EP0511081B1 - Low zeolithe or zeolithe free detergent - Google Patents

Abstract

Washing product (detergent), useful especially for washing dishes, characterised in that it contains: - less than 5% by weight, preferably less than 1% by weight and, even more preferably, a zero quantity of zeolite(s), - less than 40% by weight, preferably less than 20% by weight and, even more preferably, a zero content of phosphate and - from 5 to 75% by weight and, preferably, from 15 to 50% by weight of at least one oxidised polysaccharide. e

Description

The subject of the present invention is a product of washing, especially for washing dishes, reduced or zero in zeolite and containing essentially a chlorine-releasing agent.

It also targets products of the genre in question which are further reduced or zero in phosphates.

Phosphates have long played a role predominant in washing products, especially in as sequestrants of the cations that form salts insoluble in water, in particular calcium ions and magnesium; the excellent performance they allow to reach resident in their particular structure.

But one of the acute problems facing the industry washing products to face, is the character very polluting of said phosphates. Indeed, their presence in wastewater causes the well-known phenomenon of eutrophication; and for this reason the use of phosphates in detergents (dishes, laundry or others) must meet constraints, in particular ecological, more and more severe.

This ecological aspect is all the more marked as the powerful detergents commonly used and, in particular, products used in communities, contain high amounts of phosphates which can exceed 50%.

Many attempts have therefore been made in the purpose of removing all or part of the phosphates in the detergents, including those intended for washing dishes and similar objects (glassware, porcelain, cutlery, pots, pans).

In particular, it was proposed to have recourse, in as a total or partial replacement agent for phosphates, nitrilotriacetic acid (NTA) and / or its salts, especially sodium nitrilotriacetate, such as recommended in patents FR 2 208 975 and EP 82 564. However, in addition to their imperfect biodegradability, these products are believed to fix heavy metals, which could get into the drinking water.

As a result of which, these products are prohibited in some countries. More generally, it is often made it compulsory to limit their introduction rate to 5% in detergents.

It was also proposed as part of the search for solutions to limit the use of phosphates, to use polycarboxylic polymers specific based on defined mixtures of acids monoolefinic and monoolefinic dicarboxyls and non-esters ionic of said acids.

In particular, it was recommended, as described in EP 267 371 and FR 2 613 378, to use derivatives of acrylic and / or methacrylic acid as well than maleic and / or itaconic acid derivatives, and peculiar to copolymers of maleic anhydride and acrylic acid.

However, these products are ecologically few acceptable due to their very low biodegradability.

It was also proposed to have recourse, in total or partial replacement of phosphates, at zeolites of natural or synthetic origin, as described in patent EP 249,163.

However, if the zeolites contribute by their cation exchange power, especially calcium and magnesium, upon elimination of said cations, their substitution with phosphates does not allow to reach a degree of washing satisfying the requirements of the practice.

In order to improve the quality of washing washing products based on zeolites and containing little or no no phosphates, it has been proposed to combine said zeolites to various other agents such as in particular nitrilotriacetic acid or, as envisioned in the patent FR 2 620 727, to a polyacrylic acid and / or a polyacrylate polymer.

However, whether or not they are associated with such agents, zeolites have the disadvantage major not to be solubilizable in the baths of washing and thus, to remain at least partially deposited on certain objects, among others the articles of glassware, on which they remain visible after machine washing and evaporation of washing water.

Thus the incorporation of zeolite (s) in doses is generally not recommended, especially practical, when washing dishes, particular glassware.

However, the incorporation of zeolite (s) into reduced contents, i.e. at doses lower than about 5% by weight in the detergents, can be beneficial in some cases, according to the teachings of Patent EP 30,986 and CH 673,033 describing the use of these products respectively as abrasive agents of dry soiling and anti-corrosion / anti-caking agents.

Washing products which may be free of phosphates and zeolites and containing starches which must be strongly oxidized have been described in following patents FR-A-2,074,026, FR-A-2,126,386 and FR-A-2 063 914, the products described in this latter patent being intended for washing fabrics. Patent application DE-A-2023944 recommends increasing the number of functions starch hydrolysate acids oxidized by carboxymethylation, said hydrolysates being used in detergent compositions.

Furthermore, US Pat. No. 3,803,285 describes the use of oxidized starch derivatives to improve the physical characteristics of the detergent granules.

• une bonne efficacité de lavage et ce, pour des types variés de salissures et d'articles à traiter,
• une bonne compatibilité avec les exigences de protection de l'environnement et notamment la possibilité de réduire significativement l'apport simultané de phosphates et/ou d'autres additifs susmentionnés écologiquement inacceptables, voire de s'en affranchir.

However, it follows from the above that until then there had been no means capable of allowing washing products of this kind to have all the qualities required for the intended applications and in particular:

• good washing efficiency for various types of soiling and articles to be treated,
• good compatibility with environmental protection requirements and in particular the possibility of significantly reducing the simultaneous supply of phosphates and / or other aforementioned ecologically unacceptable additives, or even of eliminating them.

And the Applicant Company has had the merit of find that such a means could be constituted by putting in use, in washing products such as question, at least one oxidized polysaccharide.

• moins de 5% en poids, de préférence moins de 1% en poids et, plus préférentiellement encore, une quantité nulle de zéolithe(s),
• moins de 40% en poids, de préférence moins de 20% en poids de phosphate et
• de 5 à 75% en poids et, de préférence, de 15 à 50% en poids d'au moins un polysaccharide oxydé qui est choisi dans le groupe comprenant :
  • les produits d'oxydation de di-, tri- et 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,
  • les mélanges quelconques contenant au moins deux quelconques des susdits produits d'oxydation,
  ledit polysaccharide oxydé étant obtenu à partir d'un produit dont seule, parmi l'ensemble des fonctions potentiellement oxydables qu'il comporte, la fonction terminale (de type aldéhydique avant oxydation) est substantiellement oxydée et ce, en une fonction de type aldonique.

Consequently, the subject of the invention is a washing product, useful in particular for washing dishes, characterized in that it contains:

• less than 5% by weight, preferably less than 1% by weight and, more preferably still, a zero amount of zeolite (s),
• less than 40% by weight, preferably less than 20% by weight of phosphate and
• from 5 to 75% by weight and, preferably, from 15 to 50% by weight of at least one oxidized polysaccharide which is chosen from the group comprising:
  • oxidation products of di-, tri- and oligosaccharides having a terminal function of the aldonic type,
  • oxidation products of starch, cellulose and hemicellulose hydrolysates having an aldonic terminal function,
  • any mixtures containing at least any two of the above oxidation products,
  said oxidized polysaccharide being obtained from a product of which only, among all of the potentially oxidizable functions which it comprises, the terminal function (of aldehyde type before oxidation) is substantially oxidized and this, in function of aldonic type.

Furthermore, as already pointed out, the presence of oxidized polysaccharide within the product of washing according to the invention makes it possible, remarkably, to get rid of any use of phosphates and, according to another advantageous embodiment of the invention, said product has a lower content at 1% and preferably substantially zero in phosphates.

In the context of the present invention, more particularly by "dishes", all of objects used, whether domestic or not (communities, hospitals, schools, various industries), for the presentation and / or absorption of food and / or drinks and in particular, without this list not either restrictive, plates, dishes, cutlery, glasses, cups, saucers, bottles, pans and others food containers, objects similar to those above but not necessarily used to be put in contact with food (cutlery, glassware, porcelain, pots, flasks, vases) as well that objects intended to contain, at least temporarily, non-food substances of all natures and needing to be, at some point, rid of said substances such as articles of laboratory glassware (flasks, test tubes, test tubes, pipettes, flasks).

The oxidized polysaccharide can in particular be consisting of the product resulting from the oxidation of a starch hydrolyzate obtained by the acid route and / or enzymatic, said hydrolyzate generally having a DE (Dextrose-Equivalent) from about 5 to about 90 and containing varying proportions of dimers, trimers, glucose oligomers and polymers. It can also be consisting of the product resulting from the oxidation of a hemicellulose hydrolyzate such as D-galacto-D-mannan, a D-gluco-D-mannane, an L-arabino-D-xylane or a D-xylo-arabinane.

Within washing products conforming to the invention, the above-mentioned oxidation products may be present, in whole or in part, in the form of salts acids, in particular in the form of metal salts alkaline.

Such oxidized polysaccharides can, in particular if we are looking for a truly qualifiable oxidation of "selective" at the level of the terminal function of aldonic type, obtained by the oxidation process catalytic described by the Applicant Company in its Patent EP 232 202.

They can in particular consist of an oxidation product of a starch hydrolyzate having a DE of about 5 to about 90 and have 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: I = 100 x OF 180 x 45 100 + DE x 218 180 - OF .

In the context of the present invention, use in particular oxidized polysaccharides who have an acid number between about 5 and about 14 and which are obtained by oxidation of hydrolysates starch having an ED of between about 20 and about 65.

According to another advantageous embodiment, the oxidized polysaccharide is an oxidized product presenting, especially by its level of reducing sugars, good stability, in particular in terms of its coloring, when said oxidized product is used (when the correct detergent is prepared or used to the invention), at any time and for example during atomization operations, in an environment presenting alkaline pH and / or high temperature, environment suitable for coloring (more or less yellowing pronounced) any composition containing it.

As such, the Applicant Company has designed and implemented to develop, as new products, polysaccharides oxidized "stabilized" with low rates, generally less than about 0.6%, preferably less than 0.1% and even more preferably less at 0.05% by weight, in reducing sugars.

In particular, the Applicant Company has found that the hydrogenation techniques applied to oxidized polysaccharides, in particular of the hydrolysate type oxidized starch, allowed to obtain such products, in particular oxidized products having a rate practically zero in reducing sugars, "stabilized" as to possible yellowing in the presence of an environment (pH alkaline, high temperature) favoring this type of phenomenon.

By hydrogenation techniques, we mean especially the techniques of catalytic hydrogenation using, continuously or discontinuously, at least a 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.

We will particularly use techniques using hydrogenation, fixed or not fixed on a support inert, Raney nickel as catalyst and this, in presence or not of an additional source of hydrogen.

Other hydrogenation techniques may be employees appealing, in the absence of a catalyst hydrogenation, to sources of hydrogen other than hydrogen gas, for example metal borohydrides alkaline, in particular sodium borohydride.

Oxidized polysaccharides, in particular of the type oxidized starch hydrolyzate, "stabilized" following the implementation of these hydrogenation techniques, in particular those with an ED between 5 and 90, a acid number I between 1 and 20 and "stabilized" by catalytic hydrogenation, further impart to the compositions and washing products in which they are introduced, performance generally comparable to that observed with the same oxidized products but not "stabilized", or even improved performance for certain parameters.

• aussi bien dans le cadre du lavage de la vaisselle que dans celui d'autres articles, et notamment du linge, et
• pour des taux associés en zéolithe(s) ou phosphates significativement réduits, voire substantiellement nuls, y compris pour des taux substantiellement nuls à la fois en zéolithe(s) et phosphates, et
• sans obligation aucune de faire appel à des produits de type acide nitrilotriacétique, acide polyacrylique ou leurs sels respectifs.

It is remarkable to note that the characteristic presence of at least one oxidized polysaccharide within the washing products according to the invention, allows the latter to meet the requirements of industrial practice, in particular in terms of efficiency and protection of the environment and this:

• for washing dishes as well as for other items, including linen, and
• for associated levels of zeolite (s) or phosphates significantly reduced, or even substantially zero, including for substantially zero levels of both zeolite (s) and phosphates, and
• without any obligation to use products such as nitrilotriacetic acid, polyacrylic acid or their respective salts.

As will be illustrated below, it is appropriate to point out, among other things, the remarkable effectiveness of detergents according to the invention with regard to the elimination of dirt of an oxidizable or proteinic nature.

It will be noted, in particular, that said products, unlike some formulations of the prior art, do not result in substantial agent deactivation money laundering agents, in particular chlorine, commonly used in detergents for washing dishes.

Without wishing to be bound by any theory, the Applicant Company attributes, at least in part, the excellent performance of washing products according to the invention, to the stabilizing action that would play oxidized polysaccharides with respect to said agents whitening as well as a certain complexing / dispersing action oxidized polysaccharides in baths detergents.

In the context of the present invention, the term "zeolite" includes all ion exchange materials aluminosilicate type, whether they are crystalline in nature or amorphous, of natural or synthetic origin, as described, for example, in the FR patents 2,620,727, CH 673,033, EP 30,986 and EP 249,163 mentioned above. Such products are, by way of example, commercially available under the designations "zeolite A", "zeolite B", "zeolite X" or "zeolite HS".

We can in particular use a silico-aluminate crystalline sodium type "zeolite A", in association or not with another zeolite.

It should be emphasized that, as stated above, if the presence of zeolite (s) at reduced in the detergents according to the invention is envisaged, it is in no way compulsory.

In practice, the detergent conforming to the invention, which constitutes a new industrial product, also includes one or more other constituents chosen, without this list being exhaustive, in the group comprising detergents, sequestering agents other than zeolites and phosphates, surfactants, bleaching, anti-foaming agents, anti-deposition agents, alkaline agents, structuring agents, flow agents, thickening agents, anticorrosive agents, abrasive agents, agents solubilizers, bulking agents, enzymes and agents for stabilizing enzymes, bactericides, agents opacifiers, optical brighteners, coloring agents, perfumes, for example those described in terms of patents FR 2 208 975, FR 2 608 168, FR 2 620 727 and EP 30,986, EP 82,564 and EP 267,371 mentioned above.

Detergents and surfactants can, for example, be chosen from anionic products synthetics, such as water-soluble metal salts alkali sulfates and organic sulfonates including alkyl radicals of about 8 to 22 carbon atoms, such as sodium dodecylbenzene sulfonates or potassium.

They can also be chosen from non-ionic products, such as in particular alkylpoly-glucosides or ethoxylated fatty alcohols.

The sequestering agents may, for example, be chosen from mono- or polyphosphates, in particular ortho-, pyro-, tripoly- and hexametaphosphates, and more particularly the tripolyphosphates of sodium (TPP-Na), phosphonic acids and / or their salts respective, citric acid, polyacrylic acid (PA), nitrilotriacetic acid (NTA) and / or their respective salts, especially their sodium salts, EDTA.

However, as already noted, the presence characteristic of at least one oxidized polysaccharide, in particular oxidized "selectively" at the level of its terminal function, within detergents in accordance with the invention, allows, remarkably, said products to be effective for constituent rates in phosphates, NTA, AP (or their respective salts) generally lower than those commonly encountered on the market, even for substantially zero rates in each of these compounds.

Furthermore, and this is another aspect particularly advantageous of the present invention, the implementation work of at least one oxidized polysaccharide, in particular "selectively" oxidized at its terminal function, achieves washing efficiency (dishes especially but also linen) complies with the requirements of practice even for rates substantially zero in both phosphates and zeolites.

The bleaching agents that can be used call in the constitution of compliant washing products to the invention are in particular the liberating agents chlorine, such as chlorinated trisodium phosphates, alkali metal hypochlorites, (poly) acids chlorocyanurics and their salts, dichlorodimethylhydantoin.

Advantageously, when it is present, the chlorine-releasing agent will be used in the form trichloroisocyanuric acid (ATCC) and / or dichloroisocyanurates sodium (DCC-Na) or potassium (DCC-K), hydrated or not.

However, one can also appeal, by particularly in products intended for washing clothes, to peroxygen bleaches and in particular to perborates, percarbonates, persilicates, persulfates or perphosphates of alkali metals, and peculiar to sodium perborate.

The alkaline agent may, among other things, be chosen in the group comprising sodium hydroxide, the borates, carbonates and meta- or disilicates of alkali metals, and in particular be made of carbonate and / or sodium metasilicate, the latter product having further protective action against metals and other hard surfaces (enamels, fine porcelain patterns).

The thickening agent may, purely indicative, consist of a colloidogenic mineral clay, in particular of the smectite, montmorillonite, bentonite type, attapulgite, hectorite or saponite.

The structuring agent may, in particular, be chosen, as recommended in patent EP 215 637, from sugars, hydrogenated sugars and any mixtures of these 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 hydrogenation products of these.

The structuring agents may in particular be consisting of or containing, at least in part, sorbitol and in particular be in the form of hydrogenated products obtained by hydrogenation of starch hydrolysates DE variables.

• l'agent anti-redéposition pourra être constitué de carboxyméthylcellulose (CMC),
• l'agent de charge pourra être constitué de sulfate de sodium,
• les enzymes pourront être choisies dans le groupe comprenant les enzymes amylolytiques, cellulolytiques, lipolytiques et protéolytiques,
• l'agent antimousse pourra être de type siliconé ou de type ester d'acide phosphorique ou phosphonique et être choisi, en particulier, parmi les esters alkyliques d'acides phosphoniques tels que décrits au niveau des brevets FR 2 608 168 et FR 2 620 727 susmentionnés.

Also for information only:

• the anti-redeposition agent may consist of carboxymethylcellulose (CMC),
• the bulking agent may consist of sodium sulfate,
• the enzymes may be chosen from the group comprising amylolytic, cellulolytic, lipolytic and proteolytic enzymes,
• the antifoaming agent may be of the silicone type or of the phosphoric or phosphonic acid ester type and may be chosen, in particular, from the alkyl esters of phosphonic acids as described in patents FR 2 608 168 and FR 2 620 727 mentioned above.

Washing products according to the invention, useful especially for washing dishes done "at by hand "or in industrial or domestic machines, preferably present in solid form, in particular in the form of free flowing particles such as granules or powders. They can however also present themselves in more agglomerated aspects (compact powders, lozenges) or in the form of liquids, gels or pasta.

Preparation of washing products according to the invention does not impose the implementation of any process and / or equipment other than those commonly used by skilled in the art and may, for example, call upon conventional drying techniques for aqueous suspensions by atomization and / or conventional techniques granulation.

The use of at least one polysaccharide oxidized in the washing products according to the invention and its possible presence with a zeolite, can be operated in a variety of ways, in the form of powders, liquids or powder / liquid mixtures, in one or more steps, each of said stages taking place in the presence or not of all or part of the other constituents of said products.

We could, for example, bring said polysaccharide oxidized to a washing "pre-composition" occurring already in powder form and containing the majority, or all of the other components of the product final.

Similarly, it will be possible, as an indication, to have a composition of matter intended for the preparation of washing products according to the invention, said composition already associating said polysaccharide oxidized to at least one of the other constituents of the product final, including any zeolites and / or phosphates.

Such a composition of matter may in particular appear as free flowing particles obtained, for example, by granulation of a mixture associating, in the presence or not of third constituents, zeolite (s) and oxidized polysaccharide (s) and this, with a weight ratio zeolite (s) / oxidized polysaccharide (s) generally less than 1/1. The granulation can be performed for example on an AEROMATIC granulator or a plate granulator.

Washing products obtained in forms "non-solid" such as liquids, gels or pastes will have generally a dry matter content of around 15 to about 80%, in particular 30 to 50% and may, as an example, be obtained by increasing, by a any means and in particular by simple dissolution or suspended in water or other liquid, moisture of detergents according to the invention beforehand prepared in the form of powders or granules.

They may also, in other cases, present a significantly different formula from that used for powders or granules, in particular with regard to the content of surfactant adjuvants.

The invention can be understood even better. using the examples which follow and which show some particularly advantageous embodiments products according to the invention whose use must not not be considered strictly limited to the areas more particular of the washing of the crockery and the linen but, on the contrary, to be understood as applying to all types of washing operations, especially those applied to objects or substrates (floors, walls, large volumes, etc.) which should be eliminated dirt of the same nature as that described below.

To demonstrate the effectiveness of the detergents in accordance with the invention for washing dishes, the Applicant Company carried out comparative tests using, on the one hand, a product of the prior art, designated by the letter T and whose constitution appears in Table I below and, on the other hand, three washing products according to the invention, designated respectively by the letters A, B and C and whose respective levels of oxidized polysaccharide (s) (s) and possibly in phosphates are listed in Table II with regard to the 40% of phosphates (Na tripolyphosphate) contained in the product T. Constituents Trademark or formula Producing company % in weight Ethoxylated fatty alcohol PLURAFAC LF 403 BASF 2 Na metasilicate SiO ₂ Na ₂ O anhydrous PROLABO 40 Na carbonate Na ₂ CO ₃ PANREAC 6 Na sulfate Na ₂ SO ₄ PANREAC 10 Na dichloroisocyanurate Cl ₂ O ₃ N ₃ Na ALDRICH 2 Na tripolyphosphate Na ₅ P ₃ O ₁₀ BUDENHEIM 40 Constituents Composition (% by weight) T AT B VS Na tripolyphosphate 40 20 10 - Oxidized polysaccharide - 20 30 40

As part of these tests, the Applicant Company used as an oxidized polysaccharide contained in the detergents according to the invention, a product resulting from the oxidation of a starch hydrolyzate having a DE of about 37, said product having an index of acid I of about 8.6.

Said comparative tests consist of tests which have been carried out using a washing machine wash MIELE LUXE G 540 brand dishes with capacity of 12 place settings.

The machine is supplied with running water with a hardness of 22 ° TH. Water hardness checked after passage on resin is 4 ° TH. Resins are regenerated every six tries. Average water temperature supply temperature is 20-21 ° C.

The standard cover used corresponds to that specified in standard NF 73175. For reasons of space, the twelve teaspoons and the large round dish did not been used.

The parts are arranged in the machine according to the manufacturer's information, unchangeable for all attempts.

A washing cycle includes: a 4 min prewash, a wash at 55 ° C for 27 min, an intermediate rinse of 2 min, rinsing at 70 ° C for 22 min and drying for 16 min. The total duration of the washing cycle is approximately 1 hour 20 minutes min.

40 g of detergent is weighed exactly in all cases. Rinse aid and regenerating salt are SUN brand.

The soiling is that recommended in the NF C 73176 standard, namely egg, margarine, tea, milk reconstituted from powder, semolina and spinach.

• oeuf, semoule et épinards sur les asiettes,
• thé sur les tasses,
• lait sur les verres,
• margarine sur le plat ovale,
• oeuf et épinards sur les fourchettes,
• semoule sur les cuillères à soupe,
• les soucoupes, couteaux, cuillères à dessert, le plat creux rond, le bol, les cuillères et fourchettes de service et les cuillères à sauce ne sont pas salis.

After having undergone the preparations described in standard NF C 73176, this soiling is deposited on cutlery with the following distribution:

• egg, semolina and spinach on the plates,
• tea on the cups,
• milk on the glasses,
• oval margarine,
• egg and spinach on the forks,
• semolina on the tablespoons,
• saucers, knives, dessert spoons, round hollow dish, bowl, serving spoons and forks and sauce spoons are not soiled.

Let the dirt dry for 30 minutes placed on the cutlery before loading them in the washing machine. Dirty dishes then remain 15 to 20 hours in the machine with the door closed.

• Catégorie N°1: pièces propres ne présentant aucune tache; correspond à 2 points.
• Catégorie N°2: pièces comportant des défauts mineurs: portant de une à quatre taches chacune, l'ensemble de ces taches ayant une surface totale inférieure ou égale à 4 mm²; correspond à 1 point.
• Catégorie N°3: pièces inacceptables portant plus de quatre taches ou des taches ayant une surface totale supérieure à 4 mm²; correspond à 0 point.

After washing and drying in the washing machine, each piece is carefully removed from the machine and examined carefully to be classified into one of the following three categories:

• Category N ° 1: clean parts showing no stains; corresponds to 2 points.
• Category N ° 2: parts with minor defects: bearing from one to four stains each, all of these stains having a total surface less than or equal to 4 mm ² ; corresponds to 1 point.
• Category N ° 3: unacceptable parts with more than four stains or stains with a total surface greater than 4 mm ² ; corresponds to 0 point.

Total points obtained divided by two the total number of pieces gives a defining percentage washing efficiency.

1. seules sont prises en compte les salissures restantes,

2. salissures restantes, plus gouttes d'eau séchées, plus voiles.

For each test, we adopted two methods of evaluation:

1. only the remaining soils are taken into account,

2. remaining dirt, more dried water drops, more veils.

Each product is subjected to three tests.

EXAMPLE 1

A first series of tests was carried out with the product T according to the prior art, containing 40% by weight of phosphates. The results obtained for product T in the context of washing tests carried out according to standard NF C 73176, are collated in table III below.

It follows overall from Table III that the dishes washed with product T have a very clean appearance and shiny with, on the whole, little residue of dirt and few traces of dried water. There are very light spinach and semolina kernels with little trace of dried water on the plates, little residue of dirt and traces of dried water on the cutlery and the glasses as well as a slight presence of traces of tea on the cups.

EXAMPLE 2

Il résulte globalement du tableau IV que la vaisselle lavée avec le produit A selon l'invention a un aspect général très brillant et très net avec des restes de salissures et de gouttelettes d'eau séchées peu importantes.During this first series of tests, the washing product A according to the invention was tested under the same conditions as product T according to the prior art, the latter having given the results given in table III. The results obtained for product A are shown in Table IV below.

It follows overall from Table IV that the dishes washed with product A according to the invention has a very shiny and very clean general appearance with little residue of dirt and dried water droplets.

We note the presence of some slight remains spinach and semolina grains and few traces of water dried on some plates, light soiling and traces of dried water on some cutlery.

The cups are clean except for a few slight traces of tea coloring. The glasses are very clean with traces of dried water and remnants of minor soiling.

The comparison of the results taken respectively in Tables III and IV shows that a washing product according to the invention, namely typically containing at least one oxidized polysaccharide, appears globally as effective as a product according to the prior art and despite the substitution of a substantial fraction (in this case 50%) of the phosphates contained in said product according to the prior art.

This substitution jointly allows detergents according to the invention to constitute means ensuring the limitation of nuisances caused by phosphates vis-à-vis the environment.

EXAMPLE 3

The Applicant Company has, on the occasion of a second series of tests carried out according to standard NF C 73176, compared the effectiveness of washing product B according to the invention to that of product T according to the prior art (implementation works with 38 g of detergent, the duration total washing cycle being approximately 1 h 10 min).

The results obtained for the washing products T and B are shown respectively in tables V and VI below.

We note, in this series of essays, that after washing dishes with product T according to art previous, there is presence of traces of dried water and leftover dirt on cutlery and cups, as well as leftover spinach, semolina grains and traces of dried water on some plates.

In addition, traces of soiling and fairly marked traces of dried water on forks and knives, more or less important tea colorings on several cups as well as leftover spinach and slight traces of dried water on the glasses.

However, dishes washed with product B according to the invention has a clean and shiny appearance with relatively little residue of dirt and traces of water dried. We note the presence of some remains of dirt and traces of dried water on some plates, slight remains of spinach and semolina grains as well only a few traces of dried water on the forks.

In particular, there is very little dirt and traces of water on the cups, which are very crisp and free from traces of tea coloring as well very few traces of dirt and dried water on the glasses.

These results confirm the interest of the implementation characteristic work of at least one oxidized polysaccharide within the detergents according to the invention, which prove to be as effective, or even more effective for certain aspects, that the prior art products and by jointly reducing very significantly (in this case, 75% reduction) quantities of phosphates likely to reach the environment.

EXAMPLE 4

During this second series of tests, the product of washing C according to the invention was tested under the same conditions that the product T according to the prior art, the latter having given the results given in table V.

The results obtained for product C are collated in Table VII below.

Dishes washed with product C according to the invention has a very clear and very bright general appearance, showing very slight traces of dirt and Few dried water droplets. We observe only light remains of spinach and semolina and some traces of dried water on some plates. The cutlery is generally clean with slight traces of dirt and dried water spots for some people.

In addition, the cups are very sharp, without coloring of tea or dirt or traces of dried water and clean glasses with a number only limited soiling and traces of dried water.

These results confirm the interest of washing according to the invention with regard to washing dishes and, in particular glassware.

The washing products according to the invention, by the characteristic presence of at least one polysaccharide oxidized, in particular from an oxidized starch hydrolyzate, in their composition, show washing performance quite remarkable, and this while allowing significantly reduce the need for implementation concomitant with phosphates and / or other likely additives to harm the environment.

All the more surprising and unexpected and as follows from example 4, the presence of at least an oxidized polysaccharide makes it possible to completely overcome of such an implementation, in particular of phosphates and this, including in detergents according to the invention, for contents also substantially zero in zeolite (s).

• d'une part, un produit de lavage selon l'art antérieur désigné par la lettre T₁ dont la constitution apparaít au niveau du tableau VIII ci-après. Constituants Marque de fabrique ou formule Société productrice % en poids Antimousse UKANIL 2136 ICI 0,2 Dodécylbenzène sulfonate FLUKA 6 Alcool gras éthoxylé KC 7/L Alcool cétostéarylique éthoxylé EMPILAN KM 11 MARCHON 5 Sulfate de Na Na₂ SO₄ PANREAC 21 Métasilicate de Na SiO₂Na₂O anhydre PROLABO 3 Carbonate de Na Na₂ CO₃ PANREAC 5 Perborate de Na Na BO₃ 4H₂O FLUKA 18 Tétraacétyléthylène diamine LEVER 2 Carboxyméthyl cellulose BLANOSE 7M65 AQUALON 1 Zéolithe A Na₂O Al₂O₃ 2SiO₂ x H₂O (x= 4 à 5) MONTEDISON 25 Polyacrylate de Na SOKALAN C 245 BASF 4 Enzyme ESPERASE NOVO 0,6 Eau qsp 100
• et, d'autre part, un produit de lavage selon l'invention désigné par la lettre P, dont les taux respectifs en zéolithe(s), en polysaccharide(s) oxydé(s) et en polyacrylates de sodium (PNa) sont repris au niveau du tableau IX ci-après. Constituants Composition (% en poids) Produit de lavage T₁ P Zéolithe A 25 - Polyacrylates 4 2 Polysaccharide oxydé - 30

To demonstrate the good effectiveness of the detergents in accordance with the invention in the case of washing laundry, comparative tests were carried out using

• on the one hand, a washing product according to the prior art designated by the letter T ₁ , the constitution of which appears in table VIII below. Constituents Trademark or formula Producing company % in weight Defoamer UKANIL 2136 HERE 0.2 Dodecylbenzene sulfonate FLUKA 6 Ethoxylated fatty alcohol KC 7 / L Ethoxylated cetostearyl alcohol EMPILAN KM 11 MARCHON 5 Na sulfate Na ₂ SO ₄ PANREAC 21 Na metasilicate SiO ₂ Na ₂ O anhydrous PROLABO 3 Na carbonate Na ₂ CO ₃ PANREAC 5 Na perborate Na BO ₃ 4H ₂ O FLUKA 18 Tetraacetylethylene diamine RISING 2 Carboxymethyl cellulose BLANOSE 7M65 AQUALON 1 Zeolite A Na ₂ O Al ₂ O _{3 2} SiO ₂ x H ₂ O (x = 4 to 5) MONTEDISON 25 Na polyacrylate SOKALAN C 245 BASF 4 Enzyme ESPERASE NOVO 0.6 Water qs 100
• and, on the other hand, a washing product according to the invention designated by the letter P, the respective levels of zeolite (s), oxidized polysaccharide (s) and sodium polyacrylates (PNa) are included at the level of table IX below. Constituents Composition (% by weight) Washing product T ₁ P Zeolite A 25 - Polyacrylates 4 2 Oxidized polysaccharide - 30

As part of these tests, as an oxidized polysaccharide contained in the product of washing P according to the invention, an oxidation product of a starch hydrolyzate having an ED of about 37, said oxidation product with an acid number I of 8.6 approximately and having, moreover, been "stabilized" by Raney nickel catalytic hydrogenation.

Said comparative tests consist of washing tests which were carried out using a washing machine brand VEDETTE 8596 CHOICE SYSTEM top loading.

The tests are carried out at a temperature of 60 ° C. with a temperature rise of 21 minutes, then a stop at 60 ° C for 22 minutes. The complete cycle lasts 90 minutes. The volume of washing water is 11 liters.

The water hardness is 30 ° TH.

The washing load consists of 2.2 kg of pieces of white fabric (cotton) whose dimensions are 55 cm x 70 cm.

At each wash, a charge of 2.2 kg pieces of white fabric, a set of "fabrics soiled "of different natures and which contain soiling predetermined and pre-deposited on these fabrics.

• 2 bandes de coton de marque EMPA 103 constituées de 7 morceaux cousus entre eux, à savoir:
  • un morceau de coton blanc (de type EMPA 221),
  • 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,
• 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 EMPA 103 brand cotton strips made up of 7 pieces sewn together, namely:
  • a piece of white cotton (type EMPA 221),
  • 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,
• 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 brand cocoa (ref. WFK 20F),
• 2 strips of white polyester / cotton fabric (65/35) from EMPA brand (ref .: EMPA 213).

The dose of detergent is 8 g / l of water.

To assess the quality of the washing, we have share measured removal of dirt and stains and on the other hand determined the effect of the washes on the degree of whiteness.

To assess the removal of dirt and spots, we proceeded by photometry (measurements of the amount of light reflected from the fabric); so we can calculate the percentages of soil removal. We uses a device to measure the reflection of the light, marketed under the brand ACS 1400 SPECTRO.

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 in which:

A =

reflectance of the blank control sample,

B =

reflectance of the soiled control sample,

C =

reflectance of the soiled sample after test.

The reflectances are determined using the blue trichromatic component.

The number of measurements made is 6 per soiling and by formulation.

Regarding the degree of whiteness, we measure the effect of washing (conservation, increase or decrease of the initial whiteness) on two coupons white cotton EMPA 221 and on two coupons polyester / cotton white unsoiled EMPA 213, which are incorporated into the washing bath.

• 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. 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.

The results obtained respectively with the washing product T according to the prior art and the washing product P according to the invention are shown in table X below. Product T ₁ according to the prior art Product P according to the invention FABRIC: COTTON EMPA 103 degree of white (variation in%) - 0.18 + 0.03 blood (% elimination) 58.7 55.5 ecru (% elimination) 8.1 13.4 red wine (% elimination) 48.4 47.9 cocoa (% elimination) 35.1 32.9 blood - milk - carbon black (% elimination) 43.0 38.8 sulfur black (% elimination) 7.5 7.7 FABRIC: POLYESTER / COTTON 65/35 degree of white (variation in%) - 1.09 - 1.02 cocoa (% elimination) 90.1 84.4 tea (% elimination) 89.4 91.4

These results represent the average of 6 measures.

They are expressed, for each type of soiling and each type of tissue, in% of removal of said tissue soiling.

In addition, the results of tests carried out on "white" fabrics, ie not soiled, express the variation (+ = increase, - = decrease), expressed in%, of degree of whiteness of the fabric following the washing operation.

Overall, it appears from Table X that the presence characteristic of at least one oxidized polysaccharide, in particular of the oxidized starch hydrolyzate type, within detergents according to the invention allows these last to meet the criteria generally required in washing terms.

If the washing product P according to the invention proves, for certain parameters, slightly less efficient than the control product T ₁ , which has a relatively high rate of zeolites and a higher rate of polyacrylates, the fact remains that the washing product according to the invention has an efficiency as good, or even improved for certain other parameters such as the degree of whiteness and the elimination of certain stains of an oxidizable nature.

These results confirm, in particular, the possibility to obtain, by the characteristic implementation according to the invention of at least one oxidized polysaccharide, detergents which are able to meet the requirements of the technique in terms of washing efficiency, while exhibiting substantially zero rates at the both in phosphates and zeolites and without using concomitant overdose with weak constituents biodegradable such as polyacrylates.

Claims (12)

1. A washing product, more particularly a dishwashing product, characterized in that it contains :

   less than 5% by weight, preferably less than 1% by weight and, more preferably, 0% by weight zeolithe(s),

   less than 40% by weight, preferably less than 20% by weight and, more preferably, 0% by weight phosphate and

   5 to 75% by weight and preferably 15 to 50% by weight of at least one oxidized polysaccharide selected from the group consisting of :

   the oxidation products of di-, tri- and oligosaccharides having a terminal function of the aldonic type,

   oxidation products of starch, cellulose and hemicellulose hydrolyzates containing a terminal function of the aldonic type,

   any mixtures containing at least two of any of the above-mentioned oxidation products, said oxidized polysaccharide being obtained from a product in which only the terminal function (of the aldehyde type before oxidation) among its potentially oxidizable functions is substantially oxidized.
2. A washing product as claimed in claim 1, characterized in that it contains less than 1% and preferably 0% phosphates.
3. A washing product as claimed in claim 1 or 2, characterized in that the oxidized polysaccharide is an oxidation product of a starch hydrolyzate obtained by the acidic and/or enzymatic route and having a DE of about 5 to about 90 and preferably 20 to 65.
4. A washing product as claimed in claim 3, characterized in that the oxidized polysaccharide has an acid index I of about 1 to about 20 and preferably 5 to 14.
5. A washing product as claimed in any of claims 1 to 4, characterized in that the oxidized polysaccharide contains less than 0.6%, preferably less than 0.1% and, more preferably, less than 0.05% by weight reducing sugars.
6. A washing product as claimed in claim 5, characterized in that the oxidized polysaccharide has been subjected after oxidation to a catalytic hydrogenation treatment in which preferably at least one catalyst selected from the group consisting of nickel, platinum, palladium, cobalt, molybdenum and combinations of these metals, more particularly Raney nickel, is used continuously or discontinuously.
7. A washing product as claimed in any of claims 1 to 6, characterized in that it contains one or more constituents selected from the group consisting of detergents, sequestrants other than zeolites and phosphates, surfactants, bleaches, foam inhibitors, redeposition inhibitors, alkaline agents, structuring agents, flow aids, thickeners, corrosion inhibitors, abrasives, solubilizers, fillers, enzymes, enzyme stabilizers, bactericides, opacifiers, optical brighteners, colourants and fragrances.
8. A washing product as claimed in claim 7, characterized in that it contains at least one bleaching agent, preferably a chlorine donor and, more preferably, at least one agent from the group consisting of trichloroisocyanuric acid, sodium dichloroisocyanurate and potassium dichloroisocyanurate.
9. A composition for the production of the washing product claimed in any of claims 1 to 8, characterized in that it contains at least one oxidized polysaccharide selected from the group consisting of :

   the oxidation products of di-, tri- and oligosaccharides having a terminal function of the aldonic type,

   oxidation products of starch, cellulose and hemicellulose hydrolyzates containing a terminal function of the aldonic type,

   any mixtures containing at least two of any of the above-mentioned oxidation products, said oxidized polysaccharide being obtained from a product in which only the terminal function (of the aldehyde type before oxidation) among its potentially oxidizable functions is substantially oxidized.
10. A composition as claimed in claim 9, characterized in that it contains at least one zeolite, the ratio by weight of zeolite to oxidized polysaccharide being at most 1:1 and the composition being in the form of free-flowing particles.
11. The use for dishwashing either by hand or in an institutional or domestic machine, of an oxidized polysaccharide selected from the group consisting of :

    the oxidation products of di-, tri- and oligosaccharides having a terminal function of the aldonic type,

    oxidation products of starch, cellulose and hemicellulose hydrolyzates containing a terminal function of the aldonic type,

    any mixtures containing at least two of any of the above-mentioned oxidation products, said oxidized polysaccharide being obtained from a product in which only the terminal function (of the aldehyde type before oxidation) among its potentially oxidizable functions is substantially oxidized.
12. The use of the washing product claimed in any of claims 1 to 8 for the washing of objects and/or substrates other than dishes, more particularly for washing linen.