WO1995032273A1 - Powder detergent composition comprising stabilized percarbonate - Google Patents

Powder detergent composition comprising stabilized percarbonate Download PDF

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Publication number
WO1995032273A1
WO1995032273A1 PCT/FR1995/000663 FR9500663W WO9532273A1 WO 1995032273 A1 WO1995032273 A1 WO 1995032273A1 FR 9500663 W FR9500663 W FR 9500663W WO 9532273 A1 WO9532273 A1 WO 9532273A1
Authority
WO
WIPO (PCT)
Prior art keywords
sodium
silicate
percarbonate
cogranule
potassium
Prior art date
Application number
PCT/FR1995/000663
Other languages
French (fr)
Inventor
Daniel Joubert
Patrick Boittiaux
Original Assignee
Rhone-Poulenc Chimie
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone-Poulenc Chimie filed Critical Rhone-Poulenc Chimie
Priority to AU26202/95A priority Critical patent/AU2620295A/en
Priority to EP95920966A priority patent/EP0759969A1/en
Publication of WO1995032273A1 publication Critical patent/WO1995032273A1/en
Priority to NO964888A priority patent/NO964888L/en
Priority to FI964627A priority patent/FI964627A0/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents

Definitions

  • the present invention relates to a detergent powder composition for washing laundry in a washing machine containing a bleaching system based on alkali metal percarbonate.
  • the purpose of the bleaching systems included in detergent compositions for washing the laundry is to remove colored stains by oxidation, to disinfect and deodorize the laundry.
  • the bleaching agents usually used are oxygen donors of the persalt or sodium perborate type which release H 2 O 2 in solution.
  • sodium percarbonate is a less stable bleaching agent than sodium perborate and other similar products that carry hydrogen peroxide, especially when the laundry is stored in humid atmospheres, which has up to 'now limited its use in consumer formulations.
  • the object of the invention is to provide powdered detergent compositions for washing machine in a machine based on stabilized percarbonate.
  • cogranules consisting of alkali metal carbonate, alkali metal silicate and water associated with the silicate, when they are introduced by simple powder mixing in a formulation containing percarbonate sodium as a bleaching agent, improve the storage stability of percarbonate.
  • Such cogranules are the subject of European patent application EP-A-0488 868 filed by the Applicant. These products are known for their "builder” properties and their detergent behavior, which is particularly suitable for washing machine and dishwasher applications. They are used as tripolyphosphate (TPP) substituents in these detergent compositions; in fact, they provide in particular both the dispersing power of TPP thanks to the silicate and the softening effect of the washing water thanks to the carbonate.
  • TPP tripolyphosphate
  • the invention relates to a detergent powder composition for washing clothes in a washing machine containing a stable bleaching system based on sodium or potassium percarbonate, characterized in that it contains as stabilizing agent of said percarbonate a cogranulate consisting of sodium or potassium carbonate, sodium or potassium silicate and water associated with silicate, the weight ratio (water associated with silicate) / (silicate expressed as dry) being 33 / 100 to 120/100.
  • co-granules known from EP-A-0488 868 are obtained by adsorption and / or absorption of an aqueous solution of hydrated alkali metal silicate on a particulate inorganic support chemically inert with respect to the silicate, namely a metal carbonate alkaline.
  • the preparation of the cogranules can be done by any available means of bringing the silicate solution into contact with the carbonate particles.
  • a preparation process consists in (a) spraying an aqueous solution based on alkali metal silicate or based on a mixture of silicate and alkali metal carbonate on a moving bed of particles based on alkali metal carbonate or based on the identical silicate-carbonate mixture cited above, traveling in a rotary granulation device, the speed of movement of the particles, the thickness of the moving bed and the flow rate of the sprayed solution being such that each particle is transformed into a plastic cogranulate by coming into contact with other particles, (b) drying, optionally, said co-granules obtained in (a), these steps being implemented so that the weight ratio (water associated with silicate) / (sili ⁇ cate expressed in sec) remains between 33/100 and 120/100.
  • the cogranules are subjected to a densification operation.
  • the alkali metals of the silicate and of the carbonate can be identical or different and chosen from sodium and potassium. However, it is preferred to use a sodium carbonate and silicate.
  • the sodium silicate advantageously has a Si0 2 / Na 2 0 molar ratio of 1.6 to 3.5, preferably 1.8 to 2.6 and very particularly close to 2.
  • the cogranulate can, in in addition, contain a siliconate or siliconate derivatives, that is to say salts of siliconic acid or its derivatives.
  • R is a hydrocarbon residue generally of 1 to 18 carbon atoms, optionally substituted by an amino, ether, ester, epoxy, mercapto, cyano, polyglycol group; m is a number varying from 0.1 to 3; M is an alkali or alkaline earth metal or an ammonium or phosphonium group.
  • R is a hydrocarbon residue of
  • R can be an alkyl radical, for example methyl, ethyl, propyl, butyl, isobutyl; an alkenyl radical, for example vinyl; an aryl radical, for example phenyl or naphthyl; an aralkyl radical, for example benzyl or phenylethyl; an alkylaryl radical, for example tolyl, xylyl; or an araryl radical such as biphenylyl.
  • M we can more particularly cite sodium or potassium, as well as the groups N * R ' 4 and P + R' 4 , in which R ', identical or different, represent hydrocarbon residues of 1 to 6 carbon atoms.
  • Use is more particularly made of alkali metal silicates.
  • the alkaline earth siliconates can also be used.
  • alkylsiliconates and in particular alkaline alkylsiliconates, for example sodium or potassium methylsiliconates.
  • the siliconates can be prepared for example by hydrolysis of the corresponding silanes presenting 3 hydrolysable 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 that there is at least one equivalent in base per atom of silicon (see for example the patents US-A-2,441,422 and US-A-2,441,423).
  • Rhodorsil Siliconate 51T® sold by Demand, which is a solution of approximately 50% of dry extract of potassium methylsiliconate.
  • products derived from siliconates is meant here the condensation products of the products corresponding in particular to formula (1) described above, or those resulting from the at least partial polymerization of silicone compounds or polymers.
  • alkali metal alkylsiliconates can be converted into polyalkylsi- loxanes, in particular by the action of carbon dioxide or other acidifying agent.
  • the siliconate and / or its derivatives are introduced into the cogranule by bringing an aqueous solution of siliconate (or its derivatives) into contact with the other solid and liquid components, namely carbonate and silicate.
  • the siliconate solution is added by any means known per se to a silicate-carbonate cogranule described above.
  • An example of a general process for preparing a cogranule containing a siliconate is as follows, which consists in (1) implementing a process for preparing the agents in the form of cogranules described in EP-A-0488 868, (2) to be used contact an aqueous solution of siliconate or its derivatives on the cogranules thus obtained and (3) possibly to be dried.
  • the maximum amount of siliconate or its derivatives present in this product corresponds to the limit of the adsorbent and / or absorbent power of the agent, as described above.
  • the maximum limit of adsorption and / or absorption of an agent based on alkali metal silicate supported on alkali metal carbonate and water associated with silicate, the ratio (water associated silicate) / (silicate expressed as dry) being greater than or equal to 33/100, is generally situated around 13%, preferably 10% of its total weight,
  • the minimum quantity of siliconate or of its derivatives present in this product preferably corresponds to 2% of the total weight of the product, and more advantageously to 3%.
  • the bleaching system comprises a conventional percarbonate and said co-granules.
  • Percarbonate does not undergo any particular treatment.
  • the improvement is obtained by a simple dry mixing of the pulverulent or granular products.
  • the cogranule is introduced in an advantageous manner at a rate of 8 to 22% by weight of the composition and preferably from 12 to 18%.
  • Sodium or potassium percarbonate is advantageously introduced in an amount of 6 to 20% by weight of the composition and preferably from 7 to 13%.
  • an activated bleaching system which comprises, in addition to percarbonate, a bleaching activator, in particular tetraacetylethylenedia mine (TAED), pentaacetylglucose (PAG), tetraaceous - tylglycoluryl (TAGU) or isonanoyloxybenzènesulfonate (ISONOBS).
  • TAED tetraacetylethylenedia mine
  • PAG pentaacetylglucose
  • TAGU tetraaceous - tylglycoluryl
  • ISONOBS isonanoyloxybenzènesulfonate
  • the rate of addition of the activator can be at two levels, which corresponds to so-called “standard” formulations for the low level and to so-called formulations. "compact" for the high level.
  • a powder washing composition in accordance with the invention can be prepared from the above-mentioned constituents by simple dry mixing of the bleaching agent, and optionally the bleaching activator, with the stabilizing agent. , in the proportions indicated above, and addition of other conventional components of the detergent compositions for washing the laundry, indicated below.
  • the stabilized bleaching system which is the subject of the invention, there is at least one surfactant in the detergent composition, advantageously in an amount which can range from 8 to 20%, preferably of the order of 10 to 15%. the weight of said composition.
  • alkali metal soap type alkaline salts of C 8 -C 24 fatty acids
  • alkali sulfonates C 8 -C 13 alkylbenzene sulfonates, C 12 -C 16 alkyl sulfonates
  • alcohols C 6 -C 16 fatty oxyethylenated and sulfated
  • alkali sulfosuccinates C 12 -C 16 alkyl sulfosuccinates
  • phosphates and phosphonates at a rate of 20 to 40% of the total weight of the formulation,. sodium silicate at a rate of 0.5 to 15% of the total weight of the formulation,
  • zeolites at a rate of 10 to 25% of the total weight of the formulation
  • sodium carbonate in an amount of 5 to 15% of the total weight of the formulation, the total amount of "builder” corresponding to approximately 0.2 to 80%, preferably 20 to 45% of the total weight of said detergent composition.
  • the cogranules used also exert the basic properties, in particular of the "builder" type for which they are known; these cogranules being used as percarbonate stabilizers in the compositions according to the invention, they are not included in the total amount of "builder” indicated above.
  • fillers of the sodium sulfate type for detergents in powder in an amount which can range up to 50% of the total weight of said detergent composition.
  • the invention also relates to the use of a cogranule consisting of sodium or potassium carbonate, sodium or potassium silicate and water associated with silicate, the ratio (water associated with silicate) / (silicate expressed as dry) being of the order of 33/100 to 120/100, as stabilizing agent for a bleaching system at sodium or potassium percarbonate base.
  • the cogranule may also contain a siliconate and / or its derivatives, as described above.
  • cogranules also makes it possible to stabilize a bleaching system based on sodium or potassium percarbonate activated by a bleach activating agent, such as TAED, PAG, TAGU, or ISONOBS.
  • a bleach activating agent such as TAED, PAG, TAGU, or ISONOBS.
  • carbonate-silicate cogranules as a stabilizing agent for percarbonate has the advantage of facilitating the preparation of the composition in so far as the stabilizer is a ready-to-use powder.
  • the invention therefore also relates to a process for the preparation of detergent compositions as described above by simple dry mixing of the constituents, for example by mixing on the one hand the bleaching system, optionally comprising the activator, and the stabilizing agent and, on the other hand, the other components.
  • Detergent compositions with low addition of bleach activator are prepared in accordance with the invention.
  • a cogranule manufactured and marketed by RHONE-POULENC under the brand Nabion 15 is used. It is made up of 29% sodium silicate, of Si0 2 / Na 2 0 ratio equal to 2, of 55% of sodium carbonate and 16% water. The water content associated with the silicate expressed by the weight ratio (water associated with the silicate) / (silicate expressed as dry) is 35%.
  • This cogranule is dry mixed with the TAED activator, sodium percarbonate and sodium sulfate to form mixtures A, the composition of which is shown in Table 1 below.
  • Comparative mixtures are prepared by substituting the co-granules of Nabion 15 with free sodium silicate and sodium carbonate in the proportions indicated in Table 1.
  • Mixtures A are subjected to a storage period of four months at an average temperature of 20 °
  • mixtures A are added to the same mixture B, the composition of which is as follows.
  • the bleaching performance of the compositions is evaluated by simulated washing in a simplified machine of standardized soiled tissue test pieces, using a Tergotometer (US testing Company, Hobdoken, U.S.A.).
  • Washes are carried out in hard water at 25 ° TH French, at a washing temperature of 40 ° C, the concentration of use of the formulas being 7 g / liter. The performance is compared between the compositions before and after storage for four months.
  • Washing performance is estimated by measuring the difference in reflectance of the test pieces before and after washing ( ⁇ R) and expressed in the form of a performance index which is the average of the measurements of ⁇ R over 2 times 8 test pieces, in 5 different points of the test pieces.
  • compositions of Examples 1 and 2 containing cogranule retain their effectiveness better after aging of the powder than the compositions of Comparative Examples 1 and 2.
  • This overall positive result on the conservation of the performance level is to be linked to the best conservation, in powder detergent, of oxidizing species active on soiling, in this case the stabilization of sodium percarbonate.
  • the stabilizing effect of the cogranules is more marked in the case of Examples 3 and 4 with a high level of TAED addition (2.9%) by comparison with Examples 1 and 2 with a low level of TAED addition (1, 4%).
  • the stabilizing effect is more marked in the case of compositions with a low level of percarbonate (examples 2 and 4) in comparison with the compositions with a high level of percarbonate (examples 1 and 3).
  • the good stabilization of systems activated by TAED that is to say percarbonate-TAED couplings, makes the use of the cogranules according to the invention particularly advantageous in modern formulations of compact type and for washing at low temperatures.

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  • Inorganic Chemistry (AREA)
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Abstract

Powder detergent composition for machine washing clothes and containing a bleaching system comprising sodium or potassium percarbonate, optionally activated by a bleach activator, stabilized by a cogranulate consisting of sodium or potassium carbonate, sodium or potassium silicate and water combined with alkaline silicate, the weight ratio of water combined with silicate to silicate being 33/100-120/100. The invention also concerns the use of such cogranulates for stabilizing a bleaching agent system comprising percarbonate.

Description

COMPOSITION DETERGENTE EN POUDRE A BASE DE PERCARBONATE STABILISEE .STABILIZED PERCARBONATE POWDER DETERGENT COMPOSITION.
La présente invention concerne une composi¬ tion détergente en poudre pour le lavage du linge en machine à laver contenant un système de blanchiment à base de percarbonate de métal alcalin. Les systèmes de blanchiment inclus dans des compositions détergentes pour le lavage du linge ont pour but d'éliminer les souillures colorées par oxydation, de désinfecter et de désodoriser le linge.The present invention relates to a detergent powder composition for washing laundry in a washing machine containing a bleaching system based on alkali metal percarbonate. The purpose of the bleaching systems included in detergent compositions for washing the laundry is to remove colored stains by oxidation, to disinfect and deodorize the laundry.
Les agents de blanchiment habituellement utilisés sont des donneurs d'oxygène du type persel ou perborate de sodium qui libèrent H202 en solution.The bleaching agents usually used are oxygen donors of the persalt or sodium perborate type which release H 2 O 2 in solution.
Or, en raison de l'impact négatif du bore sur l'environnement, il apparaît souhaitable de remplacer progressivement le perborate par du percarbonate. Cependant, le percarbonate de sodium est un agent de blanchiment moins stable que le perborate de sodium et les autres produits de même nature vecteurs d'eau oxygénée, en particulier lorsque le stockage de la lessive a lieu dans des atmosphères humides, ce qui a jusqu'à présent limité son emploi dans les formulations grand public.However, due to the negative impact of boron on the environment, it appears desirable to gradually replace perborate with percarbonate. However, sodium percarbonate is a less stable bleaching agent than sodium perborate and other similar products that carry hydrogen peroxide, especially when the laundry is stored in humid atmospheres, which has up to 'now limited its use in consumer formulations.
De nombreuses solutions ont été proposées pour remédier à l'instabilité du percarbonate et, parmi d'autres produits, le silicate de sodium est connu comme agent de stabilisation du percarbonate.Many solutions have been proposed to remedy the instability of percarbonate and, among other products, sodium silicate is known as a stabilizing agent for percarbonate.
L'invention a pour but de procurer des compositions détergentes en poudre pour le lavage du linge en machine à base de percarbonate stabilisé.The object of the invention is to provide powdered detergent compositions for washing machine in a machine based on stabilized percarbonate.
Il a été constaté, de façon surprenante, que des cogranulés constitués de carbonate de métal alcalin, de silicate de métal alcalin et d'eau associée au silicate, lorsqu'ils sont introduits par simple mélange en poudre dans une formulation contenant du percarbonate de sodium comme agent de blanchiment, améliorent la stabilité au stockage du percarbonate.It has been found, surprisingly, that cogranules consisting of alkali metal carbonate, alkali metal silicate and water associated with the silicate, when they are introduced by simple powder mixing in a formulation containing percarbonate sodium as a bleaching agent, improve the storage stability of percarbonate.
De tels cogranulés font l'objet de la demande de brevet européen EP-A-0488 868 déposée par la Demande- resse. Ces produits sont connus pour leurs propriétés "builder" et leur comportement détersif particulièrement approprié aux applications lave-linge et lave-vaisselle. Ils sont utilisés comme substituants du tripolyphosphate (TPP) dans ces compositions détergentes; en effet, ils apportent en particulier à la fois le pouvoir dispersant du TPP grâce au silicate et l'effet d'adoucissement de l'eau de lavage grâce au carbonate.Such cogranules are the subject of European patent application EP-A-0488 868 filed by the Applicant. These products are known for their "builder" properties and their detergent behavior, which is particularly suitable for washing machine and dishwasher applications. They are used as tripolyphosphate (TPP) substituents in these detergent compositions; in fact, they provide in particular both the dispersing power of TPP thanks to the silicate and the softening effect of the washing water thanks to the carbonate.
Ainsi, l'invention a pour objet une composi¬ tion détergente en poudre pour le lavage du linge en machine à laver contenant un système de blanchiment stable à base de percarbonate de sodium ou de potassium, caractérisée en ce qu'elle contient en tant qu'agent stabilisateur dudit percarbonate un cogranulé constitué de carbonate de sodium ou de potassium, de silicate de sodium ou de potassium et d'eau associée au silicate, le rapport pondéral (eau associée au silicate)/(silicate exprimé en sec) étant de 33/100 à 120/100.Thus, the invention relates to a detergent powder composition for washing clothes in a washing machine containing a stable bleaching system based on sodium or potassium percarbonate, characterized in that it contains as stabilizing agent of said percarbonate a cogranulate consisting of sodium or potassium carbonate, sodium or potassium silicate and water associated with silicate, the weight ratio (water associated with silicate) / (silicate expressed as dry) being 33 / 100 to 120/100.
Les cogranulés connus de EP-A-0488 868 sont obtenus par adsorption et/ou absorption d'une solution aqueuse de silicate hydraté de métal alcalin sur un support inorganique particulaire chimiquement inerte vis- à-vis du silicate, à savoir un carbonate de métal alcalin.The co-granules known from EP-A-0488 868 are obtained by adsorption and / or absorption of an aqueous solution of hydrated alkali metal silicate on a particulate inorganic support chemically inert with respect to the silicate, namely a metal carbonate alkaline.
Ils sont caractérisés notamment par leur teneur en eau "associée" au silicate. Par cette expres¬ sion, on entend l'eau restant associée au silicate après adsorption et/ou absorption, c'est-à-dire l'eau de la solution supportée qui n'est pas combinée au support minéral, notamment sous forme d'hydrate cristallisé. La quantité de support minéral mise en contact avec la solution de silicate est ajustée de sorte que le rapport pondéral (eau associée au silicate)/(sili¬ cate exprimé en sec) soit supérieur à 33/100. La limite supérieure du rapport pondéral (eau restant associée au silicate)/(silicate exprimé en sec) correspond aux limites pour lesquelles on garde un silicate sous forme pulvérulente à écoulement fluide ("free flowing"), c'est- à-dire utilisable en détergence. Pour fixer les idées, le rapport pondéral (eau restant associée au silicate)/- (silicate exprimé en sec) doit être inférieur ou égal à environ 120/100.They are characterized in particular by their water content "associated" with silicate. By this expression, we mean the water remaining associated with the silicate after adsorption and / or absorption, that is to say the water of the supported solution which is not combined with the mineral support, in particular in the form of 'crystallized hydrate. The amount of mineral support used contact with the silicate solution is adjusted so that the weight ratio (water associated with the silicate) / (sili¬ cate expressed as dry) is greater than 33/100. The upper limit of the weight ratio (water remaining associated with the silicate) / (silicate expressed in dry) corresponds to the limits for which a silicate is kept in powder form with fluid flow ("free flowing"), that is to say usable in detergency. To fix the ideas, the weight ratio (water remaining associated with silicate) / - (silicate expressed in dry) must be less than or equal to approximately 120/100.
La préparation des cogranulés peut se faire par tous les moyens disponibles de mise en contact de la solution de silicate et des particules de carbonate. Un procédé de préparation consiste à (a) pulvériser une solution aqueuse à base de silicate de métal alcalin ou à base d'un mélange de silicate et de carbonate de métal alcalin sur un lit roulant de particu¬ les à base de carbonate de métal alcalin ou à base du mélange identique silicate-carbonate cité ci-dessus défilant dans un dispositif rotatif de granulation, la vitesse de défilement des particules, l'épaisseur du lit roulant et le débit de la solution pulvérisée étant tels que chaque particule se transforme en un cogranulé plastique en entrant en contact avec d'autres particules, (b) sécher, éventuellement, lesdits cogranulés obtenus en (a), ces étapes étant mises en oeuvre de telle sorte que le rapport pondéral (eau associée au silicate)/(sili¬ cate exprimé en sec) reste compris entre 33/100 et 120/100.The preparation of the cogranules can be done by any available means of bringing the silicate solution into contact with the carbonate particles. A preparation process consists in (a) spraying an aqueous solution based on alkali metal silicate or based on a mixture of silicate and alkali metal carbonate on a moving bed of particles based on alkali metal carbonate or based on the identical silicate-carbonate mixture cited above, traveling in a rotary granulation device, the speed of movement of the particles, the thickness of the moving bed and the flow rate of the sprayed solution being such that each particle is transformed into a plastic cogranulate by coming into contact with other particles, (b) drying, optionally, said co-granules obtained in (a), these steps being implemented so that the weight ratio (water associated with silicate) / (sili¬ cate expressed in sec) remains between 33/100 and 120/100.
De préférence, entre les étapes (a) et (b), on soumet les cogranulés à une opération de densifica- tion.Preferably, between steps (a) and (b), the cogranules are subjected to a densification operation.
Ainsi, on peut citer, à titre d'exemple d'agents à base de silicate et de carbonate tels que décrits ci-.dessus, le Nabion ® fabriqué et commercialisé par Rhône-Poulenc.Thus, mention may be made, by way of example of agents based on silicate and carbonate such as described above, Nabion ® manufactured and marketed by Rhône-Poulenc.
Les métaux alcalins du silicate et du carbonate peuvent être identiques ou différents et choisis parmi le sodium et le potassium. On préfère cependant utiliser un carbonate et un silicate de sodium.The alkali metals of the silicate and of the carbonate can be identical or different and chosen from sodium and potassium. However, it is preferred to use a sodium carbonate and silicate.
Le silicate de sodium présente avantageuse¬ ment un rapport molaire Si02/Na20 de 1,6 à 3,5, de préfé¬ rence de 1,8 à 2,6 et tout particulièrement voisin de 2. Le cogranulé peut, en outre, contenir un siliconate ou des dérivés de siliconate, c'est-à-dire des sels de l'acide siliconique ou de ses dérivés.The sodium silicate advantageously has a Si0 2 / Na 2 0 molar ratio of 1.6 to 3.5, preferably 1.8 to 2.6 and very particularly close to 2. The cogranulate can, in in addition, contain a siliconate or siliconate derivatives, that is to say salts of siliconic acid or its derivatives.
Ces produits répondent notamment à la formule suivante ( 1 ) :These products correspond in particular to the following formula (1):
R-Si(0M)m(0H)3__ (1)R-Si (0M) m (0H) 3 __ (1)
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 groupe amino, éther, ester, époxy, mercapto, cyano, polyglycol; m est un nombre variant de 0,1 à 3; M est un métal alcalin ou alcalino-terreux ou un groupe ammonium ou phosphonium. De préférence, R est un reste hydrocarboné deand / or the condensation products thereof, formula in which R is a hydrocarbon residue generally of 1 to 18 carbon atoms, optionally substituted by an amino, ether, ester, epoxy, mercapto, cyano, polyglycol group; m is a number varying from 0.1 to 3; M is an alkali or alkaline earth metal or an ammonium or phosphonium group. Preferably, R is a hydrocarbon residue of
1 à 10 atomes de carbone et plus particulièrement de 1 à 6 atomes de carbone.1 to 10 carbon atoms and more particularly from 1 to 6 carbon atoms.
Plus précisément, R peut être un radical alkyle, par exemple méthyle, éthyle, propyle, butyle, isobutyle; un radical alcényle, par exemple vinyle; un radical aryle, par exemple phényle ou naphtyle; un radical aralkyle, par exemple benzyle ou phényléthyle; un radical alkylaryle, par exemple tolyle, xylyle; ou un radical araryle comme le biphénylyle. Pour M, on peut citer plus particulièrement le sodium ou le potassium, ainsi que les groupes N*R'4 et P+R'4, dans lesquels R', identiques ou différents, représentent des restes hydrocarbonés de 1 à 6 atomes de carbone. On utilise plus particulièrement les silico¬ nates alcalins. On peut aussi employer les siliconates alcalino-terreux.More specifically, R can be an alkyl radical, for example methyl, ethyl, propyl, butyl, isobutyl; an alkenyl radical, for example vinyl; an aryl radical, for example phenyl or naphthyl; an aralkyl radical, for example benzyl or phenylethyl; an alkylaryl radical, for example tolyl, xylyl; or an araryl radical such as biphenylyl. For M, we can more particularly cite sodium or potassium, as well as the groups N * R ' 4 and P + R' 4 , in which R ', identical or different, represent hydrocarbon residues of 1 to 6 carbon atoms. Use is more particularly made of alkali metal silicates. The alkaline earth siliconates can also be used.
De même, on met en oeuvre particulièrement les alkylsiliconates et notamment les alkylsiliconates alcalins, par exemple les méthylsiliconates de sodium ou de potassium.Likewise, particular use is made of alkylsiliconates and in particular alkaline alkylsiliconates, for example sodium or potassium methylsiliconates.
On peut aussi utiliser les siliconates de formule ( 1 ) dans laquelle R est un radical vinyle ou phényle, et plus particulièrement le siliconate alcalin de ce type.It is also possible to use the siliconates of formula (1) in which R is a vinyl or phenyl radical, and more particularly the alkali siliconate of this type.
Les siliconates peuvent être préparés par exemple par hydrolyse des silanes correspondants présen¬ tant 3 groupes hydrolysables tels que des atomes d'halog- gène, des radicaux alcoxy, suivie d'une dissolution du produit obtenu dans une solution d'une base inorganique forte dans des proportions telles qu'il y ait au moins un équivalent en base par atome de silicium (voir par exemple les brevets US-A-2 441 422 et US-A-2 441 423).The siliconates can be prepared for example by hydrolysis of the corresponding silanes presenting 3 hydrolysable 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 that there is at least one equivalent in base per atom of silicon (see for example the patents US-A-2,441,422 and US-A-2,441,423).
Comme exemple de siliconates de ce type disponibles dans le commerce, on peut citer notamment le Rhodorsil Siliconate 51T®, commercialisé par la Demande¬ resse, qui est une solution à environ 50 % d'extrait sec de méthylsiliconate de potassium.As an example of commercially available siliconates of this type, mention may in particular be made of Rhodorsil Siliconate 51T®, sold by Demand, which is a solution of approximately 50% of dry extract of potassium methylsiliconate.
Par produits dérivés des siliconates, on entend ici les produits de condensation des produits répondant notamment à la formule (1) décrits ci-dessus, ou ceux résultant de la polymérisation au moins partielle en composés ou polymères siliconiques.By products derived from siliconates is meant here the condensation products of the products corresponding in particular to formula (1) described above, or those resulting from the at least partial polymerization of silicone compounds or polymers.
On sait par exemple que les alkylsiliconates de métal alcalin peuvent être transformés en polyalkylsi- loxanes, notamment par l'action de l'anhydride carbonique ou autre agent acidifiant.It is known, for example, that the alkali metal alkylsiliconates can be converted into polyalkylsi- loxanes, in particular by the action of carbon dioxide or other acidifying agent.
Il va de soi que, dans le cadre de la présente invention, on peut utiliser en combinaison deux ou plusieurs siliconates ou dérivés.It goes without saying that, in the context of the present invention, it is possible to use in combination two or more siliconates or derivatives.
Le siliconate et/ou ses dérivés sont intro¬ duits dans le cogranule par mise en contact d'une solution aqueuse de siliconate (ou de ses dérivés) avec les autres composants solides et liquides, à savoir carbonate et silicate.The siliconate and / or its derivatives are introduced into the cogranule by bringing an aqueous solution of siliconate (or its derivatives) into contact with the other solid and liquid components, namely carbonate and silicate.
De préférence, la solution de siliconate est ajoutée par tout moyen connu en soi à un cogranule silicate-carbonate décrit précédemment.Preferably, the siliconate solution is added by any means known per se to a silicate-carbonate cogranule described above.
Un exemple de procédé général de préparation de cogranule contenant un siliconate est le suivant, qui consiste à ( 1 ) mettre en oeuvre un procédé de préparation des agents sous forme de cogranulés décrit dans EP-A-0488 868, (2) à mettre en contact une solution aqueuse de siliconate ou de ses dérivés sur les cogranulés ainsi obtenus et (3) éventuellement à sécher.An example of a general process for preparing a cogranule containing a siliconate is as follows, which consists in (1) implementing a process for preparing the agents in the form of cogranules described in EP-A-0488 868, (2) to be used contact an aqueous solution of siliconate or its derivatives on the cogranules thus obtained and (3) possibly to be dried.
Cet ajout de siliconate (et son éventuel séchage) est réalisé de façon contrôlée de manière à respecter un rapport pondéral (eau associée au silica¬ te)/(silicate exprimé en sec) de l'ordre de 33/100 à 120/100 comme indiqué ci-dessus.This addition of siliconate (and its possible drying) is carried out in a controlled manner so as to respect a weight ratio (water associated with silica¬ te) / (silicate expressed as dry) of the order of 33/100 to 120/100 as indicated above.
La quantité maximale de siliconate ou de ses dérivés présente dans ce produit correspond à la limite du pouvoir adsorbant et/ou absorbant de l'agent, tel que décrit précédemment. Cependant, pour fixer les idées, la limite maximale d'adsorption et/ou d'absorption d'un agent à base de silicate de métal alcalin supporté sur du carbonate de métal alcalin et d'eau associée au silicate, le rapport (eau associée au silicate)/(silicate exprimé en sec) étant supérieur ou égal à 33/100, est généralement située aux environs de 13 %, de préférence de 10 %, de son poids total,The maximum amount of siliconate or its derivatives present in this product corresponds to the limit of the adsorbent and / or absorbent power of the agent, as described above. However, to fix ideas, the maximum limit of adsorption and / or absorption of an agent based on alkali metal silicate supported on alkali metal carbonate and water associated with silicate, the ratio (water associated silicate) / (silicate expressed as dry) being greater than or equal to 33/100, is generally situated around 13%, preferably 10% of its total weight,
La quantité minimale de siliconate ou de ses dérivés présente dans ce produit correspond préféren- tiellement à 2 % du poids total du produit, et de manière plus avantageuse à 3 %.The minimum quantity of siliconate or of its derivatives present in this product preferably corresponds to 2% of the total weight of the product, and more advantageously to 3%.
Dans une composition de lavage en poudre conforme à l'invention, le système de blanchiment comprend un percarbonate classique et lesdits cogranulés. Le percarbonate ne subit aucun traitement particulier. Les cogranulés, contenant ou non des siliconates, stabilisent le percarbonate sans qu'il y ait besoin d'un contact intime entre les deux produits. De façon inatten- due, l'amélioration est obtenue par suite d'un simple mélange à sec des produits pulvérulents ou granulaires. Le cogranule est introduit de manière avanta¬ geuse à raison de 8 à 22 % en poids de la composition et de préférence de 12 à 18 %. Le percarbonate de sodium ou de potassium est introduit de manière avantageuse à raison de 6 à 20 % en poids de la composition et de préférence de 7 à 13 %.In a powder washing composition according to the invention, the bleaching system comprises a conventional percarbonate and said co-granules. Percarbonate does not undergo any particular treatment. The co-granules, whether or not containing siliconates, stabilize the percarbonate without the need for intimate contact between the two products. Unexpectedly, the improvement is obtained by a simple dry mixing of the pulverulent or granular products. The cogranule is introduced in an advantageous manner at a rate of 8 to 22% by weight of the composition and preferably from 12 to 18%. Sodium or potassium percarbonate is advantageously introduced in an amount of 6 to 20% by weight of the composition and preferably from 7 to 13%.
Pour obtenir un effet de blanchiment à basse température, on peut utiliser un système de blanchiment activé qui comporte, en plus du percarbonate, un activa- teur de blanchiment, notamment la tétraacétyléthylènedia- mine (TAED) , le pentaacétylglucose (PAG), le tétraacé- tylglycoluryl (TAGU) ou l' isonanoyloxybenzènesulfonate ( ISONOBS) . 'activateur est de préférence présent à raison de 0,5 à 6 % en poids de la composition, et plus préférentiellement de 1 à 5 % en poids.To obtain a bleaching effect at low temperature, it is possible to use an activated bleaching system which comprises, in addition to percarbonate, a bleaching activator, in particular tetraacetylethylenedia mine (TAED), pentaacetylglucose (PAG), tetraaceous - tylglycoluryl (TAGU) or isonanoyloxybenzènesulfonate (ISONOBS). activator is preferably present in an amount of 0.5 to 6% by weight of the composition, and more preferably from 1 to 5% by weight.
Le taux d'ajout de l'activateur peut être à deux niveaux, ce qui correspond à des formulations dites "standard" pour le bas niveau et à des formulations dites "compactes" pour le haut niveau.The rate of addition of the activator can be at two levels, which corresponds to so-called "standard" formulations for the low level and to so-called formulations. "compact" for the high level.
Une composition de lavage en poudre conforme à l'invention peut être préparée à partir des consti- tuants mentionnés ci-dessus par simple mélange à sec de l'agent de blanchiment, et éventuellement de 1 'activateur de blanchiment, avec l'agent stabilisateur, en les proportions indiquées précédemment, et ajout d'autres composants classiques des compositions détergentes pour le lavage du linge, indiqués ci-après.A powder washing composition in accordance with the invention can be prepared from the above-mentioned constituents by simple dry mixing of the bleaching agent, and optionally the bleaching activator, with the stabilizing agent. , in the proportions indicated above, and addition of other conventional components of the detergent compositions for washing the laundry, indicated below.
A côté du système de blanchiment stabilisé faisant l'objet de l'invention est présent dans la composition détergente au moins un agent tensio-actif avantageusement en quantité pouvant aller de 8 à 20 %, de préférence de l'ordre de 10 à 15 % du poids de ladite composition.Besides the stabilized bleaching system which is the subject of the invention, there is at least one surfactant in the detergent composition, advantageously in an amount which can range from 8 to 20%, preferably of the order of 10 to 15%. the weight of said composition.
Parmi ces agents tensio-actifs on peut citer:Among these surfactants, mention may be made of:
- les agents tensio-actifs anioniques du type savons de métaux alcalins (sels alcalins d'acides gras en C8-C24), sulfonates alcalins (alcoylbenzène sulfonates en C8-C13, alcoylsulfonates en C12-C16), alcools gras en C6- C16 oxyéthylénés et sulfatés, alkylphénols en C8-C13 oxyéthylénés et sulfatés, les sulfosuccinates alcalins (alcoylsulfosuccinates en C12-C16)... - les agents tensio-actifs non ioniques du type alcoylphénols en C6-C12 polyoxyéthylénés, alcools aliphatiques en C8-C22 oxyéthylénés, les copolymères bloc oxyde d'éthylène - oxyde de propylène, les amides carboxyliques éventuellement polyoxyéthylénés, - les agents tensio-actifs amphotères du type alcoyldiméthylbétaïnes,- anionic surfactants of the alkali metal soap type (alkaline salts of C 8 -C 24 fatty acids), alkali sulfonates (C 8 -C 13 alkylbenzene sulfonates, C 12 -C 16 alkyl sulfonates), alcohols C 6 -C 16 fatty oxyethylenated and sulfated, C 8 -C 13 alkylphenols oxyethylenated and sulfated, alkali sulfosuccinates (C 12 -C 16 alkyl sulfosuccinates) ... 6 -C 12 polyoxyethylenated, oxyethylenated C 8 -C 22 aliphatic alcohols, block copolymers of ethylene oxide - propylene oxide, optionally polyoxyethylenated carboxylic amides, - amphoteric surfactants of the alkyldimethylbetaine type,
- les agents tensio-actifs cationiques du type chlorures ou bromures d'alkyltriméthylammonium, d'alkyldiméthyléthylammonium. Divers constituants peuvent en outre être présents dans la composition détergente tels que :- cationic surfactants of the chlorides or bromides of alkyltrimethylammonium, of alkylldimethylethylammonium. Various constituents can also be present in the detergent composition such as:
- des "builders" du type :- "builders" of the type:
. phosphates et phosphonates, à raison de 20 à 40 % du poids total de la formulation, . silicate de sodium à raison de 0,5 à 15 % du poids total de la formulation,. phosphates and phosphonates, at a rate of 20 to 40% of the total weight of the formulation,. sodium silicate at a rate of 0.5 to 15% of the total weight of the formulation,
. zéolithes à raison de 10 à 25 % du poids total de la formulation,. zeolites at a rate of 10 to 25% of the total weight of the formulation,
. carbonate de sodium à raison de 5 à 15 % du poids total de la formulation, la quantité totale de "builder" correspondant à environ 0,2 à 80 %, de préférence de 20 à 45 % du poids total de ladite composition détergente.. sodium carbonate in an amount of 5 to 15% of the total weight of the formulation, the total amount of "builder" corresponding to approximately 0.2 to 80%, preferably 20 to 45% of the total weight of said detergent composition.
Il va de soi que dans la composition déter- gente, les cogranulés utilisés exercent également les propriétés de base, notamment de type "builder" pour lesquelles ils sont connus; ces cogranulés étant utilisés comme stabilisateurs du percarbonate dans les composi¬ tions selon l'invention, ils ne sont pas compris dans la quantité totale de "builder" indiquée ci-dessus. des agents anti-redéposition du type carboxyméthylcellulose, méthylcellulose en quantité pouvant aller jusqu'à environ 5 % du poids total de ladite composition détergente, - des agents anti-incrustation du type copolymères d'acide acrylique et d'anhydride maléique en quantité pouvant aller jusqu'à 10 % environ du poids total de ladite composition détergente,It goes without saying that in the detergent composition, the cogranules used also exert the basic properties, in particular of the "builder" type for which they are known; these cogranules being used as percarbonate stabilizers in the compositions according to the invention, they are not included in the total amount of "builder" indicated above. anti-redeposition agents of the carboxymethylcellulose type, methylcellulose in an amount which can range up to approximately 5% of the total weight of said detergent composition, - anti-encrustation agents of the copolymer type of acrylic acid and maleic anhydride in an amount which can range up to approximately 10% of the total weight of said detergent composition,
- des charges du type sulfate de sodium pour les détergents en poudre en quantité pouvant aller jusqu'à 50 % du poids total de ladite composition détergente.fillers of the sodium sulfate type for detergents in powder in an amount which can range up to 50% of the total weight of said detergent composition.
L'invention a également pour objet l'utili¬ sation d'un cogranule constitué de carbonate de sodium ou de potassium, de silicate de sodium ou de potassium et d'eau associée au silicate, le rapport (eau associée au silicate)/( silicate exprimé en sec) étant de l'ordre de 33/100 à 120/100, en tant qu'agent stabilisateur d'un système de blanchiment à base de percarbonate de sodium ou de potassium.The invention also relates to the use of a cogranule consisting of sodium or potassium carbonate, sodium or potassium silicate and water associated with silicate, the ratio (water associated with silicate) / (silicate expressed as dry) being of the order of 33/100 to 120/100, as stabilizing agent for a bleaching system at sodium or potassium percarbonate base.
Pour une telle utilisation, le cogranule peut en outre contenir un siliconate et/ou ses dérivés, comme il a été décrit précédemment.For such use, the cogranule may also contain a siliconate and / or its derivatives, as described above.
L'utilisation de cogranulés permet également de stabiliser un système de blanchiment à base de percarbonate de sodium ou de potassium activé par un agent activateur de blanchiment, comme la TAED, le PAG, le TAGU, ou l'ISONOBS.The use of cogranules also makes it possible to stabilize a bleaching system based on sodium or potassium percarbonate activated by a bleach activating agent, such as TAED, PAG, TAGU, or ISONOBS.
L'utilisation de tels cogranulés carbonate- silicate en tant qu'agent stabilisateur du percarbonate présente l'avantage de faciliter la préparation de la composition dans la mesure où le stabilisateur est une poudre prête à l'emploi.The use of such carbonate-silicate cogranules as a stabilizing agent for percarbonate has the advantage of facilitating the preparation of the composition in so far as the stabilizer is a ready-to-use powder.
L'invention a donc également pour objet un procédé de préparation de compositions détergentes comme décrites précédemment par simple mélange à sec des constituants, par exemple en mélangeant d'une part le système de blanchiment, comprenant éventuellement l'acti¬ vateur, et l'agent stabilisateur et, d'autre part, les autres composants.The invention therefore also relates to a process for the preparation of detergent compositions as described above by simple dry mixing of the constituents, for example by mixing on the one hand the bleaching system, optionally comprising the activator, and the stabilizing agent and, on the other hand, the other components.
Les exemples suivants illustrent l'invention, sans toutefois en limiter la portée.The following examples illustrate the invention, without however limiting its scope.
Les pourcentages dont il est question ci- dessous sont des pourcentages en poids de la composition détergente finale.The percentages discussed below are percentages by weight of the final detergent composition.
EXEMPLES 1 et 2EXAMPLES 1 and 2
Des compositions détergentes à bas ajout d'activateur de blanchiment (1,4 %) sont préparées conformément à l'invention. On utilise un cogranule fabriqué et commer¬ cialisé par RHONE-POULENC sous la marque Nabion 15. Il est constitué de 29% de silicate de sodium, de rapport Si02/Na20 égal à 2, de 55% de carbonate de sodium et de 16% d'eau. La teneur en eau associée au silicate exprimée par le rapport pondéral (eau associée au silicate)/(si¬ licate exprimé en sec) est de 35%.Detergent compositions with low addition of bleach activator (1.4%) are prepared in accordance with the invention. A cogranule manufactured and marketed by RHONE-POULENC under the brand Nabion 15 is used. It is made up of 29% sodium silicate, of Si0 2 / Na 2 0 ratio equal to 2, of 55% of sodium carbonate and 16% water. The water content associated with the silicate expressed by the weight ratio (water associated with the silicate) / (silicate expressed as dry) is 35%.
Ce cogranule est mélangé à sec avec l'acti¬ vateur TAED, du percarbonate de sodium et du sulfate de sodium pour former les mélanges A dont la composition est indiquée dans le tableau 1 suivant.This cogranule is dry mixed with the TAED activator, sodium percarbonate and sodium sulfate to form mixtures A, the composition of which is shown in Table 1 below.
Des mélanges comparatifs sont préparés en substituant les cogranulés de Nabion 15 par du silicate de sodium et du carbonate de sodium libres en des proportions indiquées dans le tableau 1.Comparative mixtures are prepared by substituting the co-granules of Nabion 15 with free sodium silicate and sodium carbonate in the proportions indicated in Table 1.
Les mélanges A sont soumis à une période de stockage de quatre mois à une température moyenne de 20°Mixtures A are subjected to a storage period of four months at an average temperature of 20 °
C, 60 % d'humidité relative, en enceinte non totalement étanche, reproduisant le stockage en cartonnettes de lessive commerciales.C, 60% relative humidity, in an enclosure that is not completely waterproof, reproducing storage in commercial laundry boxes.
Pour obtenir les compositions détergentes complètes prêtes pour les essais de lavage, les mélanges A sont ajoutés à un même mélange B dont la composition est la suivante. Mélange B tensio actif anionique (lab) 4,3 tensio actifs non ioniques 8,6 zeolithe 4A 17,9 carbonate de sodium 10,7 silicate de sodium, Rm 2, atomisé 3,6To obtain the complete detergent compositions ready for the washing tests, the mixtures A are added to the same mixture B, the composition of which is as follows. Mixture B anionic surfactant (lab) 4.3 nonionic surfactants 8.6 zeolite 4A 17.9 sodium carbonate 10.7 sodium silicate, Rm 2, atomized 3.6
SOKALAN CP5 de BASF* 3,6BASK SOKALAN CP5 * 3.6
Enzymes 0,2 carboxyméthylcellulose 0,7 sulfate de sodium 21,9. * SOKALAN CP5 de BASF est un copolymère polyacrylate/ma- léate de sodium.Enzymes 0.2 carboxymethylcellulose 0.7 sodium sulfate 21.9. * BASK SOKALAN CP5 is a polyacrylate / ma- sodium leate.
Les performances de blanchiment des composi¬ tions sont évaluées par simulation de lavage en machine simplifié d'éprouvettes de tissus salis normalisées, en Tergotomètre (US testing Company, Hobdoken, U.S.A.).The bleaching performance of the compositions is evaluated by simulated washing in a simplified machine of standardized soiled tissue test pieces, using a Tergotometer (US testing Company, Hobdoken, U.S.A.).
Les lavages sont effectués en eau dure à 25° TH français, à une température de lavage de 40° C, la concentration d'utilisation des formules étant de 7 g/litre. On effectue la comparaison des performances entre les compositions avant et après le stockage de quatre mois.Washes are carried out in hard water at 25 ° TH French, at a washing temperature of 40 ° C, the concentration of use of the formulas being 7 g / liter. The performance is compared between the compositions before and after storage for four months.
Les performances de lavage sont estimées par la mesure de la différence de réflectance des éprouvettes avant et après lavage (ΔR) et exprimées sous la forme d'un index de performances qui est la moyenne des mesures de ΔR sur 2 fois 8 éprouvettes, en 5 points différents des éprouvettes.Washing performance is estimated by measuring the difference in reflectance of the test pieces before and after washing (ΔR) and expressed in the form of a performance index which is the average of the measurements of ΔR over 2 times 8 test pieces, in 5 different points of the test pieces.
Les salissures de thé et de vin rouge ont été utilisées en particulier en raison de leur bonne réaction aux effets d'oxydation donnés par les percarbonates et les perborates. Les résultats sont reportés dans le tableau 1. Tea and red wine stains have been used in particular because of their good reaction to the oxidation effects given by percarbonates and perborates. The results are reported in Table 1.
Figure imgf000015_0001
Ces résultats montrent que les compositions des exemples 1 et 2 contenant du cogranule conservent mieux leur efficacité après vieillissement de la poudre que les compositions des exemples comparatifs 1 et 2. Ce résultat positif global sur la conserva¬ tion du niveau des performances est à relier à la meilleure conservation, au sein de la lessive poudre, des espèces oxydantes actives sur les salissures, en l'occu- rence à la stabilisation du percarbonate de sodium.
Figure imgf000015_0001
These results show that the compositions of Examples 1 and 2 containing cogranule retain their effectiveness better after aging of the powder than the compositions of Comparative Examples 1 and 2. This overall positive result on the conservation of the performance level is to be linked to the best conservation, in powder detergent, of oxidizing species active on soiling, in this case the stabilization of sodium percarbonate.
EXEMPLES 3 ET 4EXAMPLES 3 AND 4
Les mêmes essais ont été réalisés avec des compositions à haut ajout d'activateur TAED (2,9%). Le Tableau 2 donne un récapitulatif des formulations et de leurs performances. The same tests were carried out with compositions with a high addition of TAED activator (2.9%). Table 2 provides a summary of the formulations and their performance.
Figure imgf000017_0001
Ces résultats montrent de même que les compositions des exemples 3 et 4 conservent mieux leur efficacité après stockage que les compositions des exemples comparatifs 3 et 4 ne contenant pas de cogra- nulés.
Figure imgf000017_0001
These results likewise show that the compositions of Examples 3 and 4 retain their effectiveness better after storage than the compositions of Comparative Examples 3 and 4 containing no co-granules.
L'effet stabilisateur des cogranulés est plus marqué dans le cas des exemples 3 et 4 à haut niveau d'ajout de TAED (2,9 %) par comparaison avec les exemples 1 et 2 à bas niveau d'ajout de TAED (1,4 %). En outre, l'effet stabilisateur est plus marqué dans le cas de compositions à bas niveau de percarbonate (exemples 2 et 4) par comparaison avec les compositions à haut niveau de percarbonate (exemples 1 et 3). La bonne stabilisation des systèmes activés par la TAED, c'est-à-dire des couplages percarbonate- TAED, rend l'utilisation des cogranulés selon l'invention particulièrement intéressante dans les formulations modernes de type compact et pour les lavages à basses températures.The stabilizing effect of the cogranules is more marked in the case of Examples 3 and 4 with a high level of TAED addition (2.9%) by comparison with Examples 1 and 2 with a low level of TAED addition (1, 4%). In addition, the stabilizing effect is more marked in the case of compositions with a low level of percarbonate (examples 2 and 4) in comparison with the compositions with a high level of percarbonate (examples 1 and 3). The good stabilization of systems activated by TAED, that is to say percarbonate-TAED couplings, makes the use of the cogranules according to the invention particularly advantageous in modern formulations of compact type and for washing at low temperatures.
Rappelons que la préparation de telles compositions est très aisée puisqu'il n'y a pas à réaliser de traitement préliminaire pour stabiliser le percarbonate. Recall that the preparation of such compositions is very easy since there is no need to carry out a preliminary treatment to stabilize the percarbonate.

Claims

REVENDICATIONS
1. Composition détergente en poudre pour le lavage du linge en machine à laver, contenant un système de blanchiment stable à base de percarbonate de sodium ou de potassium, caractérisée en ce qu'elle contient en tant qu'agent stabilisateur dudit percarbonate, un cogranule constitué de silicate de sodium ou de potas¬ sium, de carbonate de sodium ou de potassium et d'eau associée au silicate, le rapport pondéral (eau associée au silicate)/(silicate exprimé en sec) étant de 33/100 à 120/100.1. Powder detergent composition for washing clothes in a washing machine, containing a stable bleaching system based on sodium or potassium percarbonate, characterized in that it contains, as stabilizing agent for said percarbonate, a cogranule consisting of sodium or potassium silicate, sodium or potassium carbonate and water associated with silicate, the weight ratio (water associated with silicate) / (silicate expressed as dry) being from 33/100 to 120 / 100.
2. Composition selon la revendication 1 dans laquelle l'agent stabilisateur du percarbonate est un cogranule de silicate de sodium et de carbonate de sodium, le rapport molaire Si02/Na20 étant de 1,6 à 3,5.2. Composition according to claim 1 wherein the stabilizing agent of the percarbonate is a cogranule of sodium silicate and sodium carbonate, the molar ratio Si0 2 / Na 2 0 being from 1.6 to 3.5.
3. Composition selon la revendication 1, dans laquelle le cogranule comprend en outre un siliconate ou un de ses dérivés, le siliconate ou ses dérivés étant des produits répondant à la formule suivante ( 1 ) :3. Composition according to claim 1, in which the cogranule further comprises a siliconate or one of its derivatives, the siliconate or its derivatives being products corresponding to the following formula (1):
R-Si(0M)m(0H)3_m (1)R-Si (0M) m (0H) 3 _ m (1)
et/ou les produits de condensation de ceux-ci, formule dans laquelle R est un reste hydrocarboné de 1 à 18 atomes de carbone, le cas échéant substitué par un groupe amino, éther, ester, époxy, mercapto, cyano, polyglycol; m est un nombre variant de 0,1 à 3; M est un métal alcalin ou alcalino-terreux ou un groupe ammonium ou phosphonium, la quantité de siliconate ou de ses dérivés représentant de 2 à 10 % du poids total du cogranule.and / or the condensation products thereof, formula in which R is a hydrocarbon residue of 1 to 18 carbon atoms, optionally substituted by an amino, ether, ester, epoxy, mercapto, cyano, polyglycol group; m is a number varying from 0.1 to 3; M is an alkali or alkaline earth metal or an ammonium or phosphonium group, the amount of siliconate or of its derivatives representing from 2 to 10% of the total weight of the cogranule.
4. Composition selon la revendication 3, dans laquelle le cogranule comprend du carbonate de sodium et du silicate de sodium, le rapport molaire Si02/Na20 étant de 1,6 à 3,5, et le siliconate est un méthylsiliconate de sodium ou de potassium.4. Composition according to claim 3, in which the cogranule comprises sodium carbonate and sodium silicate, the molar ratio Si0 2 / Na 2 0 being from 1.6 to 3.5, and the siliconate is a methylsiliconate sodium or potassium.
5. Composition selon l'une des revendications 1 à 4, dans laquelle le cogranule est présent à raison de 8 à 22 % en poids de la composition. 5. Composition according to one of claims 1 to 4, wherein the cogranule is present in an amount of 8 to 22% by weight of the composition.
6. Composition selon la revendication 5, dans laquelle le cogranule est présent à raison de 12 à 18 % en poids.6. Composition according to claim 5, in which the cogranule is present in an amount of 12 to 18% by weight.
7. Composition selon l'une des revendications 1 à 6, dans laquelle le percarbonate est présent à raison de 6 à 20 % en poids.7. Composition according to one of claims 1 to 6, wherein the percarbonate is present in an amount of 6 to 20% by weight.
8. Composition selon la revendication 7, dans laquelle le percarbonate est présent à raison de 7 à 13 % en poids.8. Composition according to claim 7, in which the percarbonate is present in an amount of 7 to 13% by weight.
9. Composition selon 1 'une quelconque des revendications 1 à 8, caractérisée en ce que le système de blanchiment comprend en outre un agent activateur de blanchiment.9. Composition according to any one of claims 1 to 8, characterized in that the bleaching system further comprises a bleach activating agent.
10. Composition selon la revendication 9, dans laquelle 1 'activateur de blanchiment est présent à raison de 0,5 à 6 % en poids.10. The composition of claim 9, wherein the bleach activator is present in an amount of 0.5 to 6% by weight.
11. Composition selon la revendication 10, dans laquelle l'activateur est présent à raison de 1 à 5 % en poids.11. The composition of claim 10, wherein the activator is present in an amount of 1 to 5% by weight.
12. Utilisation d'un cogranule constitué de silicate de sodium ou de potassium, de carbonate de sodium ou de potassium et d'eau associée au silicate, le rapport (eau associée au silicate)/(silicate exprimé en sec) étant de 33/100 à 120/100, en tant qu'agent stabili¬ sateur d'un système de blanchiment à base de percarbonate de sodium ou de potassium.12. Use of a cogranule consisting of sodium or potassium silicate, sodium or potassium carbonate and water associated with silicate, the ratio (water associated with silicate) / (silicate expressed as dry) being 33 / 100 to 120/100, as stabilizing agent for a bleaching system based on sodium or potassium percarbonate.
13. Utilisation selon la revendication 12 de cogranulés de silicate de sodium et de carbonate de sodium, le rapport molaire Si02/Na20 étant de 1,6 à 3,5.13. Use according to claim 12 of cogranules of sodium silicate and sodium carbonate, the molar ratio Si0 2 / Na 2 0 being from 1.6 to 3.5.
14. Utilisation selon la revendication 12 d'un cogranule comprenant en outre un siliconate ou un de ses dérivés, le siliconate ou ses dérivés étant des produits répondant à la formule suivante ( 1 ) :14. Use according to claim 12 of a cogranule further comprising a siliconate or a of its derivatives, the siliconate or its derivatives being products corresponding to the following formula (1):
R-Si(OM)m(OH)3.m (1),R-Si (OM) m (OH) 3 . m (1),
et/ou les produits de condensation de ceux-ci, formule dans laquelle R est un reste hydrocarboné de 1 à 18 atomes de carbone, le cas échéant substitué par un groupe amino, éther, ester, époxy, mercapto, cyano, polyglycol; , m est un nombre variant de 0,1 à 3; M est un métal alcalin ou alcalino-terreux ou un groupe ammonium ou phosphonium, la quantité de siliconate ou de ses dérivés représentant de 2 à 10 % du poids total du cogranule.and / or the condensation products thereof, formula in which R is a hydrocarbon residue of 1 to 18 carbon atoms, optionally substituted by an amino, ether, ester, epoxy, mercapto, cyano, polyglycol group; , m is a number varying from 0.1 to 3; M is an alkali or alkaline earth metal or an ammonium or phosphonium group, the amount of siliconate or of its derivatives representing from 2 to 10% of the total weight of the cogranule.
15. Utilisation selon la revendication 14 d'un cogranule comprenant du carbonate de sodium et du silicate de sodium, le rapport molaire Si02/Na20 étant de 1,6 à 3,5, et le siliconate étant un méthylsiliconate de sodium ou de potassium.15. Use according to claim 14 of a cogranule comprising sodium carbonate and sodium silicate, the molar ratio Si0 2 / Na 2 0 being from 1.6 to 3.5, and the siliconate being a sodium methylsiliconate or potassium.
16. Utilisation selon les revendications 12 à 15 desdits cogranulés pour la stabilisation d'un système de blanchiment à base de percarbonate de sodium ou de potassium activé par un agent activateur de blanchiment.16. Use according to claims 12 to 15 of said co-granules for the stabilization of a bleaching system based on sodium or potassium percarbonate activated by a bleach activating agent.
17. Procédé de préparation d'une composition détergente selon les revendications 1 à 11, dans lequel on mélange à sec le système de blanchiment à base de percarbonate de sodium ou de potassium et l'agent stabilisateur et on ajoute les autres composants par simple mélange à sec. 17. Process for preparing a detergent composition according to claims 1 to 11, in which the bleaching system based on sodium or potassium percarbonate and the stabilizing agent is dry mixed and the other components are added by simple mixing dried up.
PCT/FR1995/000663 1994-05-20 1995-05-19 Powder detergent composition comprising stabilized percarbonate WO1995032273A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU26202/95A AU2620295A (en) 1994-05-20 1995-05-19 Powder detergent composition comprising stabilized percarbonate
EP95920966A EP0759969A1 (en) 1994-05-20 1995-05-19 Powder detergent composition comprising stabilized percarbonate
NO964888A NO964888L (en) 1994-05-20 1996-11-18 Detergent powder mixture comprising stabilized percarbonate
FI964627A FI964627A0 (en) 1994-05-20 1996-11-19 Powder detergent composition containing stabilized percarbonate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9406193A FR2720074B1 (en) 1994-05-20 1994-05-20 Detergent powder composition based on percarbonate stabilized by adding silicate / carbonate cogranules.
FR94/06193 1994-05-20

Publications (1)

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EP (1) EP0759969A1 (en)
AU (1) AU2620295A (en)
FI (1) FI964627A0 (en)
FR (1) FR2720074B1 (en)
NO (1) NO964888L (en)
WO (1) WO1995032273A1 (en)

Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO1997017421A1 (en) * 1995-11-09 1997-05-15 Henkel Kommanditgesellschaft Auf Aktien Washing agents containing amorphous alkali silicates and peroxide bleaching agents
WO1997043370A1 (en) * 1996-05-09 1997-11-20 Unilever Plc Detergent compositions

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JPS63196698A (en) * 1987-02-09 1988-08-15 花王株式会社 Powdery cleanser composition
EP0486079A1 (en) * 1990-11-14 1992-05-20 Eka Nobel Ab Silicate
EP0488868A2 (en) * 1990-11-30 1992-06-03 Rhone-Poulenc Chimie Alcaline metal silicate based builder for detergent compositions
EP0561656A1 (en) * 1992-03-20 1993-09-22 Rhone-Poulenc Chimie Builder based on silicate and a mineral product

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FR2541301A1 (en) * 1982-04-08 1984-08-24 Colgate Palmolive Co SOFTENING DETERGENT COMPOSITION FOR LAUNDRY, PARTICLES FOR THE MANUFACTURE OF SUCH COMPOSITIONS AND METHOD OF MANUFACTURE THEREOF
JPS63196698A (en) * 1987-02-09 1988-08-15 花王株式会社 Powdery cleanser composition
EP0486079A1 (en) * 1990-11-14 1992-05-20 Eka Nobel Ab Silicate
EP0488868A2 (en) * 1990-11-30 1992-06-03 Rhone-Poulenc Chimie Alcaline metal silicate based builder for detergent compositions
EP0561656A1 (en) * 1992-03-20 1993-09-22 Rhone-Poulenc Chimie Builder based on silicate and a mineral product

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997017421A1 (en) * 1995-11-09 1997-05-15 Henkel Kommanditgesellschaft Auf Aktien Washing agents containing amorphous alkali silicates and peroxide bleaching agents
WO1997043370A1 (en) * 1996-05-09 1997-11-20 Unilever Plc Detergent compositions
US5854192A (en) * 1996-05-09 1998-12-29 Lever Brothers Company, Division Of Conopco, Inc. Particulate zero-phosphate aluminosilicate-built detergent compositions comprising silicate/carbonate cogranules

Also Published As

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NO964888L (en) 1997-01-17
NO964888D0 (en) 1996-11-18
FR2720074A1 (en) 1995-11-24
FI964627A (en) 1996-11-19
EP0759969A1 (en) 1997-03-05
FI964627A0 (en) 1996-11-19
FR2720074B1 (en) 1996-08-09
AU2620295A (en) 1995-12-18

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