EP0455522A1 - Phosphate free detergent - Google Patents

Phosphate free detergent 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
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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
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EP91400773A
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German (de)
French (fr)
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EP0455522B1 (en
Inventor
Serge Gosset
Didier Videau
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Roquette Freres SA
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Roquette Freres SA
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/223Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium 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.

Abstract

Detergent with a phosphates content reduced to less than 5 % by weight, or even zero, especially useful for the washing of fabrics, characterised in that it contains at least one zeolite and at least one oxidised polysaccharide chosen from the group comprising: - the oxidation products of disaccharides possessing a terminal functional group of the aldonic type, - the oxidation products of trisaccharides and of oligosaccharides which possess a terminal functional group of the aldonic type, - the oxidation products of starch hydrolysates, of cellulose and of hemicellulose possessing a terminal functional group of the aldonic type, and - any mixtures of at least any two of the abovementioned oxidation products. t

Description

La présente invention a pour objet un nouveau produit de lavage, utilisable notamment pour le lavage des tissus, du genre de ceux qui sont à teneur réduite à moins de 5% en poids, voire nulle en phosphates, et qui comportent au moins une zéolithe.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.

Depuis longtemps, les phosphates jouent un rôle prépondérant dans les produits de lavage, notamment en tant que séquestrants des cations qui forment des sels insolubles dans l'eau, en particulier les ions calcium et magnésium; les excellentes performances qu'ils permettent d'atteindre résident dans leur structure particulière.For a long time, 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.

Mais l'un des problèmes aigus auquel l'industrie des produits de lavage doit faire face, est le caractère très polluant desdits phosphates. En effet, leur présence dans les eaux usées provoque le phénomène bien connu de l'eutrophisation; et pour cette raison l'utilisation des phosphates dans les produits de lavage doit répondre à des contraintes, notamment écologiques, de plus en plus sévères.But one of the acute problems which the detergents industry has to face is the very polluting nature of said phosphates. Indeed, their presence in wastewater causes the well-known phenomenon of eutrophication; and for this reason the use of phosphates in washing products must meet increasingly severe constraints, in particular ecological ones.

Cet aspect écologique est d'autant plus marqué que les détergents puissants couramment employés et, en particulier, les produits utilisés dans les blanchisseries industrielles, contiennent des quantités élevées de phosphates pouvant dépasser 30%.This ecological aspect is all the more marked since the powerful detergents commonly used and, in particular, the products used in industrial laundries, contain high quantities of phosphates which can exceed 30%.

De nombreuses tentatives ont donc été faites pour supprimer en totalité ou au moins en partie les phosphates dans les produits de lavage.Many attempts have therefore been made to remove all or at least part of the phosphates in the detergents.

Il a notamment été proposé d'avoir recours, en tant qu'agent de remplacement total ou partiel des phosphates, à des zéolithes d'origine naturelle ou synthétique; ces produits sont bien connus pour leur pouvoir échangeur des cations, notamment du calcium et du magnésium, qui sont à l'origine de la dureté de l'eau et des problèmes d'incrustations minérales dans le linge.It has in particular been proposed to use, as a total or partial replacement agent for phosphates, zeolites of natural or synthetic origin; these products are well known for their cation exchange power, in particular calcium and magnesium, which are the cause of the hardness of water and problems of mineral encrustations in the laundry.

Toutefois, si les zéolithes contribuent à l'élimination de ces cations, leur substitution totale aux phosphates ne permet pas d'atteindre un degré de lavage satisfaisant aux exigences de la pratique.However, if the zeolites contribute to the elimination of these cations, their total substitution for phosphates does not make it possible to reach a degree of washing satisfying the requirements of the practice.

Aussi, pour améliorer la qualité du lavage de produits de lavage à base de zéolithes et contenant peu ou pas de phosphates, il a été proposé de combiner lesdites zéolithes avec divers autres agents tels que notamment l'acide nitrilotriacétique (NTA) et ses sels, en particulier le nitrilotriacétate de sodium (brevets EP 70.079 et EP 319.053).Also, to improve the quality of the washing of washing products based on zeolites and containing little or no phosphates, it has been proposed to combine said zeolites with various other agents such as in particular nitrilotriacetic acid (NTA) and its salts, in particular sodium nitrilotriacetate (patents EP 70,079 and EP 319,053).

Cependant, outre leur biodégradabilité imparfaite, ces produits sont soupçonnés de fixer les métaux lourds, lesquels pourraient passer dans les eaux de boisson. En conséquence de quoi il est généralement préconisé, voire rendu obligatoire aujourd'hui dans certains pays, de limiter à 5% leur taux d'introduction dans les produits détergents.However, in addition to their imperfect biodegradability, these products are suspected of fixing heavy metals, which could pass into drinking water. As a result of which it is generally recommended, even made compulsory today in certain countries, to limit their rate of introduction into detergent products to 5%.

Ce taux de 5% apparaît comme le taux optimum d'introduction de nitrilotriacétate de métal alcalin dans les compositions exemptes de phosphates décrites dans le brevet EP 319.053, lesquelles contiennent de 20 à 35% en poids de zéolithes.This rate of 5% appears to be the optimum rate of introduction of alkali metal nitrilotriacetate into the phosphate-free compositions described in patent EP 319,053, which contain from 20 to 35% by weight of zeolites.

Il a également été proposé, dans le cadre de produits de lavage contenant peu ou pas de phosphates, d'associer les zéolithes à des polymères polycarboxyliques particuliers à base de mélanges définis d'acides mono- et dicarboxyliques monooléfiniques et d'esters non ioniques desdits acides (brevet EP 193.360). Parmi les dérivés monooléfiniques d'acides mono- et dicarboxyliques, sont cités en particulier les dérivés d'acide acrylique et/ou méthacrylique ainsi que les dérivés d'acide maléique et/ou itaconique.It has also been proposed, in the context of detergents containing little or no phosphates, to combine the zeolites with particular polycarboxylic polymers based on defined mixtures of monoolefinic mono- and dicarboxylic acids and nonionic esters of the said zeolites acids (patent EP 193,360). Among the monoolefinic derivatives of mono- and dicarboxylic acids, mention is made in particular of acrylic and / or methacrylic acid derivatives as well as maleic and / or itaconic acid derivatives.

Il apparaît que de telles compositions peuvent être exemptes de phosphates et contenir moins de 20% en poids de zéolithes. Cependant, dans ce cas, on associe aux zéolithes, outre lesdits polymères polycarboxyliques, des argiles et du NTA.It appears that such compositions can be free of phosphates and contain less than 20% by weight of zeolites. However, in this case, we associate with zeolites, in addition to said polycarboxylic polymers, clays and NTA.

Parmi les agents polycarboxyliques les plus communément préconisés pour améliorer la qualité du lavage de produits de lavage à base de zéolithes et contenant peu ou pas de phosphates, il convient de faire référence aux polymères acryliques, et notamment aux homopolymères de l'acide acrylique ou de l'acide méthacrylique ou à leurs sels, en particulier à l'acide polyacrylique (AP) et aux polyacrylates de sodium (PNa).Among the polycarboxylic agents most commonly recommended for improving the quality of washing of washing products based on zeolites and containing little or no phosphates, reference should be made to 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).

Des compositions contenant par exemple de 2 à 7% en poids de polyacrylates et de 25 à 60% en poids de zéolithes, sont décrites dans le brevet DE 37 07 806.Compositions containing for example from 2 to 7% by weight of polyacrylates and from 25 to 60% by weight of zeolites, are described in patent DE 37 07 806.

Des produits de lavage associant zéolithes et polyacrylates sont également présentés au niveau du brevet DE 38 32 478.Washing products combining zeolites and polyacrylates are also presented in DE 38 32 478.

Il convient cependant de rappeler que les polymères acryliques, en particulier l'acide polyacrylique et ses sels, présentent l'inconvénient majeur d'être non biodégradables.It should however be recalled that acrylic polymers, in particular polyacrylic acid and its salts, have the major drawback of being non-biodegradable.

En conséquence de quoi, on estime aujourd'hui préférable de pouvoir les mettre en oeuvre à des taux ne dépassant pas 4% en poids de produit de lavage.Consequently, it is now considered preferable to be able to use them at rates not exceeding 4% by weight of washing product.

Il découle de ce qui précède que, de manière générale, il existe un besoin de mettre au point des produits de lavage à teneur réduite, voire nulle en phosphates qui, tout en assurant efficacement le rôle qui leur est alloué et ce, sans faire appel à un surdosage en zéolithes ni à la mise en oeuvre d'additifs écologiquement inacceptables, permettent d'atteindre des taux globaux en polymères et/ou monomères polycarboxyliques non ou faiblement biodégradables, compatibles avec les exigences actuelles de protection de l'environnement et, en particulier, des taux spécifiques en acide nitrilotriacétique (NTA) en acide polyacrylique (AP) ou en leurs sels respectifs, ne dépassant pas 4% en poids.It follows from the above that, in general, there is a need to develop detergents with reduced or even zero phosphate content which, while effectively ensuring the role assigned to them, without calling upon to an overdose of zeolites or to the use of ecologically unacceptable additives, make it possible to achieve overall levels of non or weakly biodegradable polycarboxylic polymers and / or monomers, compatible with current environmental protection requirements and, in in particular, specific levels of nitrilotriacetic acid (NTA), polyacrylic acid (PA) or their respective salts, not exceeding 4% by weight.

Et la Société Demanderesse a eu le mérite de trouver que ce but était atteint dès lors que l'on fait comprendre aux produits de lavage du genre en question au moins un polysaccharide oxydé choisi dans le groupe comprenant:

  • a) les produits d'oxydation de disaccharides possédant une fonction terminale de type aldonique,
  • b) les produits d'oxydation de trisaccharides et d'oligosaccharides possédant une fonction terminale de type aldonique,
  • c) les produits d'oxydation d'hydrolysats d'amidon, de cellulose et d'hémicellulose possédant une fonction terminale de type aldonique,
  • d) les mélanges quelconques d'au moins deux quelconques des susdits produits d'oxydation.
And the Applicant Company had the merit of finding that this object was achieved as soon as washing products of the kind in question are made to understand at least one oxidized polysaccharide chosen from the group comprising:
  • a) oxidation products of disaccharides having a terminal function of aldonic type,
  • b) oxidation products of trisaccharides and oligosaccharides having an aldonic terminal function,
  • c) oxidation products of starch, cellulose and hemicellulose hydrolysates having a terminal function of aldonic type,
  • d) any mixtures of at least any two of the above oxidation products.

Avantageusement, les polysaccharides oxydés pouvant être mis en oeuvre dans le cadre de la présente invention sont ceux qui sont obtenus à partir de di-, de tri- et d'oligosaccharides, d'hydrolysats d'amidon, de cellulose et d'hémicellulose dont seule, parmi l'ensemble de leurs fonctions potentiellement oxydables, leur fonction terminale (de type aldéhydique avant oxydation) est substantiellement oxydée et ce, en une fonction de type aldonique.Advantageously, 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.

De tels polysaccharides oxydés peuvent, en particulier si l'on recherche une oxydation véritablement qualifiable de "sélective" au niveau de la fonction terminale de type aldonique, être obtenus selon le procédé d'oxydation catalytique décrit par la Société Demanderesse dans son brevet EP 232.202.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 .

Les polysaccharides dont le procédé décrit dans le susdit brevet EP 232.202 rend possible l'oxydation sélective comprennent en particulier:

  • les disaccharides tels que le lactose, le maltose, l'isomaltose, le cellobiose, le xylobiose et le mannobiose, possédant une fonction terminale de type aldéhydique,
  • les hydrolysats d'amidon obtenus par voie acide et/ou enzymatique,
  • les produits d'hydrolyse des hémicelluloses tels que les D-galacto-D-mannanes, les D-gluco-D-mannanes, les L-arabino-D-xylanes, les D-xylo-L-arabinanes.
The polysaccharides whose process described in the above patent EP 232.202 makes selective oxidation possible include in particular:
  • disaccharides such as lactose, maltose, isomaltose, cellobiose, xylobiose and mannobiose, having a terminal aldehyde type function,
  • starch hydrolysates obtained by the acid and / or enzymatic route,
  • hemicellulose hydrolysis products such as D-galacto-D-mannanes, D-gluco-D-mannanes, L-arabino-D-xylanes, D-xylo-L-arabinanes.

Selon un autre mode de réalisation avantageux du produit de lavage conforme à l'invention, le polysaccharide oxydé mis en oeuvre au sein de celui-ci se présente sous la forme d'un produit d'oxydation d'un hydrolysat d'amidon ayant un DE (Dextrose Equivalent) d'environ 5 à environ 90 et présente, de préférence, un indice d'acide I compris entre environ 1 et environ 20, ledit indice d'acide I étant exprimé en nombre de grammes de fonction carboxylique pour 100 g de polysaccharide oxydé et donné par la formule:

Figure imgb0001
According to another advantageous embodiment of the washing product in accordance with the invention, 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:
Figure imgb0001

On pourra, dans le cadre de la présente invention, faire appel en particulier à des polysaccharides oxydés qui ont un indice d'acide compris entre environ 5 et environ 14 et qui sont obtenus par oxydation d'hydrolysats d'amidon ayant un DE compris entre environ 20 et environ 65.In the context of the present invention, use may in particular be made of 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.

De manière tout particulièrement avantageuse, on mettra en oeuvre des polysaccharides oxydés qui ont un indice d'acide compris entre environ 8 et environ 14 et qui sont obtenus par oxydation d'hydrolysats d'amidon ayant un DE compris entre environ 35 et environ 65.Very particularly advantageously, 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.

Selon un autre mode de réalisation avantageux, le polysaccharide oxydé est un produit oxydé présentant, notamment de par son taux en sucres réducteurs, une bonne stabilité, en particulier au niveau de sa coloration, lorsque ledit produit oxydé est mis en oeuvre (lorsque l'on prépare ou l'on utilise le produit de lavage conforme à l'invention), à un moment quelconque et par exemple lors d'opérations d'atomisation, dans un environnement présentant un pH alcalin et/ou une température élevée, environnement apte à colorer (jaunissement plus ou moins prononcé) toute composition le contenant.According to another advantageous embodiment, 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.

A ce titre, la Société Demanderesse a conçu et mis au point, en tant que produits nouveaux, des polysaccharides oxydés "stabilisés" présentant des taux peu élevés, généralement inférieurs à environ 0,6%, de préférence inférieurs à 0,1% et encore plus préférentiellement inférieurs à 0,05% en poids, en sucres réducteurs.As such, 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.

En particulier, la Société Demanderesse a trouvé que les techniques d'hydrogénation appliquées à des polysaccharides oxydés, en particulier de type hydrolysats d'amidon oxydés, permettaient d'obtenir de tels produits, notamment des produits oxydés présentant un taux pratiquement nul en sucres réducteurs, "stabilisés" quant à un éventuel jaunissement en présence d'un environnement (pH alcalin, température élevée) favorisant ce type de phénomène.In particular, 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.

Par techniques d'hydrogénation, on entend en particulier les techniques d'hydrogénation catalytique mettant en oeuvre, en continu ou en discontinu, au moins un catalyseur choisi dans les groupes IB, IIIB, IVB, VI, VII et VIII du tableau périodique et notamment dans le groupe comprenant le nickel, le platine, le palladium, le cobalt, le molybdène et les combinaisons de ces métaux.The term “hydrogenation 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.

On fera tout particulièrement appel aux techniques d'hydrogénation utilisant, fixé ou non sur un support inerte, du nickel de Raney comme catalyseur et ce, en présence ou non d'une source additionnelle d'hydrogène.Use will be made in particular of hydrogenation techniques using, fixed or not fixed on an inert support, Raney nickel as catalyst and this, in the presence or not of an additional source of hydrogen.

D'autres techniques d'hydrogénation pourront être employées faisant appel, en l'absence de catalyseur d'hydrogénation, à des sources d'hydrogène autres que les gaz hydrogène, par exemple aux borohydrures de métaux alcalins, en particulier le borohydrure de sodium.Other 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.

Les polysaccharides oxydés, en particulier de type hydrolysat d'amidon oxydé, "stabilisés" à la suite de la mise en oeuvre de ces techniques d'hydrogénation, notamment ceux présentant un DE compris entre 5 et 90, un indice d'acide I compris entre 1 et 20 et "stabilisés" par hydrogénation catalytique, confèrent en outre aux compositions et produits de lavage dans lesquels ils sont introduits, des performances comparables à celles observées avec les mêmes produits oxydés mais non "stabilisés", voire des performances améliorées pour certains paramètres.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.

En outre, il convient de rappeler, en cet endroit de la description de l'invention, que la mise en oeuvre caractéristique d'au moins un polysaccharide oxydé, en particulier d'un polysaccharide, par exemple un hydrolysat d'amidon, oxydé "sélectivement" au niveau de sa fonction aldéhydique terminale, au sein des produits de lavage selon l'invention, non seulement permet de substituer efficacement au sein de ceux-ci, au moins en partie, des composés polycarboxyliques non ou faiblement biodégradables de type NTA, AP ou leurs sels, par des produits, en l'occurrence des polysaccharides oxydés, ne posant pas de problème de biodégradabilité, mais encore n'impose aucunement l'augmentation concomitante du taux de zéolithe(s) contenue(s) dans lesdits produits en regard des taux actuellement rencontrés dans les produits de lavage du marché, lesquels se situent généralement, pour le moins, à des taux de l'ordre de 21 à 25% en poids.In addition, it should be recalled, at this point in the description of the invention, that 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.

Et il est remarquable d'observer que, de façon d'autant plus surprenante et inattendue, la présence caractéristique d'au moins un polysaccharide oxydé, en particulier d'un polysaccharide, notamment d'un hydrolysat d'amidon, oxydé "sélectivement" au niveau de sa fonction aldéhydique terminale, permet auxdits produits contenant ledit polysaccharide oxydé d'être efficaces:

  • pour des taux constitutifs en zéolithe(s) inférieurs à 20% en poids et/ou
  • pour des taux constitutifs en composés polycarboxyliques de type NTA, AP ou leurs sels, non supérieurs à 2% en poids, voire en l'absence substantielle desdits composés polycarboxyliques.
And it is remarkable to observe that, all the more surprisingly and unexpectedly, the characteristic presence of at least one oxidized polysaccharide, in particular of a polysaccharide, in particular of a starch hydrolyzate, oxidized "selectively" at the level of its terminal aldehyde function, allows said products containing said oxidized polysaccharide to be effective:
  • for constituent levels of zeolite (s) of less than 20% by weight and / or
  • for constituent levels of polycarboxylic compounds of NTA, AP type or their salts, not greater than 2% by weight, or even in the substantial absence of said polycarboxylic compounds.

En sus des avantages qui viennent d'être décrits en relation avec les produits de lavage conformes à l'invention, il convient de signaler que lesdits produits, contrairement à certains produits de l'art antérieur, n'entraînent aucune désactivation substantielle des agents de blanchiment, dont notamment le perborate, employés couramment dans les produits lessiviels pour éliminer les taches oxydables et conduisent à de hauts degrés de blancheur.In addition to the advantages which have just been described in relation to the washing products in accordance with the invention, it should be noted that said products, unlike certain products of the prior art, do not entail any substantial deactivation of the bleaching, including in particular perborate, commonly used in detergents to remove oxidizable stains and lead to high degrees of whiteness.

Sans vouloir être liée par une quelconque théorie, la Société Demanderesse attribue l'excellence de ces performances dans ce domaine à l'action stabilisante que joueraient les polysaccharides oxydés vis-à-vis des agents oxydants.Without wishing to be bound by any theory, 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.

Ce résultat est particulièrement marqué quand l'agent oxydant est un perborate, notamment de sodium, et que le produit conforme à l'invention comporte, en tant que polysaccharide oxydé, un hydrolysat d'amidon oxydé.This result is particularly marked when the oxidizing agent is a perborate, in particular of sodium, and when the product in accordance with the invention comprises, as oxidized polysaccharide, an oxidized starch hydrolyzate.

Selon un mode de réalisation avantageux du produit de lavage selon l'invention, celui-ci comprend:

  • une proportion d'environ 5 à environ 35% en poids, de préférence de 10 à 25% et, encore plus préférentiellement, de 15 à 20% en poids d'au moins une zéolithe,
  • une proportion d'environ 3 à environ 20% en poids, de préférence de 5 à 20% en poids et, encore plus préférentiellement, de 7 à 20% en poids d'au moins un polysaccharide oxydé, en particulier d'un polysaccharide oxydé "sélectivement" au niveau de sa fonction terminale de type aldéhydique.
According to an advantageous embodiment of the washing product according to the invention, it comprises:
  • a proportion of approximately 5 to approximately 35% by weight, preferably from 10 to 25% and, even more preferably, from 15 to 20% by weight of at least one zeolite,
  • a proportion of approximately 3 to approximately 20% by weight, preferably from 5 to 20% by weight and, even more preferably, from 7 to 20% by weight of at least one oxidized polysaccharide, in particular of an oxidized polysaccharide "selectively" at the level of its terminal aldehyde type function.

Selon un autre mode de réalisation avantageux du susdit produit, le rapport pondéral entre d'une part la zéolithe et d'autre part le polysaccharide oxydé est compris entre environ 0,5/1 et environ 4/1, de préférence compris entre 1/1 et 2/1.According to another advantageous embodiment of the above product, 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.

Dans le cadre de la présente invention, le terme "zéolithe" comprend tous les matériaux échangeurs d'ions de type aluminosilicates, qu'ils soient de nature cristalline ou amorphe, d'origine naturelle ou synthétique, tels que décrits par exemple dans les brevets EP 70 079 et EP 193 360 susmentionnés. De tels produits sont, par exemple, disponibles dans le commerce sous les désignations "zéolithe A", "zéolithe B", "zéolithe X" ou "zéolithe HS".In the context of the present invention, the term "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".

On pourra notamment faire appel à un silicoaluminate de sodium cristallin de type "zéolithe A".Use may in particular be made of a crystalline sodium silicoaluminate of the "zeolite A" type.

Dans la pratique, le produit de lavage conforme à l'invention, lequel constitue un produit industriel nouveau, comprend également un ou plusieurs autres constituants choisis, en particulier, dans le groupe comprenant les agents détergents, les agents tensio-actifs, les agents antiredéposition, les agents oxydants, les agents structurants, les agents anticorrosion, les agents antimousse, les enzymes, les parfums, les colorants, les agents solubilisants, etc., par exemple tels que décrits au niveau des brevets EP 70.079 et EP 319.053 susmentionnés.In practice, 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.

Les agents détergents pourront, par exemple, être choisis parmi les détergents anioniques synthétiques, tels que les sels hydrosolubles de métaux alcalins des sulfates et sulfonates organiques comprenant des radicaux alcoyle d'environ 8 à 22 atomes de carbone, comme par exemple les dodécylbenzène sulfonates de sodium ou de potassium.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.

Ils pourront également être choisis parmi les détergents non ioniques, tels que notamment les alcoylpolyglucosides ou les alcools gras éthoxylés.They may also be chosen from nonionic detergents, such as in particular alkylpolyglucosides or ethoxylated fatty alcohols.

Les agents oxydants, à savoir des produits susceptibles de libérer des ions peroxydes en quantité telle qu'ils permettent le blanchiment des taches de vin, de thé, de café, etc., pourront notamment être des perborates, des percarbonates, des persilicates ou des perphosphates de métaux alcalins, et en particulier le perborate de sodium.Oxidizing agents, i.e. products capable of releasing peroxide ions in such quantities that they allow bleaching of wine, tea, coffee stains, etc., may in particular be perborates, percarbonates, persilicates or perphosphates of alkali metals, and in particular sodium perborate.

Les agents structurants pourront, en particulier, être choisis, comme préconisé dans le brevet EP 215 637, parmi les sucres, les sucres hydrogénés et les mélanges quelconques de ceux-ci et notamment ceux constitués de ou contenant, au moins en partie, un monosaccharide tel que le glucose ou le fructose et/ou un disaccharide tel que le maltose ou le saccharose et/ou les produits d'hydrogénation de ceux-ci.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.

Les agents structurants pourront notamment être constitués de ou contenir, au moins en partie, du sorbitol et notamment se présenter sous la forme de produits hydrogénés obtenus par hydrogénation d'hydrolysats d'amidon ou de sirops de glucose.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.

En outre, le produit de lavage conforme à l'invention pourra contenir des adjuvants de détergence communément employés tels que l'acide polyacrylique (AP), l'acide nitrilotriacétique (NTA) et/ou leurs sels respectifs, notamment leurs sels de sodium.In addition, 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.

Cependant, comme il a déjà été signalé, la présence caractéristique d'au moins un polysaccharide oxydé au sein des produits pour lavage conformes à l'invention permet, de manière remarquable, auxdits produits d'être, à taux de zéolithes non supérieurs, voire inférieurs à ceux des produits de l'art antérieur, efficaces pour des taux constitutifs en NTA, en AP ou en leurs sels respectifs, inférieurs à ceux communément rencontrés dans lesdits produits de l'art antérieur, en particulier pour des taux non supérieurs à 2% en poids, et notamment substantiellement nuls.However, as has already been reported, 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.

Les produits pour lavage selon l'invention, utiles en particulier pour le lavage des tissus, effectué en machine ou "à la main", se présenteront préférentiellement sous la forme de particules s'écoulant librement et notamment sous la forme de poudres ou de granulés.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.

Leur préparation n'impose la mise en oeuvre d'aucun procédé et/ou appareillage autres que ceux communément employés par l'homme de l'art et pourra, par exemple, faire appel aux techniques classiques de séchage de suspensions aqueuses par atomisation.Their preparation does not require the implementation of any process and / or apparatus other than those commonly used by those skilled in the art and may, for example, use conventional techniques for drying aqueous suspensions by atomization.

La mise en contact d'au moins une zéolithe et d'au moins un polysaccharide oxydé au sein des produits pour lavage selon l'invention pourra être opérée selon des modalités très diverses, sous forme de poudres, de liquides ou de mélanges poudres/liquides, en une ou plusieurs étapes, en présence ou non de tout ou partie des autres constituants desdits produits.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.

On pourra, par exemple, apporter ledit polysaccharide oxydé à une "pré-composition" de lavage se présentant déjà sous forme de poudre et contenant la majorité, voire la totalité des autres constituants du produit final.It is possible, for example, to supply said oxidized polysaccharide to a washing "pre-composition" already in the form of a powder and containing the majority, if not all, of the other constituents of the final product.

L'association d'au moins une zéolithe et d'au moins un polysaccharide oxydé pourra également être réalisée au sein de produits de lavage se présentant sous une forme autre que celle de particules s'écoulant librement, en particulier sous forme de liquides, de gels ou de pâtes.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.

Ces produits, lesquels présenteront généralement une teneur en matière sèche de 15% environ à 80% environ, en particulier de 30 à 50%, pourront, à titre d'exemple, être obtenus en augmentant, par un moyen quelconque et notamment par simple dissolution ou mise en suspension dans l'eau ou un autre liquide, la teneur en eau de produits de lavage selon l'invention préalablement préparés sous forme de poudres ou de granulés.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.

Ils pourront également, dans d'autres cas, présenter une formule sensiblement différente de celle retenue pour les poudres ou granulés, notamment en ce qui concerne la teneur en adjuvants tensio-actifs.They may also, in other cases, have a substantially different formula from that used for powders or granules, in particular as regards the content of surfactant adjuvants.

L'invention pourra être encore mieux comprise à l'aide des exemples qui suivent et qui font état de certains modes de réalisation particulièrement avantageux des produits selon l'invention.The invention can be understood even better with the aid of the examples which follow and which show certain particularly advantageous embodiments of the products according to the invention.

Pour mettre en évidence l'efficacité des produits de lavage conformes à l'invention, on a effectué des essais comparatifs en utilisant, d'une part un produit de lavage selon l'art antérieur désigné par la lettre T dont la constitution apparaît au niveau du Tableau I ci-après et, d'autre part, quatre produits de lavage selon l'invention, désignés respectivement par les lettres A, B, C et D, dont les taux respectifs en zéolithe(s), en polysaccharide(s) oxydé(s) et, éventuellement en polyacrylates de sodium (PNa), sont repris au niveau du Tableau II.To demonstrate the effectiveness of the detergents in accordance with the invention, comparative tests were carried out using, on the one hand, a detergent according to the prior art designated by the letter T, the constitution of which appears at the level of Table I below and, on the other hand, four washing products according to the invention, designated respectively by the letters A, B, C and D, the respective levels of zeolite (s), of polysaccharide (s) oxidized (s) and, optionally to sodium polyacrylates (PNa), are listed in Table II.

Dans le cadre de cette première série d'essais, on met en oeuvre, en tant que polysaccharide oxydé contenu dans les produits de lavage selon l'invention, un produit d'oxydation d'un hydrolysat d'amidon ayant un DE de 61,5 environ et qui présente un indice d'acide I de 13,6 environ.

Figure imgb0002
Figure imgb0003
In the context of this first series of tests, 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.
Figure imgb0002
Figure imgb0003

Lesdits essais comparatifs consistent en des essais de lavage qui ont été effectués à l'aide d'une machine à laver de marque VEDETTE 8596 SYSTEME CHOIX à chargement par le haut.Said comparative tests consist of washing tests which were carried out using a VEDETTE 8596 CHOICE SYSTEM top loading washing machine.

Les essais sont réalisés aux deux températures suivantes: 40°C et 60°C.The tests are carried out at the following two temperatures: 40 ° C and 60 ° C.

Pour l'essai à 40°C, on prévoit une montée en température de 13 minutes, puis un palier à 40°C de 22 minutes. Le cycle complet, c'est-à-dire y compris les remplissages, rinçages et essorages, dure 80 minutes.For the test at 40 ° C, a temperature rise of 13 minutes is expected, then a plateau at 40 ° C of 22 minutes. The complete cycle, that is to say including filling, rinsing and wringing, lasts 80 minutes.

Pour l'essai à 60°C, on prévoit une montée en température de 21 minutes, puis un palier à 60°C de 22 minutes. Le cycle complet dure 90 minutes.For the test at 60 ° C, a temperature rise of 21 minutes is expected, then a plateau at 60 ° C of 22 minutes. The complete cycle lasts 90 minutes.

Dans les deux essais, le volume d'eau de lavage est de 11 litres.In the two tests, the volume of washing water is 11 liters.

Deux lessives sont effectuées par température.Two detergents are carried out per temperature.

La dureté de l'eau est de 30° TH.The water hardness is 30 ° TH.

La charge de lavage est composée de 2,2 kg de pièces de tissu blanc (coton) dont les dimensions sont de 55 cm x 70 cm.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 chaque lavage, on fait comporter à une charge de 2,2 kg de pièces de tissu blanc, un ensemble de "tissus salis" de natures différentes et qui comportent des salissures prédéterminées et prédéposées sur ces tissus.At each washing, 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.

Dans la pratique, ces tissus "présalis" qui sont épinglés sur la charge de lavage, sont les suivants:

  • 2 bandes de tissu polyester/coton (64/35) gris de marque KREFELD (réf. WFK 20 C), sali par un mélange d'huile animale et de noir de carbone,
  • 2 bandes de coton de marque EMPA 103 constituées de 8 morceaux cousus entre eux, à savoir:
    • un morceau de coton blanc (de type EMPA 221),
    • un morceau de coton gris (de type EMPA 101 sali par un mélange d'huile végétale et de noir de carbone),
    • un morceau de coton sali par du sang (de type EMPA 111),
    • un morceau de coton sali par du cacao (de type EMPA 112),
    • un morceau de coton sali par une tache mixte de lait, sang, noir de carbone ( de type EMPA 116 ),
    • un morceau de coton écru (de type EMPA 222),
    • un morceau de coton sali par du vin (de type EMPA 114),
    • un morceau de coton sali par du noir au soufre (non utilisé dans les présentes mesures),
  • 2 bandes de tissu polyester/coton (65/35) imprégnées de thé de marque KREFELD (réf. WFK 20G),
  • 2 bandes de tissu polyester/coton (65/35) imprégnées de cacao de marque KREFELD (réf. WFK 20F),
  • 2 bandes de tissu polyester/coton (65/35) blanc de marque EMPA (réf.: EMPA 213).
In practice, these "presalised" fabrics which are pinned to the washing load are the following:
  • 2 strips of gray polyester / cotton fabric (64/35) from KREFELD brand (ref. WFK 20 C), soiled with a mixture of animal oil and carbon black,
  • 2 EMPA 103 brand cotton strips made up of 8 pieces sewn together, namely:
    • a piece of white cotton (type EMPA 221),
    • a piece of gray cotton (type EMPA 101 soiled with a mixture of vegetable oil and carbon black),
    • a piece of cotton soiled with blood (type EMPA 111),
    • a piece of cotton soiled with cocoa (type EMPA 112),
    • a piece of cotton soiled by a mixed stain of milk, blood, carbon black (type EMPA 116),
    • a piece of unbleached cotton (type EMPA 222),
    • a piece of cotton soiled with wine (type EMPA 114),
    • a piece of cotton soiled with black sulfur (not used in these measurements),
  • 2 strips of polyester / cotton fabric (65/35) impregnated with KREFELD brand tea (ref. WFK 20G),
  • 2 strips of polyester / cotton fabric (65/35) impregnated with KREFELD cocoa (ref. WFK 20F),
  • 2 strips of white polyester / cotton fabric (65/35) from EMPA brand (ref .: EMPA 213).

La dose de produit de lavage est de 8 g/l d'eau.The dose of detergent is 8 g / l of water.

Pour apprécier la qualité du lavage, on a d'une part mesuré l'élimination de la salissure et des taches et, d'autre part déterminé l'effet des lavages sur le degré de blancheur.In order to assess the quality of the washing, the removal of dirt and stains was measured on the one hand and the effect of the washing on the degree of whiteness was determined on the other hand.

Pour apprécier l'élimination de la salissure et des taches, on a procédé par photométrie (mesures de la quantité de lumière réfléchie par le tissu); on peut ainsi calculer les pourcentages d'enlèvement de la salissure. On utilise un dispositif de mesure de la réflexion de la lumière, commercialisé sous la marque ACS 1400 SPECTRO.To assess the elimination of dirt and stains, we proceeded by photometry (measurements of the amount of light reflected by the fabric); it is thus possible to calculate the percentages of soil removal. A device for measuring the reflection of light, sold under the brand ACS 1400 SPECTRO, is used.

L'élimination de la salissure est exprimée par la formule: Elimination en % = C - B A - B x 100

Figure imgb0004
dans laquelle:

  • A = réflectance de l'échantillon blanc témoin,
  • B = réflectance de l'échantillon sali témoin,
  • C = réflectance de l'échantillon sali après essai.
The elimination of soiling is expressed by the formula: Elimination in% = C - B A - B x 100
Figure imgb0004
in which:
  • A = reflectance of the blank control sample,
  • B = reflectance of the soiled control sample,
  • C = reflectance of the soiled sample after test.

Les réflectances sont déterminées à l'aide de la composante trichromatique bleue.The reflectances are determined using the blue trichromatic component.

Le nombre de mesures effectuées par tissu est de 4, soit 4 mesures (c'est-à-dire en quatre endroits différents sur un même morceau de tissu) x 2 lavages x 2 bandes de tissu = 16 mesures par salissure, par formulation et par température.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 washes x 2 strips of fabric = 16 measurements per soiling, per formulation and by temperature.

Concernant le degré de blancheur, on mesure l'effet du lavage sur deux coupons de coton blanc non sali EMPA 221 et sur deux coupons de polyester/coton blanc non sali EMPA 213, qui sont incorporés au bain de lavage. Sur chaque coupon, on effectue 4 mesures, ce qui donne donc 16 mesures par formulation et par température étudiée.With regard to the degree of whiteness, 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.

Si l'on désigne

  • par Rbo, la composante trichromatique bleue obtenue avant le lavage,
  • par Rb, la composante trichromatique bleue obtenue après le lavage,
le degré de blancheur peut être évalué par la formule: BL = Rb - Rbo.
Figure imgb0005
If we designate
  • by Rbo, the blue trichromatic component obtained before washing,
  • by Rb, the blue trichromatic component obtained after washing,
the degree of whiteness can be assessed by the formula: BL = Rb - Rbo.
Figure imgb0005

Dans les essais proprement dits qui vont à présent être décrits, on a étudié l'efficacité des compositions de lavage conformes à l'invention successivement sur des salissures à base d'huile et de noir de carbone, puis sur les taches protéiniques et les taches oxydables et enfin on a déterminé le "degré de blanc" conféré par lesdits produits aux tissus traités.In the tests proper which will now be described, the effectiveness of the washing compositions in accordance with the invention was studied successively on oil-based stains and on carbon black, then on protein stains and stains oxidizable and finally it was determined the "degree of whiteness" imparted by said products to the treated fabrics.

EXEMPLE 1EXAMPLE 1 Taches produites par des mélanges d'huile minérale, végétale et/ou animale avec du noir de carbone.Stains produced by mixing mineral, vegetable and / or animal oil with carbon black.

On a effectué les essais de lavage, d'une part, sur du coton gris et, d'autre part, sur des tissus synthétiques (polyester/coton).The washing tests were carried out, on the one hand, on gray cotton and, on the other hand, on synthetic fabrics (polyester / cotton).

1) Essais sur coton gris 1) Tests on gray cotton

Par lavage, on a traité successivement chaque fois deux coupons de coton gris de marque EMPA 101 sali par un mélange d'huile végétale et de noir de carbone.By washing, two coupons of EMPA 101 brand gray cotton soiled with a mixture of vegetable oil and carbon black were treated successively.

Ce type de coton sali est représentatif des salissures pigmentaires insolubles liées au tissu par film gras, comme par exemple les cols de chemises, de vestes, les torchons et les taches grasses.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.

Les deux groupes d'essais réalisés respectivement à 40°C et 60°C ont donné pour les produits selon l'invention A, B, C et D d'une part, et le produit selon l'art antérieur T d'autre part, sur le plan de l'élimination de la salissure représentée par la formule susdite (1), les résultats réunis respectivement dans les tableaux III et IV.

Figure imgb0006
Figure imgb0007
The two groups of tests carried out respectively at 40 ° C and 60 ° C gave for the products according to the invention A, B, C and D on the one hand, and the product according to the prior art T on the other hand, in terms of elimination of the soiling represented by the above formula (1), the results gathered respectively in Tables III and IV.
Figure imgb0006
Figure imgb0007

2) Essais sur synthétique gris 2) Tests on gray synthetic

Le tissu synthétique utilisé ici est un tissu du type polyester/coton (dacron/coton) de marque KREFELD; il a été sali par un mélange d'huile animale et de noir de carbone (réf. WFK 20C).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).

Les deux groupes d'essais réalisés respectivement à 40°C et 60°C ont donné pour les compositions A, B, C et D d'une part et le produit témoin T d'autre part, sur le plan de l'élimination de la salissure représentée par la formule susdite (1), les résultats étant réunis respectivement dans les tableaux V et VI.

Figure imgb0008
The two groups of tests carried out respectively at 40 ° C and 60 ° C gave for compositions A, B, C and D on the one hand and the control product T on the other hand, in terms of elimination of the soiling represented by the above formula (1), the results being collected respectively in Tables V and VI.
Figure imgb0008

Il résulte de l'ensemble des tableaux III à VI que la présence caractéristique d'au moins un polysaccharide oxydé, en particulier d'au moins un polysaccharide oxydé "sélectivement" au niveau de sa fonction terminale de type aldéhydique, au sein des produits de lavage selon l'invention, permet et ce, pour des performances de lavage similaires, voire supérieures à celles observées avec un produit de lavage selon l'art antérieur:

  • de diminuer le taux d'incorporation en zéolithe(s) et/ou
  • de diminuer le taux d'incorporation d'un adjuvant de détergence non biodégradable communément employé tels que les polyacrylates, voire de s'affranchir totalement de l'incorporation d'un tel agent.
It follows from all of Tables III to VI that the characteristic presence of at least one oxidized polysaccharide, in particular of at least one polysaccharide oxidized "selectively" at the level of its terminal function of aldehyde type, within the products of washing according to the invention allows this, for washing performance similar to or even greater than that observed with a washing product according to the prior art:
  • reduce the rate of incorporation into zeolite (s) and / or
  • to decrease the rate of incorporation of a non-biodegradable detergency builder commonly used such as polyacrylates, or even to completely dispense with the incorporation of such an agent.

EXEMPLE 2EXAMPLE 2 Taches protéiniquesProtein stains

L'action des produits de lavage conformes à l'invention sur les taches protéiniques est étudiée en utilisant des tissus du type coton de marque EMPA, à savoir: le tissu EMPA 111 sali par du sang, le tissu EMPA 112 sali par du cacao et le tissu EMPA 116 sali par un mélange de sang, de lait et de noir de carbone, et du type polyester/coton de marque KREFELD, à savoir: le tissu WFK 20 F sali par du cacao.The action of 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.

Ces salissures sont représentatives des taches du type sang, lait, oeuf, jus de viande, mayonnaise, sauces et analogues.These soils are representative of stains such as blood, milk, egg, gravy, mayonnaise, sauces and the like.

Deux groupes d'essais réalisés à 40°C et 60°C ont donné pour les compositions A, B, C et D selon l'invention et le produit témoin T, sur le plan de l'élimination de la salissure représentée par la formule susdite (1), les résultats réunis respectivement dans les tableaux VII et VIII ci-dessous.

Figure imgb0009
Two groups of tests carried out at 40 ° C and 60 ° C gave for compositions A, B, C and D according to the invention and the control product T, with regard to the elimination of the soiling represented by the formula above (1), the results gathered respectively in Tables VII and VIII below.
Figure imgb0009

Il ressort des tableaux VII et VIII que, dans le cas des taches protéiniques, les mêmes conclusions que celles faites précédemment pour les taches produites par des mélanges huile/noir de carbone, peuvent être tirées en ce qui concerne l'efficacité des produits de lavage selon l'invention et leur intérêt comparativement à un produit de l'art antérieur qui, bien que contenant à la fois plus de zéolithe(s) et plus de polyacrylates, ne se montre pas plus performant, en particulier pour une température d'essai de 60°C.It appears from Tables VII and VIII that, in the case of protein spots, the same conclusions as those made previously for stains produced by oil / carbon black mixtures, can be drawn with regard to the effectiveness of the detergents according to the invention and their advantage compared to a product of the prior art which, although containing both more zeolite (s) and more polyacrylates, does not prove to be more efficient, in particular for a test temperature of 60 ° C.

EXEMPLE 3EXAMPLE 3 Taches oxydablesOxidizable stains

L'action des produits de lavage conformes à l'invention sur les taches oxydables est étudiée en utilisant les tissus suivants:

  • polyester/coton de marque KREFELD sali par du thé (réf.: WFK 20 G)
  • coton de marque EMPA 222, c'est-à-dire du coton écru non sali
  • coton de marque EMPA 114 sali par du vin.
The action of washing products in accordance with the invention on oxidizable stains is studied using the following fabrics:
  • KREFELD brand polyester / cotton soiled with tea (ref .: WFK 20 G)
  • EMPA 222 brand cotton, i.e. unsoiled unbleached cotton
  • EMPA 114 brand cotton soiled with wine.

Les susdits tissus sont sensibles à l'oxydation chimique; les taches provoquées sont celles que le blanchiment atténue ou fait disparaître (d'autres taches de ce type sont celles provoquées par les fruits, le café, les légumes et autres).The above fabrics are sensitive to chemical oxidation; 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).

Un groupe d'essais réalisé à 60°C a donné pour les compositions A, B, C et D et le produit témoin T, sur le plan de l'élimination de la salissure représentée par la formule susdite (1), les résultats réunis respectivement dans le tableau IX.

Figure imgb0010
A group of tests carried out at 60 ° C. gave for the compositions A, B, C and D and the control product T, with regard to the elimination of the soiling represented by the above-mentioned formula (1), the combined results respectively in Table IX.
Figure imgb0010

La moyenne des résultats obtenus sur les taches de thé et de vin et sur le coton écru reflète le comportement des produits essayés sur l'ensemble des taches de cette famille.The average of the results obtained on tea and wine stains and on unbleached cotton reflects the behavior of the products tested on all the stains in this family.

Il ressort du tableau IX que, dans le cas spécifique des taches oxydables, les produits de lavage selon l'invention permettent d'atteindre un niveau d'efficacité égal à celui du produit de lavage selon l'art antérieur. Les produits de lavage conformes à l'invention satisfont pleinement aux critères généralement requis en ce qui concerne l'élimination de ce type de salissure.It appears from Table IX that, in the specific case of oxidizable stains, the detergents according to the invention make it possible to achieve a level of efficiency equal to that of the detergent according to the prior art. The detergents according to the invention fully meet the criteria generally required with regard to the removal of this type of soiling.

EXEMPLE 4EXAMPLE 4 Degré de blancDegree of white

On utilise du coton blanc non azuré de la marque EMPA 221 et du polyester/coton non azuré de la marque EMPA 213 pour déterminer si un produit de lavage donné est apte à conserver, faire augmenter ou diminuer le degré de blancheur initial du tissu.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.

Les deux groupes d'essais réalisés respectivement à 40°C et 60°C ont donné pour les compositions A, B, C et D d'une part, et le produit témoin T d'autre part, sur le plan du degré de blancheur, les résultats réunis dans le tableau X.

Figure imgb0011
The two groups of tests carried out respectively at 40 ° C and 60 ° C gave for compositions A, B, C and D on the one hand, and the control product T on the other hand, in terms of the degree of whiteness , the results collated in Table X.
Figure imgb0011

Il ressort du tableau X que, pour le critère étudié, les produits de lavage conformes à l'invention sont, globalement, aussi performantes que le produit de lavage de l'art antérieur, lesdits produits de lavage selon l'invention permettant d'obtenir, après le lavage, un tissu dont le degré de blancheur est supérieur à celui qu'il avait avant le lavage.It appears from Table X that, for the criterion studied, the detergents in accordance with the invention are, overall, as efficient as the washing product of the prior art, said washing products according to the invention making it possible to obtain, after washing, a fabric whose degree of whiteness is greater than that which it had before washing.

EXEMPLE 5EXAMPLE 5

Dans le cadre d'une seconde série d'essais, on a comparé, selon des tests identiques à ceux décrits précédemment, l'efficacité de quatre produits de lavage conformes à l'invention référencés E, F, G et H, par rapport à celle d'un produit de l'art antérieur contenant 20% de zéolithe et 10% de tripolyphosphates.In the context of a second series of tests, the effectiveness of four detergents according to the invention, referenced E, F, G and H, were compared, according to tests identical to those described above. that of a product of the prior art containing 20% of zeolite and 10% of tripolyphosphates.

Pour préparer lesdits produits E à H, on a remplacé les 10% de tripolyptiosphates de la composition témoin par le même poids respectivement:

  • du produit d'oxydation d'un hydrolysat d'amidon d'un DE voisin de 37, et présentant un indice d'acide I voisin de 8,6 en ce qui concerne le produit E,
  • du produit d'oxydation d'un hydrolysat d'amidon d'un DE voisin de 37, présentant un indice d'acide I voisin de 8,6 et "stabilisé" par hydrogénation catalytique au nickel (taux résiduel en sucres réducteurs SR inférieur à 0,1%), en ce qui concerne le produit F,
  • du produit d'oxydation d'un hydrolysat d'amidon d'un DE voisin de 61,5, présentant un indice d'acide I voisin de 13,6 et "stabilisé" par traitement au borohydrure de sodium (taux résiduel en SR inférieur à 1%), en ce qui concerne le produit G,
  • du produit d'oxydation d'un hydrolysat d'amidon d'un DE voisin de 61,5 (I voisin de 13,6) et "stabilisé" par hydrogénation catalytique au nickel (taux résiduel en SR inférieur à 0,01%), en ce qui concerne le produit H.
To prepare said products E to H, the 10% tripolyptiosphates of the control composition were replaced by the same weight respectively:
  • of the oxidation product of a starch hydrolyzate with an ED close to 37, and having an acid number I close to 8.6 with regard to the product E,
  • of the oxidation product of a starch hydrolyzate with an ED close to 37, having an acid number I close to 8.6 and "stabilized" by catalytic nickel hydrogenation (residual rate of reducing sugars SR less than 0.1%), for product F,
  • of the oxidation product of a starch hydrolyzate with an ED close to 61.5, having an acid number I close to 13.6 and "stabilized" by treatment with sodium borohydride (lower residual rate in SR at 1%), for product G,
  • of the oxidation product of a starch hydrolyzate with an ED close to 61.5 (I close to 13.6) and "stabilized" by catalytic hydrogenation with nickel (residual rate of SR less than 0.01%) , with regard to the product H.

Il résulte desdits essais que, d'une manière générale, l'ensemble des produits de lavage E à H selon l'invention montrent des performances similaires, voire supérieures dans certains cas, à un produit de lavage de l'art antérieur associant zéolithes et phosphates.It follows from said tests that, in general, all of the detergents E to H according to the invention show performances similar, or even superior in certain cases, to a detergent of the prior art combining zeolites and phosphates.

EXEMPLE 6EXAMPLE 6

Dans le cadre d'une troisième série d'essais, on met en évidence l'intérêt des produits de lavage conformes à l'invention par le biais d'autres tests que ceux décrits précédemment et qui seront détaillés par la suite.In the context of a third series of tests, the advantage of the detergents according to the invention is highlighted by means of tests other than those described above and which will be detailed later.

Dans le cadre de ces essais, on a pris, en tant que produit témoin selon l'art antérieur, le produit de lavage désigné par la lettre T dont la constitution a été détaillée au niveau du Tableau I ci-avant.In the context of these tests, the 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.

On a d'autre part testé trois produits de lavage selon l'invention, désignés respectivement par les lettres I, J et K, dont les taux respectifs en zéolithe(s), en polysaccharide(s) oxydé(s) et, éventuellement, en polyacrylates de sodium (PNa) ou en nitrilotriacétates (NTA), sont repris au niveau du Tableau XI ci-dessous.

Figure imgb0012
On the other hand, three 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.
Figure imgb0012

Pour ces essais, on met en oeuvre, en tant que polysaccharide oxydé contenu dans les produits de lavage selon l'invention, un produit d'oxydation d'un hydrolysat d'amidon ayant un DE de 37 environ, et présentant un indice d'acide I de 8,6 environ, ledit produit d'oxydation ayant par ailleurs été traité par hydrogénation catalytique au nickel de Raney (taux résiduel en sucres réducteurs inférieur à 0,05%).For these tests, 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%).

Les tests sont réalisés à 60°C sur une machine à laver de marque WASCATOR FOM 71 à raison de 7 g/l de produit de lavage, soit 154 g par lavage.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.

La charge de lavage est de 2,5 kg de tissus contenant deux bandes d'usure à base de coton pur et un ballast de serviettes éponge et torchons de dimensions ou grammages déterminés (Norme NF T 73-600).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).

Les tests effectués visent à mesurer, pour chaque produit étudié (4 mesures par produit), l'usure chimique et le taux d'incrustation organique obtenus au niveau de la charge de lavage et ce, après 25 cycles de lavage successifs et cumulatifs.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.

L'usure chimique consiste à mesurer le degré moyen de polymérisation ou DP de la cellulose du coton avant et après la série de 25 lavages en vue d'évaluer l'attaque sur la chaîne macromoléculaire de cellulose de produits tels que le perborate et les agents alcalins.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.

La détermination du DP de la cellulose est réalisée par mesure de la viscosité d'une solution d'un échantillon de coton soumis à l'essai dans un solvant approprié (cupriéthylène diamine) par rapport à la viscosité du solvant lui-même et ce, conformément aux normes NF T 73-601, paragraphe 3.6 ou NF G 06-037.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.

Le but recherché est que l'action détergente ne provoque pas de diminution substantielle du DP de façon à ne pas faciliter la déchirure du tissu ainsi lavé.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.

Dans le cadre des présents essais, il est à noter que le coton utilisé présente, avant lavage, un DP de 1925.In the context of these tests, it should be noted that the cotton used has, before washing, a DP from 1925.

L'incrustation organique permet d'appréhender le dépôt de résidus de tensio-actif(s) ou de savon(s) complexé(s) par le calcium dans le cas d'une mauvaise séquestration.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.

Le test est effectué conformément aux normes NF T 73-601, paragraphe 3.3 et ISO 4312, paragraphe 6.The test is carried out in accordance with standards NF T 73-601, paragraph 3.3 and ISO 4312, paragraph 6.

D'une façon générale, on estime que le taux d'incrustation organique ne doit pas dépasser environ 1%.In general, it is estimated that the organic incrustation rate should not exceed around 1%.

Le Tableau XII ci-après donne, pour le produit de lavage témoin T et chacun des produits de lavage I, J et K selon l'invention, le degré moyen de polymérisation DP et le taux d'incrustation organique IO obtenus après 25 lavages effectués à 60°C.

Figure imgb0013
Table XII below 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.
Figure imgb0013

Les résultats du Tableau XII montrent globalement que les produits de lavage selon l'invention permettent d'atteindre des résultats similaires (en termes de DP), voire supérieurs (en termes de IO) à ceux enregistrés avec le produit de lavage de l'art antérieur.The results of Table XII overall show that the detergents according to the invention make it possible to achieve results similar (in terms of DP), or even superior (in terms of IO) to those recorded with the detergent of the art prior.

EXEMPLE 7EXAMPLE 7

On mesure, selon des méthodes normalisées (Normes NF T 73-601, paragraphe 3.4 et ISO 4312, paragraphe 7), le taux de cendres de bandes de coton après que celles-ci ont subi un cycle de 25 lavages successifs à 60°C avec mise en oeuvre respective de l'un ou l 'autre des susdits produits T (produit de lavage témoin), J et K (produits de lavage selon l'invention).We measure, according to standardized methods (Standards NF T 73-601, paragraph 3.4 and ISO 4312, paragraph 7), the rate of ashes of cotton strips after they have undergone a cycle of 25 successive washes at 60 ° C. with respective implementation of one or the other of the above products T (control washing product), J and K (washing products according to the invention).

La mesure du taux de cendres permet d'appréhender l'importance du dépôt de sels minéraux, notamment de type carbonate, bicarbonate, sulfate de calcium ou magnésium, sur le linge à l'issue du cycle de lavages.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.

Dans le cas de produits de lavage contenant des zéolithes, il est généralement admis qu'un taux de cendres résultant inférieur ou égal à 1%, donne entière satisfaction.In the case of washing products containing zeolites, it is generally accepted that a resultant rate of ash less than or equal to 1% is entirely satisfactory.

Les résultats du Tableau XIII ci-après montrent, encore une fois, que les produits de lavage selon l'invention permettent de satisfaire pleinement aux exigences de la technique.

Figure imgb0014
The results of Table XIII below show, once again, that the washing products according to the invention allow to fully meet the technical requirements.
Figure imgb0014

Claims (13)

Produit de lavage à teneur réduite à moins de 5% en poids, voire nulle en phosphates, utile notamment pour le lavage des tissus, caractérisé par le fait qu'il comporte au moins une zéolithe et au moins un polysaccharide oxydé choisi dans le groupe comprenant: - les produits d'oxydation de disaccharides possédant une fonction terminale de type aldonique, - les produits d'oxydation de trisaccharides et d'oligosaccharides possédant une fonction terminale de type aldonique, - les produits d'oxydation d'hydrolysats d'amidon, de cellulose et d'hémicellulose possédant une fonction terminale de type aldonique, et - les mélanges quelconques d'au moins deux quelconques des susdits produits d'oxydation. Washing product with a reduced content of less than 5% by weight, or even zero in phosphates, useful in particular for washing fabrics, characterized in that it comprises at least one zeolite and at least one oxidized polysaccharide chosen from the group comprising : - oxidation products of disaccharides having a terminal aldonic type function, - oxidation products of trisaccharides and oligosaccharides having an aldonic-type terminal function, - oxidation products of starch, cellulose and hemicellulose hydrolysates having a terminal function of aldonic type, and - any mixtures of at least any two of the above oxidation products. Produit de lavage selon la revendication 1, caractérisé par le fait que le polysaccharide oxydé est constitué d'au moins un produit obtenu à partir d'un di-, d'un tri- ou d'un oligosaccharide, d'un hydrolysat d'amidon, de cellulose ou d'hémicellulose dont seule, parmi l'ensemble de ses fonctions potentiellement oxydables, sa fonction terminale (de type aldéhydique avant oxydation) est substantiellement oxydée.Washing product according to claim 1, characterized in that the oxidized polysaccharide consists of at least one product obtained from a di-, a tri- or an oligosaccharide, a hydrolyzate of starch, cellulose or hemicellulose, of which only, among all of its potentially oxidizable functions, its terminal function (of aldehyde type before oxidation) is substantially oxidized. Produit de lavage selon l'une des revendications 1 et 2, caractérisé par le fait que le polysaccharide oxydé est un produit d'oxydation d'un hydrolysat d'amidon obtenu par voie acide et/ou enzymatique, présentant un DE d'environ 5 à environ 90.Washing product according to either of Claims 1 and 2, characterized in that the oxidized polysaccharide is an oxidation product of a starch hydrolyzate obtained by the acid and / or enzymatic route, having an ED of approximately 5 at around 90. Produit de lavage selon la revendication 3, caractérisé par le fait que le polysaccharide oxydé présente, en outre, un indice d'acide I compris entre environ 1 et environ 20.Washing product according to Claim 3, characterized in that the oxidized polysaccharide also has an acid number I of between approximately 1 and approximately 20. Produit de lavage selon la revendication 4, caractérisé par le fait que le polysaccharide oxydé est un produit d'oxydation d'un hydrolysat d'amidon présentant un DE d'environ 20 à environ 65 et que ledit polysaccharide oxydé présente un indice d'acide I compris entre environ 5 et environ 14.Washing product according to claim 4, characterized in that the oxidized polysaccharide is an oxidation product of a starch hydrolyzate having a DE from about 20 to about 65 and that said oxidized polysaccharide has an acid number I of between about 5 and about 14. Produit de lavage selon la revendication 5, caractérisé par le fait que le polysaccharide oxydé est un produit d'oxydation d'un hydrolysat d'amidon présentant un DE d'environ 35 à environ 65 et que ledit polysaccharide oxydé présente un indice d'acide I compris entre environ 8 et environ 14.Washing product according to claim 5, characterized in that the oxidized polysaccharide is an oxidation product of a starch hydrolyzate having a DE from about 35 to about 65 and that said oxidized polysaccharide has an acid number I range from about 8 to about 14. Produit de lavage selon l'une des revendications 1 à 6, caractérisé par le fait que le polysaccharide oxydé présente un taux inférieur à environ 0,6%, de préférence inférieur à 0,1% et encore plus préférentiellement inférieur à 0,05% en poids, en sucres réducteurs.Washing product according to one of Claims 1 to 6, characterized in that the oxidized polysaccharide has a level of less than about 0.6%, preferably less than 0.1% and even more preferably less than 0.05% by weight, in reducing sugars. Produit de lavage selon la revendication 7, caractérisé par le fait que le polysaccharide oxydé subit une hydrogénation catalytique, ladite hydrogénation mettant en oeuvre, en continu ou en discontinu, de préférence au moins un catalyseur choisi dans le groupe comprenant le nickel, le platine, le palladium, le cobalt, le molybdène et les combinaisons de ces métaux, et notamment du nickel de Raney.Washing product according to claim 7, characterized in that the oxidized polysaccharide undergoes catalytic hydrogenation, said hydrogenation employing, continuously or batchwise, preferably at least one catalyst chosen from the group comprising nickel, platinum, palladium, cobalt, molybdenum and combinations of these metals, and in particular Raney nickel. Produit de lavage selon l'une des revendications 1 à 8, caractérisé par le fait qu'il comprend: - une proportion d'environ 5 à environ 35% en poids, de préférence de 10 à 25% en poids et, encore plus préférentiellement, de 15 à 20% en poids d'au moins une zéolithe, - une proportion d'environ 3 à environ 20% en poids, de préférence de 5 à 20% en poids et, encore plus préférentiellement, de 7 à 20% en poids d'au moins un polysaccharide oxydé, en particulier d'un polysaccharide oxydé "sélectivement" au niveau de sa fonction terminale de type aldéhydique. Washing product according to one of claims 1 to 8, characterized in that it comprises: a proportion of approximately 5 to approximately 35% by weight, preferably from 10 to 25% by weight and, even more preferably, from 15 to 20% by weight of at least one zeolite, a proportion of approximately 3 to approximately 20% by weight, preferably from 5 to 20% by weight and, even more preferably, from 7 to 20% by weight of at least one oxidized polysaccharide, in particular of a polysaccharide oxidized "selectively" at the level of its terminal function of aldehyde type. Produit de lavage selon la revendication 9, caractérisé par le fait que le rapport pondéral entre d'une part la zéolithe et d'autre part le polysaccharide oxydé est compris entre environ 0,5/1 et 4/1, de préférence entre 1/1 et 2/1.Washing product according to claim 9, characterized in that the weight ratio between one on the one hand the zeolite and on the other hand the oxidized polysaccharide is between approximately 0.5 / 1 and 4/1, preferably between 1/1 and 2/1. Produit de lavage selon l'une des revendications 1 à 10, caractérisé par le fait que la zéolithe est un silico-aluminate de sodium, en particulier de type zéolithe A.Washing product according to one of Claims 1 to 10, characterized in that the zeolite is a sodium silico-aluminate, in particular of the zeolite A type. Produit de lavage selon l'une des revendications 1 à 11, caractérisé par le fait qu'il comporte en outre un ou plusieurs autres constituants choisis, en particulier, dans le groupe comprenant les adjuvants de détergence polycarboxyliques tels que l'acide polyacrylique (AP), l'acide nitrilotriacétique (NTA) et/ou leurs sels respectifs, les agents détergents, les agents tensioactifs, les agents antiredéposition, les agents oxydants, les agents structurants, les agents anticorrosion, les agents anti-mousse, les enzymes, les parfums, les colorants, les agents solubilisants.Washing product according to one of Claims 1 to 11, characterized in that it also comprises one or more other constituents chosen, in particular, from the group comprising polycarboxylic detergency builders such as polyacrylic acid (AP ), nitrilotriacetic acid (NTA) and / or their respective salts, detergents, surfactants, anti-redeposition agents, oxidizing agents, structuring agents, anticorrosion agents, anti-foaming agents, enzymes, perfumes, dyes, solubilizing agents. Produit de lavage selon la revendication 12, caractérisé par le fait qu'il comporte au plus 4%, de préférence au plus 2% en poids d'un adjuvant de détergence choisi dans le groupe comprenant l'acide polyacrylique (AP), l'acide nitrilotriacétique (NTA), leurs sels respectifs, notamment leurs sels de sodium, et les mélanges quelconques de ceux-ci.Washing product according to claim 12, characterized in that it comprises at most 4%, preferably at most 2% by weight of a detergency builder chosen from the group comprising polyacrylic acid (PA), nitrilotriacetic acid (NTA), their respective salts, especially their sodium salts, and any mixtures thereof.
EP91400773A 1990-03-23 1991-03-21 Phosphate free detergent Expired - Lifetime EP0455522B1 (en)

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AU2016243410A1 (en) 2015-04-03 2017-08-03 E I Du Pont De Nemours And Company Oxidized dextran
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NO911157D0 (en) 1991-03-22
ES2090268T3 (en) 1996-10-16
DK0455522T3 (en) 1996-12-30
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NO911157L (en) 1991-09-24
DE69121286D1 (en) 1996-09-19
ATE141323T1 (en) 1996-08-15
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CA2038640A1 (en) 1991-09-24
DE69121286T2 (en) 1997-02-20

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