WO2011121157A1 - Peroxide-activating composition for cold washing, preparation method thereof and use of same - Google Patents

Abstract

The present invention relates to a composition that activates persalts in the cold wash process, an improved method for the preparation thereof and the use of same. More particularly, the present invention relates to a method for preparing a catalyst composition comprising an insoluble solid support, in particular an aluminosilicate such as zeolite, which contains one or more transition metals in the structure thereof and which promotes the elimination of stains during the washing process in an aqueous medium at ambient temperature. Furthermore, the present invention relates to the use of the resulting composition as a persalt activator in the cold-wash fabric bleaching process.

Description

 PEROXIDE ACTIVATING COMPOSITION FOR COLD WASHING, PREPARATION PROCEDURE AND USE OF THE SAME

DESCRIPTION

 The present invention relates to a activating composition of persalts in the cold washing process and an improved process for its preparation and use thereof. More particularly, the present invention relates to a process for preparing a catalyst composition comprising an insoluble solid support, in particular an aluminosilicate such as zeolite, which comprises in its structure one or more transition metals and which acts to enhance elimination. stains during the washing process in aqueous medium at room temperature by activating the peroxide contained in the detergent product, without affecting the dry stability of the detergent or damaging or deteriorating neither the color nor the fiber itself of the tissues subjected to washing. In addition, the present invention relates to the use of the composition prepared according to the process of the present invention as activator of persales in the process of bleaching of tissues in the cold wash.

Bleaching is a process commonly used to remove stains on textile materials during the washing operation. The most common types of bleaching are those that use chlorine or peroxides as bleaching agents. The bleaching with chlorine, although much cheaper, has many drawbacks such as that the chlorine cannot be mixed with the detergent in the same package, tends to attack various dyes and also degrades the fabrics. Peroxide bleaching is much more effective and safer with colored textiles and can stored together with detergent and other components, to form a unique detergent-bleach package.

 However, peroxide bleaching has several drawbacks, such that for the wash solution to be effective it must be at a temperature high enough to activate the peroxide compound. For example, sodium perborate requires a water temperature above 70 ° C, which is higher than the usual domestic washing temperatures.

 In order to reduce the temperature at which peroxide washing can be used, so-called "bleach activators" have been used as an alternative. Bleaching activators are compounds that do not themselves have bleaching action, but when used in combination with a bleaching peroxide compound it forms a new peroxide compound, which is more effective at low temperatures than the initial bleaching peroxide compound. Examples of such bleaching activators are tetraacetylethylenediamine (TAED), sodium p-acetoxybenzene sulfonate and sodium p-heptanoyloxybenzene sulfonate.

 It is also known in the art that certain covalent metals, in particular manganese (II), are excellent activators of peroxide bleaching agents such as sodium percarbonate and sodium perborate. US Patent 4,481,129 discloses that such activators are more effective when used in combination with a compound that releases carbonate anions to the aqueous wash solution.

However, it has recently been published that the use of soluble manganese (II) cations as bleach activators can dye clothes due to the oxidation of manganese to a higher valence state (see, US Patent 4,536,183). The presence of a strong oxidizing agent in the wash solution can oxidize the Mn (II) to Mn (IV), which can adhere to the fabric giving it a light brown appearance.

 This problem has been solved in the art by incorporating the cation Mn (II) into solid supports (for example, zeolite), which prevents manganese from depositing on the fabric. However, the procurement procedures developed to date, which are usually based on ion exchange and / or impregnation / spray drying, present numerous drawbacks and difficulties. Among these are that they include numerous and complex stages, so they are very expensive and also produce highly polluting waste into the environment. On the other hand, in the compositions known in the prior art there is no reference to the possibility that metal ions, for example manganese, are released again from the support in which they were absorbed into the wash solution in a process known as leaching and are deposited in the washed tissues.

 In addition, in practice, there are very few commercially available detergent / bleach products comprising bleaching activating agents based on covalent metal ions on solid supports, although these have been known for several decades.

Therefore, there is a need for a process for preparing a bleaching activating agent that is simple, economical, environmentally friendly and ensures that metal ions are not released in the leaching process when said agent comes into contact with the wash solution, thus causing tissue damage.

 Therefore, the objective of the present invention is to disclose a parakeet activating composition in the cold washing process. The bleaching activator composition of the present invention comprises a solid and stable support, preferably a crystalline or pseudocrystalline aluminosilicate, more preferably a zeolite, and most preferably type A zeolite, which comprises in its structure transition metals integrated in its reticles, preferably selected from the group comprising Mn II, Co II and / or Fe II, most preferably Mn II, for the activation of persalts in tissue washing.

 The persal activator composition of the present invention is characterized in that it produces a concentration of soluble manganese ions in a leaching test well below 0.2 ppm. This avoids incurring the well-known deterioration of the fibers, which is why other similar products have not prospered commercially.

Another objective of the present invention is to disclose an improved method of preparing the aforementioned activator composition. The process of the present invention comprises two fundamental steps: dehydration of the aluminosilicate support and impregnation thereof with transition metal ions. This makes said procedure advantageously simple, economical and clean, since it does not generate waste or release to the environment water that needs to be processed. If type 4A zeolite is used as a support for the persal activator composition of the present invention, which generally contains between 18 and 21% by weight of crystallization water, it must be partially or totally dehydrated. The zeolite 4A is dehydrated in such a way that there is a loss of water of crystallization between 5 and 21% by weight. The dehydration step of the process according to the present invention can be carried out continuously or discontinuously, both at atmospheric pressure and at reduced pressure, depending on the equipment used. Dehydration is preferably carried out by calcination at a temperature between 105 and 750 ° C, preferably between 300 and 600 ° C and most preferably, between 400 and 500 ° C.

 On an industrial scale, the dehydration process can be carried out in a calciner, for example, a rotary kiln. Advantageously, it can be carried out in a rotary kiln provided with atomizing nozzles, which allow the impregnation stage to be carried out.

Once dehydrated, the aluminosilicate or zeolite support is impregnated with an aqueous solution of a transition metal salt, preferably Mn II, Co II and / or Fe II, most preferably Mn II. Advantageously, the amount of transition metal ion solution to be impregnated in the dehydrated aluminosilicate support should not exceed the amount of water removed in the dehydration stage. Surprisingly, it has been found that if the amount of transition metal ion solution does not exceed the amount of water removed, the unwanted process of leaching the transition metal ions to the transition does not occur. washing solution, which causes tissue damage. In addition, carrying out the impregnation process as mentioned above prevents an additional drying step.

 The concentration of transition metal ions in the solution to be impregnated in the aluminosilicate support can be adjusted to achieve the best results. Advantageously, it is preferred to prepare a saturated or near saturation solution of the transition metal salt used.

 The impregnation must be carried out in such a way that a homogeneous product is obtained, that is, the transition metal ion solution is distributed equally. If this does not occur, local excesses may occur that result in poor anchoring of the transition metal ions to the support structure and that are subsequently leached into the wash solution.

 The type of transition metal ion salt used in the process of the present invention should preferably be a water soluble salt and the anion is selected from the group comprising acetate, carbonate, chloride, nitrate and / or sulfate, or a mixture from the same.

In addition, the impregnation is compatible with the use of complexers such as ammonia, amines such as methylamines, ethylenediamine (EDA) and diethylenetriamine. Other ligands such as organic carboxylates or compounds containing both amino groups and carboxylate groups can also be used. The formation of these complexes can be carried out in two stages. In the first, the transition metal is introduced through the impregnation process described above and subsequently add the ligand that forms a complex.

 The impregnation step of the transition metal salt solution can be carried out in a rotary kiln equipped with atomizing nozzles, as mentioned above for the dehydration stage. That is to say, that the entire process of the present invention can be carried out in a single device, provided that the homogeneity of the prepared activator composition is guaranteed, thus reducing the preparation costs of said composition. However, the impregnation step can also be carried out in separate equipment, such as a solid-liquid mixer.

 Surprisingly, the cold scrubber activating composition, prepared according to the process of the present invention, produces a concentration of soluble manganese ions in a leaching test well below 0.2 ppm, which is the upper limit allowed for these types of preparations, as shown below in the examples of embodiments.

Without pretending to be limited to any specific scientific theory, it is possible that in the preparation procedures of this type of compositions based on ion exchange, in which a swap between an Mn ²⁺ ion and 2 Na ⁺ ions is produced, occupying the Mn ²⁺ one of the two positions previously occupied by Na ⁺ ions. The structure undergoes some distortion and that the Mn ²⁺ ions can be easily leached by the effect of a new ion exchange forced by the Ca ²⁺ ions present in excess in the wash solution With the new procedure a different and more stable compound is formed than would be obtained by ion exchange in which the manganese salt II is trapped in the zeolite structure so that it does not leach significantly.

 The persal activator composition of the present invention can be incorporated into the detergent / bleach formulation alone or in combination with the persalt that will be activated in the wash solution, for example, such as sodium percarbonate.

 Another objective of the present invention is to make known the use of the composition prepared according to the process of the present invention as activator of persales in the process of bleaching of tissues in cold washing. Another additional objective of the present invention is the use of said composition for the preparation of a product having the combined action of detergent and bleaching agent.

 In a dry stability test, no visible change was observed after 12 days of inspection when the crib activator composition of the present invention was mixed with a commercially available detergent base. Nor was there a significant loss of active oxygen in said mixture.

In addition, an evaluation of preservation of color fastness and tissue destruction was performed on a mixture of the activating composition of the present invention and a commercially available detergent base, according to the norm of the International Association of Soaps, Detergents and Products Cleaning (AISE). After 20 wash cycles at different temperatures (20 ° C, 60 ° C and 90 ° C) with different types of fabrics (cotton, polyester and polyamide) of different colors (red, blue, orange, fuchsia and black) and different types of dyes (direct, dispersed and reactive) no loss of color was observed, measured quantitatively according to the Grayscale , nor breakages attributable to the composition of the present invention were detected by Electron Microscopy (x800).

 The present invention is described in more detail below with reference to various embodiments. These examples, however, are not intended to limit the technical scope of the present invention.

 Examples

 Example 1

Different activating compositions of persales were prepared. Table 1 summarizes the main parameters used and the results obtained in relation to leaching of manganese ions.

Table 1. Parameters of the preparation process activator composition according to the present invention results obtained

The impregnated zeolite is gassed with CO ₂ .

 2 Sample 6 is refluxed in EDA.

 E emplo 2

 Leaching test

In a vessel equipped with mechanical agitation and at a temperature of 25 ° C, 4.5 liters of tap water are added. 0.3 g of the composition according to the present invention impregnated with 0.4% Mn, 2.8 g of sodium percarbonate, 15.3 g of a commercially available detergent base. A piece of white cloth (65% polyester, 35% cotton) is then introduced into the solution and kept under stirring for 1 hour at 25 ° C. After this time, stirring stops, the fabric is removed and rinsed with water. The amount of Mn II ions in the resulting suspension is determined.

 While the invention has been described with respect to examples of preferred embodiments, these should not be construed as limiting the invention, which will be defined by the broader interpretation of the following claims.

Claims

 1. A method for preparing a activating composition of persalts, in the process of bleaching of tissues in cold washing, whose activating composition comprises an aluminosilicate support impregnated with transition metal ions, characterized in that it comprises the steps of:  - dehydration of aluminosilicate support, and  - impregnation of transition metal ions in said aluminosilicate support.  2. A method according to claim 1, wherein said aluminosilicate support is crystalline or pseudocrystalline.  3. The method according to claim 1 or 2, wherein said aluminosilicate support is zeolite.  4. A method according to any one of claims 1 to 3, wherein said aluminosilicate support is type 4A zeolite.  5. A method according to any one of claims 1 to 4, wherein the dehydration step is carried out by calcination.  6. A method according to any one of claims 1 to 5, wherein the dehydration step is performed between 105 and 750 ° C. 7. Method according to any one of claims 1 to 6, wherein the dehydration step is performed between 300 and 600 ° C. 8. A method according to any one of claims 1 to 7, wherein the dehydration step is performed between 400 and 500 ° C.  9. A method according to any one of claims 1 to 8, wherein in the dehydration step a loss of crystallization water occurs in the aluminosilicate support between 5 and 21% by weight.  Method according to any one of claims 1 to 9, in which the transition metal to be impregnated in the aluminosilicate support is selected from the group comprising Mn II, Co II and Fe II.  11. A method according to any one of claims 1 to 10, wherein the transition metal is Mn II.  12. A method according to any one of claims 1 to 11, wherein the solution to be impregnated in said aluminosilicate support is a saturated or near saturation solution of a transition metal salt.  13. A method according to any one of claims 1 to 12, wherein said transition metal ion salt is a water soluble salt.  14. A method according to any one of claims 1 to 13, wherein the anion of said transition metal salt is selected from the group comprising acetate, carbonate, chloride, nitrate and / or sulfate, or a mixture thereof. 15. A method according to any one of claims 1 to 14, wherein the amount of transition metal ion solution to be impregnated in the Dehydrated aluminosilicate support does not exceed the amount of water removed in the dehydration stage.  16. A method according to any one of claims 1 to 15, wherein the solution to be impregnated further comprises a complete agent.  17. The method of claim 16, wherein the complexing agent is selected from the group comprising ammonia, methylamine, ethylenediamine (EDA), diethylenetriamine, organic carboxylates and / or compounds containing both amino groups and carboxylate groups or a mixture of the same.