EP0425369B1 - Composition pour produits de lavage, son procédé de préparation et produit de lavage la contenant - Google Patents

Composition pour produits de lavage, son procédé de préparation et produit de lavage la contenant Download PDF

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Publication number
EP0425369B1
EP0425369B1 EP90402983A EP90402983A EP0425369B1 EP 0425369 B1 EP0425369 B1 EP 0425369B1 EP 90402983 A EP90402983 A EP 90402983A EP 90402983 A EP90402983 A EP 90402983A EP 0425369 B1 EP0425369 B1 EP 0425369B1
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EP
European Patent Office
Prior art keywords
oxidized
weight
fact
zeolite
phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90402983A
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German (de)
English (en)
French (fr)
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EP0425369A1 (fr
Inventor
Didier Videau
Serge Gosset
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
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Filing date
Publication date
Application filed by Roquette Freres SA filed Critical Roquette Freres SA
Publication of EP0425369A1 publication Critical patent/EP0425369A1/fr
Application granted granted Critical
Publication of EP0425369B1 publication Critical patent/EP0425369B1/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
    • C11D3/20—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 subject of the present invention is a composition for washing products and its preparation process. It also relates to the washing product containing this composition.
  • phosphates have played a predominant role in detergents, in particular as sequestering agents for cations which form salts which are insoluble in water, in particular calcium and magnesium ions; the excellent performances which they allow to achieve reside in their particular structure.
  • EP-A-0 215 637 envisages the use of monosaccharides of the sucrose or sorbitol type in a washing product preferably free of phosphates.
  • document FR-A-2 063 914 envisages, in particular in terms of the examples, the total substitution of phosphates with dicarboxyamidons or dialdehydoamidons.
  • compositions which contain, in addition to the above gluconates and / or glucoheptonates, metasilicates, polycarboxylic acids of the citric or acrylic type, phosphates or even zeolites.
  • these compositions have not made it possible to meet all the requirements of the technique and, by way of example, it is pointed out that, in the case of compositions comprising gluconates, zeolites and phosphates, obtaining performance of Acceptable washing requires phosphate and zeolite contents incompatible with environmental protection.
  • these compositions cause a noticeable deactivation of bleaching agents, including in particular perborate, commonly used in detergents to remove oxidizable stains.
  • the object of the invention is therefore to remedy the drawbacks of the prior art and to provide washing products which respond better than those which already exist to the various requirements of the practice.
  • composition for washing products according to the invention is characterized in that it comprises at least one phosphate, at least one zeolite and at least one oxidized polysaccharide, the proportion of oxidized polysaccharide representing 5 to 40% by weight. of the total mass of the three constituents.
  • the process for preparing the composition according to the invention for washing products is characterized in that, in a composition based on phosphate and zeolite for washing products, a proportion of 5 to 40% by weight is replaced. these constituents by an equivalent proportion of at least one oxidized polysaccharide.
  • the oxidized polysaccharide is a starch hydrolyzate having an oxidized DE from 5 to 90 or a glucose syrup having an oxidized DE from 5 to 90 and whose acid number I, which is expressed in number of grams of carboxylic function per 100 g of oxidized polysaccharide, and which is given by the formula: is from 1 to 20 and preferably between 6 and 15.
  • oxidized polysaccharides which have an acid number between 8 and 14 and which are obtained by oxidation of starch hydrolysates or glucose syrups having a DE between 35 and 65.
  • the oxidized polysaccharide is an oxidized product having, in particular by its level of reducing sugars, good stability, in particular in terms of its coloring, when said oxidized product is used (when the the washing product according to the invention is prepared), at any time and for example during spraying operations, in an environment having an alkaline pH and / or a high temperature, environment capable of coloring (more or less yellowing less pronounced) any composition containing it.
  • the Applicant Company has designed and implemented to the point, as new products, of “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%, reducing sugars.
  • the Applicant Company has found that the hydrogenation techniques applied to oxidized polysaccharides, in particular of the oxidized glucose syrup type or oxidized starch hydrolysates, make it possible to obtain such products, in particular oxidized products having a rate practically zero in reducing sugars, "stabilized” with regard to possible maturing in the presence of an environment (alkaline pH, high temperature) favoring this type of phenomenon.
  • hydrolysis techniques means 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 gas, for example alkali metal borohydrides, in particular sodium borohydride.
  • Oxidized polysaccharides in particular of the oxidized starch hydrolyzate type or oxidized glucose syrup, "stabilized” following the use of these hydrogenation techniques, in particular those having a DE of between 5 and 90, an index of acid I between 1 and 20 and “stabilized” by catalytic hydrogenation, give the compositions and washing products into which they are introduced, performances comparable to those observed with the same oxidized but not “stabilized” products, or even improved performance for certain parameters.
  • the weight ratio between on the one hand the zeolite and on the other hand the oxidized polysaccharide is between 0.5 / 1 and 4/1, preferably between 1.5 / 1 and 2.5 / 1 and, more preferably still, close to 2.0 / 1.
  • the washing product according to the invention is characterized in that it contains a proportion of 5 to 40% by weight, preferably between 15 and 35% by weight of a washing composition comprising at least one phosphate, at least one zeolite and at least one oxidized polysaccharide, the proportion of oxidized polysaccharide representing approximately 5 to approximately 40% by weight of the total mass of the three constituents of the composition.
  • 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, agents structuring agents, anti-corrosion agents, anti-foaming agents, enzymes, perfumes, dyes, solubilizing agents.
  • 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, sodium dodecylbenzene sulfonates 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, sodium dodecylbenzene sulfonates or potassium.
  • nonionic detergents such as in particular alkylpolyglucosides or ethoxylated fatty alcohols.
  • the oxidizing agents namely products capable of releasing peroxide ions in an amount such that they allow the bleaching of stains in wine, tea, coffee, etc.
  • the oxidizing agents may in particular be perborates, percarbonates, persilicates or alkali metal perphosphates, and in particular sodium perborate.
  • the structuring agents may, in particular, be chosen 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.
  • washing product which forms the invention may contain commonly used detergency builders 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 Applicant Company has found that, surprisingly and unexpectedly, the washing products in accordance with the invention made it possible to remedy the drawbacks of the products of the prior art; in particular, they lead to much higher degrees of white.
  • the Applicant Company attributes the excellence of these performances to the stabilizing action which the oxidized polysaccharides play against oxidizing agents.
  • the oxidizing agent is a perborate, in particular of sodium, and when the composition in accordance with the invention comprises, as oxidized polysaccharide, an oxidized glucose syrup.
  • Said composition comprises at least one phosphate, at least one zeolite and at least one of the polysaccharides defined above.
  • a mono- or a polyphosphate preferably chosen from the group consisting of orthophosphate, pyrophosphate, tripolyphosphate, hexametaphosphate, the tripolyphosphate being more particularly preferred, in particular in the form of its sodium salt.
  • zeolite includes all ion-exchange materials of the aluminosilicate type, whether they are of crystalline or amorphous nature, of natural or synthetic origin.
  • 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.
  • composition for washing products in accordance with the invention To prepare the composition for washing products in accordance with the invention, the three above-mentioned constituents are brought together, for example by mixing, in the proportions indicated above.
  • composition thus established useful in particular for washing textiles carried out by machine or "by hand", is stable and constitutes a new industrial product. It is preferably in the form of free flowing particles, in particular in the form of a powder or granules.
  • the placing in the presence of at least one phosphate, at least one zeolite and at least one polysaccharide within the composition for washing products in accordance with the invention can be carried out according to very diverse methods, in the form powders, liquids or powder / liquid mixtures, in one or more stages.
  • Such a precomposition can in particular be obtained by granulation of a mixture of zeolite and oxidized polysaccharide, for example on an AEROMATIC type granulator or a plate granulator.
  • washing product according to the invention use is made of the conventional constituents of washing products of the prior art based on phosphate and zeolite and the assembly consisting of phosphate and zeolite is replaced by a proportion identical or similar to one of the compositions according to the invention.
  • the detergent thus established is in the form of powder; it is stable and also constitutes a new industrial product.
  • This product which contains 32% of detergency additive (phosphate and zeolite) is representative of the formulations of binary tripolyphosphate-zeolite mixture according to the prior art.
  • washing products A1, B1, C1, D1, E1 in accordance with the invention were also prepared which differ from the product according to the prior art by replacing the 32% phosphate + zeolite with each of the above compositions respectively.
  • a to E or detergency additives, in accordance with the invention the constituents of which are therefore present in the detergent in the proportions indicated in Table III.
  • TABLE III Components of the detergency additive Washing products (proportions in% by weight of the constituents of the detergency additive)
  • A1 B1 C1 From E1 Na tripolyphosphate 5 2 5 8 5 Zeolite A 15.4 20 18 16 20.6 Oxidized glucose syrup 11.6 10 9 8 6.4
  • the tests are carried out at the following three temperatures: 40 ° C, 60 ° C and 90 ° C.
  • the volume of washing water is 20 liters.
  • the water hardness is 35 ° TH.
  • the washing load is composed of 3.5 kg of white fabric pieces (cotton or synthetic) whose dimensions are 55 cm x 70 cm.
  • a set of 3.5 kg of pieces of white fabric is made to comprise a set of "soiled fabrics" of different natures and which comprise predetermined soiling and deposited on these fabrics.
  • the dose of detergent is 7 g / l of water.
  • the reflectances are determined using the blue trichromatic component, under the action of optical brighteners.
  • 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 24 measurements per soiling, per formulation and by temperature.
  • the washing tests were carried out, on the one hand, on gray cotton and, on the other hand, on synthetic fabrics.
  • soiled cotton are representative of insoluble pigmentary stains bound to the fabric by fatty film, such as, for example, shirt collars, jacket collars, tea towels and greasy stains.
  • the detergents comprising this aforementioned composition make it possible to satisfy all the criteria required in detergency.
  • the synthetic fabrics used here are fabrics of the acetate, acrylic, polyester (dacron) and polyester / cotton (dacron / cotton) type of the TEST-FABRIC brand; they were soiled with a mixture of mineral oil and vegetable oil with carbon black.
  • the action of the products in accordance with the invention on protein stains is studied using cotton-type fabrics of the EMPA brand, namely: EMPA 111 tissue soiled with blood, EMPA 112 tissue soiled with cocoa and the tissue EMPA 116 soiled with a mixture of blood, milk and carbon black.
  • These soils are representative of stains such as blood, milk, egg, meat juice, mayonnaise, sauces and the like.
  • the temperature of 40 ° C was chosen as the sole working temperature on protein stains. In fact, being an enzyme-free formulation, we chose the temperature that best reflects current market trends in washing.
  • the above fabrics are sensitive to chemical oxidation; the spots caused are those which the bleaching attenuates or makes disappear (other spots of this type are those caused by fruits, coffee, vegetables and others).
  • the products according to the invention are much more efficient and give results which, compared to the product according to the prior art, are 36% higher in the case of product C1 at 60 ° C and 51% in the case of the product A1 at 90 ° C.
  • White non-azure cotton of the brand EMPA 221 is used to determine whether a given washing product is capable of preserving, increasing or decreasing the initial degree of whiteness of the fabric.
  • washing products A1, B1, C1, D1 and E1 improve the degree of whiteness compared to the product according to the prior art; after washing, a fabric is obtained whose degree of whiteness is greater than that which it had before washing.
  • washing products F1, G1, H1 and K1 in accordance with the invention were also prepared.
  • the washing products F1 to K1 overall show, for example during washing tests carried out at 60 ° C., performances just as remarkable as those observed for the products A1 to E1 described above, in particular those observed for the product D1 whose introduction rate of oxidized polysaccharide is 8% by weight.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Glass Compositions (AREA)
EP90402983A 1989-10-23 1990-10-23 Composition pour produits de lavage, son procédé de préparation et produit de lavage la contenant Expired - Lifetime EP0425369B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8913863 1989-10-23
FR8913863A FR2653442A1 (fr) 1989-10-23 1989-10-23 Composition pour produits de lavage, son procede de preparation et produit de lavage la contenant.

Publications (2)

Publication Number Publication Date
EP0425369A1 EP0425369A1 (fr) 1991-05-02
EP0425369B1 true EP0425369B1 (fr) 1995-11-22

Family

ID=9386674

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90402983A Expired - Lifetime EP0425369B1 (fr) 1989-10-23 1990-10-23 Composition pour produits de lavage, son procédé de préparation et produit de lavage la contenant

Country Status (10)

Country Link
EP (1) EP0425369B1 (es)
JP (1) JPH03210396A (es)
AT (1) ATE130629T1 (es)
CA (1) CA2028284A1 (es)
DE (1) DE69023738T2 (es)
DK (1) DK0425369T3 (es)
ES (1) ES2082843T3 (es)
FI (1) FI905208A0 (es)
FR (1) FR2653442A1 (es)
GR (1) GR3018575T3 (es)

Cited By (1)

* 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

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2659979B1 (fr) * 1990-03-23 1994-04-29 Roquette Freres Produit de lavage a teneur reduite ou nulle en phosphates.
DE4134914A1 (de) * 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
DE4203923A1 (de) * 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
DE4317519A1 (de) * 1993-05-26 1994-12-01 Henkel Kgaa Herstellung von Polycarboxylaten auf Polysaccharid-Basis
US5437810A (en) * 1994-04-26 1995-08-01 Colgate-Palmolive Co. Aqueous liquid detergent compositions containing oxidized polysaccharides
US6017864A (en) * 1997-12-30 2000-01-25 Ecolab Inc. Alkaline solid block composition
DE19929981A1 (de) * 1999-06-30 2001-01-04 Henkel Kgaa Verfahren zur Herstellung compoundierter Stärke-Derivate
US20060122093A1 (en) * 2004-12-07 2006-06-08 Permejo Fides L R Laundry detergent composition with mixed builder system
US9695253B2 (en) 2014-03-11 2017-07-04 E I Du Pont De Nemours And Company Oxidized poly alpha-1,3-glucan
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
WO2016160738A2 (en) 2015-04-03 2016-10-06 E I Du Pont De Nemours And Company Gelling dextran ethers
WO2021247810A1 (en) 2020-06-04 2021-12-09 Nutrition & Biosciences USA 4, Inc. Dextran-alpha-glucan graft copolymers and derivatives thereof
EP4294849A1 (en) 2021-02-19 2023-12-27 Nutrition & Biosciences USA 4, Inc. Polysaccharide derivatives for detergent compositions
EP4334363A1 (en) 2021-05-04 2024-03-13 Nutrition & Biosciences USA 4, Inc. Compositions comprising insoluble 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.

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
CA964216A (en) * 1969-05-19 1975-03-11 Lyckeby Starkelseforadling Ab Modified saccharide materials
BE755050A (fr) * 1969-08-20 1971-02-19 Unilever Nv Compositions detergentes
US3629121A (en) * 1969-12-15 1971-12-21 Ibrahim A Eldib Carboxylated starches as detergent builders
US3803285A (en) * 1971-01-20 1974-04-09 Cpc International Inc Extrusion of detergent compositions
GB8522621D0 (en) * 1985-09-12 1985-10-16 Unilever Plc Detergent powder

Cited By (1)

* 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

Also Published As

Publication number Publication date
FI905208A0 (fi) 1990-10-23
DE69023738D1 (de) 1996-01-04
FR2653442B1 (es) 1994-04-22
DK0425369T3 (da) 1996-03-04
ATE130629T1 (de) 1995-12-15
GR3018575T3 (en) 1996-03-31
CA2028284A1 (en) 1991-04-24
EP0425369A1 (fr) 1991-05-02
FR2653442A1 (fr) 1991-04-26
JPH03210396A (ja) 1991-09-13
ES2082843T3 (es) 1996-04-01
DE69023738T2 (de) 1996-06-05

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