EP0425369A1 - Composition for cleaning products, its preparation process and cleaning product containing it - Google Patents

Abstract

Composition for washing products, characterised in that it comprises at least one phosphate, at least one zeolite and at least one oxidised polysaccharide, the proportion of oxidised polysaccharide representing approximately 5 to approximately 40 % by weight of the total mass of the three constituents.

Description

The subject of the present invention is a composition for washing products and its preparation process. It also relates to the washing product containing this composition.

For a long time, phosphates have played a preponderant role in washing products, in particular as sequestering agents for cations which form salts which are insoluble in water, in particular calcium and magnesium ions; the excellent performances which they allow to achieve reside in their particular structure.

But one of the acute problems which the detergents industry has to face is the very polluting nature of said phosphates. Indeed, their presence in wastewater causes the well-known phenomenon of eutrophication; and for this reason the use of phosphates in washing products must meet increasingly severe environmental constraints in particular.

This ecological aspect is all the more marked since the powerful detergents commonly used and, in particular, the products used in industrial laundries, contain high quantities of phosphates which can exceed 30%.

Many attempts have therefore been made to remove all or at least part of the phosphates in the detergents.

It has in particular been proposed to use, as a total or partial replacement agent for phosphates, zeolites of natural or synthetic origin; these products are well known for their cation exchange power, in particular calcium and magnesium, which are the cause of the hardness of water and problems of mineral encrustations in the laundry.

However, if the zeolites contribute to the elimination of these cations, their total substitution for phosphates does not make it possible to reach a degree of washing compatible with the requirements of the practice.

Also, to improve the quality of the washing of zeolite-based washing products, it has been proposed to combine it with other agents such as, for example, acrylic polymers (patent FR 2,367,783) or else nitrilotriacetate - NTA - (patent EP 0.319.053).

But these products are also decried for the problems either of pollution, or of toxicity which they generate. In fact, polyacrylates have the major drawback of being non-biodegradable. As for NTA, it is suspected of being carcinogenic, which has led some countries to ban its use.

Finally, it has been proposed to use, as phosphate substitutes, products known for their biodegradability, namely gluconates or glucoheptonates of alkali metal. These products do not alone allow, under the conditions, in particular pH, traditionally encountered in the detergency field, to complex calcium sufficiently efficiently, they are conventionally used in combination with other detergency builders.

There are therefore compositions which contain, in addition to the above-mentioned gluconates and / or glucoheptonates, metasilicates, polycarboxylic acids of the citric or acrylic type, phosphates or even zeolites. However, these compositions have not made it possible to meet all the requirements of the technique and, by way of example, it is pointed out that, in the case of compositions comprising gluconates, zeolites and phosphates, obtaining performance of acceptable washing requires phosphate and zeolite contents incompatible with environmental protection is lying. In addition, these compositions cause a noticeable deactivation of bleaching agents, including in particular perborate, commonly used in detergents to remove oxidizable stains.

Consequently, none of the ecologically acceptable washing products which exist at present have excellent washing performance, while guaranteeing good stability of the bleaching agents.

The object of the invention is therefore to remedy the drawbacks of the prior art and to provide washing products which respond better than those which already exist to the various requirements of the practice.

And the Applicant Company had the merit of finding that this object was achieved in a completely surprising manner since, in washing products of the kind of those which comprise at least one phosphate and at least one zeolite, a proportion is replaced. from about 5 to about 40% by weight of these constituents by an equivalent proportion of at least one oxidized polysaccharide.

Consequently, the composition for washing products according to the invention is characterized in that it comprises at least one phosphate, at least one zeolite and at least one oxidized polysaccharide, the proportion of oxidized polysaccharide representing approximately 5 to approximately 40%. by weight of the total mass of the three constituents.

The process for preparing the composition according to the invention for washing products is characterized in that, in a composition based on phosphate and zeolite for washing products, a proportion of approximately 5 to approximately 40% is replaced by weight of these constituents by an equivalent proportion of at least one oxidized polysaccharide.

According to an advantageous embodiment of the composition according to the invention, the oxidized polysaccharide is a di-, a tri- or an oligo- or alternatively a poly oxidized saccharide preferably chosen from the group comprising:
- oxidized disaccharides having an aldonic terminal function,
- the oxidized trisaccharides, the oxidized oligosaccharides and the oxidized products of hydrolysis of starch, cellulose and hemicelluloses comprising a terminal function of aldonic type, and
- the mixture of the above oxidized polysaccharides.

est de 1 à 20 et, de préférence, compris entre 6 et 15.Advantageously, the oxidized polysaccharide is a starch hydrolyzate having an oxidized DE from 5 to 90 or a glucose syrup having an oxidized DE from 5 to 90 and whose acid number I, which is expressed in number of grams of carboxylic function per 100 g of oxidized polysaccharide, and which is given by the formula:

is from 1 to 20 and preferably between 6 and 15.

Particularly preferred are oxidized polysaccharides which have an acid number between about 8 and about 14 and which are obtained by oxidation of starch hydrolysates or glucose syrups having a DE between about 35 and about 65.

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

As such, the Applicant Company has designed and implemented to the point, as new products, oxidized polysaccharides "stabilized" having low levels, generally less than about 0.6%, preferably less than 0.1% and even more preferably less than 0.05%, reducing sugars.

In particular, the Applicant Company has found that the hydrogenation techniques applied to oxidized polysaccharides, in particular of the oxidized glucose syrup type or oxidized starch hydrolysates, make it possible to obtain such products, in particular oxidized products having a rate practically zero in reducing sugars, "stabilized" with regard to possible maturing in the presence of an environment (alkaline pH, high temperature) favoring this type of phenomenon.

The term “hydrogenation techniques” means the catalytic hydrogenation techniques using, continuously or batchwise, at least one catalyst chosen from groups IB, IIIB, IVB, VI, VII and VIII of the periodic table and in particular in the group comprising nickel, platinum, palladium, cobalt, molybdenum and combinations of these metals.

Use will be made in particular of hydrogenation techniques using, fixed or not fixed on an inert support, Raney nickel as catalyst and this, in the presence or not of an additional source of hydrogen.

Other hydrogenation techniques may be used, using, in the absence of hydrogenation catalyst, sources of hydrogen other than hydrogen gas, for example alkali metal borohydrides, in particular sodium borohydride.

Oxidized polysaccharides, in particular of the oxidized starch hydrolyzate type or oxidized glucose syrup, "stabilized" following the use of these hydrogenation techniques, in particular those having a DE of between 5 and 90, an index of acid I between 1 and 20 and "stabilized" by catalytic hydrogenation that, confer on the compositions and washing products into which they are introduced, performance comparable to that observed with the same oxidized but not "stabilized" products, or even improved performance for certain parameters.

According to another advantageous embodiment of the above composition, it comprises:
a proportion of 5 to 40% by weight, preferably from 10 to 35% by weight of phosphate and, more preferably still, from 20 to 30% by weight of phosphate,
a proportion of 90 to 20% by weight, preferably from 80 to 30% by weight of zeolite and, more preferably still, from 60 to 40% by weight of zeolite,
- A proportion of 5 to 40% by weight, preferably from 10 to 35% by weight and, more preferably still, from 20 to 30% by weight of oxidized polysaccharide.

According to another advantageous embodiment of the above composition, the weight ratio between on the one hand the zeolite and on the other hand the oxidized polysaccharide is between approximately 0.5 / 1 and 4/1, preferably between 1.5 / 1 and 2.5 / 1 and, more preferably still, close to 2.0 / 1.

The washing product according to the invention is characterized in that it contains a proportion of 5 to 40% by weight, preferably between 15 and 35% by weight of a washing composition comprising at least one phosphate, at least one zeolite and at least one oxidized polysaccharide, the proportion of oxidized polysaccharide representing approximately 5 to approximately 40% by weight of the total mass of the three constituents of the composition.

In practice, the washing product according to the invention, which constitutes a new industrial product, also comprises one or more other constituents chosen, in particular, from the group comprising detergents, surface-active agents, anti-deposition agents , oxidizing agents, agents structuring agents, anti-corrosion agents, anti-foaming agents, enzymes, perfumes, dyes, solubilizing agents.

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

They may also be chosen from nonionic detergents, such as in particular alkylpolyglucosides or ethoxylated fatty alcohols.

The oxidizing agents, namely products capable of releasing peroxide ions in an amount such that they allow the bleaching of wine, tea, coffee stains, etc., may in particular be perborates, percarbonates, persilicates or alkali metal perphosphates, and in particular sodium perborate.

The structuring agents may, in particular, be chosen from sugars, hydrogenated sugars and any mixtures thereof and in particular those consisting of or containing, at least in part, a monosaccharide such as glucose or fructose and / or a disaccharide such as maltose or sucrose and / or the hydrogenation products thereof.

The structuring agents may in particular consist of or contain, at least in part, sorbitol and in particular be in the form of hydrogenated products obtained by hydrogenation of starch hydrolysates or glucose syrups.

In addition, the washing product which forms the invention may contain commonly used detergency builders such as polyacrylic acid (PA), nitrilotriacetic acid (NTA) and / or their respective salts, in particular their sodium salts.

As already indicated above, the Applicant Company has found that, surprisingly and unexpectedly, the washing products in accordance with the invention made it possible to remedy the drawbacks of the products of the prior art; in particular, they lead to much higher degrees of white.

Without wishing to be bound by theory, the Applicant Company attributes the excellence of these performances to the stabilizing action which the oxidized polysaccharides play with respect to the oxidizing agents.

This result is particularly marked when the oxidizing agent is a perborate, in particular of sodium, and when the composition in accordance with the invention comprises, as oxidized polysaccharide, an oxidized glucose syrup.

Proposing, therefore, to establish the composition as well as the washing product in accordance with the invention, this is done as follows or in an equivalent manner.

Said composition comprises at least one phosphate, at least one zeolite and at least one of the polysaccharides defined above.

As regards the above-mentioned phosphate, use is generally made of a mono- or a polyphosphate preferably chosen from the group consisting of orthophosphate, pyrophosphate, tripolyphosphate, hexametaphosphate, the tripolyphosphate being more particularly preferred, in particular in the form of its sodium salt.

In the context of the present invention, the term "zeolite" includes all ion exchange materials of the aluminosilicate type, whether they are of crystalline or amorphous nature, of natural or synthetic origin.

Such products, well known to those skilled in the art, are, for example, commercially available under the designations "zeolite A", "zeolite B", "zeolite X" or "zeolite HS".

Use may in particular be made of a crystalline sodium silicoaluminate of the "zeolite A" type.

To prepare the composition for washing products according to the invention, the three above-mentioned constituents are brought together, for example by mixing, in the proportions indicated above.

The composition thus established, useful in particular for washing textiles carried out by machine or "by hand", is stable and constitutes a new industrial product. It is preferably in the form of free flowing particles, in particular in the form of a powder or granules.

Its preparation does not require the implementation of any process and / or apparatus other than those commonly used by those skilled in the art and can, for example, use conventional techniques for drying aqueous suspensions by atomization. The same applies to the preparation of the washing products in accordance with the invention.

The placing in the presence of at least one phosphate, at least one zeolite and at least one polysaccharide within the composition for washing products in accordance with the invention can be carried out according to very diverse methods, in the form powders, liquids or powder / liquid mixtures, in one or more stages.

It is possible, for example, to bring the phosphate to a "precomposition" which is already in the form of particles flowing freely and associating zeolite and oxidized polysaccharide.

Such a precomposition can in particular be obtained by granulation of a mixture of zeolite and oxidized polysaccharide, for example on a granulator of the AEROMATIC type or a plate granulator.

By way of examples, five compositions in accordance with the invention are indicated below, each time specifying the ratio

In these five examples,
- The formula of the zeolite used is Na₂O Al₂O₃, 2SiO₂, xH₂O (x = 4 to 5); this is the ZEOLITHE A,
the oxidized glucose syrup is that obtained by catalytic oxidation of a glucose syrup having an ED close to 40 (I = 9),
- the phosphate is Na tripolyphosphate.

In Table I, the proportions of the three constituents have been grouped together in each of the five compositions described by way of examples and which are designated respectively by the letters A, B, C, D and E. TABLE I Constituents Composition (in%) AT B VS D E Na tripolyphosphate 15.63 6.25 15.63 25 15.63 Zeolite 48.12 62.5 56.25 50 64.37 Oxidized glucose syrup 36.25 31.25 28.12 25 20 Report R 1.33 2 2 2 3.2

To prepare the washing product according to the invention, use is made of the conventional constituents of washing products of the prior art based on phosphate and zeolite and the assembly consisting of phosphate and zeolite is replaced by a proportion identical or similar to one of the compositions according to the invention. The detergent thus established is in the form of powder; it is stable and also constitutes a new industrial product.

By way of example, the following is given (Table II) the constitution of a washing product according to the prior art. TABLE II Component Trademark or formula Producing company % in weight Marseille soap shavings CAT HENKEL 7 dedecyl benzene sulfonate FLUKA 3.5 cetyl stearic alcohol EMPILAN KN 11 MARCHON 1.75 ethoxylated alcohol EMPILAN KC 7 / L MARCHON 1.75 sodium sulfate Na₂ SO₄ PANREAC 10 sodium metasilicate SiO₂ Na₂O, 5H₂O PROLABO 10 sodium carbonate Na₂ CO₃ PANREAC 8 sodium perborate Na BO₃, 4H₂O FLUKA 25 ZEOLITHE A Na₂O Al₂O₃ 2SiO₂ x H₂O (x = 4 to 5) MONTEDISON 12 sodium tripolyphosphate na₅ P₃ WHERE RHONE-POULENC 20 carboxymethylcellulose BLANOSE 7M65 AQUALON 1

This product which contains 32% of detergency additive (phosphate and zeolite) is representative of the formulations of binary tripolyphosphate-zeolite mixture according to the prior art.

Five examples of washing products A₁, B₁, C₁, D₁, E₁ in accordance with the invention were also prepared which differ from the product according to the prior art by replacing the 32% phosphate + zeolite with each of the above compositions respectively. A to E or detergency additives, in accordance with the invention, the constituents of which are therefore present in the detergent in the proportions indicated in Table III. TABLE III Components of the detergency additive Washing products (proportions in% by weight of the constituents of the detergency additive) A₁ B₁ C₁ From E₁ Na tripolyphosphate 5 2 5 8 5 Zeolite A 15.4 20 18 16 20.6 Oxidized glucose syrup 11.6 10 9 8 6.4

To demonstrate the effectiveness of the compositions and, consequently, of the detergents according to the invention, comparative tests were carried out using, on the one hand, the above-mentioned detergent according to the prior art and, on the other hand, the five detergents according to the invention A₁ to E₁.

These comparative tests consist of washing tests which were carried out using washing machines of the WASCATOR FOM 71 brand with 70 liter front loading, the rotational speeds being 52 rpm at washing and 530 t / min spin.

The tests are carried out at the following three temperatures: 40 ° C, 60 ° C and 90 ° C.

For the test at 40 ° C, a temperature rise of 15 minutes is planned with reduced stirring, then a plateau at 40 ° C of 6 minutes with strong stirring. The complete cycle, i.e. including filling, rinsing and wringing, lasts 48 minutes.

For the test at 60 ° C, a temperature rise of 18 minutes is planned with reduced stirring, then a plateau at 60 ° C of 12 minutes with strong stirring. The complete cycle lasts 65 minutes.

For the test at 90 ° C, a temperature rise of 37 minutes with reduced stirring is expected, then a plateau at 90 ° C of 12 minutes with strong stirring. The complete cycle lasts 85 minutes.

In the three tests, the volume of washing water is 20 liters.

Three detergents are carried out per temperature.

The water hardness is 35 ° TH.

The washing load is composed of 3.5 kg of white fabric pieces (cotton or synthetic) whose dimensions are 55 cm x 70 cm.

At each washing, a load of 3.5 kg of pieces of white fabric is made to comprise a set of "soiled fabrics" of different natures and which contain predetermined soiling and deposited on these fabrics.

In practice, these "presalised" fabrics which are pinned to the washing load are the following:
- 2 strips of gray cotton each consisting of three pieces sewn together, namely a piece of TEST-FABRIC brand fabric (soiled with a mixture of mineral and vegetable oils and carbon black), a piece of brand fabric KREFELD (soiled with animal oil and carbon black) and a piece of IEC brand cloth (soiled with mineral oil and carbon black),
- 2 strips of gray TEST-FABRIC brand synthetic fabrics of the acetate, acrylic, polyester and polyester / cotton type (soiled with a mixture of mineral and vegetable oils and carbon black),
- 2 EMPA 103 brand cotton strips made up of 8 pieces sewn together, namely:
- a piece of white cotton (type EMPA 221),
- a piece of gray cotton (type EMPA 101 soiled with a mixture of vegetable oil and carbon black),
- a piece of cotton soiled with blood (type EMPA 111),
- a piece of cotton soiled with cocoa (type EMPA 112),
- a piece of cotton soiled by a mixed stain of milk, blood, carbon black (type EMPA 116),
- a piece of unbleached cotton (type EMPA 222),
- a piece of cotton soiled with wine (type EMPA 114),
- a piece of cotton soiled with black sulfur (not used in these measurements),
- 2 cotton bands impregnated with KREFELD brand tea (ref. WFK 10G).

The dose of detergent is 7 g / l of water.

To assess the quality of the washing, we measured the removal of dirt and stains on the one hand and, on the other hand, determined the effect of the washing on the graying, yellowing and the degree of whiteness.

To assess the elimination of dirt and stains, we proceeded by photometry (measurements of the amount of light reflected by the fabric); it is thus possible to calculate the percentages of soil removal. A device for measuring the reflection of light, marketed under the brand ELREPHO 2000 by the company Datacolor, is used.

x 100      (1)

dans laquelle:
A = réflectance de l'échantillon blanc témoin,
B = réflectance de l'échantillon sali témoin,
C = réflectance de l'échantillon sali après essai.The removal of soiling is expressed by the formula
Elimination in% =

x 100 (1)

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, under the action of optical brighteners.

The number of measurements made per fabric is 4, i.e. 4 measurements (that is to say in four different places on the same piece of fabric) x 3 washes x 2 strips of fabric = 24 measurements per soiling, per formulation and by temperature.

Regarding graying, yellowing and degree of whiteness, we measure the cumulative effect of three washes (we use the provisions of standard NF T 73 601) on three coupons of white cotton EMPA 221 which are incorporated into the washing bath. On each coupon, 4 measurements are made, which therefore gives 12 measurements per formulation and per temperature studied.

If we designate
- by Rgo, the green trichromatic component obtained before washing,
- by Rbo, the blue trichromatic component obtained before washing and
- by Rg and Rb, the same measurements made after washing,
- the intrinsic graying is given by the formula
G = Rgo - Rg
- intrinsic yellowing is given by the formula
J = (Rg-Rgo) - (Rb-Rbo)
- the degree of whiteness is given by the formula
BL = 3 (Rb-Rbo) - 2 (Rg-Rgo).

In the tests themselves which will now be described, the effectiveness of the washing products in accordance with the invention has been studied successively on oil-based stains and on carbon black, then on protein stains and stains oxidizable and finally it was determined the "degree of white" conferred by said products on the treated fabrics.

1. Stains produced by mixing mineral, vegetable and / or animal oil with carbon black.

The washing tests were carried out, on the one hand, on gray cotton and, on the other hand, on synthetic fabrics.

a) Tests on gray cotton

By washing, two bands of gray cotton were successively treated each time, the source and the method of soiling are indicated below:
- TEST-FABRIC brand gray cotton soiled with a mixture of mineral oil, vegetable oil and carbon black
- KREFELD brand gray cotton soiled with a mixture of animal oil and carbon black
- EMPA 101 brand gray cotton soiled with a mixture of vegetable oil and carbon black
- IEC gray cotton, EMPA 106 soiled with a mixture of mineral oil and carbon black.

These four types of soiled cotton are representative of insoluble pigmentary stains bound to the fabric by greasy film, such as, for example, shirt collars, jacket collars, tea towels and greasy stains.

The three groups of tests carried out respectively at 40 ° C, 60 ° C and 90 ° C gave for the products A₁, B₁, C₁, D₁ and E₁ in terms of the elimination of soiling represented by the above formula ( 1), the results gathered respectively in Tables IV, V and VI. TABLE IV (tests at 40 ° C) Type of fabric Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ TEST-FABRIC 44.9 37.1 39.8 38.3 43.1 43 KREFELD 70.4 71.2 71.7 69.3 73.1 71 IEC 44.2 46.7 44.0 42.5 45.4 44.1 EMPA 22.4 22.0 24.2 23.5 22.0 22.9 Average 45.5 44.2 44.9 43.4 45.9 45.3 (tests at 60 ° C) Type of fabric Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ TEST-FABRIC 63 44.7 45.5 49.2 46.5 43.4 KREFELD 64.5 79.8 84.7 85.1 81.6 79.8 IEC 54.7 49.9 50.2 50.7 50.8 47.7 EMPA 37.6 28.1 29.1 29.4 32 28.4 Average 55 50.6 52.4 53.6 52.7 49.8 (tests at 90 ° C) Type of fabric Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ TEST-FABRIC 88 92.9 86.1 93.7 94.1 94.3 KREFELD 72.3 97.2 95.9 95.9 98.6 96.8 IEC 69.1 65.2 65 66 69.2 67.8 EMPA 53.9 47.2 42.4 47.9 46.5 48.6 Average 70.8 75.6 72.3 75.9 77.1 76.9

The soiling used being different for each of the fabrics by the contribution of fatty matter (vegetable, animal, mineral or mixed), they each give a different response. Nevertheless, their average gives a good idea of natural soiling, and we then note that the formulations A₁, B₁, C₁, D₁ and E₁ give results which are as good as those of the control.

In addition to the remarkable stabilizing power of the oxidizing agents conferred by the composition according to the invention, the detergents comprising this aforementioned composition make it possible to satisfy all the criteria required in detergency.

b) Tests on gray synthetic

The synthetic fabrics used here are fabrics of the acetate, acrylic, polyester (dacron) and polyester / cotton (dacron / cotton) type of the TEST-FABRIC brand; they were soiled with a mixture of mineral oil and vegetable oil with carbon black.

The three groups of tests carried out respectively at 40 ° C, 60 ° C and 90 ° C gave for the products A₁, B₁, C₁, D₁ and E₁ in terms of the elimination of soiling represented by the above formula ( 1), the results being collected respectively in Tables VII, VIII and IX. TABLE VII (tests at 40 ° C) Type of synthetic Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ Acetate 86.9 83.1 85.2 84.9 85.2 84.5 Acrylic 53.2 55.1 56.4 58.9 59 57.7 Polyester 27.5 36.8 36.2 36.8 37.2 36.9 Cotton polyester 61.5 53 56.9 58.1 59.8 59.2 Average 57.3 57 58.7 59.7 60.3 59.6 (tests at 60 ° C) Type of synthetic Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ Acetate 81.1 85.6 84.1 86.6 68.8 82.4 Acrylic 71.2 71.9 74.5 69.9 71.5 70 Polyester 19.4 21.6 26.3 24.8 20.1 20.3 Cotton polyester 60.7 51.9 52.7 53.7 54.6 53.9 Average 58.1 57.7 59.4 58.8 58.8 56.6 (tests at 90 ° C) Type of synthetic Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ Acetate 97.2 99.6 101.4 100.4 101.1 99.3 Acrylic 99.4 100.2 99.6 97.2 98.5 100.5 Polyester 37.6 35.8 32.2 28.9 35.3 34.3 Cotton polyester 78.6 77.8 76.3 76.9 79.8 77.3 Average 78.3 78.3 77.4 75.8 78.7 77.9

The average of the results illustrates the behavior of products in accordance with the invention at 40 ° C, 60 ° C and 90 ° C respectively on synthetic fabrics. As on gray cotton, formulations A₁, B₁, C₁, D₁ and E₁ give results as good as the product according to the prior art and at all temperatures.

2. Protein stains

The action of the products in accordance with the invention on protein stains is studied using cotton-type fabrics of the EMPA brand, namely: the EMPA 111 fabric soiled with blood, the EMPA 112 fabric soiled with cocoa and the fabric EMPA 116 soiled with a mixture of blood, milk and carbon black.

These soils are representative of stains such as blood, milk, egg, gravy, mayonnaise, sauces and the like.

A group of tests carried out at 40 ° C gave for the products A₁, V₁, C₁, D₁ and E₁ with regard to the elimination of the soiling represented by the above-mentioned formula (1), the results gathered in table X . PAINTINGS (tests at 40 ° C) Type of fabric Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ EMPA 111 47.4 50.2 50.6 51.6 52 48.4 EMPA 112 29 24.2 26.1 26.5 28.7 25.1 EMPA 116 10.3 11.4 12.6 12.2 12.7 12.4 Average 28.9 28.6 29.8 30.1 31.1 28.6

The temperature of 40 ° C was chosen as the sole working temperature on protein stains. In fact, being an enzyme-free formulation, we chose the temperature that best reflects current market trends in washing.

It can be seen from the average of the measurements that the formulations A₁, B₁, C₁, D₁ and E₁ give results greater than or equal to those of the product according to the prior art.

3. Oxidizable stains

The action of washing products in accordance with the invention on oxidizable stains is studied using the following fabrics:
- KREFELD brand cotton 10 G soiled with tea
- EMPA 222 brand cotton, i.e. unsoiled unbleached cotton
- EMPA 114 brand cotton soiled with wine.

The above fabrics are sensitive to chemical oxidation; the spots caused are those which the bleaching reduces or eliminates (other spots of this type are those caused by fruits, coffee, vegetables and others).

The three groups of tests carried out respectively at 40 ° C, 60 ° C and 90 ° C gave for the products A₁, B₁, C₁, D₁ and E₁ in terms of the elimination of soiling represented by the above formula ( 1), the results gathered respectively in Tables XI, XII and XIII. TABLE XI (tests at 40 ° C) Cotton type Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ TEA 16.6 10.2 12.7 13 11.5 12.4 Ecru cotton 1.9 5.5 5.6 4.9 5 4.7 WINE 30.7 31.2 29.6 29.5 31.4 30.7 Average 16.4 15.6 16 15.8 15.9 15.9 (tests at 60 ° C) Cotton type Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ TEA 31.5 39.6 41 47.8 41.5 39.4 Ecru cotton 12 14 16.7 16.9 15.4 12.9 WINE 43.6 46.7 47.5 53.4 49.7 45.1 Average 29 33.4 35.1 39.4 35.5 32.5 (tests at 90 ° C) Cotton type Removal of dirt (in%) Prior art A₁ B₁ C₁ From E₁ TEA 61.2 89.7 89.4 88.7 87.9 80.7 Ecru cotton 22.8 48.4 44.9 45.3 47.4 39.6 WINE 71.8 97.7 93.5 96.8 98 93 Average 51.9 78.6 75.9 76.9 77.8 71.1

The average of the results obtained on tea and wine stains and on unbleached cotton reflects the behavior of the products tested on all the stains in this family.

Thus at 40 ° C, the products according to the invention A₁, B₁, C₁, D₁ and E₁ give results similar to those of the products according to the prior art.

By cons, at 60 and 90 ° C, the products according to the invention are much more efficient and give results which, compared to the product according to the prior art, are 36% higher in the case of product C₁ at 60 ° C and 51% in the case of product A₁ at 90 ° C.

The variation expressed as a% of the elimination of soiling relative to the elimination of soiling obtained with the product according to the prior art was calculated for each test and for each product, and the values calculated in the table were combined. XIV. TABLE XIV Variation (in%) of the elimination of soiling compared to the product according to the prior art A₁ B₁ C₁ From E₁ 40 ° C - 4.8 - 2.4 - 3.6 - 3 - 3 60 ° C 15.1 21 35.8 22.4 12 90 ° C 51.8 46.2 48.1 49.9 36.9

4. Degree of white

White non-azure cotton of the brand EMPA 221 is used to determine whether a given washing product is capable of preserving, increasing or decreasing the initial degree of whiteness of the fabric.

The three groups of tests carried out respectively at 40 ° C, 60 ° C and 90 ° C gave for the products A₁, B₁, C₁, D₁ and E₁ in terms of the degree of whiteness given by the above formula
BL = 3 (Rb - Rbo) - 2 (Rg - Rgo),
the results collated in table XV. TABLE XV Variation (in%) of the degree of whiteness Prior art A₁ B₁ C₁ From E₁ 40 ° C 2.5 2.5 2.9 2.6 2.7 2.4 60 ° C 8.3 8.3 8.6 8.6 8 8.2 90 ° C 12.3 15.3 15.9 13.8 18.5 17.9

It is found that, whatever the temperature of the test, the washing products A₁, B₁, C₁, D₁ and E₁ improve the degree of whiteness compared to the product according to the prior art; after washing, a fabric is obtained whose degree of whiteness is greater than that which it had before washing.

Tests using oxidized glucose syrups with different ED.

Four examples of washing products F₁, G₁, H₁ and K₁ in accordance with the invention were also prepared.

These four washing products different from the product according to the prior art described above by replacing the 32% of phosphate and zeolite with 8% of phosphate + 16% of zeolite + 8% of an oxidized glucose syrup, said oxidized product presenting respectively:
- F₁: a DE close to 21 (I = 5.0 approximately)
- G₁: a DE neighbor of 38 (I = 8.8 approximately)
- H₁: a DE neighbor of 48 (I = 11 approximately)
- K₁: a DE close to 60 (I = 13.3 approximately).

The washing products F₁ to K₁ generally show, for example during washing tests carried out at 60 ° C., performances just as remarkable as those observed for the products A₁ to E₁ described above, in particular those observed for the product D₁ whose introduction rate of oxidized polysaccharide is equal to 8% by weight.

Claims (13)

1. Composition for washing products, characterized in that it comprises at least one phosphate, at least one zeolite and at least one oxidized polysaccharide, the proportion of oxidized polysaccharide representing approximately 5 to approximately 40% by weight of the total mass of three constituents. 2. Method for preparing the composition according to claim 1, characterized in that, in a composition based on phosphate and zeolite for washing products, a proportion of approximately 5 to approximately 40% by weight of these is replaced. constituents by an equivalent proportion of at least one oxidized polysaccharide. 3. Composition according to claim 1, characterized in that the oxidized polysaccharide is a di-, a tri-, an oligo- or an oxidized polysaccharide chosen from the group comprising:
oxidized disaccharides having an aldonic terminal function,
oxidized trisaccharides, oxidized oligosaccharides and oxidized products of hydrolysis of starch, cellulose and hemicelluloses comprising a terminal function of aldonic type, and
the mixture of the above oxidized polysaccharides. 4. Composition according to one of claims 1 and 3, characterized in that the oxidized polysaccharide is a starch hydrolyzate having an oxidized DE from 5 to 90 or a glucose syrup having an oxidized DE from 5 to 90 and of which the acid number I, which is expressed in number of grams of carboxylic function per 100 g of oxidized polysaccharide, and which is given by the formula:

is from 1 to 20 and preferably between 6 and 15. 5. Composition according to one of claims 1 and 3 to 4, characterized in that the oxidized polysaccharide has an acid number between about 8 and about 14 and is obtained by oxidation of a starch hydrolyzate having a DE between about 35 and about 65. 6. Composition according to one of claims 1 and 3 to 5, characterized in that the oxidized polysaccharide has a level of less than about 0.6%, preferably less than 0.1% and even more preferably less than 0, 05%, in reducing sugars. 7. Composition according to Claim 6, characterized in that the oxidized polysaccharide is obtained by catalytic hydrogenation of a starch hydrolyzate having an oxidized DE of from 5 to 90 or of a glucose syrup having a DE of from 5 to 90 oxidized and having an acid number I between 1 and 20. 8. Composition according to one of claims 1 and 3 to 7, characterized in that the phosphate is a mono- or a polyphosphate chosen from the group consisting of orthophosphate, pyrophosphate, tripolyphosphate, hexametaphosphate. 9. Composition according to one of claims 1 and 3 to 8, characterized in that the zeolite is a sodium silico-aluminate (ZEOLITHE A). 10. Composition according to one of claims 1 and 3 to 9, characterized in that it comprises:
a proportion of 5 to 40% by weight, preferably from 10 to 35% by weight of phosphate and, more preferably still, from 20 to 30% by weight of phosphate,
a proportion of 90 to 20% by weight, preferably from 80 to 30% by weight of zeolite and, more preferably still, from 60 to 40% by weight of zeolite,
- A proportion of 5 to 40% by weight, preferably from 10 to 35% by weight and, more preferably still, from to 30% by weight of oxidized polysaccharide. 11. Composition according to one of claims 1 and 3 to 10, characterized in that the weight ratio between on the one hand the zeolite and on the other hand the oxidized polysaccharide is between approximately 0.5 / l and 4 / l, preferably between 1.5 / l and 2.5 / l and, even more preferably, around 2.0 / l. 12. Washing product characterized in that it contains a proportion of 5 to 40% by weight, preferably between 15 and 35% by weight of a washing composition comprising at least one phosphate, at least one zeolite and at least one oxidized polysaccharide, the proportion of oxidized polysaccharide representing approximately 5 to approximately 40% by weight of the total mass of the three constituents. 13. Washing product according to claim 12, characterized in that it comprises a detergent agent and / or a surface-active agent and / or an antiredeposition agent and / or an oxidizing agent and / or a structuring agent and / or an anticorrosion agent and / or an anti-foaming agent and / or an enzyme and / or a perfume and / or a dye and / or a solubilizing agent.