EP0455522A1 - Phosphatfreies Waschmittel - Google Patents

Phosphatfreies Waschmittel Download PDF

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Publication number
EP0455522A1
EP0455522A1 EP91400773A EP91400773A EP0455522A1 EP 0455522 A1 EP0455522 A1 EP 0455522A1 EP 91400773 A EP91400773 A EP 91400773A EP 91400773 A EP91400773 A EP 91400773A EP 0455522 A1 EP0455522 A1 EP 0455522A1
Authority
EP
European Patent Office
Prior art keywords
washing
weight
product according
oxidized polysaccharide
approximately
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
EP91400773A
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English (en)
French (fr)
Other versions
EP0455522B1 (de
Inventor
Serge Gosset
Didier Videau
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.)
Roquette Freres SA
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Roquette Freres SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roquette Freres SA filed Critical Roquette Freres SA
Publication of EP0455522A1 publication Critical patent/EP0455522A1/de
Application granted granted Critical
Publication of EP0455522B1 publication Critical patent/EP0455522B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
    • 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
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the present invention relates to a new washing product, usable in particular for washing fabrics, of the kind of those which are reduced in content to less than 5% by weight, or even zero in phosphates, and which comprise at least one zeolite.
  • phosphates have played a predominant role in detergents, in particular as sequestrants of cations which form salts insoluble in water, in particular calcium and magnesium ions; the excellent performances which they allow to achieve reside in their particular structure.
  • NTA nitrilotriacetic acid
  • NTA sodium nitrilotriacetate
  • compositions can be free of phosphates and contain less than 20% by weight of zeolites.
  • zeolites we associate with zeolites, in addition to said polycarboxylic polymers, clays and NTA.
  • acrylic polymers and in particular to homopolymers of acrylic acid or of methacrylic acid or their salts, in particular polyacrylic acid (PA) and sodium polyacrylates (PNa).
  • PA polyacrylic acid
  • PNa sodium polyacrylates
  • acrylic polymers in particular polyacrylic acid and its salts, have the major drawback of being non-biodegradable.
  • the oxidized polysaccharides which can be used in the context of the present invention are those which are obtained from di-, tri- and oligosaccharides, starch hydrolysates, cellulose and hemicellulose, only, among all of their potentially oxidizable functions, their terminal function (of aldehyde type before oxidation) is substantially oxidized and this, in an aldonic type function.
  • Such oxidized polysaccharides can, in particular if an oxidation truly qualifying as "selective" is sought at the level of the terminal function of aldonic type, can be obtained according to the catalytic oxidation process described by the Applicant Company in its patent EP 232.202 .
  • the oxidized polysaccharide used therein is in the form of an oxidation product of a starch hydrolyzate having a DE (Dextrose Equivalent) of about 5 to about 90 and preferably has an acid number I of between about 1 and about 20, said acid number I being expressed in number of grams of carboxylic function per 100 g of oxidized polysaccharide and given by the formula:
  • oxidized polysaccharides which have an acid number of between approximately 5 and approximately 14 and which are obtained by oxidation of starch hydrolysates having a DE between about 20 and about 65.
  • oxidized polysaccharides will be used which have an acid number of between approximately 8 and approximately 14 and which are obtained by oxidation of starch hydrolysates having a DE of between approximately 35 and approximately 65.
  • the oxidized polysaccharide is an oxidized product having, in particular by its level of reducing sugars, good stability, in particular at the level of its coloring, when said oxidized product is used (when the the washing product according to the invention is prepared or used), at any time and for example during spraying operations, in an environment with an alkaline pH and / or a high temperature, an environment capable of coloring (more or less pronounced yellowing) any composition containing it.
  • the Applicant Company has designed and developed, as new products, "stabilized" oxidized polysaccharides having low levels, generally less than about 0.6%, preferably less than 0.1% and even more preferably less than 0.05% by weight, in reducing sugars.
  • the Applicant Company has found that the hydrogenation techniques applied to oxidized polysaccharides, in particular of the oxidized starch hydrolysates type, make it possible to obtain such products, in particular oxidized products having a practically zero level of reducing sugars , "stabilized” as to a possible yellowing in the presence of an environment (alkaline pH, high temperature) favoring this type of phenomenon.
  • hydrolysis techniques means in particular the catalytic hydrogenation techniques using, continuously or batchwise, at least one catalyst chosen from groups IB, IIIB, IVB, VI, VII and VIII of the periodic table and in particular in the group comprising nickel, platinum, palladium, cobalt, molybdenum and combinations of these metals.
  • hydrogenation techniques may be used, using, in the absence of hydrogenation catalyst, sources of hydrogen other than hydrogen gases, for example alkali metal borohydrides, in particular sodium borohydride.
  • Oxidized polysaccharides in particular of the oxidized starch hydrolyzate type, "stabilized” following the implementation of these hydrogenation techniques, in particular those having a DE of between 5 and 90, an acid number I of between 1 and 20 and “stabilized” by catalytic hydrogenation, also give compositions and detergents in which they are introduced, performances comparable to those observed with the same oxidized but not “stabilized” products, or even improved performances for certain parameters.
  • the characteristic implementation of at least one oxidized polysaccharide, in particular of a polysaccharide, for example an oxidized starch hydrolyzate " selectively "at the level of its terminal aldehyde function, within the washing products according to the invention not only makes it possible to effectively substitute, within these, at least in part, non or weakly biodegradable polycarboxylic compounds of NTA type, AP or their salts, by products, in this case oxidized polysaccharides, not posing a problem of biodegradability, but still does not in any way impose the concomitant increase in the level of zeolite (s) contained in said products in with regard to the rates currently encountered in washing products on the market, which are generally, at least, at rates of the order of 21 to 25% by weight.
  • the Applicant Company attributes the excellence of these performances in this field to the stabilizing action which the oxidized polysaccharides would play vis-à-vis the oxidizing agents.
  • the oxidizing agent is a perborate, in particular of sodium
  • the product in accordance with the invention comprises, as oxidized polysaccharide, an oxidized starch hydrolyzate.
  • the weight ratio between on the one hand the zeolite and on the other hand the oxidized polysaccharide is between approximately 0.5 / 1 and approximately 4/1, preferably between 1/1 and 2/1.
  • zeolite includes all ion-exchange materials of the aluminosilicate type, whether they are of crystalline or amorphous nature, of natural or synthetic origin, as described for example in the patents EP 70 079 and EP 193 360 mentioned above. Such products are, for example, commercially available under the designations "zeolite A”, “zeolite B”, “zeolite X” or “zeolite HS”.
  • Use may in particular be made of a crystalline sodium silicoaluminate of the "zeolite A" type.
  • the washing product according to the invention which constitutes a new industrial product, also comprises one or more other constituents chosen, in particular, from the group comprising detergents, surface-active agents, anti-deposition agents , oxidizing agents, structuring agents, anti-corrosion agents, anti-foaming agents, enzymes, perfumes, dyes, solubilizing agents, etc., for example as described in the abovementioned patents EP 70,079 and EP 319,053.
  • the detergents may, for example, be chosen from synthetic anionic detergents, such as the water-soluble alkali metal salts of organic sulfates and sulfonates comprising alkyl radicals of approximately 8 to 22 carbon atoms, such as, for example, dodecylbenzene sulfonates of sodium or potassium.
  • synthetic anionic detergents such as the water-soluble alkali metal salts of organic sulfates and sulfonates comprising alkyl radicals of approximately 8 to 22 carbon atoms, such as, for example, dodecylbenzene sulfonates of sodium or potassium.
  • nonionic detergents such as in particular alkylpolyglucosides or ethoxylated fatty alcohols.
  • Oxidizing agents i.e. products capable of releasing peroxide ions in such quantities that they allow bleaching of wine, tea, coffee stains, etc.
  • the structuring agents may, in particular, be chosen, as recommended in patent EP 215 637, from sugars, hydrogenated sugars and any mixtures thereof and in particular those consisting of or containing, at least in part, a monosaccharide such as glucose or fructose and / or a disaccharide such as maltose or sucrose and / or the hydrogenation products thereof.
  • the structuring agents may in particular consist of or contain, at least in part, sorbitol and in particular be in the form of hydrogenated products obtained by hydrogenation of starch hydrolysates or glucose syrups.
  • the detergent according to the invention may contain detergency adjuvants commonly used such as polyacrylic acid (PA), nitrilotriacetic acid (NTA) and / or their respective salts, in particular their sodium salts.
  • PA polyacrylic acid
  • NTA nitrilotriacetic acid
  • the detergent according to the invention may contain detergency adjuvants commonly used such as polyacrylic acid (PA), nitrilotriacetic acid (NTA) and / or their respective salts, in particular their sodium salts.
  • the characteristic presence of at least one oxidized polysaccharide within the washing products in accordance with the invention makes it possible, in a remarkable manner, for said products to be, at a level of zeolites not greater than, or even lower than those of the prior art products, effective for constitutive levels of NTA, AP or their respective salts, lower than those commonly encountered in said products of the prior art, in particular for rates not greater than 2 % by weight, and in particular substantially zero.
  • Washing products according to the invention useful in particular for washing fabrics, performed by machine or “by hand", will preferably be in the form of particles flowing freely and in particular in the form of powders or granules.
  • the contacting of at least one zeolite and at least one oxidized polysaccharide within the washing products according to the invention can be carried out according to very diverse methods, in the form of powders, liquids or powder / liquid mixtures , in one or more stages, in the presence or not of all or part of the other constituents of said products.
  • the combination of at least one zeolite and at least one oxidized polysaccharide can also be carried out in washing products which are in a form other than that of freely flowing particles, in particular in the form of liquids, gels or pasta.
  • These products which will generally have a dry matter content of approximately 15% to approximately 80%, in particular from 30 to 50%, may, for example, be obtained by increasing, by any means and in particular by simple dissolution. or suspended in water or another liquid, the water content of washing products according to the invention previously prepared in the form of powders or granules.
  • an oxidized polysaccharide contained in the washing products according to the invention is used, an oxidation product of a starch hydrolyzate having an ED of 61, 5 approximately and which has an acid number I of approximately 13.6.
  • Said comparative tests consist of washing tests which were carried out using a VEDETTE 8596 CHOICE SYSTEM top loading washing machine.
  • the tests are carried out at the following two temperatures: 40 ° C and 60 ° C.
  • the volume of washing water is 11 liters.
  • the water hardness is 30 ° TH.
  • the washing load is made up of 2.2 kg of pieces of white fabric (cotton) whose dimensions are 55 cm x 70 cm.
  • a load of 2.2 kg of pieces of white fabric is made to consist of a set of "soiled fabrics" of different natures and which contain predetermined soiling and deposited on these fabrics.
  • the dose of detergent is 8 g / l of water.
  • the reflectances are determined using the blue trichromatic component.
  • the number of measurements made per fabric is 4, i.e. 4 measurements (that is to say in four different places on the same piece of fabric)
  • x 2 strips of fabric 16 measurements per soiling, per formulation and by temperature.
  • the effect of the washing is measured on two coupons of unsoiled white cotton EMPA 221 and on two coupons of polyester / unsoiled white cotton / EMPA 213, which are incorporated into the washing bath. On each coupon, 4 measurements are made, which therefore gives 16 measurements per formulation and per temperature studied.
  • the washing tests were carried out, on the one hand, on gray cotton and, on the other hand, on synthetic fabrics (polyester / cotton).
  • This type of soiled cotton is representative of insoluble pigmentary stains bound to the fabric by greasy film, such as, for example, shirt collars, jacket collars, tea towels and greasy stains.
  • the synthetic fabric used here is a polyester / cotton (dacron / cotton) type fabric from KREFELD; it was soiled with a mixture of animal oil and carbon black (ref. WFK 20C).
  • washing products in accordance with the invention on protein stains is studied using cotton-type fabrics of the EMPA brand, namely: EMPA 111 fabric soiled with blood, EMPA 112 fabric soiled with cocoa and EMPA 116 tissue soiled with a mixture of blood, milk and carbon black, and of the KREFELD brand polyester / cotton type, namely: the WFK 20 F fabric soiled with cocoa.
  • These soils are representative of stains such as blood, milk, egg, gravy, mayonnaise, sauces and the like.
  • the spots caused are those which the bleaching reduces or eliminates (other spots of this type are those caused by fruits, coffee, vegetables and others).
  • White non-azure cotton of the brand EMPA 221 and polyester / cotton non-azure of the brand EMPA 213 are used to determine whether a given washing product is capable of preserving, increasing or decreasing the initial degree of whiteness of the fabric.
  • washing product designated by the letter T was used as a control product according to the prior art, the constitution of which has been detailed in Table I above.
  • washing products according to the invention were tested, designated respectively by the letters I, J and K, the respective levels of zeolite (s), of oxidized polysaccharide (s) and, optionally, sodium polyacrylates (PNa) or nitrilotriacetates (NTA), are listed in Table XI below.
  • oxidized polysaccharide contained in the washing products according to the invention use is made, as oxidized polysaccharide contained in the washing products according to the invention, of an oxidation product of a starch hydrolyzate having a DE of approximately 37, and having an index of acid I of about 8.6, said oxidation product having moreover been treated by catalytic hydrogenation with Raney nickel (residual content of reducing sugars less than 0.05%).
  • the tests are carried out at 60 ° C on a machine wash brand WASCATOR FOM 71 at a rate of 7 g / l of detergent, or 154 g per wash.
  • the washing load is 2.5 kg of fabrics containing two wear strips based on pure cotton and a ballast of terry towels and cloths of determined dimensions or grammages (Standard NF T 73-600).
  • the tests carried out aim to measure, for each product studied (4 measurements per product), the chemical wear and the organic incrustation rate obtained at the level of the washing load and this, after 25 successive and cumulative washing cycles.
  • Chemical wear consists in measuring the average degree of polymerization or DP of cotton cellulose before and after the series of 25 washes in order to evaluate the attack on the macromolecular chain of cellulose of products such as perborate and agents alkaline.
  • the determination of the DP of the cellulose is carried out by measuring the viscosity of a solution of a cotton sample subjected to the test in an appropriate solvent (cupriethylene diamine) relative to the viscosity of the solvent itself, in accordance with NF T 73-601, paragraph 3.6 or NF G 06-037 standards.
  • the aim is that the detergent action does not cause a substantial decrease in the DP so as not to facilitate the tearing of the fabric thus washed.
  • the organic incrustation makes it possible to apprehend the deposit of residues of surfactant (s) or soap (s) complexed (s) by calcium in the case of poor sequestration.
  • test is carried out in accordance with standards NF T 73-601, paragraph 3.3 and ISO 4312, paragraph 6.
  • the organic incrustation rate should not exceed around 1%.
  • Table XII gives, for the control washing product T and each of the washing products I, J and K according to the invention, the average degree of polymerization DP and the rate of organic incrustation IO obtained after 25 washes carried out at 60 ° C.
  • the measurement of the ash rate makes it possible to understand the importance of the deposit of mineral salts, in particular of the carbonate, bicarbonate, calcium or magnesium sulfate type, on the laundry at the end of the washing cycle.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Lubrication Of Internal Combustion Engines (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Woven Fabrics (AREA)
  • Biological Depolymerization Polymers (AREA)
EP91400773A 1990-03-23 1991-03-21 Phosphatfreies Waschmittel Expired - Lifetime EP0455522B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9003758 1990-03-23
FR9003758A FR2659979B1 (fr) 1990-03-23 1990-03-23 Produit de lavage a teneur reduite ou nulle en phosphates.

Publications (2)

Publication Number Publication Date
EP0455522A1 true EP0455522A1 (de) 1991-11-06
EP0455522B1 EP0455522B1 (de) 1996-08-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP91400773A Expired - Lifetime EP0455522B1 (de) 1990-03-23 1991-03-21 Phosphatfreies Waschmittel

Country Status (11)

Country Link
EP (1) EP0455522B1 (de)
JP (1) JPH05214367A (de)
AT (1) ATE141323T1 (de)
CA (1) CA2038640A1 (de)
DE (1) DE69121286T2 (de)
DK (1) DK0455522T3 (de)
ES (1) ES2090268T3 (de)
FI (1) FI911409A (de)
FR (1) FR2659979B1 (de)
GR (1) GR3020943T3 (de)
NO (1) NO911157L (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993008251A1 (de) * 1991-10-23 1993-04-29 Henkel Kommanditgesellschaft Auf Aktien Wasch- und reinigungsmittel mit ausgewählten builder-systemen
WO1993016110A1 (de) * 1992-02-11 1993-08-19 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
EP0679713A1 (de) * 1994-04-26 1995-11-02 Colgate-Palmolive Company Wässrige flüssige Waschmittelzusammensetzungen enthaltend Oxidationsprodukte von Polysachariden

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
US9695253B2 (en) 2014-03-11 2017-07-04 E I Du Pont De Nemours And Company Oxidized poly alpha-1,3-glucan
WO2016160738A2 (en) 2015-04-03 2016-10-06 E I Du Pont De Nemours And Company Gelling dextran ethers
CN107404924B (zh) 2015-04-03 2022-07-19 营养与生物科学美国4公司 氧化的右旋糖酐
US20220372409A1 (en) * 2019-09-30 2022-11-24 Ecolab Usa Inc. Ware washing solution containing oxidized starch
WO2021247810A1 (en) 2020-06-04 2021-12-09 Nutrition & Biosciences USA 4, Inc. Dextran-alpha-glucan graft copolymers and derivatives thereof
EP4294849A1 (de) 2021-02-19 2023-12-27 Nutrition & Biosciences USA 4, Inc. Polysaccharidderivate für waschmittelzusammensetzungen
EP4334363A1 (de) 2021-05-04 2024-03-13 Nutrition & Biosciences USA 4, Inc. Zusammensetzungen mit unlöslichem alpha-glucan
CN117337308A (zh) 2021-05-04 2024-01-02 营养与生物科学美国4公司 包含氧化的不溶性α-葡聚糖的组合物
AU2023240144A1 (en) 2022-03-21 2024-08-22 Nutrition & Biosciences USA 4, Inc. Compositions comprising insoluble alpha-glucan.

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2023944A1 (de) * 1969-05-19 1971-03-11 Lyckeby Staerkelsefoeraedling Verfahren zur Herstellung von modi fiziertem Sacchandmaterial
US3651221A (en) * 1969-05-19 1972-03-21 Lyckeby Starkelseforading Ab Sugar substitute additive preparations of sorbitol and gluconic acid
EP0142725A1 (de) * 1983-10-24 1985-05-29 Kawaken Fine Chemicals Co., Ltd. Verfahren zur Herstellung der Gluconsäure
EP0215637A2 (de) * 1985-09-12 1987-03-25 Unilever N.V. Verfahren zur Herstellung von Reinigungsmittelpulver
EP0232202A2 (de) * 1986-01-30 1987-08-12 Roquette FrÀ¨res Verfahren zur Oxidierung von Di-, Tri-, Oligo- und Polysacchariden in Polyhydroxycarbonsäuren, dazu verwendeter Katalysator und so hergestellte Produkte

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3914293A1 (de) * 1989-04-29 1990-10-31 Kali Chemie Ag Wasch- und reinigungsmittelzusammensetzungen
FR2653442A1 (fr) * 1989-10-23 1991-04-26 Roquette Freres Composition pour produits de lavage, son procede de preparation et produit de lavage la contenant.
DE69020861T2 (de) * 1989-11-10 1995-11-30 Tno Verfahren zur Herstellung von Polydicarboxysacchariden.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2023944A1 (de) * 1969-05-19 1971-03-11 Lyckeby Staerkelsefoeraedling Verfahren zur Herstellung von modi fiziertem Sacchandmaterial
US3651221A (en) * 1969-05-19 1972-03-21 Lyckeby Starkelseforading Ab Sugar substitute additive preparations of sorbitol and gluconic acid
EP0142725A1 (de) * 1983-10-24 1985-05-29 Kawaken Fine Chemicals Co., Ltd. Verfahren zur Herstellung der Gluconsäure
EP0215637A2 (de) * 1985-09-12 1987-03-25 Unilever N.V. Verfahren zur Herstellung von Reinigungsmittelpulver
EP0232202A2 (de) * 1986-01-30 1987-08-12 Roquette FrÀ¨res Verfahren zur Oxidierung von Di-, Tri-, Oligo- und Polysacchariden in Polyhydroxycarbonsäuren, dazu verwendeter Katalysator und so hergestellte Produkte

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993008251A1 (de) * 1991-10-23 1993-04-29 Henkel Kommanditgesellschaft Auf Aktien Wasch- und reinigungsmittel mit ausgewählten builder-systemen
US5501814A (en) * 1991-10-23 1996-03-26 Henkel Kommanditgesellschaft Auf Aktien Detergents and cleaning preparations containing selected builder systems
WO1993016110A1 (de) * 1992-02-11 1993-08-19 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
US5541316A (en) * 1992-02-11 1996-07-30 Henkel Kommanditgesellschaft Auf Aktien Process for the production of polysaccharide-based polycarboxylates
EP0679713A1 (de) * 1994-04-26 1995-11-02 Colgate-Palmolive Company Wässrige flüssige Waschmittelzusammensetzungen enthaltend Oxidationsprodukte von Polysachariden
AU685588B2 (en) * 1994-04-26 1998-01-22 Colgate-Palmolive Company, The Aqueous liquid detergent compositions containing oxidized polysaccharides

Also Published As

Publication number Publication date
FR2659979A1 (fr) 1991-09-27
DE69121286D1 (de) 1996-09-19
FR2659979B1 (fr) 1994-04-29
ATE141323T1 (de) 1996-08-15
NO911157D0 (no) 1991-03-22
EP0455522B1 (de) 1996-08-14
GR3020943T3 (en) 1996-12-31
FI911409A0 (fi) 1991-03-22
FI911409A (fi) 1991-09-24
DE69121286T2 (de) 1997-02-20
NO911157L (no) 1991-09-24
JPH05214367A (ja) 1993-08-24
CA2038640A1 (en) 1991-09-24
DK0455522T3 (da) 1996-12-30
ES2090268T3 (es) 1996-10-16

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