EP0422998A1 - Aqueous zeolite suspensions containing a siliconate - Google Patents

Aqueous zeolite suspensions containing a siliconate Download PDF

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Publication number
EP0422998A1
EP0422998A1 EP90402759A EP90402759A EP0422998A1 EP 0422998 A1 EP0422998 A1 EP 0422998A1 EP 90402759 A EP90402759 A EP 90402759A EP 90402759 A EP90402759 A EP 90402759A EP 0422998 A1 EP0422998 A1 EP 0422998A1
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EP
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Prior art keywords
siliconate
suspension
weight
stabilizer
derivative
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EP90402759A
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German (de)
French (fr)
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EP0422998B1 (en
Inventor
Daniel Joubert
Marc Malassis
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/162—Organic compounds containing Si
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C11D3/1286—Stabilised aqueous aluminosilicate suspensions

Definitions

  • the present invention relates to aqueous suspensions of zeolite.
  • aqueous suspensions of zeolites present many industrial handling difficulties due to their very particular rheological behavior.
  • suspensions have a dilating behavior and their viscosity is very high. They are therefore difficult to pump, which makes their use, for example their introduction into possibly sprayable detergent mixtures, difficult or even impossible. In addition, these suspensions tend to sediment or gel, which makes them difficult to transport or store. So there is a real problem there.
  • the main object of the invention is therefore a system for obtaining aqueous suspensions of low viscosity zeolite, in particular pumpable.
  • Another object of the invention is a system which also makes it possible to obtain a stable aqueous suspension.
  • the suspensions according to the invention comprise zeolites and they are characterized in that they also comprise a siliconate and / or a siliconate derivative.
  • the aqueous zeolite suspension also comprises at least one stabilizer.
  • siliconates or derivatives has the effect of considerably lowering the viscosity of the zeolite suspensions. It also makes it possible to obtain manipulable suspensions with a higher dry extract, for example of at least 55%. Finally, it has been noted that the siliconates do not influence the exchange capacity of the zeolites.
  • the zeolites used in the context of the present invention include crystalline, amorphous and mixed crystalline-amorphous, natural or synthetic zeolites.
  • finely divided zeolites are used having an average diameter of primary particles of between 0.1 and 10 ⁇ m and, advantageously, between 0.5 and 5 ⁇ m, as well as a theoretical cation exchange power greater than 100 mg of CaCO3 / g of anhydrous product and preferably greater than 200 mg.
  • Use is also more particularly made of zeolites of type A, X or Y and in particular 4A and 13X.
  • zeolites obtained by the processes described in the French patent applications in the name of the Applicant No. 2,376,074, 2,384,716, 2,392,932, 2,528,722, the teaching of which is also incorporated herein request.
  • the last cited reference refers in particular to zeolites having a speed constant, related to the surface of the zeolites per liter of solution greater than 0.15 s ⁇ 1.lm ⁇ 2, preferably greater than 0.25 and advantageously between 0 , 4 and 4 s ⁇ 1.lm ⁇ 2.
  • These zeolites have particularly advantageous qualities in the use in detergency.
  • the suspensions may have a variable zeolite concentration depending on the application. In detergency, this concentration is generally between 40 and 51% by weight.
  • the pH of the suspensions is also a function of their use. Still in the detergency application, this pH expressed at 1% by weight of dry zeolite is approximately 11.
  • Siliconates are well known products, they are salts of siliconic acid or its derivatives.
  • R is a hydrocarbon residue generally of 1 to 18 carbon atoms, optionally substituted by a halogen atom, an amino, ether, ester, epoxy, mercapto, cyano, (poly) glycol group.
  • n is an integer or fractional number varying between 0.1 and 3.
  • M is an alkali metal or an ammonium or phosphonium group.
  • R is a hydrocarbon residue of 1 to 10 carbon atoms and more particularly of 1 to 6 atoms.
  • 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 phenylethyl, alkylaryl such as for example tolyl, xylyl, or an araryl radical such as biphenylyl.
  • 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 phenylethyl
  • alkylaryl such as for example tolyl, xylyl, or an araryl radical such as biphenylyl.
  • R ′ are identical or different and are hydrocarbon residues of 1 to 6 carbon atoms.
  • alkaline siliconates are used.
  • Alkaline earth siliconates can also be used.
  • alkylsiliconates and in particular alkaline alkylsiliconates such as, for example, sodium or potassium methylsiliconates.
  • alkali or alkaline earth siliconates are products, most of which are commercially available.
  • silanes having 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 US-A-2,441,422, US-A-2,441,423 ).
  • the dispersant can also be chosen from siliconate derivatives.
  • derivative products 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 into silicone compounds or polymers.
  • alkali metal alkylsiliconates can be transformed into polyalkylsiloxanes, in particular by the action of carbon dioxide or other acidifying agent.
  • the siliconates are usually used in the form of aqueous solutions.
  • the amount of siliconate used depends on the specific surface of the zeolite. This amount is usually between 0.01 and 2%, more particularly between 0.05 and 0.3% by weight relative to the final suspension. This quantity is understood here for a solution at 50% by weight in water of the siliconate or derivative.
  • siliconates has the effect of making the zeolite suspensions pumpable and manipulable due to their low viscosity.
  • suspensions which are stable that is to say which do not settle or little.
  • these suspensions can be transported or stored without difficulty.
  • the suspensions comprise, in addition to the siliconate, a stabilizer.
  • magnesium is preferably used.
  • the cation can, moreover, be provided in the form of a halide, in particular a chloride, more particularly magnesium chloride, for example magnesium chloride hexahydrate, is used.
  • a halide in particular a chloride, more particularly magnesium chloride, for example magnesium chloride hexahydrate, is used.
  • the amount of cation used generally varies between 0.002 and 0.5% relative to the weight of the final suspension.
  • stabilizers which can be used according to the invention, mention may be made of natural polysaccharides of animal origin such as chitosame and chitin; of vegetable origin such as carragenanes, alginates, gum arabic, guar, carob, tara, cassia, konjak mannan, and finally those of bacterial or biogum origin.
  • animal origin such as chitosame and chitin
  • vegetable origin such as carragenanes, alginates, gum arabic, guar, carob, tara, cassia, konjak mannan, and finally those of bacterial or biogum origin.
  • Biogums are polysaccharides of high molecular weight, generally greater than a million, obtained by fermentation of a carbohydrate under the action of a microorganism.
  • biogum which can be used in the suspension which is the subject of the present invention there may be mentioned more particularly, xanthan gum, that is to say that obtained by fermentation under the action of bacteria or fungi belonging to the genus Xanthomonas such as Xanthomonas begoniae, Xanthomonas campestris, Xanthomonas carotae, Xanthomonas hederae, Xanthomonas incanae, Xanthomonas malvacearum, Xanthomonas papavericola, Xanthomonas phaseoli, Xanthomonas pisi, Xanthomonas vasculorum, Xanthomonas vesicatoria, Xanthomonas vitians, Xanthomonas pelargonii.
  • Xanthan gum that is to say that obtained by fermentation under the action of bacteria or fungi belonging to the genus Xant
  • Xanthan gums are commonly found commercially.
  • gellan gum obtained from Pseudomonas Elodea, Rhamsan and Welan gums obtained from Alcaligenes.
  • cellulose and starch or their derivatives. Mention may be made, for example, of carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxymethylcellulose, cyanoethylated starch, carboxymethylated starch.
  • polysaccharides are used in solid form, in powder, or in aqueous solution.
  • carboxylic acids and their salts and in particular acetic, formic, oxalic, malic, citric and tartaric acids.
  • alkaline salts such as NaHCO3, NaCl, Na2CO3, Na2SO4 and sodium pyrophosphate or tripolyphosphate.
  • water-soluble polymers of acrylic acid crosslinked with a sucrose polyallylether for example in a proportion of approximately 1% and having an average of approximately 5.8 allyl groups for each sucrose molecule.
  • polymers with a molecular weight greater than 1,000,000 polymers of this type can be found in the CARBOPOL series for example CARBOPOL 934, 940 and 941.
  • CARBOPOL 934, 940 and 941 the quantities used in percentage by weight relative to the final suspension vary between 0.001 and 2%.
  • the zeolite suspensions according to the invention are prepared in a simple manner by introducing the additives described above into the suspension.
  • the pH of the suspensions can be adjusted to the desired value in a known manner by the addition of any suitable neutralizing agent.
  • Suspensions comprising zeolites and stabilized by the systems which have just been described can be used in numerous applications.
  • They can be used in the form of suspensions based essentially on zeolites and the stabilizing additives mentioned above. In this case they can enter into the preparation of detergent compositions. They can be used in any field other than detergency for which zeolites are used, for example in stationery.
  • the present invention also relates to detergent compositions, in particular for liquid detergents, comprising, in addition to the suspensions based on zeolite and stabilizers of the invention, all the other additives known in detergency such as bleaching agents, foam control agents, anti-redeposition agents, perfumes, dyes, enzymes, optical agents.
  • the dry extract of the suspension is given in percentage by weight in% of anhydrous zeolite determined by a measurement of loss on ignition at 850 ° C. for one hour.
  • the pH indicated is given for an aqueous dispersion containing 1% of dry zeolite and it is measured using a high alkalite pH electrode.
  • the exchange capacity is given by the amount of calcium (expressed in mg of CaCO3) exchanged with 1 g of anhydrous zeolite at 25 ° C.
  • the measurement is carried out in the following manner: 0.4 g of zeolite (expressed as anhydrous) is introduced into a solution of 5.10 ⁇ 3 mole / l CaCl2. The mixture is kept stirring for 15 minutes. After filtration, the excess calcium is dosed at pH 10 in return by EDTA in the presence of a colored indicator, black eriochrome T.
  • the RHEOMAT 30 equipped with the centered measurement system B is used as rheometer.
  • the measurement consists in performing a cycle in speed gradient (ascent plus descent).
  • the range of speed gradient explored is between 0.0215 and 157.9 s ⁇ 1, which corresponds to rotational speeds of the mobile from 0.0476 to 350 revolutions per minute.
  • the viscosities reported in the examples correspond to measurements obtained during the descent in speed gradient.
  • Sedimentation is determined by introducing the zeolite suspension into graduated cylinders of 50 or 100 cc. The volumes of supernatant and decantate are measured every five days. The test pieces are left at room temperature (20 ° C) or placed in a thermostatically controlled enclosure.
  • the zeolite used is a 4A zeolite with an average diameter of primary particles of 3.5 ⁇ m.
  • Table 1 Example 1 comparison 2 comparison 3 according to the invention 4 according to the invention Suspension% anhydrous zeolite 47.5 47.5 47.2 47.6 Exchange capacity 303 303 303 303 Siliconate% suspension 0 0 0.17 0.08 pH 10.88 11.07 10.87 11.06 Viscosity (in poise) at 5 s ⁇ 1 12.5 27.4 0.17 6.5
  • the siliconate used is the product sold under the name RHODORSIL SILICONATE 51T by the Applicant with the formula CH3Si (OK) 3.
  • Examples 8 to 9 describe the use of xanthan gum as a stabilizer. We always use the same siliconate. The results are given in Table 3. The amount of xanthan gum used is 0.12% and 0.1% by weight relative to the suspension for Examples 8 and 9 respectively.
  • Example 10 relates to the use of oxalic acid as a stabilizer. This is used at 1% by weight relative to the suspension.
  • the siliconate is the same as in Examples 8 and 9.
  • Example 11 relates to the use of Carbopol 941 as a stabilizer at 0.1% by weight relative to the suspension.
  • Table 3 Examples 8 9 10 11 Suspension% anhydrous zeolite 47.5 49.3 49.3 49.7 Exchange capacity 288 288 288 Siliconate (% suspension) 0.17 0.2 0.1 0.1 pH 10.86 11.46 11.03 10.66 Viscosity in poise at 5 s ⁇ 1 10.2 10.2 6.5 3.1 Sunageant (% volume) 5 days 3 1.5 2 2 10 days 4 2 7 Decantate% 5 days ⁇ 0.5 "1 0 1 10 days 0.5 1 "1
  • a suspension of the same zeolite as the preceding examples is used at a concentration of 49.7% and without any additive.
  • the pH is 11.57.

Abstract

Aqueous zeolite suspensions. These suspensions of reduced viscosity are characterised in that they comprise a siliconate and/or a siliconate derivative. They can be employed more particularly in the preparation of detergent compositions.

Description

La présente invention concerne les suspensions aqueuses de zéolite.The present invention relates to aqueous suspensions of zeolite.

L'utilisation des zéolites en détergence est bien connue. Cette utilisation s'est développée notamment par suite de la substi­tution au moins partielle des zéolites aux phosphates dans les lessives. On a reproché, en effet, à ces derniers produits de provo­quer une eutrophisation des eaux et donc de poser des problèmes écologiques.The use of zeolites in detergency is well known. This use has developed in particular as a result of the at least partial substitution of zeolites for phosphates in detergents. In fact, these latter products have been criticized for causing eutrophication of the waters and therefore posing ecological problems.

Toutefois, les suspensions aqueuses de zéolites présentent beaucoup de difficultés de manipulation industrielle en raison de leur comportement rhéologique très particulier.However, aqueous suspensions of zeolites present many industrial handling difficulties due to their very particular rheological behavior.

En effet, ces suspensions ont un comportement dilatant.Leur viscosité est très élevée. Elles sont donc difficilement pompables, ce qui rend leur utilisation, par exemple leur introduction dans des bouillies de lessive éventuellement atomisables, difficile voire impossible. En outre, ces suspensions ont tendance à sédimenter ou à gélifier, ce qui les rend difficilement transportables ou stockables. Il y a donc là un réel problème.These suspensions have a dilating behavior and their viscosity is very high. They are therefore difficult to pump, which makes their use, for example their introduction into possibly sprayable detergent mixtures, difficult or even impossible. In addition, these suspensions tend to sediment or gel, which makes them difficult to transport or store. So there is a real problem there.

L'objet principal de l'invention est par conséquent un système permettant d'obtenir des suspensions aqueuses de zéolite à faible viscosité, notamment pompables.The main object of the invention is therefore a system for obtaining aqueous suspensions of low viscosity zeolite, in particular pumpable.

Un autre objet de l'invention est un système permettant en outre l'obtention d'une suspension aqueuse stable.Another object of the invention is a system which also makes it possible to obtain a stable aqueous suspension.

Dans ce but, les suspensions selon l'invention comprennent des zéolites et elles sont caractérisées en ce qu'elles comportent en outre un siliconate et/ou un dérivé de siliconate.For this purpose, the suspensions according to the invention comprise zeolites and they are characterized in that they also comprise a siliconate and / or a siliconate derivative.

Selon un mode de réalisation particulier de l'invention, la suspension aqueuse de zéolite comprend en outre au moins un stabilisant.According to a particular embodiment of the invention, the aqueous zeolite suspension also comprises at least one stabilizer.

L'emploi des siliconates ou dérivés a pour effet de baisser considérablement la viscosité des suspensions de zéolite. Il permet aussi d'obtenir des suspensions manipulables à extrait sec plus élevé par exemple d'au moins 55%. Enfin, on a pu remarquer que les siliconates n'influent pas sur la capacité d'échange des zéolites.The use of siliconates or derivatives has the effect of considerably lowering the viscosity of the zeolite suspensions. It also makes it possible to obtain manipulable suspensions with a higher dry extract, for example of at least 55%. Finally, it has been noted that the siliconates do not influence the exchange capacity of the zeolites.

D'autres caractéristiques et avantages de l'invention seront mieux compris à la lecture de la description et des exemples concrets mais non limitatifs qui vont suivre.Other characteristics and advantages of the invention will be better understood on reading the description and concrete but nonlimiting examples which follow.

Les zéolites utilisées dans le cadre de la présente inven­tion comprennent les zéolites cristallines, amorphes et mixtes cristallines-amorphes, naturelles ou synthétiques.The zeolites used in the context of the present invention include crystalline, amorphous and mixed crystalline-amorphous, natural or synthetic zeolites.

Bien entendu, on choisira de préférence celles capables de réagir suffisamment rapidement avec les ions calcium et/ou magnésium, de manière à pouvoir adoucir les eaux de lavage.Of course, preferably those capable of reacting quickly enough with the calcium and / or magnesium ions will be chosen so as to be able to soften the washing waters.

Généralement, on utilise les zéolites finement divisées présentant un diamètre moyen de particules primaires compris entre 0,1 et 10µm et, avantageusement, entre 0,5 et 5µm, ainsi qu'un pouvoir d'échange théorique de cations supérieur à 100 mg de CaCO₃/g de produit anhydre et de préférence supérieur à 200 mg.Generally, finely divided zeolites are used having an average diameter of primary particles of between 0.1 and 10 μm and, advantageously, between 0.5 and 5 μm, as well as a theoretical cation exchange power greater than 100 mg of CaCO₃ / g of anhydrous product and preferably greater than 200 mg.

On utilise aussi plus particulièrement les zéolites de type A, X ou Y et notamment 4A et 13X.Use is also more particularly made of zeolites of type A, X or Y and in particular 4A and 13X.

A titre d'exemple de zéolites pouvant être employées dans le cadre de la présente invention, on peut citer les produits faisant l'objet des demandes de brevets français n° 2 225 568, 2 269 575, 2 283 220 dont l'enseignement est incorporé ici.By way of example of zeolites which can be used in the context of the present invention, mention may be made of the products which are the subject of French patent applications No. 2,225,568, 2,269,575, 2,283,220, the teaching of which is incorporated here.

On peut citer plus particulièrement les zéolites obtenues par les procédés décrits dans les demandes de brevets français au nom de la Demanderesse n° 2 376 074, 2 384 716, 2 392 932, 2 528 722 dont l'enseignement est aussi incorporé à la présente demande. La dernière référence citée fait notamment état de zéolites présentant une constante de vitesse, rapportée à la surface des zéolites par litre de solution supérieure à 0,15 s⁻¹.l.m⁻², de préférence supérieure à 0,25 et avantageusement comprise entre 0,4 et 4 s⁻¹.l.m⁻². Ces zéolites ont des qualités particulièrement intéressantes dans l'uti­lisation en détergence.Mention may more particularly be made of the zeolites obtained by the processes described in the French patent applications in the name of the Applicant No. 2,376,074, 2,384,716, 2,392,932, 2,528,722, the teaching of which is also incorporated herein request. The last cited reference refers in particular to zeolites having a speed constant, related to the surface of the zeolites per liter of solution greater than 0.15 s⁻¹.lm⁻², preferably greater than 0.25 and advantageously between 0 , 4 and 4 s⁻¹.lm⁻². These zeolites have particularly advantageous qualities in the use in detergency.

La demande n° 2 392 932 notamment fait état de zéolites obtenues par un procédé consistant à injecter une solution de sili­cate de sodium dans l'axe d'un venturi alors qu'on injecte une solution d'aluminate de sodium coaxialement au même venturi avec recyclage du mélange obtenu.Application No. 2,392,932 in particular mentions zeolites obtained by a process consisting in injecting a sodium silicate solution in the axis of a venturi while a sodium aluminate solution is injected coaxially with the same venturi with recycling of the mixture obtained.

On obtient notamment des zéolites de formule :
x Na₂O, y Al₂O₃, zSiO₂, wH₂O
dans laquelle si y = 1, x = 1, z = 1,8 à 2, w = 0 à 5 et présentant une granulométrie répondant à la distribution suivante en nombre 95% < 10µm, 99% < 15µm, 50% compris entre 2 et 6µm pour le diamètre moyen.In particular, zeolites of the formula are obtained:
x Na₂O, y Al₂O₃, zSiO₂, wH₂O
in which if y = 1, x = 1, z = 1.8 to 2, w = 0 to 5 and having a particle size corresponding to the following distribution in number 95% <10µm, 99% <15µm, 50% between 2 and 6µm for the average diameter.

Les suspensions peuvent présenter une concentration en zéolite variable et fonction de l'application. En détergence, cette concentration est généralement comprise entre 40 et 51% en poids.The suspensions may have a variable zeolite concentration depending on the application. In detergency, this concentration is generally between 40 and 51% by weight.

Le pH des suspensions est aussi fonction de leur utilisa­tion. Toujours dans l'application détergence, ce pH exprimé à 1% en poids de zéolite sèche, est d'environ 11.The pH of the suspensions is also a function of their use. Still in the detergency application, this pH expressed at 1% by weight of dry zeolite is approximately 11.

Selon la caractéristique essentielle de l'invention, on emploie dans les suspensions du type décrit ci-dessus un siliconate et/ou un dérivé de siliconate.According to the essential characteristic of the invention, there is used in suspensions of the type described above a siliconate and / or a siliconate derivative.

Les siliconates sont des produits bien connus, ce sont des sels de l'acide siliconique ou de ses dérivés.Siliconates are well known products, they are salts of siliconic acid or its derivatives.

On peut citer notamment les produits répondant à la formule (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 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 (1):
R - Si (OM) m (OH) 3-m (1)
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, ether, ester, epoxy, mercapto, cyano, (poly) glycol group.

m est un nombre entier ou fractionnaire variant entre 0,1 et 3.m is an integer or fractional number varying between 0.1 and 3.

M est un métal alcalin ou un groupe ammonium ou phospho­nium.M is an alkali metal or an ammonium or phosphonium group.

De préférence, R est un reste hydrocarboné de 1 à 10 atomes de carbone et plus particulièrement de 1 à 6 atomes.Preferably, R is a hydrocarbon residue of 1 to 10 carbon atoms and more particularly of 1 to 6 atoms.

Plus précisément, R peut être un radical alkyle par exemple méthyle, éthyle, propyle, butyle, isobutyle; un radical alcényle comme par exemple vinyl, un radical aryle, par exemple phényle ou naphtyle, un radical arylalkyle comme par exemple benzyle ou phényl­éthyle, alkylaryle comme par exemple tolyle, xylyle, ou un radical araryle comme le biphénylyle.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 phenylethyl, alkylaryl such as for example tolyl, xylyl, or an araryl radical such as biphenylyl.

Pour M, on peut citer plus particulièrement le sodium ou le potassium ainsi que les groupes N⁺R′₄, P⁺R′₄ dans lesquels R′ sont identiques ou différents et sont des restes hydrocarbonés de 1 à 6 atomes de carbone.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.

On utilise plus particulièrement les siliconates alcalins. On peut aussi employer les siliconates alcalinoterreux.More particularly, alkaline siliconates are used. Alkaline earth siliconates can also be used.

De même, on met en oeuvre particulièrement les alkylsi­liconates et notamment les alkylsiliconates alcalins comme par exemple les méthylsiliconates de sodium ou de potassium.Likewise, particular use is made of alkylsiliconates and in particular alkaline alkylsiliconates such as, for example, sodium or potassium methylsiliconates.

On peut aussi utiliser les siliconates de formule 1 pour lesquels R est un radical vinyle ou phényle, et plus particulièrement les siliconates alcalins de ce type.It is also possible to use the siliconates of formula 1 for which R is a vinyl or phenyl radical, and more particularly the alkali siliconates of this type.

Il est à noter que les siliconates alcalins ou alcalino­terreux sont des produits dont la plupart sont disponibles dans le commerce.It should be noted that alkali or alkaline earth siliconates are products, most of which are commercially available.

Ils peuvent être préparés par exemple par hydrolyse des silanes correspondants présentant 3 groupes hydrolysables tels que des atomes d'halogène, 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 US-A-2 441 422, US-A-2 441 423).They can be prepared for example by hydrolysis of the corresponding silanes having 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 US-A-2,441,422, US-A-2,441,423 ).

Comme exemple de siliconates de ce type disponibles dans le commerce, on peut citer notamment le RHODORSIL R SILICONATE 51T, commercialisé par la Demanderesse, qui est un méthylsiliconate de potassium.As an example of commercially available siliconates of this type, mention may in particular be made of RHODORSIL R SILICONATE 51T, sold by the Applicant, which is a potassium methylsiliconate.

Comme cela a été indiqué plus haut, le dispersant peut être choisi aussi parmi les dérivés des siliconates.As indicated above, the dispersant can also be chosen from siliconate derivatives.

Par produits dérivés, on entend ici les produits de conden­sation des produits répondant notamment à la formule (1) décrit ci-dessus, ou ceux résultant de la polymérisation au moins partielle en composés ou polymères siliconiques.By derivative products 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 into silicone compounds or polymers.

On sait par exemple que les alkylsiliconates de métal alcalin peuvent être transformés en polyalkylsiloxanes, notamment par l'action de l'anhydride carbonique ou autre agent acidifiant.It is known, for example, that the alkali metal alkylsiliconates can be transformed into polyalkylsiloxanes, 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 dans la suspension 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 in the suspension two or more siliconates or derivatives.

Les siliconates s'utilisent habituellement sous forme de solutions aqueuses.The siliconates are usually used in the form of aqueous solutions.

La quantité de siliconate utilisée est fonction de la surface spécifique de la zéolite. Cette quantité est habituellement comprise entre 0,01 et 2% plus particulièrement entre 0,05 et 0,3% en poids par rapport à la suspension finale. Cette quantité s'entend ici pour une solution à 50% en poids dans l'eau du siliconate ou dérivé.The amount of siliconate used depends on the specific surface of the zeolite. This amount is usually between 0.01 and 2%, more particularly between 0.05 and 0.3% by weight relative to the final suspension. This quantity is understood here for a solution at 50% by weight in water of the siliconate or derivative.

Comme cela a été indiqué plus haut, l'emploi des silicona­tes a pour effet de rendre les suspensions de zéolite pompables et manipulables par suite de leur faible viscosité.As indicated above, the use of siliconates has the effect of making the zeolite suspensions pumpable and manipulable due to their low viscosity.

Cependant, il peut être aussi utile de disposer de suspensions qui soient stables, c'est-à-dire qui ne décantent pas ou peu. Dans ce cas, ces suspensions peuvent être transportées ou stockées sans difficultés.However, it can also be useful to have suspensions which are stable, that is to say which do not settle or little. In this case, these suspensions can be transported or stored without difficulty.

Dans ce but et selon un mode de réalisation particulier de l'invention, les suspensions comprennent, outre le siliconate, un stabilisant.For this purpose and according to a particular embodiment of the invention, the suspensions comprise, in addition to the siliconate, a stabilizer.

Différents types de stabilisants peuvent être utilisés.Different types of stabilizers can be used.

C'est ainsi que l'on peut employer dans le cadre de la présente invention comme stabilisant un cation du groupe des alcalino-terreux.Thus it is possible to use in the context of the present invention as stabilizing a cation from the group of alkaline earths.

On pourra se référer à FR-A-2.568.790 au nom de la Demanderesse dont l'enseignement est incorporé ici à la présente demande.Reference may be made to FR-A-2,568,790 in the name of the Applicant, the teaching of which is incorporated here into the present application.

A titre de cation, on utilise de préférence le magnésium.As the cation, magnesium is preferably used.

Le cation peut, par ailleurs, être apporté sous la forme d'un halogénure notamment d'un chlorure, plus particulièrement on utilise le chlorure de magnésium, par exemple le chlorure de magnésium hexahydraté.The cation can, moreover, be provided in the form of a halide, in particular a chloride, more particularly magnesium chloride, for example magnesium chloride hexahydrate, is used.

La quantité de cation employée varie généralement entre 0,002 et 0,5% par rapport au poids de la suspension finale.The amount of cation used generally varies between 0.002 and 0.5% relative to the weight of the final suspension.

Comme autres types de stabilisants utilisables selon l'invention, on peut citer les polysaccharides naturels d'origine animale tels que le chitosame et chitine; d'origine végétale tels que carragenanes, alginates, gommes arabiques, guar, caroube, tara, cassia, konjak mannane, et enfin ceux d'origine bactérienne ou biogommes.As other types of stabilizers which can be used according to the invention, mention may be made of natural polysaccharides of animal origin such as chitosame and chitin; of vegetable origin such as carragenanes, alginates, gum arabic, guar, carob, tara, cassia, konjak mannan, and finally those of bacterial or biogum origin.

Les biogommes sont des polysaccharides de poids moléculaire élevé, généralement supérieur à un million, obtenus par fermentation d'un hydrate de carbone sous l'action d'un microorganisme.Biogums are polysaccharides of high molecular weight, generally greater than a million, obtained by fermentation of a carbohydrate under the action of a microorganism.

Comme biogomme pouvant être utilisées dans la suspension faisant l'objet de la présente invention, on peut mentionner plus particulièrement, la gomme xanthane c'est-à-dire celle obtenue par fermentation sous l'action de bactéries ou de champignons appartenant au genre Xanthomonas telles que Xanthomonas begoniae, Xanthomonas campestris, Xanthomonas carotae, Xanthomonas hederae, Xanthomonas incanae, Xanthomonas malvacearum, Xanthomonas papavericola, Xanthomonas phaseoli, Xanthomonas pisi, Xanthomonas vasculorum, Xanthomonas vesicatoria, Xanthomonas vitians, Xanthomonas pelargonii.As biogum which can be used in the suspension which is the subject of the present invention, there may be mentioned more particularly, xanthan gum, that is to say that obtained by fermentation under the action of bacteria or fungi belonging to the genus Xanthomonas such as Xanthomonas begoniae, Xanthomonas campestris, Xanthomonas carotae, Xanthomonas hederae, Xanthomonas incanae, Xanthomonas malvacearum, Xanthomonas papavericola, Xanthomonas phaseoli, Xanthomonas pisi, Xanthomonas vasculorum, Xanthomonas vesicatoria, Xanthomonas vitians, Xanthomonas pelargonii.

Les gommes xanthanes se trouvent couramment dans le commerce.Xanthan gums are commonly found commercially.

Un exemple de produit de ce type est celui vendu sous le nom RHODOPOL par la Demanderesse.An example of a product of this type is that sold under the name RHODOPOL by the Applicant.

Comme autres gommes, on peut citer la gellan gum obtenue à partir de Pseudomonas Elodea, les gommes Rhamsan et Welan obtenues à partir d'Alcaligenes.As other gums, mention may be made of gellan gum obtained from Pseudomonas Elodea, Rhamsan and Welan gums obtained from Alcaligenes.

On citera en outre les gommes synthétiques ou modifiées chimiquement comprenant les cellulosiques.Mention will also be made of synthetic or chemically modified gums comprising cellulosics.

On peut ainsi mettre en oeuvre celles choisies dans le groupe des polyholosides macromoléculaires notamment la cellulose et l'amidon ou leurs dérivés. On peut citer par exemple la carboxyméthylcellulose, la méthylcellulose, l'éthylcellulose, l'hydroxyméthylcellulose, l'amidon cyanoéthylé, l'amidon carboxymé­thylé.It is thus possible to use those chosen from the group of macromolecular polyholosides, in particular cellulose and starch or their derivatives. Mention may be made, for example, of carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxymethylcellulose, cyanoethylated starch, carboxymethylated starch.

Les produits décrits ci-dessus (polysacharides, biogommes, gommes modifiées) sont mis en oeuvre sous forme solide, en poudre, ou en solution aqueuse.The products described above (polysaccharides, biogums, modified gums) are used in solid form, in powder, or in aqueous solution.

Ils sont généralement utilisés dans une quantité qui varie entre 0,001 et 2%, et plus particulièrement de 0,01 et 0,5% en poids par rapport à la suspension finale.They are generally used in an amount which varies between 0.001 and 2%, and more particularly from 0.01 and 0.5% by weight relative to the final suspension.

Comme autre type de stabilisants, on peut citer les acides carboxyliques et leurs sels et en particulier les acides acétique, formique, oxalique, malique, citrique et tartrique.As another type of stabilizer, mention may be made of carboxylic acids and their salts and in particular acetic, formic, oxalic, malic, citric and tartaric acids.

On peut aussi mentionner les sels alcalins tels que NaHCO₃, NaCl, Na₂CO₃, Na₂SO₄ et le pyrophosphate ou tripolyphosphate de sodium.Mention may also be made of alkaline salts such as NaHCO₃, NaCl, Na₂CO₃, Na₂SO₄ and sodium pyrophosphate or tripolyphosphate.

Pour ces deux types de stabilisants, on utilise des quantités en pourcentage pondéral par rapport à la suspension de 0,05 à 10%.For these two types of stabilizers, amounts in weight percentage relative to the suspension of 0.05 to 10% are used.

On peut encore employer les polymères solubles dans l'eau de l'acide acrylique réticulés avec un polyallyléther de sucrose, par exemple dans une proportion d'environ 1% et ayant une moyenne d'environ 5,8 groupes allyle pour chaque molécule de sucrose, les polymères ayant un poids moléculaire supérieur à 1 000 000. Les polymères de ce type peuvent être trouvés dans la série des CARBOPOL par exemple CARBOPOL 934, 940 et 941. Pour ce dernier type de stabi­lisant, les quantités utilisées en pourcentage pondéral par rapport à la suspension finale varient entre 0,001 et 2%.It is also possible to use the water-soluble polymers of acrylic acid crosslinked with a sucrose polyallylether, for example in a proportion of approximately 1% and having an average of approximately 5.8 allyl groups for each sucrose molecule. , polymers with a molecular weight greater than 1,000,000. Polymers of this type can be found in the CARBOPOL series for example CARBOPOL 934, 940 and 941. For the latter type of stabilizer, the quantities used in percentage by weight relative to the final suspension vary between 0.001 and 2%.

Il va de soi que les stabilisants mentionnés ci-dessus peuvent être utilisés seuls ou en combinaison.It goes without saying that the stabilizers mentioned above can be used alone or in combination.

La préparation des suspensions de zéolite selon l'invention se fait d'une manière simple par introduction des additifs décrits ci-dessus dans la suspension.The zeolite suspensions according to the invention are prepared in a simple manner by introducing the additives described above into the suspension.

Si nécessaire le pH des suspensions peut être ajusté à la valeur désirée d'une manière connue par addition de tout agent neutralisant convenable.If necessary, the pH of the suspensions can be adjusted to the desired value in a known manner by the addition of any suitable neutralizing agent.

Les suspensions comprenant les zéolites et stabilisées par les systèmes qui viennent d'être décrits peuvent être utilisées dans de nombreuses applications.Suspensions comprising zeolites and stabilized by the systems which have just been described can be used in numerous applications.

Elles peuvent être utilisées sous la forme de suspensions à base essentiellement de zéolites et des additifs stabilisants men­tionnés ci-dessus. Dans ce cas elles peuvent entrer dans la prépara­tion de compositions lessivielles. Elles peuvent être utilisées dans tout autre domaine que la détergence pour lequel les zéolites sont employées par exemple en papeterie.They can be used in the form of suspensions based essentially on zeolites and the stabilizing additives mentioned above. In this case they can enter into the preparation of detergent compositions. They can be used in any field other than detergency for which zeolites are used, for example in stationery.

La présente invention concerne aussi les compositions lessivielles notamment pour lessives liquides, comprenant outre les suspensions à base de zéolite et des stabilisants de l'invention, tous les autres additifs connus en détergence tels que des agents de blanchiment, des agents de contrôle des mousses, des agents antiré­déposition, des parfums, des colorants, des enzymes, des agents optiques.The present invention also relates to detergent compositions, in particular for liquid detergents, comprising, in addition to the suspensions based on zeolite and stabilizers of the invention, all the other additives known in detergency such as bleaching agents, foam control agents, anti-redeposition agents, perfumes, dyes, enzymes, optical agents.

Des exemples concrets vont maintenant être donnés.Concrete examples will now be given.

EXEMPLESEXAMPLES

Quelques définitions et précisions sont données au préa­lable.Some definitions and details are given beforehand.

L'extrait sec de la suspension est donné en pourcentage pondéral en % de zéolite anhydre déterminé par une mesure de perte au feu à 850°C pendant une heure.The dry extract of the suspension is given in percentage by weight in% of anhydrous zeolite determined by a measurement of loss on ignition at 850 ° C. for one hour.

Le pH indiqué est donné pour une dispersion aqueuse conte­nant 1% de zéolite sèche et il est mesuré à l'aide d'une électrode pH haute alcalinite.The pH indicated is given for an aqueous dispersion containing 1% of dry zeolite and it is measured using a high alkalite pH electrode.

La capacité d'échange est donnée par la quantité de calcium (exprimée en mg de CaCO₃) échangée par 1 g de zéolite anhydre à 25°C. On réalise la mesure de la manière suivante : 0,4 g de zéolite (exprimé en anhydre) est introduit dans une solution de 5.10⁻³ mole/l CaCl₂. Le mélange est maintenu sous agitation pendant 15 minutes. Après filtration, l'excès de calcium est dosé à pH 10 en retour par l'EDTA en présence d'un indicateur coloré, le noir d'ériochrome T.The exchange capacity is given by the amount of calcium (expressed in mg of CaCO₃) exchanged with 1 g of anhydrous zeolite at 25 ° C. The measurement is carried out in the following manner: 0.4 g of zeolite (expressed as anhydrous) is introduced into a solution of 5.10⁻³ mole / l CaCl₂. The mixture is kept stirring for 15 minutes. After filtration, the excess calcium is dosed at pH 10 in return by EDTA in the presence of a colored indicator, black eriochrome T.

On notera que le système de l'invention stabilisant-disper­sant ne perturbe pas cette capacité.It will be noted that the system of the invention stabilizer-dispersant does not disturb this capacity.

En ce qui concerne la rhéologie, on utilise comme rhéomètre le RHEOMAT 30 équipé du système de mesure B centré. La mesure consis­te à effectuer un cycle en gradient de vitesse (montée plus descen­te). La gamme de gradient de vitesse explorée est comprise entre 0,0215 et 157,9 s⁻¹, ce qui correspond à des vitesses de rotation du mobile de 0,0476 à 350 tours par minute. les viscosités rapportées dans les exemples correspondent à des mesures obtenues durant la descente en gradient de vitesse.As regards rheology, the RHEOMAT 30 equipped with the centered measurement system B is used as rheometer. The measurement consists in performing a cycle in speed gradient (ascent plus descent). The range of speed gradient explored is between 0.0215 and 157.9 s⁻¹, which corresponds to rotational speeds of the mobile from 0.0476 to 350 revolutions per minute. the viscosities reported in the examples correspond to measurements obtained during the descent in speed gradient.

La sédimentation est déterminée en introduisant la suspen­sion de zéolite dans des éprouvettes graduées de 50 ou 100 cc. Les volumes de surnageant et de décantat sont mesurés tous les cinq jours. Les éprouvettes sont laissées à température ambiante (20°C) ou placées en enceinte thermostatée.Sedimentation is determined by introducing the zeolite suspension into graduated cylinders of 50 or 100 cc. The volumes of supernatant and decantate are measured every five days. The test pieces are left at room temperature (20 ° C) or placed in a thermostatically controlled enclosure.

La zéolite utilisée est une zéolite 4A de diamètre moyen de particules primaires de 3,5µm.The zeolite used is a 4A zeolite with an average diameter of primary particles of 3.5 μm.

EXEMPLES 1 A 4A EXAMPLES 1 TO 4 A

Les résultats sont donnés dans le tableau 1 ci-dessous : Tableau 1 Exemple 1 comparatif 2 comparatif 3 selon l'invention 4 selon l'invention Suspension % de zéolite anhydre 47,5 47,5 47,2 47,6 Capacité d'échange 303 303 303 303 Siliconate % suspension 0 0 0,17 0,08 pH 10,88 11,07 10,87 11,06 Viscosité (en poise) à 5 s⁻¹ 12,5 27,4 0,17 6,5 The results are given in table 1 below: Table 1 Example 1 comparison 2 comparison 3 according to the invention 4 according to the invention Suspension% anhydrous zeolite 47.5 47.5 47.2 47.6 Exchange capacity 303 303 303 303 Siliconate% suspension 0 0 0.17 0.08 pH 10.88 11.07 10.87 11.06 Viscosity (in poise) at 5 s⁻¹ 12.5 27.4 0.17 6.5

Le siliconate utilisé est le produit vendu sous la dénomina­tion RHODORSIL SILICONATE 51T par la Demanderesse de formule CH₃Si(OK)₃.The siliconate used is the product sold under the name RHODORSIL SILICONATE 51T by the Applicant with the formula CH₃Si (OK) ₃.

EXEMPLES 5 A 7EXAMPLES 5 TO 7

Ces exemples concernent l'utilisation des cations magnésium comme stabilisant en addition au siliconate. Le siliconate est le même que celui employé pour les exemples précédents.These examples relate to the use of magnesium cations as a stabilizer in addition to siliconate. The siliconate is the same as that used for the previous examples.

Les résultats sont rassemblés dans le tableau 2 ci-dessous.The results are collated in Table 2 below.

Bien que la présence d'un stabilisant augmente la viscosité de la suspension, celle-ci reste encore très faible. Tableau 2 Exemples 5 6 7 Suspension % de zéolite anhydre 47,7 47,6 47,2 Capacité d'échange 302 302 302 mgCaCO₃/g zéolite siliconate 0,2 0,2 0,17 % suspension MgCl₂, 6H₂O % 0,3 0 0 Silicate de Mg % 0 0,2 0 pH 10,96 10,96 10,87 Viscosité poise à 4,74 s⁻¹ 1,2 0,3 0,17 Décantation surnageant (% volume) 10 22 15 volume au bout de 5 jours au bout de 5 jours au bout de 48 heures Although the presence of a stabilizer increases the viscosity of the suspension, it still remains very low. Table 2 Examples 5 6 7 Suspension% anhydrous zeolite 47.7 47.6 47.2 Exchange capacity 302 302 302 mgCaCO₃ / g zeolite siliconate 0.2 0.2 0.17 % suspension MgCl₂, 6H₂O% 0.3 0 0 Mg% silicate 0 0.2 0 pH 10.96 10.96 10.87 Poise viscosity at 4.74 s⁻¹ 1.2 0.3 0.17 Supernatant decantation (% volume) 10 22 15 volume after 5 days after 5 days after 48 hours

EXEMPLES 8 A 11EXAMPLES 8 TO 11

Les exemples 8 à 9 décrivent l'utilisation de la gomme xanthane comme stabilisant. On utilise toujours le même siliconate. Les résultats sont donnés dans le tableau 3. La quantité de gomme xanthane employée est de 0,12% et 0,1% en poids par rapport à la suspension pour les exemples 8 et 9 respectivement.Examples 8 to 9 describe the use of xanthan gum as a stabilizer. We always use the same siliconate. The results are given in Table 3. The amount of xanthan gum used is 0.12% and 0.1% by weight relative to the suspension for Examples 8 and 9 respectively.

L'exemple 10 concerne l'utilisation de l'acide oxalique comme stabilisant. Celui-ci est utilisé à 1% en poids par rapport à la suspension. Les siliconate est le même qu'aux exemples 8 et 9.Example 10 relates to the use of oxalic acid as a stabilizer. This is used at 1% by weight relative to the suspension. The siliconate is the same as in Examples 8 and 9.

L'exemple 11 concerne l'utilisation du Carbopol 941 comme stabilisant à 0,1% en poids par rapport à la suspension. Tableau 3 Exemples 8 9 10 11 Suspension % de zéolite anhydre 47,5 49,3 49,3 49,7 Capacité d'échange 288 288 288 Siliconate (% suspension) 0,17 0,2 0,1 0,1 pH 10,86 11,46 11,03 10,66 Viscosité en poise à 5 s⁻¹ 10,2 10,2 6,5 3,1 Sunageant (% volume) 5 jours 3 1,5 2 2 10 jours 4 2 7 Décantat % 5 jours < 0,5 « 1 0 1 10 jours 0,5 1 « 1 Example 11 relates to the use of Carbopol 941 as a stabilizer at 0.1% by weight relative to the suspension. Table 3 Examples 8 9 10 11 Suspension% anhydrous zeolite 47.5 49.3 49.3 49.7 Exchange capacity 288 288 288 Siliconate (% suspension) 0.17 0.2 0.1 0.1 pH 10.86 11.46 11.03 10.66 Viscosity in poise at 5 s⁻¹ 10.2 10.2 6.5 3.1 Sunageant (% volume) 5 days 3 1.5 2 2 10 days 4 2 7 Decantate% 5 days <0.5 "1 0 1 10 days 0.5 1 "1

EXEMPLE 12 COMPARATIFCOMPARATIVE EXAMPLE 12

On utilise une suspension de la même zéolite que les exemples précédents à une concentration de 49,7% et sans aucun additif. Le pH est de 11,57. On observe alors une viscosité à 5s⁻¹ de 59 poises. Au bout de 5 jours, on a 3,5% de surnageant et 60% de décantat.A suspension of the same zeolite as the preceding examples is used at a concentration of 49.7% and without any additive. The pH is 11.57. We then observe a viscosity at 5s⁻¹ of 59 poises. After 5 days, there is 3.5% of supernatant and 60% of decantate.

Claims (25)

1 - Suspension aqueuse à base d'une zéolite, caractérisée en ce qu'elle comporte en outre un siliconate et/ou un dérivé de siliconate.1 - Aqueous suspension based on a zeolite, characterized in that it also comprises a siliconate and / or a siliconate derivative. 2 - Suspension selon la revendication 1, caractérisée en ce que la zéolite représente de 40 à 51 % du poids de ladite suspension et le siliconate et/ou dérivé de siliconate exprimé en poids de solution de siliconate et/ou de dérivé de siliconate à 50 % en poids dans l'eau, de 0,01 à 2 % du poids de ladite suspension.2 - Suspension according to claim 1, characterized in that the zeolite represents from 40 to 51% by weight of said suspension and the siliconate and / or siliconate derivative expressed by weight of siliconate solution and / or siliconate derivative at 50 % by weight in water, from 0.01 to 2% of the weight of said suspension. 3 - Suspension selon la revendication 1 ou 2, caractérisée en ce que le siliconate et/ou dérivé de siliconate exprimé en poids de solution à 50 % en poids dans l'eau de siliconate et/ou de dérivé de siliconate, représente de 0,05 à 0,3 % du poids de ladite suspension.3 - Suspension according to claim 1 or 2, characterized in that the siliconate and / or derivative of siliconate expressed by weight of solution at 50% by weight in water of siliconate and / or derivative of siliconate, represents from 0, 05 to 0.3% of the weight of said suspension. 4 - Suspension selon l'une quelconque des revendications 1 à 3 caractérisée en ce qu'elle comprend un siliconate comportant comme radical organique un groupe alkyle, vinyle ou phényle.4 - Suspension according to any one of claims 1 to 3 characterized in that it comprises a siliconate comprising as organic radical an alkyl, vinyl or phenyl group. 5 - Suspension selon l'une quelconque des revendications 1 à 4 caractérisée en ce qu'elle comprend un siliconate alcalin ou alcalino-terreux.5 - Suspension according to any one of claims 1 to 4 characterized in that it comprises an alkali or alkaline earth siliconate. 6 - Suspension selon l'une des revendications précédentes, caractérisée en ce qu'elle comprend en outre au moins un stabilisant.6 - Suspension according to one of the preceding claims, characterized in that it further comprises at least one stabilizer. 7 - Suspension selon la revendication 6, caractérisée en ce que le stabilisant est un cation du groupe des alcalino-terreux.7 - Suspension according to claim 6, characterized in that the stabilizer is a cation from the group of alkaline earths. 8 - Suspension selon la revendication 6, caractérisée en ce que le stabilisant est choisi dans le groupe comprenant les polysaccharides d'origine animale, végétale ; les biogommes.8 - Suspension according to claim 6, characterized in that the stabilizer is chosen from the group comprising polysaccharides of animal, vegetable origin; biogums. 9 - Suspension selon la revendication 8, caractérisée en ce que la biogomme est une gomme xanthane.9 - Suspension according to claim 8, characterized in that the biogum is a xanthan gum. 10 - Suspension selon la revendication 6 caractérisée en ce que le stabilisant est choisi dans le groupe comprenant les polyholosi­des-macromoléculaires, notamment la cellulose et l'amidon ou leurs dérivés.10 - Suspension according to claim 6 characterized in that the stabilizer is chosen from the group comprising polyholosides-macromolecular, in particular cellulose and starch or their derivatives. 11 - Suspension selon la revendication 6, caractérisée en ce que le stabilisant est choisi dans le groupe des acides carboxyliques, des sels alcalins.11 - Suspension according to claim 6, characterized in that the stabilizer is chosen from the group of carboxylic acids, alkaline salts. 12 - Suspension selon la revendication 6, caractérisé en ce que le stabilisant est un polymère de l'acide acrylique réticulé avec un polyallyléther de sucrose.12 - Suspension according to claim 6, characterized in that the stabilizer is a polymer of acrylic acid crosslinked with a polyallylether of sucrose. 13 - Procédé de préparation d'une suspension aqueuse à base d'une zéolite caractérisé en ce qu'on introduit un siliconate et/ou un dérivé de siliconate dans un suspension aqueuse de zéolite et on mélange.13 - Process for the preparation of an aqueous suspension based on a zeolite, characterized in that a siliconate and / or a siliconate derivative is introduced into an aqueous suspension of zeolite and mixed. 14 - Procédé selon la revendication 13 caractérisé en ce que le siliconate et/ou dérivé de siliconate et la suspension aqueuse de zéolite sont mis en oeuvre en quantité telle que la zéolite représente de 40 à 51 % du poids de la suspension aqueuse finale et le siliconate et/ou dérivé de siliconate, exprimé en poids de solution de siliconate et/ou dérivé de siliconate à 50 % en poids dans l'eau, représente de 0,01 à 2 % du poids de suspension aqueuse finale.14 - Process according to claim 13 characterized in that the siliconate and / or siliconate derivative and the aqueous suspension of zeolite are used in an amount such that the zeolite represents from 40 to 51% of the weight of the final aqueous suspension and the siliconate and / or siliconate derivative, expressed by weight of siliconate solution and / or siliconate derivative at 50% by weight in water, represents from 0.01 to 2% of the weight of final aqueous suspension. 15 - Procédé selon la revendication 13 ou 14 caractérisé en ce que la quantité de siliconate et/ou dérivé de siliconate mise en oeuvre, exprimée en poids de solution de siliconate et/ou dérivé de siliconate à 50 % en poids dans l'eau, représente de 0,05 à 0,3 % du poids de la suspension aqueuse finale.15 - Process according to claim 13 or 14 characterized in that the amount of siliconate and / or derivative of siliconate used, expressed by weight of solution of siliconate and / or derivative of siliconate at 50% by weight in water, represents from 0.05 to 0.3% of the weight of the final aqueous suspension. 16 - Procédé selon l'une quelconque des revendications 13 à 15, caractérisé en ce que ledit siliconate comporte comme radical organique un groupe alkyle, vinyle ou phényle.16 - Process according to any one of claims 13 to 15, characterized in that said siliconate comprises as organic radical an alkyl, vinyl or phenyl group. 17 - Procédé selon l'une quelconque des revendications 13 à 16, caractérisé en ce que ledit un siliconate est alcalin ou alcalino-terreux.17 - Method according to any one of claims 13 to 16, characterized in that said a siliconate is alkaline or alkaline earth. 18 - Procédé selon l'une quelconque des revendications 13 à 17, caractérisé en ce qu'on introduit en outre au moins un stabilisant.18 - Process according to any one of claims 13 to 17, characterized in that at least one stabilizer is introduced. 19 - Procédé selon la revendication 18, caractérisé en ce que le stabilisant est un cation du groupe des alcalino-terreux.19 - Process according to claim 18, characterized in that the stabilizer is a cation from the group of alkaline earths. 20 - Procédé selon la revendication 18, caractérisé en ce que le stabilisant est choisi dans le groupe comprenant les polysaccharides d'origine animale, végétale; les biogommes.20 - Process according to claim 18, characterized in that the stabilizer is chosen from the group comprising polysaccharides of animal or vegetable origin; biogums. 21 - Procédé selon la revendication 20, caractérisé en ce que la biogomme est une gomme xanthane.21 - Process according to claim 20, characterized in that the biogum is a xanthan gum. 22 - Procédé selon la revendication 18, caractérisé en ce que le stabilisant est choisi dans le groupe comprenant les polyholosi­des-macromoléculaires, notamment la cellulose et l'amidon ou leurs dérivés.22 - Process according to claim 18, characterized in that the stabilizer is chosen from the group comprising polyholosides-macromolecular, in particular cellulose and starch or their derivatives. 23 - Procédé selon la revendication 18, caractérisé en ce que le stabilisant est choisi dans le groupe des acides carboxyliques, des sels alcalins.23 - Process according to claim 18, characterized in that the stabilizer is chosen from the group of carboxylic acids, alkaline salts. 24 - Procédé selon la revendication 18, caractérisé en ce que le stabilisant est un polymère de l'acide acrylique réticulé avec un polyallyléther de sucrose.24 - Process according to claim 18, characterized in that the stabilizer is a polymer of acrylic acid crosslinked with a polyallylether of sucrose. 25 - Composition lessivielle, caractérisée en ce qu'elle comprend une suspension selon l'une quelconque des revendications 1 à 12.25 - Detergent composition, characterized in that it comprises a suspension according to any one of claims 1 to 12.
EP90402759A 1989-10-09 1990-10-05 Aqueous zeolite suspensions containing a siliconate Expired - Lifetime EP0422998B1 (en)

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FR8913138 1989-10-09
FR8913138A FR2652819B1 (en) 1989-10-09 1989-10-09 SUSPENSION OF ZEOLITE COMPRISING A SILICONATE.

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AU720214B2 (en) * 1996-03-25 2000-05-25 Eka Chemicals Ab Zeolite dispersion
EP1247834A1 (en) * 1999-10-21 2002-10-09 Daiso Co., Ltd. Crosslinking agent based on polyallyl ether compound

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US5800603A (en) * 1996-03-25 1998-09-01 Eka Chemicals Ab Zeolite dispersion
DE102010031624A1 (en) * 2010-07-21 2012-01-26 Wacker Chemie Ag Water-soluble organosiliconate powder
JP5798200B2 (en) * 2011-02-03 2015-10-21 アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． Modified starch for use in personal care applications
CA2832814C (en) * 2011-04-12 2019-04-02 Basf Se Hydrophobic, functionalised particles

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US5618874A (en) 1997-04-08
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DK0422998T3 (en) 1996-07-15
US5401432A (en) 1995-03-28
JPH0633408B2 (en) 1994-05-02
PT95533B (en) 1997-07-31
YU188590A (en) 1993-10-20
CA2027012A1 (en) 1991-04-10
NO904359L (en) 1991-04-10
PT95533A (en) 1991-08-14
IE903593A1 (en) 1991-05-08
NO177064B (en) 1995-04-03
ATE139560T1 (en) 1996-07-15
NO177064C (en) 1995-07-12
NO904359D0 (en) 1990-10-08
EP0422998B1 (en) 1996-06-19
GR3020637T3 (en) 1996-10-31
FR2652819A1 (en) 1991-04-12
KR910008123A (en) 1991-05-30
YU47377B (en) 1995-01-31
BR9005013A (en) 1991-09-10
JPH03188196A (en) 1991-08-16
DE69027504D1 (en) 1996-07-25
DE69027504T2 (en) 1996-12-12

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