EP0849355A2 - Composants de lavage et de nettoyage sous forme de poudre - Google Patents

Composants de lavage et de nettoyage sous forme de poudre Download PDF

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Publication number
EP0849355A2
EP0849355A2 EP97121407A EP97121407A EP0849355A2 EP 0849355 A2 EP0849355 A2 EP 0849355A2 EP 97121407 A EP97121407 A EP 97121407A EP 97121407 A EP97121407 A EP 97121407A EP 0849355 A2 EP0849355 A2 EP 0849355A2
Authority
EP
European Patent Office
Prior art keywords
weight
component according
acid
cleaning agent
detergent
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.)
Granted
Application number
EP97121407A
Other languages
German (de)
English (en)
Other versions
EP0849355B1 (fr
EP0849355A3 (fr
Inventor
Günther Dr. Schimmel
Harald Dr. Bauer
Josef Holz
Volker Thewes
Richard Dr. Mertens
Peter Dr. Hardt
Matthias Dr. Berghahn
Thomas Dr. Müller
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.)
clariant Produkte Deutschland GmbH
Evonik Operations GmbH
Original Assignee
Clariant GmbH
Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19719888A external-priority patent/DE19719888A1/de
Application filed by Clariant GmbH, Stockhausen GmbH and Co KG, Chemische Fabrik Stockhausen GmbH filed Critical Clariant GmbH
Publication of EP0849355A2 publication Critical patent/EP0849355A2/fr
Publication of EP0849355A3 publication Critical patent/EP0849355A3/fr
Application granted granted Critical
Publication of EP0849355B1 publication Critical patent/EP0849355B1/fr
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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D3/08—Silicates
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers

Definitions

  • the invention relates to a powder detergent and cleaning agent component, a method for their manufacture and their use.
  • washing and cleaning agents contain a variety of ingredients, one Perform a number of different functions. Important for the quality of such washing and Detergent is both the type and amount of ingredients used and the type and order of the combination of these ingredients.
  • the main components in modern textile detergents include surfactants, Bleach, washing alkalis and the so-called builders.
  • the main components for detergents and dishwashing detergents are primarily builders, bleach, alkalis, Dispersants and enzymes.
  • An ideal builder for textile detergents fulfills a number of functions and carries, for example significantly to water softening. In addition, it should have the highest possible carrying capacity for liquid components and sufficient buffering of the wash liquor enable.
  • NaTPP sodium tripolyphosphate
  • zeolites A and P zeolites A and P
  • crystalline silicates such as Na 2 Si 2 O 5 , which is also referred to as SKS-6.
  • the water softening (removal or binding of the calcium and / or magnesium ions causing the water hardness) is carried out with the aforementioned builders in different ways Way.
  • the sodium tripolyphosphate dissolves and forms with the calcium and magnesium ions soluble complexes that do not interfere with the washing process.
  • the zeolites and the layered silicates form with the calcium and magnesium ions insoluble complexes.
  • the zeolites produce significantly higher amounts of insoluble Preserve complexes. These particles present as a solid in the wash liquor must be kept in suspension by additional detergent ingredients do not deposit on the textile fiber. The same applies to other (solid) dirt particles and any precipitated components of water hardness.
  • Detergents for machine cleaning of dishes also need components included, which are able to keep the detached dirt in suspension and the To prevent re-depositing on the wash ware.
  • Suitable additional detergent ingredients are the so-called cobuilders, which are also known as Polyelectrolyte compounds are called. These include citric acid, nitrilotriacetic acid, Homopolymers and copolymers of acrylic acid, polyaspartic acid and starch oxidation products. The aforementioned ingredients can also be found in detergents and dishwashing detergents deploy.
  • polycarboxylates which are polymers with a molecular weight from about 2,000 to 100,000. They consist of different carboxylic acids and the corresponding monomers. In powder detergents and Also in dishwashing detergents, they are usually in the form of their neutral sodium salts, solid or in aqueous solution.
  • the amount of builder is usually 10 to 40% by weight and that of cobuilders usually 1 to 10% by weight, based on the total amount powder detergent.
  • the quantities added in a similar order of magnitude.
  • Powdered laundry detergents that contain crystalline silicates as builders usually require lower amounts of cobuilders than those containing only zeolite A as a builder.
  • zeolite A cannot be used in dishwashing detergents because of its insolubility only soluble components come into question here.
  • the quality or the mode of action of such a builder / cobuilder system for textile detergents can be measured, for example, with the so-called secondary washing behavior.
  • the secondary washing behavior indicates in particular to what extent such a builder / cobuilder system is able to prevent deposits on the laundry fibers.
  • the washed fabric is ashed and the amount of ash is determined gravimetrically.
  • the mode of operation of the aforementioned builder / cobuilder systems can be used for dishwashing detergents with regard to the re-soiling of already cleaned dishes by visual sampling be recorded quantitatively with the help of a grading system.
  • the sodium polycarboxylates are used in the production of washing powder introduced both as an aqueous solution and in powder form.
  • the aqueous Solution sprayed on the other solid detergent components to make a free-flowing product Get product.
  • This is a component with particularly good drenchability Layered silicate SKS-6 from Hoechst AG, Frankfurt am Main, which is capable of a good one To ensure that the washing powder flows freely.
  • the object of the invention is therefore to provide a composition with which the aforementioned disadvantages can be overcome and with the excellent Washing and cleaning results, in particular with regard to the secondary washing ability, can be achieved.
  • a powder detergent component characterized in that it is a reaction product of an alkaline silicate and an acidic polycarboxylate.
  • the weight ratio of alkaline silicate to acidic polycarboxylate is preferred (40 to 1): 1.
  • the weight ratio of alkaline silicate to acidic polycarboxylate is particularly preferred (20 to 2): 1.
  • the acidic polycarboxylate is a homo- and / or / which is not or only partially neutralized Copolymer of acrylic acid, methacrylic acid, maleic acid, polyaspartic acid, sugar carboxylic acid and / or other monomers used.
  • the powder detergent and cleaning agent component preferably contains 50 to 98 % By weight of alkaline silicate and 2 to 50% by weight of a copolymer of 10 to 70% by weight Maleic acid, 20 to 85% by weight acrylic acid and / or methacrylic acid, 1 to 50% by weight Vinyl acetate and 0 to 10% by weight of further monomers with a degree of neutralization of 0 up to 70%.
  • the alkaline silicate is preferably an amorphous sodium silicate.
  • the alkaline silicate is particularly preferably a crystalline one Sodium silicate.
  • the alkaline silicate is particularly preferably a crystalline one Layered sodium silicate.
  • the further elements and / or connections are preferably aluminum, Titanium, iron, calcium, magnesium and / or their compounds.
  • the above object is also achieved by a method for producing a powder Detergent and cleaning agent component, characterized in that apply an acidic polycarboxylate solution to an alkaline silicate.
  • the acidic polycarboxylate solution is preferably brought into a solid mixer which is a Contains liquid injection device based on the alkaline silicate.
  • reaction product of alkaline sodium silicate and acidic polycarboxylate solution is preferred at temperatures of 40 to 150 ° C for a time of 5 to 120 minutes dried.
  • the invention also relates to the use of the powdery form according to the invention Detergent and cleaning agent component for the production of detergents.
  • the powdered detergent and cleaning agent component according to the invention is preferred used for the production of detergents using the dry mix method.
  • the invention also relates to the use of the powdery form according to the invention Detergent and detergent component for the production of detergent compositions.
  • the powdered detergent and cleaning agent component according to the invention is preferred for the production of detergent compositions for cleaning hard Surfaces used.
  • the invention also relates to the use of the powdery form according to the invention Detergent and cleaning agent component for the production of dishwashing detergent compositions.
  • the powdered detergent and cleaning agent component according to the invention is preferred for the preparation of dishwasher detergent compositions for machine cleaning used by dishes.
  • the powder detergent component according to the invention are non-neutralized and / or partially neutralized acid group-containing polycarboxylates neutralized polymers containing acid groups.
  • These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with other ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, Ethyl acrylic acid, vinyl acetic acid, allylacetic acid, maleic acid, fumaric acid, Itaconic acid, meth (allysulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethyl propane sulfonic acid, and monomers containing phosphoric acid groups, such as, for example Vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropanephosphonic acid and their salts and hydroxyethyl (meth) acrylate sulfates, allyl alcohol sulfates and phosphates.
  • ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, Ethyl acrylic acid, vinyl acetic acid, allylacetic acid,
  • Graft polymers of monosaccharides are also suitable for the use according to the invention, Oligosaccharides, polysaccharides and modified polysaccharides as described in DE-A-40 03 172 and DE-A-44 15 623 are described.
  • the graft polymers described in EP-A-0 457 025 with proteins animal and of vegetable origin, especially with modified proteins, are also for the application according to the invention well suited.
  • polyaspartic acids or their derivatives in or not partially neutralized form are polyaspartic acids or their derivatives in or not partially neutralized form.
  • the polyaspartic acids are in the form of their alkali metal or ammonium salts. From this you can get the non-neutralized or only partially neutralized products by adding appropriate amounts of organic or inorganic acids and, if necessary, separating them of the resulting salts.
  • Such products can also be achieved through the thermal conversion of maleic acid and ammonia or by the condensation of aspartic acid and the subsequent hydrolysis of the resulting polysuccinimide.
  • the manufacture of such products is for example in DE-A-36 26 672, DE-A-43 07 114, DE-A-44 27 287, EP-A-0 612 784, EP-A-0 644 257 and PCT / WO 92/14753.
  • Particularly suitable for the production of the powdered washing and Detergent components are graft polymers of acrylic acid, methacrylic acid, maleic acid and further ethylenically unsaturated monomers on salts of polyaspartic acid, as usually occurs in the previously described hydrolysis of the polysuccinimide.
  • the otherwise necessary addition of acid to produce the only partially neutralized Form of polyaspartic acid can be dispensed with.
  • the amount of polyaspartate is usually chosen so that the degree of neutralization of all carboxyl groups incorporated in the polymer 80%, preferably 60%, does not exceed.
  • copolymers are prepared by the following examples, polymer 1 to polymer 5 described.
  • thermometer and metering devices 150 g of maleic anhydride, 200 g of sodium hydroxide solution (50 wt .-%), 360 g of water and 0.01 g of ammonium iron sulfate (Mohr's salt) submitted and heated to 90 ° C with stirring.
  • the total time of metering is 4 hours.
  • the mixture is stirred for one hour under reflux and distilled then about 420 g of water.
  • a viscous solution with a dry matter content is obtained of about 55% by weight, a pH of 4.8 and a Brookfield viscosity of 55,000 mPa * s at 20 ° C.
  • the weight average molecular weight, determined by means of gel permeation chromatography, is 21,000 g / mol.
  • the mixture is stirred for an hour and then about 300 g of water are distilled off.
  • Man obtains a viscous, brown product with a dry matter content of about 55% by weight, a pH of 5.0 and a Brookfield viscosity of 84,000 mPa * s at 20 ° C.
  • the Weight-average molecular weight, determined by means of gel permeation chromatography, is 60,000 g / mol.
  • Examples 1 to 8 below describe the preparation of the powdery form according to the invention Detergent and cleaning agent components and their application.
  • the powders Compared to pure SKS-6, the powders have a significantly reduced alkalinity, as shown in Figure 1 from the representation of the reserve alkalinity (titration curve of 2 g of product with 1N HCl).
  • the reserve alkalinity indicates how much acid is required to lower a substance to a certain pH above 5.
  • Production of the washing and cleaning agent component according to the invention each using 2 kg of SKS-6 powder example Amount of polycarboxylate solution pH of the moist component after drying Flowability % H 2 O % Active ingredient cobuilder wet dried 1 222 11.66 3.5 5.6 15 23 2nd 500 11.59 5.5 11.5 11 28 3rd 1,140 11.4 8th 22 11 270
  • Powdery textile detergents are produced in accordance with Examples 4 and 5, but instead of pure SKS-6 a mixture of SKS-6 and the powdery detergent and cleaning agent component SKS-6 / polycarboxylate in accordance with Example 3 is used.
  • SKS-6 powdery detergent and cleaning agent component
  • Example 3 powdery detergent and cleaning agent component
  • Examples 4 and 6 and 5 and 7 are the same and therefore placed side by side (Table 2).
  • the detergents from Examples 4 to 7 are subjected to a washing test and tested for their Secondary washing effect checked. This is done by using 5 standard fabrics together 4.5 kg of ballast tissue are washed 25 times and after every fifth wash by ashing of the standard tissue, the inorganic tissue deposits are determined. The Results are shown in Table 3.
  • Examples 9 and 10 below relate to the production and testing of a Dishwashing detergent composition.
  • Example 9 The detergent additive used in Example 9 is one according to Table 1, Example 3. Its composition corresponds approximately to the sum of SKS-6 and sodium polycarboxylate in example 10.
  • the washing and cleaning agent component according to the invention in the present dishwashing agent formulation Example 9 is particularly high Cleaning ability off (test according to DIN 44990). It is particularly suitable for burned and to remove protein-containing food residues and tea stains. In addition, it has a pronounced Dispersion behavior, especially towards fiber-containing food residues.
  • the detergent and cleaning agent component according to the invention prevents Present dishwashing detergent glass and decor damage.

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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)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
EP97121407A 1996-12-21 1997-12-05 Composants de lavage et de nettoyage sous forme de poudre Expired - Lifetime EP0849355B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19653949 1996-12-21
DE19653949 1996-12-21
DE19719888 1997-05-12
DE19719888A DE19719888A1 (de) 1996-12-21 1997-05-12 Pulverförmige Wasch- und Reinigungsmittel-Komponente

Publications (3)

Publication Number Publication Date
EP0849355A2 true EP0849355A2 (fr) 1998-06-24
EP0849355A3 EP0849355A3 (fr) 1999-12-15
EP0849355B1 EP0849355B1 (fr) 2004-03-17

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EP97121407A Expired - Lifetime EP0849355B1 (fr) 1996-12-21 1997-12-05 Composants de lavage et de nettoyage sous forme de poudre

Country Status (11)

Country Link
US (1) US7256169B2 (fr)
EP (1) EP0849355B1 (fr)
JP (1) JP3258952B2 (fr)
CN (1) CN1186110A (fr)
CA (1) CA2226071C (fr)
CZ (1) CZ414697A3 (fr)
ES (1) ES2218632T3 (fr)
HU (1) HUP9702513A3 (fr)
NO (1) NO975974L (fr)
PL (1) PL323895A1 (fr)
TW (1) TW386109B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999057237A1 (fr) * 1998-04-30 1999-11-11 Henkel Kommanditgesellschaft Auf Aktien Produit solide pour lave-vaisselle, a base de phosphate et de silicates lamellaires cristallins
EP1205537A3 (fr) * 2000-11-14 2002-06-19 Clariant GmbH Composition d' adjuvant
US6455491B2 (en) 1999-12-16 2002-09-24 Clariant Gmbh Granular alkali metal phyllosilicate compound
EP1253189A3 (fr) * 2001-04-28 2003-06-18 Clariant GmbH Composition d'adjuvant
WO2010030323A1 (fr) 2008-09-15 2010-03-18 Nanochem Solutions, Inc. Procédé de fabrication de copolymères greffés à partir du poly(aspartate) de sodium et copolymère greffé résultant

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10334047A1 (de) 2003-07-25 2005-02-24 Clariant Gmbh Adsorbat aus Schichtsilicat und seine Verwendung
KR100817687B1 (ko) * 2004-09-10 2008-03-27 주식회사 엘지생활건강 산성형태의 수용성 고분자와 유기산을 함유하는 저밀도분말세제 조성물 및 그의 제조방법
KR100751556B1 (ko) 2005-08-22 2007-08-22 주식회사 엘지생활건강 분말 세제 조성물 및 그 제조방법
KR101392380B1 (ko) * 2007-02-21 2014-05-07 주식회사 엘지생활건강 산성형태의 수용성 고분자를 함유하는 분말세제 입자 및그의 제조방법
EP2277982B1 (fr) 2009-07-17 2012-01-18 Clariant Finance (BVI) Limited Composition de nettoyage à changement de couleur
JP5385773B2 (ja) * 2009-12-22 2014-01-08 花王株式会社 衣料洗剤用高分子ビルダー
JP5628552B2 (ja) * 2010-04-30 2014-11-19 花王株式会社 アルカリ金属珪酸塩粒子

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US5663133A (en) * 1995-11-06 1997-09-02 The Procter & Gamble Company Process for making automatic dishwashing composition containing diacyl peroxide
CA2248160C (fr) * 1996-03-08 2002-08-06 The Procter & Gamble Company Preparation de particules de sulfate alkyle secondaire possedant une meilleure solubilite

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999057237A1 (fr) * 1998-04-30 1999-11-11 Henkel Kommanditgesellschaft Auf Aktien Produit solide pour lave-vaisselle, a base de phosphate et de silicates lamellaires cristallins
US6462006B1 (en) 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
US6455491B2 (en) 1999-12-16 2002-09-24 Clariant Gmbh Granular alkali metal phyllosilicate compound
EP1205537A3 (fr) * 2000-11-14 2002-06-19 Clariant GmbH Composition d' adjuvant
US6844310B2 (en) 2000-11-14 2005-01-18 Clariant Gmbh Process of preparing a crystalline sodium silicate builder composition
EP1253189A3 (fr) * 2001-04-28 2003-06-18 Clariant GmbH Composition d'adjuvant
US6908896B2 (en) 2001-04-28 2005-06-21 Clariant Gmbh Builder composition prepared by heat-treating a crystalline layered Na silicate
WO2010030323A1 (fr) 2008-09-15 2010-03-18 Nanochem Solutions, Inc. Procédé de fabrication de copolymères greffés à partir du poly(aspartate) de sodium et copolymère greffé résultant
EP2326672A4 (fr) * 2008-09-15 2011-10-12 Nanochem Solutions Inc Procédé de fabrication de copolymères greffés à partir du poly(aspartate) de sodium et copolymère greffé résultant

Also Published As

Publication number Publication date
EP0849355B1 (fr) 2004-03-17
ES2218632T3 (es) 2004-11-16
JP3258952B2 (ja) 2002-02-18
HU9702513D0 (en) 1998-03-02
CA2226071A1 (fr) 1998-06-21
TW386109B (en) 2000-04-01
PL323895A1 (en) 1998-06-22
NO975974D0 (no) 1997-12-19
JPH10251686A (ja) 1998-09-22
NO975974L (no) 1998-06-22
CN1186110A (zh) 1998-07-01
CZ414697A3 (cs) 1998-07-15
HUP9702513A3 (en) 2000-08-28
EP0849355A3 (fr) 1999-12-15
HUP9702513A2 (hu) 1999-06-28
US7256169B2 (en) 2007-08-14
CA2226071C (fr) 2003-01-07
US20040176268A1 (en) 2004-09-09

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