FR2659979A1 - WASHING PRODUCT WITH REDUCED OR NULL PHOSPHATE CONTENT. - Google Patents

Abstract

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

Description

The present invention relates to a new washing product,

  particularly useful for washing fabrics, of the kind of those which are reduced in content at least

  5% by weight, or even zero in phosphates, and which

at least one zeolite.

  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 detergents must meet constraints, including ecological, more and more severe. This ecological aspect is all the more marked as

  commonly used strong detergents and, in particular,

  products used in laundries

  have high levels of phosphorus

phates may exceed 30%.

  Many attempts have been made to remove all or at least some of the phosphates

in washing products.

  In particular, it was proposed to

  as a full or partial replacement agent for phos-

  phates, zeolites of natural or synthetic origin

  than; these products are well known for their power

  cation exchanger, in particular calcium and magnesium

  sium, which are responsible for the hardness of the water and

  problems of mineral incrustations in the linen.

  However, if zeolites contribute to eliminating

  of these cations, their total substitution with phosphates does not make it possible to reach a degree of

  satisfying the requirements of practice.

  Also, to improve the quality of the wash of zeolite-based washings containing little or no phosphates, it has been proposed to combine said zeolites with various other agents such as in particular

  nitrilotriacetic acid (NTA) and its salts, in particular

  bind sodium nitrilotriacetate (EP 70 079 and

EP 319,053).

  However, in addition to their imperfect biodegradability, these products are suspected of fixing heavy metals, which could pass into drinking water As a result of which it is generally recommended, or even made compulsory today in some countries, to limit to 5% their introduction rate in detergent products. This 5% level appears as the optimum rate of introduction of alkali metal nitrilotriacetate in the phosphate-free compositions described in patent EP 319 053, which contain from 20 to 35% by weight.

weight of zeolites.

  It has also been proposed, in the context of washing products containing little or no phosphates, to associate zeolites with particular polycarboxylic polymers based on defined mixtures of mono and dicarboxylic monoolefinic acids and nonionic esters of said acids. (patent EP 193 360) Among the monoolefinic derivatives of mono and dicarboxylic acids, mention is made in particular of acrylic and / or methacrylic acid derivatives as well as maleic and / or itaconic acid derivatives. It appears that such compositions can be phosphate-free and contain less than 20% by weight of zeolites. However, in this case, zeolites, in addition to said polycarboxylic polymers, are associated with

clays and NTA.

  Among the polycarboxylic agents most commonly recommended for improving the quality of the washing of zeolite-based detergents containing little or no phosphates, reference should be made to acrylic polymers, and in particular homopolymers of acrylic acid or methacrylic acid or their salts, in particular polyacrylic acid (PA) and

sodium polyacrylates (P Na).

  Compositions containing, for example, from 2 to 7% by weight of polyacrylates and from 25 to 60% by weight of

  zeolites are described in DE 37 07 806.

  Washing products combining zeolites and polyacrylates are also presented at the patent level

DE 38 32 478.

  It should be remembered, however, that poly-

  acrylate, in particular polyacrylic acid and its salts, have the major disadvantage of being

biodegradable.

  As a result, it is now considered preferable to be able to implement them at

  not exceeding 4% by weight of detergent.

  It follows from the foregoing that, in general, there is a need to develop reduced or no phosphates washing products which, while effectively performing the role allotted to them, without appealing overdose of zeolites or the use of ecologically unacceptable additives, can achieve overall

  polycarboxylic polymers and / or monomers

  biodegradable, compatible with the requirements

  environmental protection and, in particular,

  specific nitrilotriacetic acid (NTA) levels of polyacrylic acid (PA) or

  respective quantities, not exceeding 4% by weight.

  And the Applicant Company had the merit of finding

  ver this aim was achieved when the washing products of the kind in question are made to understand at least one oxidized polysaccharide selected from the group comprising: a) disaccharide oxidation products having a terminal function of the aldonic type,

  (b) the products of oxidation of trisaccharides and oligo-

  saccharides having a terminal function of the aldonic type; c) the oxidation products of starch, cellulose and hemicellulose hydrolysates having an aldonic end function; d) any mixtures of at least two

said oxidation products.

  Advantageously, the oxidized polysaccharides which may be used in the context of the present invention are those obtained from di-, tri and oligosaccharides, starch hydrolysates, cellulose and

  hemicellulose which alone, among all their

  potentially oxidizable, their terminal function (of the aldehyde type before oxidation) is substantially

  oxidized and this, in a function of the aldonic type.

  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.

  The polysaccharides whose process described in

  patent EP 232 202 makes possible the selective oxidation of

  They include in particular: disaccharides such as lactose, maltose, isomaltose, cellobiose, xylobiose and mannobiose, having an aldehyde terminal function, starch hydrolysates obtained by the acidic and / or enzymatic route, the hydrolysis products of hemicelluloses such as D-galacto-D-mannan, Dgluco-D-mannan, L-arabino-D-xylan, D-xylo-L-arabinan. According to another advantageous embodiment of the washing product according to the invention, the oxidized polysaccharide implemented therein is in the form of an oxidation product of a starch hydrolyzate having a DE (Dextrose Equivalent) of about 5 to about 90 and preferably has an acid number I of from about 1 to about 20, wherein said acid number I is expressed in grams of carboxylic function for g of oxidized polysaccharide and given by the formula: DE x 45 I = 100 × 180 + DE 1 × 218 DE In the context of the present invention, use may in particular be made of oxidized polysaccharides which have an acid number between about 5 and about 14 and which are obtained by oxidation of starch hydrolysates having an ED ranging from about 20 to about 65. Most preferably, oxidized polysaccharides which have an acid number between about 8 and about 14 and which are obtained by oxidation of starch hydrolysates

  having an DE of from about 35 to about 65.

  It should be remembered, in this place of the

  description of the invention, that the implementation

  of at least one oxidized polysaccharide, in particular

  A polysaccharide, for example a starch hydrolyzate, "selectively" oxidized at its terminal aldehyde function, in the washings according to the invention not only makes it possible to substitute effectively within them, at least in part,

  polycarboxylic compounds with little or no biodegradation

  NTA, AP or their salts, by products, in this case oxidized polysaccharides, which do not pose

  problem of biodegradability, but still does not impose any

  concomitant increase in the level of zeolite (s) contained in those products in relation to the rates currently encountered in washing products on the market, which are generally at least

  rates of the order of 21 to 25% by weight.

  And it is remarkable to observe that, all the more surprising and unexpected, the characteristic presence of at least one oxidized polysaccharide, in particular a polysaccharide, in particular a starch hydrolyzate, "selectively" oxidized at the level of its terminal aldehyde function, allows said products containing said oxidized polysaccharide to be effective: for constitutive levels of zeolite (s) less than 20% by weight and / or

  for constitutive levels of polycarboxylic compounds

  NTA, AP or their salts, not exceeding 2% by weight, or even in the substantial absence of such

polycarboxylic compounds.

  In addition to the benefits that have just been described in

  relationship with the washing products according to the invention.

  It should be pointed out that these products, unlike certain products of the prior art, do not cause any substantial deactivation of the bleaching agents, in particular perborate, which are commonly used in detergent products to eliminate oxidizable stains and lead to high degrees of whiteness. Without wishing to be bound by any theory, the Applicant Company attributes the excellence of these performances in this field to the stabilizing action that the oxidized polysaccharides would play vis-à-vis the oxidizing agents. This result is particularly marked when the oxidizing agent is a perborate, in particular sodium, and the product according to the invention comprises, as

  oxidized polysaccharide, an oxidized starch hydrolyzate.

  According to an advantageous embodiment of the washing product according to the invention, this comprises: a proportion of about 5 to about 35% by weight, of

  preferably from 10 to 25% and even more preferably

  from 15 to 20% by weight of at least one zeolite, from about 3 to about 20% by weight, of

  preferably from 5 to 20% by weight and even more preferably

  approximately 7 to 20% by weight of at least one poly-

  oxidized saccharide, in particular of a polysaccharide

  "selectively" oxidized at the end of its functional

aldehyde type.

  According to another advantageous embodiment of the aforesaid product, the weight ratio between, on the one hand, the zeolite and, on the other hand, the oxidized polysaccharide is between about 0.5 / 1 and about 4/1, preferably

between 1/1 and 2/1.

  In the context of the present invention, the term "zeolite" includes all ion exchange materials

  aluminosilicates, whether of a crys-

  tall oil or amorphous, of natural or synthetic origin, as described for example in patents EP 70 079 and

  EP 193,360 mentioned above. Such products are, for example,

  ple, 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 practice, the washing product conforms to

  invention, which constitutes a new industrial product

  veal, also includes one or more other

  selected from, for example, detergents, surfactants, antiredeposition agents, oxidizing agents,

  structuring agents, anti-corrosion agents, anti-corrosion

  foam, enzymes, perfumes, dyes, solubilizing agents, etc., for example as described

  at the level of patents EP 70 079 and EP 319 053

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

  dodecylbenzene sulphonates of sodium or potassium.

  They may also be selected from

  nonionic detergents, such as, in particular, alkyl

  polyglucosides or ethoxylated fatty alcohols.

  Oxidizing agents, ie products that

  to release peroxide ions in such quantities as to allow the bleaching of wine stains,

  tea, coffee, etc., may in particular be

  rats, percarbonates, persilicates or perphos

  alkali metal phates, and in particular the perborate

sodium.

  In addition, the washing product according to the invention

  may contain common detergency adjuvants

  such as polyacrylic acid (PA), nitrilotriacetic acid (NTA) and / or their respective salts,

especially their sodium salts.

  However, as already mentioned, the pre-

  The characteristic presence of at least one oxidized polysaccharide in the washing products in accordance with the invention makes it possible, in a remarkable manner, for said products to be at zeolite levels no greater than or even lower than those of the products of the prior art. , effective for constitutive levels of NTA, AP or their respective salts,

  lower than those commonly encountered in

  prior art and in particular not superior

at 2% by weight.

  The washing products according to the invention, which are particularly useful for washing fabrics, carried out by machine or "by hand", will preferably be presented

  in the form of free-flowing particles, particularly

  in the form of powders or granules.

  Their preparation does not require the implementation of

  a process and / or apparatus other than those commonly employed by those skilled in the art and may, for example, use conventional drying techniques

  aqueous suspensions by atomization.

  The contacting of at least one zeolite and at least one oxidized polysaccharide in the washing products according to the invention may be carried out in very different ways, in the form of powders,

  liquids or powder / liquid mixtures, in one or more

  stages, whether or not 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. The invention can be better understood from the following examples which show some particularly advantageous embodiments.

products according to the invention.

  To demonstrate the effectiveness of the washing products according to the invention, comparative tests were carried out using, on the one hand, a washing product according to the prior art designated by the letter T whose constitution appears at the level of of Table I below

  and, on the other hand, four detergents according to the invention.

  designated by the letters A, B, C and

  D, whose respective zeolite (s), polysaccharide

  oxidized wrinkle (s) and, optionally, polyacrylates of

  sodium (P Na) are listed in Table II.

  In the context of these tests, the oxidized polysaccharide contained in the washing products according to the invention is used to produce an oxidation product of a starch hydrolyzate having an ED of approximately 61.5 and which has an acid number I of about 13.6.

TABLE I

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

Cetostearyl alcohol

  as ethoxylated EMPILAN KM 11 MARCHON 5 Na Sulfate 2 SO 4 PANREAC 21 Metasilicate of Na Si O 2 Na 2 O anhydrousPROLABO 3 Na carbonate 2 CO 3 PANREAC 5 Na Na perborate BO 3 4 H 20 FLUKA 18 Tetraacethylethylene diamine LEVER 2 Carboxymethyl cellulose BLANOSE 7 M 65 AQUALON 1 Zeolite A Na 2 OA 1203 25 i O 2 x H 20 (x = 4 to 5) MONTEDISON 25 Na polyacrylate SOKALAN C 245 BASF 4 Enzyme ESPERASE NOVO 0.6 Water qs 10

TABLE II

  Constituents Composition (% by weight)

T A B C D

  Zeolite A 25 18 18 19 19 Polyacrylates 4 2 oxidized saccharide 1 18 14 1 Oxidized polysaccharide 10 18 14 10 11 Said comparative tests consist of washing tests carried out using a VEDETTE 8596 brand washing machine. CHOICE SYSTEM with loading by

the top.

  The tests are carried out at the following two temperatures: 40 QC and 600 C. For the test at 40 QC, a temperature rise of 13 minutes is expected, then a plateau at 40 QC of 22 minutes The complete cycle, ie to say including

  Filling, rinsing and spinning, lasts 80 minutes.

  For the test at 600 C, a rise in temperature of 21 minutes is expected, then a plateau at 600 C of 22

  minutes The complete cycle lasts 90 minutes.

  In both tests, the volume of wash water is

of 11 liters.

  Two detergents are carried out by temperature.

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

55 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 to the wash load, are as follows: 2 strips of KREFELD brand polyester / cotton fabric (64/35) gray (ref WFK 20 C), soiled with a mixture of animal oil and carbon black, 2 EMPA 103 brand cotton bands consisting of 8 pieces sewn together, namely: a piece of white cotton (type EMPA 221), a piece of gray cotton (type EMPA 101 soiled by a mixture of vegetable oil and carbon black), a piece of cotton soiled with blood (type EMPA 111), a piece of cotton soiled with cocoa (type EMPA 112), a piece of soiled cotton 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 sulfur black (not used in the present measurements), 2 strips of KREFELD tea-impregnated polyester / cotton fabric (65/35) (ref WFK 20 G), 2 b KREFELD brand cocoa impregnated polyester / cotton fabric (65/35) (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 per fabric is

  4, ie 4 measurements (ie in four different places)

  on the same piece of fabric) x 2 washes x 2 strips of fabric = 16 measurements per soiling, per formulation and

by temperature.

  Regarding the degree of whiteness, the effect of the washing is measured on two EMPA 221 white cotton swabs and two EMPA 213 white cotton / cotton swabs, which are incorporated in the washing bath. we take 4 measurements, which gives us 16

  measurements by formulation and temperature studied.

  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.

  In the actual tests which will now be described, the effectiveness of the washing compositions according to the invention has been studied successively on oil-based stains and carbon black, then on protein stains and stains. oxidizable and finally the "degree of white" conferred by said

treated tissue products.

EXAMPLE 1

  Spots produced by mixtures of mineral oil, vegetable

  and / or animal with carbon black.

  The washing tests were performed on the one hand,

  on gray cotton and, on the other hand, on synthetic

ticks (polyester / cotton).

  1) Tests on gray cotton By washing, each time two EMPA 101 brand gray cotton coupons were treated successively with a

  mixture of vegetable oil and carbon black.

  This type of soiled cotton is representative of

  insoluble pigments related to the fabric by fatty film, for example the collars of shirts, jackets,

cloths and greasy stains.

  The two groups of tests performed respectively

  at 400 ° C. and 600 ° C. gave for the products according to the invention.

  A, B, C and D on the one hand, and the product according to the prior art T on the other hand, in terms of the removal of the soil represented by the aforesaid formula (1), the results respectively gathered in Tables III and IV.

TABLE III

  (4 QOC test) Type Removal of dirt (in%> of fabric T A B C D

EMPA 101 17.4 17.5 16.3 16.7 16.1

TABLE IV

  (60 C test) Type Removal of dirt (%) of fabric T A B C D

EMPA 101 17.7 18.8 23.1 16.9 17.1

  2) Tests on gray synthetic The synthetic fabric used here is a fabric of the type polyester / cotton (dacron / cotton) brand KREFELD; it was soiled by a mixture of animal oil and black of

carbon (ref WFK 20 C).

  The two groups of tests carried out respectively at 40 ° C. and 600 ° C. gave, for the compositions A, B, C and D, on the one hand, and the control product T, on the other hand, in terms of the elimination of the soiling. represented by the

  aforementioned formula (1), the results being brought together respectively

in Tables V and VI.

TABLE V

  (test at 40 C) Type of soil removal (in%) synthetic T A B C D Polyester / cotton 20.2 20.0 18.1 19.0 18.8

WFK 20 C

TABLE VI

  (60 C test) Type of soil removal (in%) synthetic T A B C D Polyester / cotton 19.9 20.1 24.7 19.2 19.5

WFK 20 C

  As a result of all of Tables III to VI, the characteristic presence of at least one oxidized polysaccharide, in particular at least one polysaccharide "selectively" oxidized at its terminal function of the type

  aldehyde, in the detergents according to the invention

  This allows, for washing performance similar to or even greater than that observed with a washing product according to the prior art: to reduce the rate of incorporation into zeolite (s) and / or to reduce the rate of incorporation of a non-biodegradable detergency builder commonly used such as polyacrylates, or even to be completely free of

the incorporation of such an agent.

EXAMPLE 2

Protein stains

  The action of washing products in accordance with the

  vention on proteinaceous stains is studied using

  EMPA brand cotton fabrics, namely: blood-soaked EMPA 111 fabric, EMPA 112 tissue soiled with cocoa and EMPA fabric 116 soiled with a mixture of blood, milk and carbon black, and of the KREFELD brand polyester / cotton type, namely: the WFK 20 F fabric soiled with cocoa. This staining is representative of blood, milk, egg, gravy, mayonnaise, sauces and the like. Two groups of tests carried out at 40 ° C. and 60 ° C. gave, for the compositions A, B, C and D according to the invention and the control product T, from the point of view of the elimination of the soil represented by the aforesaid formula ( 1), the results shown respectively in Tables VII and

VIII below.

TABLE VII

  (40 C test) Type of soil removal (in%) tissue TABCD EMPA 111 (blood) 54.3 55.9 51.1 53.5 58.8 EMPA 112 (cocoa) 22.8 22.9 24 , 4 24.3 20.7 EMPA 116 (mixed) 20.3 19.9 16.6 16.0 22.0 Medium cotton 32.5 32.9 30.7 31.3 33.8 WFK 20 F (cocoa ) 75.3 76.2 68.3 69.0 68.0

TABLE VIII

  (60 C test) Type of soil removal (%) tissue TABCD EMPA 111 (blood) 65.4 75.3 64.8 67.5 66.0 EMPA 112 (cocoa) 25.8 24.5 30 , 3 21.3 20.6 EMPA 116 (mixed) 31.3 38.0 33.0 36.1 32.2 Medium cotton 40.8 45.9 42.7 41.6 39.6 WFK 20 F (cocoa ) 76.3 76.5 80.0 73.3 77.2 Tables VII and VIII show that in the case of proteinaceous stains, the same conclusions as previously made for stains produced by oil / black blends carbon, can be drawn with regard to the effectiveness of the detergents according to the invention and their interest compared to a product of the prior art which, although containing both more zeolite (s) and more polyacrylates , is not more efficient, especially for a test temperature of 60 C.

EXAMPLE 3

Oxidizable stains

  The action of washing products in accordance with the

  prevention on oxidizable stains is studied using the following tissues: KREFELD brand polyester / cotton soiled with tea (ref: WFK 20 G) EMPA 222 brand cotton, that is unbleached unbleached cotton

  branded EMPA 114 cotton with wine.

  The aforementioned tissues are sensitive to oxidation

* chemical; the stains provoked are those that white

  chilies reduce or eliminate (other stains of this type are those caused by fruits, coffee,

vegetables and others).

  A group of tests carried out at 600 ° C. gave, for the compositions A, B, C and D and the control product T, in terms of the elimination of the soil represented by the aforesaid formula (1), the results respectively obtained

in Table IX.

TABLE IX

  Type of soil removal (%) fabric TABCD EMPA 222 (ecru) 14.7 13.1 12.5 12.7 13.1 EMPA 114 (cocoa) 76.8 78.6 68.0 75.7 75 , 0 Average cotton 45.7 45.8 40.2 44.2 44 WFK 20 G (tea) 85.9 85.4 65.6 82.0 83.5 The average of the results obtained on tea stains and wine and off-white cotton reflects the behavior

  products tried on all the tasks of this

  thousand. It appears from Table IX that, in the specific case of oxidizable stains, the detergents according to the invention make it possible to reach a level of efficiency.

  equal to that of the washing product according to the prior art.

  The washing products according to the invention fully meet the criteria generally required with regard to

  relates to the elimination of this type of soiling.

EXAMPLE 4

  Degree of whiteness EMPA 221 non-azur white cotton and EMPA 213 non-azurized polyester / cotton are used to determine whether a particular detergent is able to maintain, increase or decrease the degree of

initial whiteness of the fabric.

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

paintings.

PAINTINGS

  Tests Variation (in%) of degree of whiteness

T A B C D

  Cotton 40 C + 3.1 + 3.1 + 2.6 + 2.5 + 2.7 Cotton 60 C + 4.5 + 4.3 + 5.7 + 4.3 + 4.4 Polyester / Cotton 40 C + 0,7 + 0,1 + 0,3 + 0,5 + 0,2 Polyester / cotton 60 C + 1,2 + 0,8 + 1,6 + 1,3 + 1,2 The table shows X that, for the criterion studied, the washing products in accordance with the invention are, overall, as effective as the washing product of the prior art, said washing products according to the invention making it possible to obtain, after washing , a fabric whose degree of whiteness is greater than that which it had before washing.

Claims (8)

  1 washing product reduced to less than 1% by weight, or no phosphates, useful -partement for washing tissues, characterized in that it comprises at least one zeolite and at least one oxidized polysaccharide selected from the group comprising: oxidation products of disaccharides having an aldonic terminal function,   the products of oxidation of trisaccharides and oligo-   saccharides having an aldonic terminal function, the oxidation products of starch hydrolysates, cellulose and hemicellulose having an aldonic end function, and any mixtures of at least two said oxidation products.   Washing product according to Claim 1, characterized in that the oxidized polysaccharide consists of at least one product obtained from a di-, a tri or an oligosaccharide, a hydrolyzate of starch, cellulose or hemicellulose which, among all its potentially oxidizable functions, only its terminal function (of the aldehyde type before oxidation) is substantially oxidized.   3 detergent according to one of the claims   1 and 2, characterized in that the oxidized polysaccharide is an oxidation product of a starch hydrolyzate obtained by the acidic and / or enzymatic route, having a DE from about 5 to about 90.   4. Washing product according to claim 3, characterized in that the oxidized polysaccharide additionally has an acid number I between about 1 and about 20.   Washing agent according to Claim 4, characterized in that the oxidized polysaccharide is an oxidation product of a starch hydrolyzate having an ED of from about 20 to about 65 and said oxidized polysaccharide has an acid number. I between about 5 and about 14.   Washing product according to claim 5, characterized in that the oxidized polysaccharide is an oxidation product of a starch hydrolyzate having an ED of from about 35 to about 65 and said oxidized polysaccharide exhibits an index of acid I between about 8 and about 14.   7 Washing product according to one of the claims   1 to 6, characterized in that it comprises: a proportion of about 5 to about 35% by weight, of   preferably from 10 to 25% by weight and even more preferably   approximately 15 to 20% by weight of at least one zeolite, a proportion of from about 3 to about 20% by weight, of   preferably from 5 to 20% by weight and even more preferably   approximately 7 to 20% by weight of at least one poly-   oxidized saccharide, in particular of a polysaccharide   "selectively" oxidized at the end of its functional aldehyde type.   8 A detergent according to claim 7, characterized in that the weight ratio between, on the one hand, the zeolite and, on the other hand, the oxidized polysaccharide is between about 0.5 / 1 and 4/1, preferably between 1/1 and 2/1.   9 Washing product according to one of the claims   1 to 8, characterized in that the zeolite and a sodium silicoaluminate, in particular of the zeolite A type.   Washing product according to one of the claims   1 to 9, characterized in that it further comprises one or more other constituents chosen, in particular, from the group comprising polycarboxylic detergency builders such as polyacrylic acid (PA), nitrilotriacetic acid (NTA ) and / or their salts   respective detergents, surfactants,   antiredeposition agents, oxidizing agents, structuring agents, anti-corrosion agents,   anti-foam agents, enzymes, perfumes, colourants   solubilizing agents. 11. Washing product according to claim 10, characterized in that it comprises at most 4%, preferably at most 2% by weight of a detergency builder chosen from the group comprising polyacrylic acid.   (AP), nitrilotriacetic acid (NTA), their salts   including their sodium salts, and mixtures any of these.