FR2675514A1 - WASHING PRODUCT WITH REDUCED OR ZERO CONTENT. - 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

1

  WASHING PRODUCT WITH REDUCED OR ZERO CONTENT

  The subject of the present invention is a washing product, in particular for washing dishes, with reduced or no zeolite content and essentially containing

a chlorine releasing agent.

  It also covers products of the kind in question which are also reduced or

phosphates.

  Phosphates have long played a major role in detergents, particularly as cation sequestrants which form water-insoluble salts, especially calcium and magnesium ions; the excellent performance they allow

  to reach resident in their particular structure.

  But one of the acute problems facing the detergent industry is the highly polluting nature of the phosphates. Indeed, their presence in wastewater causes the well-known phenomenon of eutrophication; and for this reason the use of phosphates in washing products (crockery, linen or other) must meet constraints, in particular

  ecological, more and more severe.

  This ecological aspect is all the more marked as

  commonly used strong detergents and, in particular,

  products used in communities, contain high levels of phosphates

exceed 50%.

  Numerous attempts have therefore been made to remove all or part of the phosphates in the detergents, including those for washing dishes and similar objects (glassware, porcelain,

  cutlery, pots, pans, etc.).

  In particular, it has been proposed to use, as a total or partial replacement agent for phosphates, nitrilotriacetic acid (NTA) and / or its salts, in particular sodium nitrilotriacetate, as

  recommended in patents FR 2 208 975 and EP 82 564.

  However, in addition to their imperfect biodegradability, these products are believed to bind heavy metals, which

  could go into the drinking water.

  As a result, these products are

  in some countries More generally, it is often made mandatory to limit their introduction rate to 5%

in washing products.

  It was also proposed, as part of the search for solutions to limit the use of

  phosphates, to use polycarboxylic polymers

  particular mixtures based on defined mixtures of mono and dicarboxylic monoolefinic and non-

ionic properties of said acids.

  In particular, it has been recommended, as described in patents EP 267 374 and FR 2 613 378, to use derivatives of acrylic and / or methacrylic acid as well as derivatives of maleic and / or itaconic acid, and in particular to copolymers of maleic anhydride and

acrylic acid.

  However, these products are ecologically

  acceptable because of their very low biodegradability.

  It has also been proposed to use, as a total or partial replacement of phosphates, zeolites of natural or synthetic origin, as described

in EP 249,163.

  However, if zeolites contribute by their cation exchange capacity, and especially calcium and magnesium, the elimination of said cations, their substitution of phosphates does not achieve a

  degree of washing satisfying the requirements of the practice.

  In order to improve the quality of the wash of zeolite-based washers containing little or no phosphates, it has been proposed to combine said zeolites with various other agents such as in particular nitrilotriacetic acid or, as envisaged in the patent. EP 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 major disadvantage of not being solubilizable in washing baths and thus remain at least partially deposited

  on certain objects, including glassware-

  on which they remain viewable after the

  machine washing and evaporation of the wash water.

  Thus, the incorporation of zeolite (s) at high doses is generally not recommended, in practice, as part of the washing of dishes,

particular of glassware.

  However, the incorporation of zeolite (s) at reduced levels, namely at doses of less than about 5% by weight in the detergents, may be beneficial in some cases, according to the teachings of patents EP 30 986 and CH 673 033 describing the use of these products respectively as abrasives of

  dry soils and anti-corrosion / anti-agglomeration agents

  rant. However, it follows from the foregoing that there was no way until now to allow washing products of this kind, to present all the qualities required for the intended applications and in particular: a good efficiency of washing and this, for various types of soils and articles to be treated,

  good compatibility with the protection requirements

  environmental protection and in particular the possibility of

  significantly reduce the simultaneous supply of phos-

  phates and / or other additives

  unacceptable, or even free from it.

  And the Applicant Company had the merit of finding

  that such a means could be constituted by the implementation, within the washing products of the kind in

  question, at least one oxidized polysaccharide.

  Accordingly, the invention relates to 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 5 to 75% by weight and, preferably, from 15 to 50% by weight.

  weight of at least one oxidized polysaccharide.

  In addition, as already pointed out, the

  presence of oxidized polysaccharide in the detergent

  according to the invention makes it possible, in a remarkable way, to

  phosphates and, according to another advantageous embodiment of the invention, said product has a content of less than 1% and,

  preferably, substantially zero in phosphates.

  In the context of the present invention, the term "dishes" is understood more particularly to mean all

  objects used, whether in a domestic setting or not (collec-

  hospitals, schools, various industries, etc.), for the presentation and / or absorption of food and / or drinks and in particular, without this list being exhaustive, plates, dishes, cutlery, glasses,

  cups, saucers, bottles, pans and other recipes

  food items, objects similar to those

  mentioned but not necessarily used to be in contact with food (cutlery, glassware, porcelain, pots, flasks, vases, etc.) and objects intended to contain, at least temporarily,

  non-food substances of all kinds and necessary

  to be, at a given moment, free of the said

  substances such as laboratory glassware

  (flasks, test tubes, test tubes, pipettes,

balloons, etc.).

  According to a preferred embodiment of the

  washing device according to the invention, the oxidized polysaccharide is chosen from the group comprising:

  the oxidation products of di-, tri- and oligosaccharide-

  possessing a terminal function of the aldonic type, the oxidation products of hydrolysates of starch, of cellulose and of hemicellulose having an aldonic end function,

  any mixtures containing at least two

  conques of the aforesaid oxidation products.

  The oxidized polysaccharide may especially be

  by the product resulting from the oxidation of a starch hydrolyzate obtained by the acidic and / or enzymatic route, said

  hydrolyzate usually having a DE (Dextrose-Equiva-

  slow) from about 5 to about 90 and containing varying proportions of dimers, trimers, oligomers and glucose polymers. It can also be constituted by the product resulting from the oxidation of a hemicellulose hydrolyzate such as a D- galacto-D-mannan, a D-gluco-D-mannan, a

  L-arabino-D-xylan or D-xylo-arabinan.

  In washing products that comply with the

  the above-mentioned oxidation products may be present, in whole or in part, in the form of acid salts,

  especially in the form of alkali metal salts.

  Advantageously, the oxidized polysaccharides may be used in the context of the present invention

  are those obtained from products and especially

  tris, oligosaccharides, starch hydrolysates,

  of cellulose and hemicellulose, of which only one

  seems potentially oxidizable functions that they comprise, the terminal function (of the aldehyde type before oxidation) is substantially oxidized and this, in one

aldonic type function.

  Such oxidized polysaccharides may, in particular

  if one is looking for a truly

  reliable "at the end of the aldonic type terminal function, be obtained according to the catalytic oxidation process described by the applicant company in its

EP 232,220.

  They may in particular consist of an oxidation product of a starch hydrolyzate having an ED of from about 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 for g of oxidized polysaccharide and given by the formula: DE x 45 I = 100 x 180 100 + DE x 218 DE In the context of the present invention, use may in particular be made of polysaccharides which have an acid number of from about 5 to about 14 and are obtained by oxidation of starch hydrolysates having an DE of from about 20 to about 65. In another advantageous embodiment, the oxidized polysaccharide is an oxidized product having, in particular as a result of its reducing sugar content, a good stability, in particular with regard to its coloration, when the said oxidized product is used (when the washing product in accordance with the invention is prepared or used at l invention), at any time and for example during

  atomization operations, in an environment in which

  both an alkaline pH and / or a high temperature, environment suitable for dyeing (yellowing more or less

  pronounced) any composition containing it. As such, the Applicant Company has designed and developed, as new products, polysaccharides

  oxidized "stabilized" wrinkles with low levels, generally less than about 0.6%, preferably

  less than 0.1% and even more preferentially

  0.05% by weight of reducing sugars.

  In particular, the Applicant Company has found that the hydrogenation techniques applied to oxidized polysaccharides, in particular oxidized starch hydrolysates, made it possible to obtain such products,

  in particular oxidised products with a practically

  There is no reduction in reducing sugars, "stabilized" as to possible yellowing in the presence of an environment (alkaline pH, high temperature) favoring this type of phenomenon. By hydrogenation techniques, is meant in particular catalytic hydrogenation techniques using, continuously or discontinuously, at least one catalyst selected 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 using Raney nickel as a catalyst, whether or not fixed on an inert support, will be particularly used as catalyst.

  presence or absence of an additional source of hydrogen.

  Other hydrogenation techniques may be employed, in the absence of a hydrogenation catalyst, using sources of hydrogen other than hydrogen gas, for example metal borohydrides.

  alkali, in particular sodium borohydride.

  Oxidized polysaccharides, in particular of oxidized starch hydrolyzate type, "stabilized" following the implementation of these hydrogenation techniques, in particular those having an DE of between 5 and 90, an acid number I between 1 and 20 and "stabilized" by catalytic hydrogenation, also give the compositions and washing products in which they are intro-ducts, performance generally comparable to those observed with the same products oxidized but not "stabilized ", or even improved performance for

some parameters.

  It is remarkable to note that the presence of

  of at least one oxidized polysaccharide in the washing products according to the invention, allows these

  to meet the requirements of industrial practice.

  particularly in terms of efficiency and protection of the environment, both in the washing of dishes and in other articles, especially laundry, and for associated 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 of the nitriloacetic acid, polyacrylic acid or

their respective salts.

  As will be exemplified later, it should be noted, inter alia, the remarkable effectiveness of the washing products according to the invention as regards

  the elimination of fouling of oxidizable or protein nature

  Picnic. It will be noted, in particular, that said products, unlike certain formulations of the prior art, do not cause any substantial deactivation of the bleaching agents, especially chlorine-releasing agents, commonly used in laundry products.

  intended for washing dishes.

  Without wishing to be bound by any theory, the Applicant Company attributes, at least in part, the excellence of the performance of the washing products according to the invention, to the stabilizing action that the oxidized polysaccharides would play vis-à-vis said agents. bleaching and a certain complexing / dispersing action of the oxidized polysaccharides in the detergent baths. In the context of the present invention, the term "zeolite" includes all ion exchange materials

  aluminosilicates, whether of a crys-

  tall or amorphous, of natural or synthetic origin, as described, for example, in FR Patents

  2,620,727, CH 673,033, EP 30,986 and EP 249,163 mentioned above.

  Such products are, by way of examples, commercially available under the designations

  "zeolite A", "zeolite B", "zeolite X" or "zeolite HS".

  It will be possible to use a silicone

  crystalline sodium aluminate of the "zeolite A" type, in

  association or not with another zeolite.

  It should be emphasized that, as stated above, the presence of zeolite (s) at reduced rates in the washing products according to the invention

  is considered, it is in no way obligatory.

  In practice, the washing product conforms to

  invention, which constitutes a new industrial product

  veal, also includes one or more other

  chosen, without this list being limited.

  in the group consisting of detergents, sequestering agents other than zeolites and phosphates, surfactants,

  bleaching agents, anti-foam agents, antirede

  alkaline agents, structuring agents, fluxing agents, thickeners, anticorrosive agents, abrasives, solubilizers, fillers, enzymes and enzyme stabilizers, bactericides, opacifying agents, optical brighteners, coloring agents, perfumes, etc., for example those described in 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.

  The detergent and surfactant agents may, for example, be chosen from synthetic anionic products, such as the water-soluble alkali metal salts of organic sulphates and sulphonates comprising alkyl radicals of approximately 8 to 22 carbon atoms, for example sodium dodecylbenzene sulfonates

or potassium.

  They may also be selected from

  nonionic products, such as, in particular, alkylpoly-

  glycosides or ethoxylated fatty alcohols.

  The sequestering agents may, for example,

  ples, be chosen from mono or polyphosphates,

  especially ortho-, pyro-, tripoly and hexametaphos-

  phates, and more particularly sodium tripolyphosphates (TPPNa), phosphonic acids and / or their respective salts, citric acid, polyacrylic acid (AP),

  nitrilotriacetic acid (NTA) and / or their respective salts

  including their sodium salts, EDTA, etc.

  However, as already mentioned, the pre-

  characteristic of at least one oxidized polysaccharide, in particular "selectively" oxidized at its terminal function, in the washing products according to the invention, makes it possible, in a remarkable manner,

  said products to be effective for

  phosphates, NTA, AP (or their respective salts) generally lower than those commonly encountered on the market, or even for substantially zero

each of these compounds.

  Moreover, and this is another particular aspect

  Advantageously of the present invention, the use of at least one oxidized polysaccharide, in particular "selectively" oxidized at its terminal function, makes it possible to achieve washing efficiency (in particular dishes but also linen) in accordance with the requirements of practice and this even for rates substantially

  in both phosphates and zeolites.

  Bleaching agents that can be done

  appeal in the constitution of washing products con-

  Forms according to the invention are in particular the chlorine-releasing agents, such as chlorinated trisodium phosphates, alkali metal hypochlorites, (poly) acids.

  chlorocyanuric acids and their salts, dichlorodimethylhydrochloride

  Dantoine. Advantageously, when it is present, the chlorine-releasing agent will be used in the form of

  trichloroisocyanuric acid (ATCC) and / or dichloro-

  isocyanurates of sodium (DCC-Na) or potassium (DCC-K),

hydrated or not.

  However, it is also possible to use peroxygen bleaching agents and in particular perborates, percarbonates, persilicates, persulphates or perphosphates of alkali metals, especially in products intended for washing clothes, and

particularly sodium perborate.

  The alkaline agent may, among others, be selected from the group comprising sodium hydroxide, borates, carbonates and meta or disilicates of alkali metals, and in particular be composed of carbonate and / or sodium metasilicate, which last product having a protective action against metals and

  other hard surfaces (enamels, porcelain patterns).

  The thickening agent may, for information only, consist of a colloidogenic mineral clay, in particular of the smectite, montmorillonite, bentonite,

attapulgite, hectorite or saponite.

  The structuring agent may, in particular, be chosen, as recommended in patent EP 215 637, from

  sugars, hydrogenated sugars and mixtures

  conques 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 hydrogenated products

of these.

  The structuring agents may in particular consist of or contain, at least in part, sorbitol

  and in particular to be in the form of hydro-

  generated by hydrogenation of starch hydrolysates

Of variables.

  Also purely indicative: the anti-redeposition agent may consist of carboxymethylcellulose (CMC), the filler may consist of sodium sulfate, the enzymes may be selected from the group comprising amylolytic, cellulolytic, lipolytic enzymes and proteolytic agents, the antifoam agent may be of the silicone type or of the phosphoric or phosphonic acid ester type and may be chosen, in particular, from alkyl esters of phosphonic acids such as those described in US Pat.

  patents FR 2,608,168 and FR 2,620,727 mentioned above.

  The washing products according to the invention, useful in particular for the washing of dishes carried out "by hand" or in industrial or domestic machines, will preferably be in a solid form, in

  particular in the form of free-flowing particles

  However, they may also be in more agglomerated forms (compact powders, pellets) or in the form of liquids.

gels or pasta.

  The preparation of detergents according to the

  The invention does not require the use of any method and / or apparatus other than those commonly employed by those skilled in the art and may, for example, use the conventional techniques for drying aqueous suspensions by atomization and / or conventional granulation techniques. The use of at least one oxidized polysaccharide within the washing products according to the invention and its possible contact with a zeolite can be carried out according to very different conditions, in the form of powders, liquids or mixtures. powders / liquids, in one or more steps, each of said steps being done in the presence or absence of all or part of the

  other constituents of the said products.

  For example, it is possible to provide said polysac-

  charid oxidized to a "pre-composition" washing is presented

  both already in powder form and containing most or all of the other constituents of the final product. Similarly, it will be possible, as an indication, to have a composition of matter for the preparation of washing products according to the invention, said composition already combining said oxidized polysaccharide with at least one of the other constituents of the product.

  final, including any zeolites and / or phosphates.

  Such a composition of material may in particular be in the form of free-flowing particles obtained, for example, by granulation of a mixture associating, in the presence or absence of third constituents, zeolite (s) and oxidized polysaccharide (s) (s). ) and this, with a weight ratio zeolite (s) / polysaccharide (s) oxidized (s) generally less than 1/1 The granulation can be performed for example on a granulator type AEROMATIC

or a plate granulator.

  Washing products obtained in forms

  "non-solids" such as liquids, gels or pastes

  will generally have a solids content of from about 80% to about 30%, in particular from 30% to 50%, and may, by way of example, be obtained by increasing

  any means, such as by simple dissolution or suspension in water or other liquid,

  of washing products according to the invention previously prepared in the form of powders or granules. They may also, in other cases, present

  a formula substantially different from that used for powders or granulates, in particular as regards

  the content of surfactant adjuvants.

  The invention can be better understood from the following examples which show some particularly advantageous embodiments of the products according to the invention, the use of which should not be considered strictly limited to the more specific fields of the invention. washing dishes and linen but, on the contrary, be understood as applying to

  all types of washing operations, in particular those

  objects or substrates (floors, walls, containers of large volumes, etc.) which should be

  soils of the same nature as those described below.

  To demonstrate the effectiveness of the washing products according to the invention for washing dishes, the Applicant Company has carried out comparative tests using, firstly 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 detergents according to the invention, designated respectively by the letters A, B and C and whose respective levels of oxidized polysaccharide (s) ( s) and optionally in phosphates are shown in Table II with respect to the% of phosphates (Na tripolyphosphate) contained in the product T.

TABLE I

  Brand Name * Manufacture constituents or formula by weight ethoxylated fatty alcohol PLURAFAC LF 403 BASF o 2 Metasilicate of Na Si O 2 Na 2 O anhydrous PROLABO 40 Na carbonate Na 2 C 03 PANREAC 6 l Na 2 Sulfate 2 504 PANREAC 10 f Dichloroisocyanurate of Na C 12 03 N 3 Na ALDRICH 2 Tripolyphosphate of Na Na 5 P 3010 BUDENHEIM 40

TABLE II

  Constituents Composition (% by weight)

T A B C

Na 40 Tripolyphosphate 10 -

Oxidized polysaccharide 20 30 40

  As part of these tests, the Company requests

  As the oxidized polysaccharide contained in the detergents according to the invention, it has used a product resulting from the oxidation of a starch hydrolyzate having a DE of about 37, said product having a cleavage index.

acid I of about 8.6.

  Said comparative tests consist of washing tests which were carried out using a MIELE LUXE G 540 brand dish washing machine with a

capacity of 12 place settings.

  The machine is supplied with running water with a hardness of 220TH The hardness of the water checked after passing on resin is 40TH The resins are regenerated every six tests The average temperature of the supply water is 20-21 C. The typical cover used corresponds to that specified in standard NF 73175 For reasons of space, the twelve teaspoons and the large round dish do not have

been used. The parts are arranged in the machine according to the indications of the

  constructor, immutably for all

attempts.

  A wash cycle comprises: a 4 min prewash, a 27 min wash at 550 C, an intermediate rinse of 2 min, a rinse at 700 C of 22 min and a drying time of 16 min. The total duration of the wash cycle is about 1 hr 20 min. g of detergent are exactly weighed

  in all cases The rinsing product and the regenerated salt

are of SUN brand.

  Soils are those recommended in standard NF C 73176, namely egg, margarine, tea, milk reconstituted from powder, semolina

and spinach.

  After having undergone the preparations described in standard NF C 73176, these soils are deposited on cutlery with the following distribution: egg, semolina and spinach on the plates, tea on the cups, milk on the glasses, margarine on the oval dish, egg and spinach on the forks, semolina on tablespoons, saucers, knives, dessert spoons, the round hollow dish, the bowl, the spoons and forks of

  service and the sauce spoons are not soiled.

  It is allowed to dry for 30 minutes the stains deposited on the cutlery before loading them in the washing machine The dirty dishes then remain

  at 8 pm in the closed door machine.

  After washing and drying in the washing machine, each piece is carefully removed from the machine and examined carefully to be classified in one of three categories: _ Category No 1: clean parts with no

task; corresponds to 2 points.

  Category N 02: parts with minor defects: one to four spots each, all of which have a total area of less than

  equal to 4 mm 2; corresponds to 1 point.

  Category N 03: Unacceptable parts with more than four spots or spots with a total area

  superior to 4 mm 2; corresponds to O point.

  The total points obtained divided by twice the total number of coins gives a percentage defining

the effectiveness of the washing.

  At each test, we adopted two evaluation methods: 1 only the remaining dirt, 2 remaining stains, more dried water drops, more veils are taken into account.

  Each product is subjected to three trials.

* 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 the product T in the context of washing tests carried out according to the NF C standard.

  73176, are summarized in Table III below.

TABLE III

  Product T Product T Remaining soil Dirt + veils + traces water lerrial series Designation tableware Test 1 Test 2 Test 3 Test 1 Test 2 Test 3 127 pieces% efficiency% efficiency% efficiency% efficiency% efficiency% efficiency 12 plates 91,7 87, 5 87.5 91.7 87.5 87.5 12 soup plates 100 100 100 100 95.8 100 12 dessert plates 91.7 91.7 87.5 91.7 91.7 87.5 12 saucers 95.8 95.8 100 95.8 95.8 100 12 forks 87.5 83.3 79.2 87.5 83.3 75 12 knives 91.7 95.8 91.7 87.5 87.5 87 , 5 12 tablespoons 95.8 95.8 95.8 91.7 91.7 87.5 12 dessert spoons 95.8 95.8 95.8 95.8 91.7 95.8 12 glasses 83, 3 95.8 91.7 83.3 91.7 83.3 12 cups 100 87.5 100 95.8 87.5 100 1 oval dish) 1 round hollow dish) 1 bowl dsevc) 100 100 100 85.7 87 5 85.7 2 serving spoons 1 serving fork 1 serving spoon% efficiency wash per test 93.7 93.3 93.3 91.7 90.15 90.15% efficiency wash per assessment 93.4 90.7% efficiency total wash It is generally apparent from Table III that the dishes washed with the product T have a very clean and shiny appearance with, overall, little residue of dirt and few traces of water. Very light spices of spinach and semolina grains with very little dried water on the plates, few traces of soil and traces of water on the cutlery and glasses, and a slight the presence of traces of tea on the cups. EXAMPLE 2 During this first series of tests, the washing product A according to the invention was tested in the same

  the conditions of the product T according to the prior art, the latter giving the results shown in Table III The results obtained for the product A are shown in Table IV below.

TABLE IV

  Product A Remaining stains Dirt + sails + traces water series Series Designation Test 1 Test 2 Test 3 Test 1 Test 2 Test 3 127 parts% efficiency% efficiency% efficiency% efficiency% efficiency% efficiency 12 flat plates 95.8 87.5 91 , 7 95.8 87.5 91.7 12 soup plates 100 95.8 95.8 100 95.8 95.8 12 dessert plates 91.7 87.5 87.5 91.7 87.5 87.5 12 saucers 95.8 100 95.8 95.8 100 91.7 12 forks 87.5 91.7 87.5 87.5 91.7 87.5 12 knives 87.5 91.7 87.5 87 , 5 87.5 83.3 12 tablespoons 95.8 95.8 83.3 91.7 87.5 79.2 12 dessert spoons 95.8 91.7 95.8 91.7 91.7 95 , 8 12 glasses 83.3 83.3 95.8 83.3 83.3 91.7 12 cups 75 95.8 70.8 75 95.8 70.8 1 oval dish) 1 round hollow dish) i bowl 2 service spoons 92.9 100 100 92.9 85.7 85.7 2 serving spoons 1 serving fork) 1 serving spoon)% efficiency wash per test 90.9 92, 89 89 90.15 90, 55 87.4% efficiency wash by evaluation 91.1 89.4% efficiency lav The overall result of Table IV is that the dishes washed with the product A according to the invention have a very bright and very clean overall appearance with residues of 50%.

  Dirt and dried water droplets

  aunts. Some slight spinach and semolina residues are noticeable, and there are few traces of dried water on some plates, light stains and

  traces of water dried on some cutlery.

  The cups are sharp with the exception of a few slight traces of tea coloring. The glasses are very clean with traces of dried water and remnants of

small dirt.

  The comparison of the results shown in Tables III and IV respectively shows that a detergent

  according to the invention, namely containing in a characteristic manner

  at least one oxidized polysaccharide, proves to be

  as effective as a product according to the prior art, 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 makes it possible, in conjunction with the washing products according to the invention, to constitute means ensuring the limitation of the nuisances caused by the phosphates with respect to the environment. EXAMPLE 3 The Applicant Company, in a second series of tests carried out according to standard NF C 73176, compared the effectiveness of the washing product B according to the invention with that of the product T according to the prior art (carried out at a rate of 38 g of washing product, the total duration of the washing cycle being approximately 1 h 10 min). The results obtained for the washing products T and B are respectively given in Tables V

and VI below.

TABLE V

  Product T Remaining stains Dirt + veils + traces of water 2 nd series Dish design Test 1 Test 2 Test 3 Test 1 Test 2 Test 3 127 pieces% efficiency% efficiency% efficiency% efficiency% efficiency% efficiency 12 flat plates 79.2 66.7 79.2 75 66.7 75 12 soup plates 91.7 87.5 87.5 79.2 83.3 87.5 12 dessert plates 91.7 75 83.3 91.7 66.7 75 12 sub-plates cups 87.5 83.3 91.7 75 75 87.5 12 forks 70.8 75 75 62.5 58.3 70.8 12 knives 75 83.3 75 62.5 70.8 62.5 12 spoons soup 83.3 79.2 79.2 62.5 66.7 75 12 dessert spoons 87.5 91.7 83.3 70.8 83.3 79.2 12 glasses 83.3 79.2 83.3 75 75 75 12 cups 33.3 41.7 58.3 33.3 41.7 58.3 1 oval dish) 1 round dish) 1 bowl 92.9 85.7 92.9 85.7 78.6 78 , 6 2 serving spoons) 1 service range) 1 serving spoon% efficiency wash per test 79.1 76.8 80.3 69.7 69.3 74.8% efficiency wash per assessment 78.7 71.3 % total wash efficiency 75 (n (n

TABLE VI

  Product B Remaining soil Dirt + veils + traces water Designation tableware Test 1 Test 2 Test 3 Test 1 Test 2 Test 3 127 pieces% efficiency% efficiency% efficiency% efficiency% efficiency% efficiency 12 plates 91.7 91.7 91.7 91.7 91.7 87.5 12 soup plates 91.7 95.8 95.8 91.7 91.7 95.8 12 dessert plates 79.2 83.3 83.3 79.2 79.2 79 , 2 12 saucers 91.7 91.7 83.3 91.7 91.7 83.3 12 forks 62.5 79.2 70.8 62.5 75 66.7 12 knives 87.5 83.3 83.3 79.2 75 75 12 tablespoons 83.3 87.5 87.5 75 79.2 83.3 12 dessert spoons 87.5 91.7 91.7 79.2 87.5 87.5 12 glasses 95.8 83.3 83.3 87.5 83.3 79.2 12 cups 100 95.8 95.8 100 95.8 91.7 1 oval dish) 1 round hollow dish) 1 bollrsdsevc) 92, 9 85.7 100 85.7 71.4 85.7 2 serving spoons 1 serving fork) 1 serving spoon)% efficiency wash per test 87, 4 88.2 87.4 83.9 84.3 83, 1% efficiency wash by evaluation 87.7 83.7% efficiency total wash 85.7 N) o K) Cn ( It is found in this series of esais that after washing the dishes with the product T according to the prior art, there is presence of traces of dried water and remains of dirt on the cutlery and cups, and only spinach, semolina and traces

  dried water on some plates.

  In addition, there are traces of dirt and traces of dried water quite marked on forks and knives, tea coloring more or less important in several cups and the remains of spinach and spinach.

  slight traces of water on the glasses.

  On the other hand, dishes washed with product B

  according to the invention has a clean and bright appearance with relative

  very little residue of soiling and traces of water

  The presence of some remains of

  and dried traces of water on some plates, light spinach and semolina

  only some dried water marks on the forks.

  In particular, there is little soil and traces of water on the cups, which are very clean and free of traces of tea coloring and very few traces of dirt and water dried on

the glasses.

  These results confirm the interest of the characteristic implementation of at least one oxidized polysaccharide in the washing products according to the invention, which are as effective or even more efficient for certain aspects than the products of the art. previous and

  by allowing jointly to reduce very significantly

  (in this case, 75% reduction) the

  quantities of phosphates likely to reach the

ronment.

EXAMPLE 4

  During this second series of tests, the product of

  washing C according to the invention was tested in the same conditions

  the product T according to the prior art, the latter having given the results shown in Table V. The results obtained for the product C are

  summarized in Table VII below.

TABLE VII

  Product C Remaining stains Soils + veils + traces of water Designation tableware Test 1 Test 2 Test 3 Test 1 Test 2 Test 3 127 parts% efficiency% efficiency% efficiency% efficiency% efficiency% efficiency 12 plates 83.3 87.5 83, 3 83.3 87.5 83.3 12 soup plates 95, 8 95.8 100 95.8 95.8 95.8 12 plates & dessert 83.3 87.5 87.5 83.3 83.3 87.5 12 saucers 91.7 95.8 95.8 91.7 95.8 95.8 12 forks 79.2 79.2 83.3 75 70.8 70.8 12 knives 91.7 91.7 91 7 79.2 83.3 79.2 12 tablespoons 91.7 95.8 83.3 83.3 83.3 75 12 dessert spoons 100 100 100 95.8 91.7 95.8 12 glasses 100 95 , 8 91.7 91.7 91.7 87.5 12 cups 95.8 91.7 95.8 95.8 91.7 95.8 1 oval dish) 1 round hollow dish) 1 bowl) 100 92.9 92.9 85.7 78.6 78.6 2 serving spoons 1 serving fork 1 serving spoon% efficiency wash per test 91.7 92.1 91.3 87.4 87 86.2% efficiency wash by evaluation 91.7 86.9% efficiency total wash 89.3 0% K) (n washed with the product C according to the invention has a very clean and very bright general appearance, having very slight remains of dirt and small droplets of water dried only slight remains of spinach and semolina grains are observed and some dried water on some plates The cutlery is overall clean with light stains and dried water stains

for some people.

  In addition, the cups are very clean, without

  ration of tea or soiling or dried water marks and the glasses net with, for some only, a number

  limited soiling and traces of dried water.

  These results confirm the interest of the washing products according to the invention with regard to the washing of

  dishes and, in particular, glassware.

  The washing products according to the invention, by virtue of the characteristic presence of at least one oxidized polysaccharide, in particular an oxidized starch hydrolyzate, in their composition, exhibit quite remarkable washing performances, and this while significantly reducing the need for implementation

  concomitant with phosphates and / or other additives

harmful to the environment.

  All the more surprisingly and unexpectedly and as results from Example 4, the presence of at least one oxidized polysaccharide makes it possible to completely get rid of such an implementation, in particular of phosphates, and this, including in washing products according to the invention, for contents also substantially zero zeolite (s). In order to demonstrate the good effectiveness of the washing products according to the invention in the case of washing the linen, comparative tests have been carried out using

  on the one hand, a detergent according to the prior art

  designated by the letter T 1 whose constitution

  appears in Table VIII below.

TABLE VIII

  Brand Name% Manufacturing constituents or production formula by weight napkins UKANIL 2136 ICI 0,2 Dodecylbenzene sulphonate FLUKA 6 Ethoxylated fatty alcohol KC 7 / L

cetostearyl alcohol

  only ethoxylated EMPILAN KM 11 MARCHON 5 Na Sulfate 2 SO 4 PANREAC 21 Metasilicate of Na Si O 2 Na 2 O anhydrous PROLABO 3 Na Na 2 CO 3 CO 2 PANREAC 5 Na Na perborate BO 3 4 H 20 FLUKA 18 Tetraacetylethylene diamine LEVER 2 arboxymethyl cellulose BLANOSE 7 M 65 AQUALON 1 zeolite A Na 2 OA 1203 25 i O 2 x H 20 (x = 4 to 51 MONTEDISON 25 Na-olyacrylate SOKALAN C 245 BASF 4 Enzyme ESPERASE NOVO 0.6 Water qs 100

  and, on the other hand, a detergent according to the invention.

  designated by the letter P, whose respective rates in

  zeolite (s), in oxidized polysaccharide (s) and in poly-

  Sodium acrylates (P Na) are listed in Table

IX below.

TABLE IX

  Constituents Composition (% by weight) Washing product T 1 P

Zeolite A 25 -

  Polyacrylates 4 2 Oxidized polysaccharide In the context of these tests, the oxidized polysaccharide contained in the washing product P according to the invention is used to produce an oxidation product of a starch hydrolyzate having a DE of about 37, said oxidation product having an acid number I of about 8.6 and having, moreover, been "stabilized" by

  catalytic hydrogenation with Raney nickel.

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

top loading.

  The tests are carried out at a temperature of 600 ° C. with a rise in temperature of 21 minutes, then a plateau at 60 ° C. of 22 minutes. The complete cycle lasts 90 minutes.

  minutes The volume of wash water is 11 liters.

The hardness of the water is 30 'TH.

  The washing load is composed of 2.2 kg of pieces of white fabric (cotton) whose dimensions are

cm x 70 cm.

  At each wash, a load of 2.2 kg of pieces of white fabric, a set of

  dirty "of different natures and which

  predetermined and predefined sures on these tissues.

  In practice, these "presalis" fabrics which are pinned on the washing load, are the following: 2 EMPA 103 brand cotton strips consisting of 7 pieces sewn together, namely: a piece of white cotton (EMPA type) 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 (EMPA type)

114)

  a piece of cotton soiled with sulfur black, 2 strips of polyester / cotton fabric (65/35) impregnated with KREFELD brand tea (ref WFK 20 G), 2 strips of polyester / cotton fabric (65/35) impregnated with cocoa brand KREFELD (ref WFK 20 F),

  2 strips of white polyester / cotton fabric (65/35)

EMPA (ref: EMPA 213).

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

  In order to assess the quality of the washing, on the one hand the elimination of dirt and stains was measured and, on the other hand, the effect of the washes on the

degree of whiteness.

  To appreciate the removal of dirt and stains, photometry (measurements of the amount of light reflected by the tissue) was carried out; It is thus possible to calculate the percentages of soil removal. A device for measuring the reflection of the soil is used.

  light, marketed under the brand ACS 1400 SPECTRO.

  The removal of the soil is expressed by the formula: Elimination in% C B x 100 (1) A -B in which: A = reflectance of the blank sample, B = reflectance of the control soil sample,

  C = reflectance of the soiled sample after testing.

  Reflectances are determined using the

blue trichromatic component.

  The number of measurements made is 6

soiling and by formulation.

  Regarding the degree of whiteness, we measure

  The effect of washing (preservation, increase or decrease

  the initial whiteness) on two EMPA 221 unsanded white cotton coupons and on two EMPA 213 white non-salted polyester / cotton coupons, which are

incorporated in the wash bath.

  If we denote by Rbo, the blue trichromatic component obtained before washing, with Rb, the blue trichromatic component obtained after washing, the degree of whiteness can be evaluated 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 taken from the

Table X below.

PAINTINGS

FABRIC: COTTON EMPA 103

degree of white (% change)

-______________________________

blood (% elimination)

_______________________________

ecru (% elimination)

_______________________________

red wine (% elimination)

_______________________________

cocoa (% elimination)

_______________________________

  carbon black milk blood (% elimination) _black sulfur (% black elimination of sulfur (% elimination) Product T 1 according to the prior art 0,18

_______________

58.7

_______________

8.1 48.4

_______________

, 1

_______________

  43.0 7.5 Product P according to the invention

+ 0.03

, 5 13.4 47.9 32.9 38.8 7.7

FABRIC: POLYESTER / COTTON 65/35

  degree of whiteness (% change) 1.09 1.02 cocoa (% elimination) 90.1 84.4 tea (% removal) 89.4 91.4 These results represent the average of 6 measurements. They are expressed, for each type of soil and each type of fabric, in% removal of said soil. In addition, the results of tests carried out on

  "white" tissues, ie not soiled, express the variability

  (+ = increase, = decrease), expressed in%, of the

  degree of whiteness of the fabric following the washing operation.

  Overall, Table X shows that the pre-

  The characteristic presence of at least one oxidized polysaccharide, in particular of the oxidized starch hydrolyzate type, in the washing products according to the invention makes it possible for the latter to satisfy the criteria generally required in the form of

terms of laundry.

  If the washing product P according to the invention is

  reveals, for some parameters, slightly less

  Although the control product T 1, which has a relatively high content of zeolites and a higher content of polyacrylates, the fact remains that the detergent according to the invention has as good or even improved efficacy for certain other parameters such as the degree of whiteness and the elimination of

  some fouling of oxidizable nature.

  These results confirm, in particular, the pos-

  it is possible 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 and this, while presenting substantially zero levels of both phosphates and zeolites and without concomitant overdose in weakly constituents

  biodegradable such as polyacrylates.

Claims (11)

  1 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 and, more preferably still, a zero phosphate content and from 5 to 75% by weight and, preferably, from 15 to 50% by weight.   weight of at least one oxidized polysaccharide.   Washing product according to claim 1,   characterized by the fact that it has a lower   less than 1%, preferably zero in phosphates.   3 detergent according to one of the claims   1 and 2, characterized by the fact that polysaccharide   oxidized wrinkle is selected from the group consisting of:   the oxidation products of di-, tri- and oligosaccharide-   possessing a terminal function of the aldonic type, the oxidation products of hydrolysates of starch, of cellulose and of hemicellulose having an aldonic end function,   any mixtures containing at least two   conques of the aforesaid oxidation products.   4. Washing product according to claim 3, characterized in that the oxidized polysaccharide is obtained from a product of which only one of all its potentially oxidizable functions, the terminal function (of the aldehyde type before oxidation) is substantially oxidized.   Washing agent according to one of Claims 2 to 4, 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   from about 5 to about 90, preferably from 20 to 65.   Washing agent according to claim 5, characterized in that the oxidized polysaccharide has an acid number I of between about 1 and about 20, preferably between 5 and 14.   Washing agent according to one of Claims 1 to 6, characterized in that the polysaccharide   oxidized content is less than about 0.6%, preferably   less than 0.1% and, even more preferably,   less than 0.05% by weight of reducing sugars.   8 A detergent according to claim 7, characterized in that the oxidized polysaccharide has been subjected, after oxidation, to a catalytic hydrogenation treatment, said treatment employing, continuously or batchwise, preferably at least one catalyst selected from the group consisting of nickel, platinum, palladium, cobalt, molybdenum and combinations of   these metals, and especially Raney nickel.   9 Washing product according to one of the claims   1 to 8, characterized in that it contains one or more components selected from the group consisting of detergents, sequestering agents other than zeolites and phosphates, surfactants, bleaching agents, defoamers , the agents   antiredeposition, alkaline agents, structural agents   flow agents, thickeners, anti-corrosion agents, abrasives, solubilizers, fillers, enzymes,   enzyme stabilizers, bacterial agents,   acids, opacifying agents, optical brighteners, coloring agents and perfumes.   Washing agent according to claim 9, characterized in that it contains at least one bleaching agent, preferably a chlorine-releasing agent and, more preferably still, at least one of   agents of the group consisting of trichloroisocyanuric acid   that sodium dichloroisocyanurate and dichloro- potassium isocyanurate.   11 Composition of matter for the preparation of a   detergent according to one of claims 1 to 10,   characterized in that it contains at least one oxidized polysaccharide. 12 Composition of material according to claim 11, characterized in that it contains at least one zeolite, the weight ratio zeolite / oxidized polysaccharide being at most equal to 1/1, said composition being   in the form of freely flowing particles.   Use of an Oxidized Polysaccharide, in Particular an Oxidized Starch Hydrolyzate, for Washing   dishwashing, done by hand or in an industrial machine trielle or domestic.   14 Use of a detergent according to one   claims 1 to 10 for washing objects and / or   substrates other than dishwashing, in particular for laundry.