EP0437988A2 - Detergent additive based on polyphosphate and an active optical agent, method of its production and its use in detergent composition - Google Patents

Abstract

Detergent compound characterised in that it comprises a support consisting of an at least partially hydrated polyphosphate, the said polyphosphate incorporating or supporting at least one substance intended to be distributed uniformly on an item of washing and a product chosen from the group comprising the siliconates, the derivatives of siliconates and the silicone resins. The invention applies particularly to the case where the abovementioned substance is chosen from the group of optically active agents such as the optical whitening agents.

Description

The present invention relates to a detergent compound based on polyphosphate, of a product chosen from the group comprising siliconates, siliconate derivatives and silicone resins and of a substance intended to be distributed uniformly over a washing room as well as its preparation. It also relates to the detergent use of this compound.

Detergent compositions in the form of powder in particular, contain in addition to their usual constituents of the builders or surfactants type, many additives such as dyes, optical brighteners, photobleaching agents, softening agents, antiseptic agents, etc.

However, generally speaking, these additives, which function through adsorption on the textile fibers, require a homogeneous distribution over the part to be washed. Indeed, if they are located in particular places on the article to be treated, there appears, at the end of the detergent or after drying of it, colored spots or halos, which constitutes a disadvantage completely unacceptable and which also leads to a lowering of the expected performance of the product.

However, if these additives are directly incorporated into the washing powder, this homogeneous distribution is difficult to obtain given the very great risks of contact of the additive with the laundry before the powder is dissolved. This is particularly the case for hand washing in a bowl.

This case is in fact considered to be the most difficult, given the direct contact of the powder and the linen and the fact of the use of small volumes of water and washing habits favoring the dusting of the powder on the linen.

It is therefore essential to have a means allowing this homogeneous distribution.

In addition, incidentally and for commercial reasons, in the case of colored additives, it is sought to obtain a visual effect in the washing powder by the presence of colored grains. So these grains must be large enough not to give a uniform coloration of the detergent powder. This last requirement increases the risk of localized distribution of the colored additive on the laundry.

The main object of the invention is therefore a means or a system making possible the homogeneous distribution of a detergent additive on the article to be washed, this whatever the type of washing used.

A second object of the invention is the preparation of such a system.

For this purpose, the detergent compound according to the invention is characterized in that it comprises an at least partially hydrated polyphosphate, this polyphosphate incorporating or supporting at least one substance intended to be distributed uniformly over the part to be washed and a product chosen from the group comprising siliconates, siliconate derivatives and silicone resins.

Furthermore, the process for preparing the detergent compound consists in mixing with the anhydrous or partially hydrated polyphosphate an aqueous solution comprising the substance and the aforementioned product.

• mélange du polyphosphate anhydre ou partiellement hydraté et de la substance précitée, puis addition d'eau audit mélange, cette eau pouvant au moins en partie être apportée sous la forme d'une solution aqueuse de ladite substance
• addition du produit choisi parmi les siliconates, les dérivés de siliconates et les résines siliconiques au mélange résultant de l'étape précédente et addition éventuellement d'une quantité supplémentaire d'eau, cette eau pouvant au moins en partie être apportée sous la forme d'une solution aqueuse dudit produit.

According to a preferred variant of the invention, the process for preparing the detergent compound comprises the following steps:

• mixing of the anhydrous or partially hydrated polyphosphate and the aforementioned substance, then addition of water to said mixture, this water being able at least in part to be supplied in the form of an aqueous solution of said substance
• addition of the product chosen from siliconates, siliconate derivatives and silicone resins to the mixture resulting from the previous step and optionally addition of an additional quantity of water, this water being able at least in part to be provided in the form of an aqueous solution of said product.

Finally, the invention relates to a detergent composition which is characterized in that it comprises a detergent compound of the above type or prepared by the process described above.

The detergent compound defined above ensures a delayed release of the additive, and thus makes it possible to reduce the risks of additive - laundry contact. It therefore provides a completely homogeneous distribution of this additive on the laundry and this even for hand washing in a bowl. In addition, this presentation of the additive makes it possible to impart a visual effect to the washing powder if necessary.

Other details and characteristics will appear better on reading the description which follows as well as concrete but nonlimiting examples, relating to the implementation of the invention.

The detergent compound according to the invention therefore consists of three types of elements, namely an at least partially hydrated polyphosphate incorporating or supporting on the one hand, at least one substance intended to be uniformly distributed over a part to be washed (called in the rest of the description "the substance"), and on the other hand a product chosen from siliconates, siliconate derivatives and silicone resins, (called in the rest of the description "the product").

According to a preferred embodiment of the invention, the detergent compound has the following particular structure:

The aforementioned substance is located at least partly inside or at the heart of the polyphosphate-based support grain. The aforementioned product is located at least partially on the surface of said support or is adsorbed thereon.

The optimum embodiment is that for which all of the above substance is placed inside the polyphosphate grain and all of the above product on the surface thereof or adsorbed thereon. Of course, any intermediate configuration can be envisaged without departing from the scope of the present invention, in which a part of the substance would be present on the surface of the polyphosphate and a part of the product would be located inside of it.

Furthermore, the support based on polyphosphate can be composed of pyrophosphate or tripolyphosphate. However, in the context of the invention, it is preferred to use tripolyphosphate (TPP).

In addition, the polyphosphate of the compound according to the invention is at least partially hydrated, that is to say that it has a hydration rate of at least 8% by weight.

More particularly, this hydration rate is at least 10%, preferably at least 15% and in particular between 15 and 18%. This hydration results from the process for preparing the compound. As will be described later, it is this water of hydration which makes it possible to introduce the substance into the heart of the support.

Advantageously, the support must have a density of between 0.4 and 0.8 and preferably between 0.6 and 0.8.

Indeed, with a density greater than 0.8, polyphosphate and in particular TPP, in the form of particles, very difficultly absorbs water, which consequently hinders the introduction via water, substance at the heart of the particles, and that in sufficient quantity.

On the other hand, if the density of the support is less than 0.4, the compound is difficult to handle. In addition, it is advantageous to have a density of at least 0.6 in order to obtain a sufficient attrition resistance to avoid dusting of the compound according to the invention and consequently a uniform coloring of the washing powder.

With regard to the particle size of the polyphosphate and in particular of the TPP, particles are generally used whose average size is between 200 μm and 800 μm, and preferably between 600 μm and 700 μm. This particle size is recommended to obtain the optical effect described above, when the aforementioned substance is colored.

Another preferred characteristic of the invention in the case of a TPP support is that it is in the form of phase 1.

Finally, it is preferred to use an alkaline polyphosphate. More particularly, the sodium TPP is retained as a support according to the invention.

Generally, the polyphosphate content is between 78 and 91.8% by weight, expressed as anhydrous polyphosphate and relative to the total weight of the detergent compound.

Another constituent of the detergent compound according to the present invention is the substance intended to be distributed uniformly over a room to be washed. It is understood that the compound of the invention can comprise several substances of this type at the same time. Said substance can in particular be an optically active agent. This agent can be chosen from the group of optical brighteners, photobleaching agents, and dyes.

Thus, in the group of optical brighteners, for cotton fabrics, polyamides and polyesters, mention may be made, by way of nonlimiting examples, of compositions of stilbene, triazole and benzidine-sulfone, in particular sulfonated substituted triazinyl-stilbene, naphthotriazole- sulfonated stilbene, benzidine-sulfone, etc., the most preferred being combinations of stilbene and triazole.

et dont les atomes d'hydrogène portés par les carbones repérés 1 à 8 peuvent être substitués notamment par des atomes de Cl, Br et I.As photobleaching agents, mention may be made, inter alia, of porphine derivatives, but also the compounds described in French patent application FR-A- 2,564,481 in the name of RHONE-POULENC CHEMISTRY, the teaching of which is incorporated here in the present description and corresponding to the water-soluble salts or disels of the acid corresponding to the following general formula (1):

and whose hydrogen atoms carried by the carbons marked 1 to 8 can be substituted in particular by atoms of Cl, Br and I.

Among these products, there may be mentioned for example eosin "Yellow", but also 1,2-dibromo fluorescein, that is to say the dibromo salt or disel of formula (1), dibromo-3, 4 fluorescein, phloxin i.e. 1,2,3,4 tetrabromo-5,6,7,8 fluorescein, 1,2-diodo fluorescein, 3,4-diodo fluorescein and tétraiodo-1,2,3,4 tétrachloro-5,6,7,8 fluoresceine or "Rose Bengal".

In the group of dyes which can be used as constituents of the washing compound according to the invention, there may be mentioned for example E 100 (curcumin), E 102 (tartrazine), E 120 (cochineal), E 123 (amaranth) , E 127 (erythrosine), E 131 (patent blue), E 132 (indigotine), E 140 (chlorophylls).

More particularly, as a substance according to the invention, belonging to the group of photobleaching agents, it is possible to choose a derivative of tetrabenzo-tetraazoporphine.

As a derivative of this type which can also be used in the context of the invention, mention may be made of TINOLUX BBS from the company CIBA-GEIGY.

According to the invention, the content of substance intended to be distributed uniformly of the aforementioned type for example is generally 0.1 to 2% by weight relative to the total weight of the detergent compound.

Finally, the detergent compound comprises a product chosen from siliconates, siliconate derivatives and silicone resins.

Siliconates are well known products, they are salts of siliconic acid or its derivatives.

et/ou les produits de condensation de ceux-ci, formule dans laquelle R est un reste hydrocarboné généralement de 1 à 18 atomes de carbone, le cas échéant substitué par un atome d'halogène, un groupe amino, éther, ester, époxy, mercapto, cyano, (poly)glycol;Mention may in particular be made of the products corresponding to formula (2):

and / or the condensation products thereof, formula in which R is a hydrocarbon residue generally of 1 to 18 carbon atoms, optionally substituted by a halogen atom, an amino group, ether, ester, epoxy, mercapto, cyano, (poly) glycol;

m is an integer or fractional number varying between 0.1 and 3;

M is an alkali metal or an ammonium or phosphonium group.

Preferably, R is a hydrocarbon residue of 1 to 10 carbon atoms and more particularly of 1 to 6 atoms.

More specifically, R can be an alkyl radical, for example methyl, ethyl, propyl, butyl, isobutyl; an alkenyl radical such as for example vinyl, an aryl radical, for example phenyl or naphthyl, an arylalkyl radical such as for example benzyl or phenyl-ethyl, alkylaryl such as for example tolyl, xylyl, or an araryl radical such as biphenylyl.

For M, there may be mentioned more particularly sodium or potassium as well as the groups N⁺R'₄, P⁺R'₄ in which R 'are identical or different and are hydrocarbon residues of 1 to 6 carbon atoms.

More particularly, alkaline siliconates are used. Alkaline earth siliconates can also be used.

Likewise, particular use is made of alkylsiliconates and in particular alkaline alkylsiliconates such as, for example, sodium or potassium methylsiliconates.

It is also possible to use the siliconates of formula (2) for which R is a vinyl or phenyl radical, and more particularly the alkali siliconates of this type.

It should be noted that alkali or alkaline earth siliconates are products, most of which are commercially available.

They can be prepared for example by hydrolysis of the corresponding silanes having 3 hydrolyzable groups such as halogen atoms, alkoxy radicals, followed by dissolution of the product obtained in a solution of a strong inorganic base in proportions such as there is at least one equivalent in base per atom of silicon (see for example US-A-2,441,422, US-A-2,441,423).

As an example of commercially available siliconates of this type, mention may in particular be made of RHODORSIL® SILICONATE 51T, marketed by the Applicant, which is a potassium methylsiliconate.

As indicated above, the hydrophobing agent can also be chosen from siliconate derivatives.

By derivative products is meant here the condensation products of the products corresponding in particular to formula (2) described above, or those resulting from the at least partial polymerization into silicone compounds or polymers.

A third type of supported products which can be used in the context of the present invention is that of silicone resins.

These silicone resins are well-known branched organopolysiloxane polymers which are commercially available. They have, per molecule, at least two different units chosen from those of formula R₃SiO₀ _, ₅ (unit M), R₂SiO (unit D), RSiO₁ _, ₅ (unit T) and SiO₂ (unit Q).

The radicals R are identical or different and are chosen from linear or branched alkyl radicals, vinyl, phenyl, trifluoro-3,3,3 propyl radicals.

Preferably, the alkyl radicals have 1 to 6 carbon atoms inclusive.

More particularly, mention may be made, as alkyl radicals R, of methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals.

These resins are preferably hydroxylated and in this case have a weight content of hydroxyl group of between 0.1 and 10%.

Examples of resins include MQ resins, MDQ resins, TD resins and MDT resins.

Resins having a molecular mass of less than 25,000 can be used more particularly.

As resins of this type, use may in particular be made of the products sold by the Applicant under the names RHODORSIL 865 A or 878 A.

According to the invention, the content of supported product and in particular of siliconate is generally from 0.1 to 2% by weight relative to the total weight of the detergent compound.

We will now describe more precisely the process for preparing the detergent compound.

Firstly, according to a first variant, the polyphosphate, and in particular the TPP, anhydrous or partially hydrated, can be mixed in a single step with the aforementioned substance and product, at least one of these being provided in the form of an aqueous solution.

Another variant of the process according to the invention consists in preparing the detergent compound in two mainly stages.

In the first step, the polyphosphate, and in particular the TPP, anhydrous or partially hydrated, is mixed with the aforementioned substance and water is brought to this mixture for the hydration of the polyphosphate. You can do it by different methods.

We can first mix the polyphosphate and the substance and then add water to the mixture obtained.

According to a preferred method, the polyphosphate, the water and the substance are mixed at the same time. In the latter case, the substance can be brought in the form of an aqueous solution and it is this solution which at least partially provides the necessary water.

The water brought in at this stage penetrates into the polyphosphate grain and at the same time allows the introduction of the substance inside the grain itself.

The second step consists in adding the above-mentioned product to the mixture obtained previously. Here too, we can operate in several ways.

We can first of all simply mix the elements.

You can also mix and add water. This addition of water can be done after the dry mixing of the elements. Preferably, however, this addition is carried out simultaneously with the mixing. In this case, the product can be brought in the form of an aqueous solution which will thus provide the necessary water.

Furthermore, the amount of water used in the first step represents at least 50% of the water used entirely in the process for the desired hydration rate of the polyphosphate.

Advantageously, between each step, a maturing of each of the resulting mixtures is carried out. Such an operation ensures better diffusion of the water and of the constituents of the compound and promotes the crystallization of the water in the TPP particles thus treated. Ripening allows each mixture to cool because the hydration of TPP is an exothermic reaction. It is carried out by stirring each mixture obtained for a period of approximately 20 minutes in an atmosphere having a non-saturated vapor pressure.

Finally, the detergent compound according to the invention finds its application as a constituent in any detergent application, in particular compositions of the powder type.

In a manner known per se, these compositions can comprise a builder of the phosphate, polyphosphate, zeolite, silicate or carbonate type. They can also include surfactants, anionic, nonionic, cationic, amphoteric. They can also include bleaching agents of the perborate type, foam control agents, anti-deposition agents, fluorescent agents and all additives of the perfume, enzymes, sequestering, soluble polymers, dyes type for example.

The content of detergent compound in a detergent composition is generally between 1 and 10% by weight.

Concrete examples will now be given.

EXAMPLES

First, some definitions and clarifications are provided below.

The mixing of the constituent elements of the compound was carried out thanks to the use of a laboratory mixer of 5 liters of useful capacity of LODIGE brand and of a laboratory sprayer.

The detergent powder was obtained by mixing 5% by weight of the compound according to the invention with a detergent reconstituted in the laboratory according to French standard NF C73171.

The coloring test was carried out according to the following procedure using standard cotton No. 405, sold by Test Fabrics (USA):

It is deposited in the form of an accordion at the bottom of a plastic basin 50 g of already bleached fabric.

Then add 1 liter of city water at 30 ° C, hardness 17.9 ° French (a degree of French hardness is equivalent to 10 mg Ca CO₃ / l), then press the fabric well on the bottom of the basin to remove air bubbles. The water height above the fabric should be 2 cm.

For a period of 20 seconds, 5 g of washing powder containing 5% of the compound according to the invention are spread over the surface of the liquid.

After 1 minute, the tissue is taken out of the basin, rinsed for 30 seconds under the tap with tap water, then wrung out.

Finally, cut the upper part of the fabric (20 x 20 cm) and dry at 150-160 ° with the iron.

Spectrophotometric measurements

A white cotton sample is brought into contact on the one hand with an aqueous solution of TINOLUX BBS alone and on the other hand, with an aqueous solution of the detergent compound according to the invention, for 20 minutes at 35 ° C. The difference between the measurements carried out gives the quantity of TINOLUX BBS absorbed on the tissue, in% compared to the quantity fixed in the case of the Tinolux solution alone, which serves as a reference.

EXAMPLE 1

In a LODIGE Laboratory mixer, 1740 g of sodium TPP of the RHODIA PHOS G type marketed by RHONE-POULENC, of density = 0.75, are mixed with 20 g of TINOLUX BBS previously diluted in 120 g of water, by spraying this solution on the TPP.

A maturing step is then carried out with stirring for 20 minutes in an unsaturated atmosphere.

Then 20 g of SILICONATE 51T diluted in 100 g of water are then added to the mixture thus obtained by spraying. We end with a new period of ripening.

The staining test carried out under the conditions described above and with the compound thus prepared gives very good results because no stain appears on the treated tissue (note 1).

In addition, spectrophotometric measurements indicate that TINOLUX BBS is well fixed on cotton, and this at 85%.

COMPARATIVE EXAMPLE 2

This example highlights the essential role of the product supported in the compound according to the invention.

1960 g of sodium TPP of the same type as in Example 1 are mixed with a solution comprising 20 g of TINOLUX BBS and 20 g of water. We then proceed to the ripening stage.

The same staining test, but carried out with the compound of this example 2, gives very poor results since the tissue is heavily stained with colored spots (note 5).

Claims (19)

Detergent compound characterized in that it comprises a support constituted by an at least partially hydrated polyphosphate, said polyphosphate incorporating or supporting at least one substance intended to be distributed uniformly over a washing room and a product chosen from the group comprising siliconates, siliconate derivatives and silicone resins. Detergent compound according to claim 1, characterized in that the above-mentioned substance is located at least partially inside the polyphosphate. Detergent compound according to claim 1 or 2, characterized in that the aforementioned product is located at least partly on the surface of the polyphosphate. Detergent compound according to one of the preceding claims, characterized in that the polyphosphate has a hydration rate of at least 8%. Detergent compound according to one of the preceding claims, characterized in that the polyphosphate has a density between 0.4 and 0.8, preferably between 0.6 and 0.8. Detergent compound according to one of the preceding claims, characterized in that the polyphosphate has a particle size of between 200 and 800 µm, preferably between 600 and 700 µm. Detergent compound according to one of the preceding claims, characterized in that the polyphosphate is a pyrophosphate or a tripolyphosphate. Detergent compound according to one of the preceding claims, characterized in that the polyphosphate used is a tripolyphosphate in the form of phase 1. Detergent compound according to one of the preceding claims, characterized in that the polyphosphate is an alkaline tripolyphosphate and in particular sodium tripolyphosphate. Detergent compound according to one of the preceding claims, characterized in that the above-mentioned substance is an optically active agent chosen from the group of optical brighteners, photobleaching agents and dyes. Detergent compound according to claim 10, characterized in that the aforementioned substance, chosen from photobleaching agents, is a derivative of tetrabenzo-tetraazoporphine. Detergent compound according to one of the preceding claims, characterized in that the content of the above-mentioned substance is between 0.1 and 2% by weight relative to the total weight of the compound. Washing compound according to one of the preceding claims, characterized in that the siliconate is an alkaline siliconate, in particular an alkaline alkylsiliconate. Detergent compound according to one of the preceding claims, characterized in that the content of the abovementioned product is between 0.1 and 2% by weight relative to the total weight of the compound. Process for the preparation of the washing compound according to one of Claims 1 to 14, characterized in that it consists in mixing with the anhydrous or partially hydrated polyphosphate, the substance and the aforementioned product, at least one of these being provided under form of an aqueous solution. Process for the preparation of the washing compound according to one of Claims 1 to 14, characterized in that it comprises the following stages: a) the anhydrous or partially hydrated polyphosphate and the aforementioned substance are mixed and water is added to said mixture, this water being able at least in part to be supplied in the form of an aqueous solution of said substance. b) the above-mentioned product is added to the mixture resulting from the previous step and an additional quantity of water is optionally added, this quantity being able at least in part to be provided in the form of an aqueous solution of said product. Method according to claim 16, characterized in that a ripening is carried out at the end of each of the aforementioned steps a) and b). Process according to claim 16 or 17, characterized in that at least 50% of the water used in the process is supplied during step a). Detergent composition, characterized in that it comprises a detergent compound of the type according to claims 1 to 14 or of the type prepared by the process according to claims 15 to 18.