • nonionic surfactant By way of example of a nonionic surfactant, mention may be made of polyoxyalkylenated alkylphenols, the alkyl substituent of which is C 6 -C 12 and containing from 5 to 25 oxyalkylene units (oxyethylene, oxypropylene, oxybutylene), polyoxyalkylenated alkylarylphenols of which the alkyl substituent is C 1 -C 6 and comprising 5 to 25 oxyalkylene units (oxyethylene, oxypropylene), aliphatic C 8 -C 22 polyoxyalkylene alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropylene) the condensation of ethylene oxide or propylene oxide, with propylene glycol, ethylene glycol and / or glycerol.
  • polyoxyalkylenated alkylphenols the alkyl substituent of which is C 6 -C 12 and containing from 5 to 25 oxyalkylene units (oxyethylene, oxypropy
  • nonionic surfactants there may be mentioned glucosamides, glucamides, glycerolamides, the products resulting from the condensation of ethylene oxide or propylene oxide, with ethylenediamine, the oxides of amines such as C 10 -C 18 alkyl oxides dimethylamines, C 8 -C 22 alkoxy oxides ethyl dihydroxy ethylamines, alkylpolyglycosides described in US-A-4,565,647, C 8 fatty acid amides -C 20 , ethoxylated fatty amides, ethoxylated amines.
  • polyoxyalkylenated aliphatic alcohols as well as polyoxyalkylenated alkylphenols, these surfactants being used alone or as a mixture.
  • alkylphenols use is more particularly made of compounds having 1 or 2 alkyl groups, linear or branched, having 4 to 12 carbon atoms, in particular octyl, nonyl or dodecyl.
  • Ethoxylated alkylphenols or ethoxy-propoxylated (EO units + OP) have generally 1 or 2 alkyl groups, linear or branched, having 4 to 12 atoms of carbon, in particular octyl, nonyl or dodecyl.
  • surfactants of this type mention may be made most particularly of ethoxylated nonylphenol with 6 OE units, ethoxylated nonylphenol with 9 OE units, ethoxylated nonylphenol with 10 OE units, ethoxylated nonylphenol with 12 OE units, ethoxy-propoxylated nonylphenols with 25 OE + OP units, ethoxy-propoxylated nonylphenols with 30 OE + OP units, ethoxy-propoxylated nonylphenols with 40 units OE + OP.
  • the quaternary ammoniums are suitable for carrying out the invention.
  • the surfactants included in the formulation according to the invention can also be chosen from amphoteric surfactants.
  • amphoteric surfactants for example, alkyl betaines, alkyl dimethylbetaines, alkylamidopropylbetaines, alkylamidopropyl-dimethylbetaines, alkyltrimethyl-sulfobetaines, imidazoline derivatives such as alkyl amphoacetates, alkylamphodiacetates, alkylamphopropionates, alkylampho dipropionates, alkylsultaines or alkylamidopropyl-hydroxysultaines, products condensation of fatty acids and protein hydrolysates, these compounds being able be used alone or as a mixture.
  • Mirapon® Excel, Mirataine® CBS, Mirataine® CB surfactants, the range of Miranol®, Amphionic® SFB, Amphionic® XL may be particularly suitable for the realization of the present invention.
  • the amount of surfactants is between 0.1 and 5% by weight. Preferably, it is between 0.8 and 3% by weight.
  • the formulation according to the present invention may further comprise the additives classics of this type of application in particular.
  • the formulations can contain dyes, perfumes, preservatives.
  • the additive content is less than 2% by weight, or even 1% by weight. weight.
  • the content of these compounds depends on the effect to be obtained and this is very often achieved with contents as low as 0.1 to 0.2% by weight.
  • the complement to 100% by weight of the formulation consists of water.
  • all is dispersed first the cellulose microfibrils in at least a fraction of the water entering the formulation.
  • the viscosity characteristics of the formulation can be adapted according to the quality of the agitation. So when the commotion is slow, i.e. with a speed of less than 1000rpm, the viscosity of the resulting formulation is lower than the viscosity of a formulation obtained with the same amount of microfibrils, but prepared under intense agitation, for example greater than 5000 rpm. Therefore, more intense agitation will decrease the amount of microfibrils needed to obtain the viscosity level wish.
  • the devices with which the formulation is prepared are conventional and are in particular devices of the Ultra-Turrax® type, devices with blades deflocculers or mixers.
  • the agitation of the first stage, that of the dispersion of the microfibrils in water may or may not be conserved.
  • the preparation of the formulation is usually carried out at the temperature ambient.
  • formulations according to the invention in particular find their application in the descaling of sanitary facilities whether in the household or institutional field (community).
  • a suspension comprising an amount of cellulose microfibrils in an aqueous solution comprising 10% hydrochloric acid, so as to obtain a pH of 0.
  • These cellulose microfibrils were supplied by GENERALE SUCRIERE; they were prepared according to Example 20 of European patent application EP-A-0 726 356.
  • Example 1a consists in suspending the microfibrils using a pale deflocculator, with a speed of 1400 rpm.
  • Example 1b consists in suspending the microfibrils using an Ultra-Turrax, with a speed of 500 rpm.
  • the viscosity measurement was carried out with a Brookfield device (needle No. 3).
  • the purpose of this example is to evaluate the viscosity of a suspension of microfibrils with a pH of 2.
  • the suspension comprises 0.8% microfibrils and was obtained by shaking with a pale deflocculator rotating at 500 rpm.
  • the viscosities measured with a Brookfield device are as follows: 0.3 rpm 7200 mPa.s 3 rpm 1000 mPa.s 30 rpm 770 mPa.s

Claims (17)

  1. Entkalkungsformulierung, dadurch gekennzeichnet, daß sie Cellulose-Mikrofibrillen umfaßt, die mindestens 80%, vorzugsweise mindestens 85% von Zellen mit Primärwänden und höchstens 20%, vorzugsweise höchstens 15% von Zellen mit Sekundärwänden umfassen und einen Kristallinitätsgrad unter 50%, vorzugsweise unter 40% aufweisen.
  2. Formulierung nach dem vorangegangenen Anspruch, dadurch gekennzeichnet, daß die Mikrofibrillen einen mittleren Durchmesser zwischen 20 und 40 Å, vorzugsweise zwischen 30 und 40 Å aufweisen.
  3. Formulierung nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß die Mikrofibrillen aus der Pulpe von Pflanzen mit Primärwänden stammen.
  4. Formulierung nach dem vorangegangenen Anspruch, dadurch gekennzeichnet, daß die Mikrofibrillen von der Rübe, von der Kleie von Getreiden stammen.
  5. Formulierung nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß der Gehalt an Cellulose-Mikrofibrillen zwischen 0,05 und 1,5 Gew.-% und vorzugsweise zwischen 0,1 und 1% beträgt.
  6. Formulierung nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß sie mindestens eine organische Säure oder Mineralsäure oder eine Mischung dieser zwei Säuretypen umfaßt.
  7. Formulierung nach dem vorangegangenen Anspruch, dadurch gekennzeichnet, daß die organische Säure ausgewählt wird unter den aliphatischen Mono- oder Polycarbonsäuren, die 1 bis 12 Kohlenstoffatome umfassen.
  8. Formulierung nach dem vorangegangenen Anspruch, dadurch gekennzeichnet, daß die organische Säure ausgewählt wird unter der Ameisensäure, Essigsäure, Maleinsäure, Citronensäure, Sulfaminsäure, Oxalsäure, Adipinsäure, Succinsäure, Glutarsäure, wobei diese Säuren allein oder in einer Mischung vorliegen.
  9. Formulierung nach Anspruch 6, dadurch gekennzeichnet, daß die Mineralsäure unter Salzsäure und Phosphorsäure oder deren Mischungen ausgewählt wird.
  10. Formulierung nach einem der vorangegangenen Ansprüche 6 bis 9, dadurch gekennzeichnet, daß die Säuremenge so ist, daß der pH unter oder gleich 2 und vorzugsweise unter 1,5 ist.
  11. Formulierung nach einem der vorangegangenen Ansprüche 6 bis 10, dadurch gekennzeichnet, daß die Säuremenge so ist, daß der pH unter oder gleich 1 und vorzugsweise unter oder gleich 0,5 ist.
  12. Formulierung nach einem der vorangegangenen Ansprüche 6 bis 11, dadurch gekennzeichnet, daß die Säuremenge zwischen 1 und 20 Gew.-%, vorzugsweise zwischen 3 und 15% liegt.
  13. Formulierung nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß sie mindestens ein grenzflächenaktives Detergens, ausgewählt unter den nichtionischen, kationischen, amphoteren grenzflächenaktiven Mitteln oder deren Mischungen, umfaßt.
  14. Formulierung nach dem vorangegangenen Anspruch, dadurch gekennzeichnet, daß der Gehalt an grenzflächenaktiven Mitteln zwischen 0,1 und 5 Gew.-%, vorzugsweise zwischen 0,8 und 3% beträgt.
  15. Formulierung nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß sie Zusatzstoffe, wie Färbemittel, Konservierungsmittel, Parfumstoffe, umfaßt.
  16. Formulierung nach dem vorangegangenen Anspruch, dadurch gekennzeichnet, daß der Gehalt an Zusatzstoffen unter 2%, vorzugsweise unter 1% liegt.
  17. Formulierung nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß sie Wasser umfaßt.
EP96927113A 1995-10-03 1996-07-31 Kesselstein entfernende reinigungsformulierungen auf basis mikrofibrillierter cellulose Expired - Lifetime EP0854908B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9511697 1995-10-03
FR9511697A FR2739394B1 (fr) 1995-10-03 1995-10-03 Formulations detartrantes et nettoyantes a base de microfibrilles de cellulose
PCT/FR1996/001206 WO1997012954A1 (fr) 1995-10-03 1996-07-31 Formulations detartrantes et nettoyantes a base de microfibrilles de cellulose

Publications (2)

Publication Number Publication Date
EP0854908A1 EP0854908A1 (de) 1998-07-29
EP0854908B1 true EP0854908B1 (de) 2000-03-01

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EP96927113A Expired - Lifetime EP0854908B1 (de) 1995-10-03 1996-07-31 Kesselstein entfernende reinigungsformulierungen auf basis mikrofibrillierter cellulose

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US (1) US5998349A (de)
EP (1) EP0854908B1 (de)
JP (1) JP3014768B2 (de)
KR (1) KR100256136B1 (de)
CN (1) CN1105171C (de)
AT (1) ATE190088T1 (de)
AU (1) AU697812B2 (de)
BR (1) BR9610769A (de)
CA (1) CA2231512A1 (de)
CZ (1) CZ291536B6 (de)
DE (1) DE69606878T2 (de)
EA (1) EA000499B1 (de)
ES (1) ES2146011T3 (de)
FR (1) FR2739394B1 (de)
HU (1) HUP9900048A2 (de)
IL (1) IL123918A (de)
MX (1) MX9802600A (de)
PL (1) PL325996A1 (de)
PT (1) PT854908E (de)
TR (1) TR199800652T1 (de)
WO (1) WO1997012954A1 (de)

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BR9610769A (pt) 1999-07-13
ATE190088T1 (de) 2000-03-15
ES2146011T3 (es) 2000-07-16
CN1201484A (zh) 1998-12-09
MX9802600A (es) 1998-11-30
KR19990064005A (ko) 1999-07-26
CZ99098A3 (cs) 1998-08-12
JPH11500176A (ja) 1999-01-06
IL123918A (en) 2001-03-19
AU697812B2 (en) 1998-10-15
EP0854908A1 (de) 1998-07-29
KR100256136B1 (ko) 2000-05-15
HUP9900048A2 (hu) 1999-05-28
TR199800652T1 (xx) 1998-06-22
EA199800265A1 (ru) 1998-10-29
CN1105171C (zh) 2003-04-09
DE69606878D1 (de) 2000-04-06
DE69606878T2 (de) 2000-08-17
WO1997012954A1 (fr) 1997-04-10
PT854908E (pt) 2000-06-30
JP3014768B2 (ja) 2000-02-28
FR2739394A1 (fr) 1997-04-04
US5998349A (en) 1999-12-07
AU6704896A (en) 1997-04-28
PL325996A1 (en) 1998-08-17
EA000499B1 (ru) 1999-08-26
FR2739394B1 (fr) 1997-12-05
CA2231512A1 (fr) 1997-04-10
CZ291536B6 (cs) 2003-03-12

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