EP0427577B1 - Aqueous zeolite suspension comprising of a silicon resin - Google Patents

Aqueous zeolite suspension comprising of a silicon resin Download PDF

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Publication number
EP0427577B1
EP0427577B1 EP90402760A EP90402760A EP0427577B1 EP 0427577 B1 EP0427577 B1 EP 0427577B1 EP 90402760 A EP90402760 A EP 90402760A EP 90402760 A EP90402760 A EP 90402760A EP 0427577 B1 EP0427577 B1 EP 0427577B1
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EP
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Prior art keywords
suspension
stabilizer
weight
suspension according
chosen
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German (de)
French (fr)
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EP0427577A1 (en
Inventor
Philippe Jost
Marc Malassis
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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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
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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 zeolite suspensions.
  • aqueous suspensions of zeolites present many industrial handling difficulties due to their very particular rheological behavior.
  • suspensions have a dilating behavior. 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 aqueous zeolite suspension also comprises at least one stabilizer.
  • silicone resins 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 observed that the resins 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 last reference cited 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 ⁇ , preferably greater than 0.25 and advantageously between 0.4 and 4 s ⁇ 1.lm ⁇ .
  • These zeolites have particularly interesting qualities in the use in detergency.
  • Application FR-A-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 at the same venturi with recycling of the mixture obtained.
  • the suspensions can have a variable zeolite concentration depending on the application. This concentration is between 40 and 51% by weight.
  • the pH of the suspensions is also a function of their use. In the detergency application, this pH expressed at 1% by weight of dry zeolite is approximately 11.
  • a silicone resin having the definition given above is used in suspensions of the type described above.
  • silicone resins are branched organopolysiloxane polymers which are well known and commercially available.
  • radicals R of the units constituting these resins are preferably alkyl radicals having 1 to 6 carbon atoms inclusive.
  • alkyl radicals R of the methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals.
  • These resins are preferably hydroxylated and in this case have a weight content of hydroxyl group of between 0.1 and 10%.
  • resins examples include MQ resins, MDQ resins, TD resins and MDT resins.
  • Resins having a molecular mass of less than 25,000 can be used more particularly.
  • the resins can be used in the solid state or in the form of aqueous emulsions or of emulsions or solution in an organic solvent.
  • the amounts used are between 0.01 and 2% by weight of the composition, more particularly between 0.05 and 0.3% by weight of solid products, relative to the final suspension.
  • 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 uses magnesium chloride, for example magnesium chloride hexahydrate.
  • 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 plant 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
  • plant 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 .
  • Xanthan gum that is to say that obtained by fermentation under the action of bacteria or fungi belonging to the genus Xanthomonas such as X
  • 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. 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.
  • 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 molecule of sucrose. , 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.
  • the amounts used as a percentage by weight relative to the final suspension vary between 0.001 and 2%.
  • aqueous suspensions based on zeolite according to the invention are prepared by chaining the following steps: the desired amount of silicone resin, and optionally at least one stabilizer, is introduced into an aqueous zeolite suspension, and mixing is carried out.
  • 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.
  • the dry extract of the aqueous zeolite 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 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.
  • the 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.
  • a resin is used in which R is methyl. This resin is used here in the solid state. It is marketed by the applicant under the reference RHODORSIL® 865 A in the form of an emulsion.
  • Test 1 is carried out with 0.17% by weight of resin relative to the suspension and 1% by weight of oxalic acid.
  • Test 2 is made for comparison on the same suspension brought to the same pH with oxalic acid alone in the same quantity; the suspension of test 2 is stable but it is found to be viscous.
  • Test 3 is carried out for comparison on a suspension containing 49.7% of zeolite but not containing either resin or oxalic acid; it is found that the suspension of test 3 is not stable.
  • Test 1 2 comparison 3 comparison Anhydrous zeolite% weight suspension 49.3 49.3 49.7 pH 10.87 10.86 11.57 Viscosity (in mPa.s) at 5s ⁇ 1 4030 7130 5920 Sedimentation Supernatant% volume 5 days 3 3.5 10 days 8 6 15 days Decantate % volume 5 days ⁇ 1 60 10 days ⁇ 1 90 15 days

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Detergent Compositions (AREA)
  • Fluid-Damping Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Silicon Polymers (AREA)

Abstract

Stable suspensions of zeolite particulates, in water, well adapted for detergency applications, have a pumpable low viscosity and include an effective viscosity reducing amount of a silicone resin and, advantageously, a suspension stabilizer, e.g., an alkaline earth metal cation or a biogum polysaccharide.

Description

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

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.Indeed, these suspensions have a dilating behavior. 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, la suspension selon l'invention comprend des zéolites et elle est caractérisé par les points suivants :

  • elle comporte en outre une résine silicone présentant, par molécule, au moins deux motifs différents choisis parmi ceux de formules : R₃SiO0,5 (motif M), R₂SiO (motif D), RSiO1,5 (motif T) et SiO₂ (motif Q), les radicaux R, identiques ou différents, étant choisis parmi les radicaux vinyle, phényle, trifluoro-3,3,3 propyle et les radicaux alkyle linéaires ou ramifiés ;
  • la zéolite représente de 40 à 51 % du poids de ladite suspension et la résine silicone de 0,01 à 2 % du poids de ladite suspension.
For this purpose, the suspension according to the invention comprises zeolites and it is characterized by the following points:
  • it further comprises a silicone resin having, per molecule, at least two different units chosen from those of formulas: R₃SiO 0.5 (unit M), R₂SiO (unit D), RSiO 1.5 (unit T) and SiO₂ (unit Q), the radicals R, identical or different, being chosen from vinyl, phenyl, trifluoro-3,3,3 propyl and linear or branched alkyl radicals;
  • the zeolite represents from 40 to 51% of the weight of said suspension and the silicone resin from 0.01 to 2% of the weight of said suspension.

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'art antérieur (cf. US-A-4 639 321 et EP-A-0 102 923) décrivent des compositions détergentes liquides et aqueuses comprenant des zéolites et des huiles de silicones. Mais les huiles silicones en question ont une structure linéaire alors que les résines de silicones de la présente invention sont des polymères réticulés. Par ailleurs, les huiles silicones de l'art antérieur jouent soit un rôle d'amélioration des propriétés de textiles comme par exemple les propriétés de toucher à la main (document US), soit celui d'un agent anti-mousse (document EP).The prior art (cf. US-A-4 639 321 and EP-A-0 102 923) describe liquid and aqueous detergent compositions comprising zeolites and silicone oils. However, the silicone oils in question have a linear structure whereas the silicone resins of the present invention are crosslinked polymers. Furthermore, the silicone oils of the prior art play either a role in improving the properties of textiles such as, for example, the properties of touching by hand (US document), or that of an anti-foaming agent (EP document). .

L'emploi des résines silicones 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 résines n'influent pas sur la capacité d'échange des zéolites.The use of silicone resins 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 observed that the resins 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 qui va suivre.Other characteristics and advantages of the invention will be better understood on reading the description which follows.

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.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.

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. 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⁻, de préférence supérieure à 0,25 et avantageusement comprise entre 0,4 et 4 s⁻¹.l.m⁻. 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 last reference cited 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⁻, preferably greater than 0.25 and advantageously between 0.4 and 4 s⁻¹.lm⁻ . These zeolites have particularly interesting qualities in the use in detergency.

La demande FR-A-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 FR-A-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 at the same venturi with recycling of the mixture obtained.

On obtient notamment des zéolites de formule :

        x Na₂O, y Al₂O₃, z SiO₂, w H₂0

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 % < 10 µm, 99 % < 15 µm, 50 % compris entre 2 et 6 µm pour le diamètre moyen.In particular, zeolites of formula are obtained:

x Na₂O, y Al₂O₃, z SiO₂, w H₂0

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 number distribution 95% <10 µm, 99% <15 µm, 50% between 2 and 6 µm for the average diameter.

Les suspensions peuvent présenter une concentration en zéolite variable et fonction de l'application. Cette concentration est comprise entre 40 et 51 % en poids.The suspensions can have a variable zeolite concentration depending on the application. This concentration is between 40 and 51% by weight.

Le pH des suspensions est aussi fonction de leur utilisation. 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. 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 une résine silicone ayant la définition donnée précédemment.According to the essential characteristic of the invention, a silicone resin having the definition given above is used in suspensions of the type described above.

Ces résines silicones sont des polymères organopolysiloxanes ramifiés bien connus et disponibles dans le commerce.These silicone resins are branched organopolysiloxane polymers which are well known and commercially available.

Les radicaux R des motifs constituant ces résines sont de préférence les radicaux alkyles présentant 1 à 6 atomes de carbone inclus.The radicals R of the units constituting these resins are preferably alkyl radicals having 1 to 6 carbon atoms inclusive.

Plus particulièrement, on peut citer comme radicaux R alkyle, les radicaux méthyle, éthyle, isopropyle, tertiobutyle et n-hexyle.More particularly, mention may be made, as alkyl radicals R, of the methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals.

Ces résines sont de préférence hydroxylées et ont dans ce cas une teneur pondérale en groupe hydroxyle comprise entre 0,1 et 10 %.These resins are preferably hydroxylated and in this case have a weight content of hydroxyl group of between 0.1 and 10%.

Comme exemple de résines, on peut citer les résines MQ, les résines MDQ, les résines TD et les résines MDT.Examples of resins that may be mentioned are MQ resins, MDQ resins, TD resins and MDT resins.

On peut utiliser plus particulièrement les résines présentant une masse moléculaire inférieure à 25000.Resins having a molecular mass of less than 25,000 can be used more particularly.

Comme résines de ce type, on peut utiliser notamment les produits commercialisés par la Demanderesse sous les noms RHODORSIL® 865 A ou 878 A.As resins of this type, use may in particular be made of the products sold by the Applicant under the names RHODORSIL® 865 A or 878 A.

Les résines peuvent être utilisées à l'état solide ou sous forme d'émulsions aqueuses ou d'émulsions ou solution dans un solvant organique.The resins can be used in the solid state or in the form of aqueous emulsions or of emulsions or solution in an organic solvent.

Les quantités utilisées sont comprises entre 0,01 et 2 % en poids de la composition, plus particulièrement entre 0,05 et 0,3 % en poids de produits solides, par rapport à la suspension finale.The amounts used are between 0.01 and 2% by weight of the composition, more particularly between 0.05 and 0.3% by weight of solid products, relative to the final suspension.

Comme cela a été indiqué plus haut, l'emploi des résines a pour effet de rendre les suspensions de zéolite pompables et manipulables par suite de leur faible viscosité.As indicated above, the use of resins 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.Reference may be made to FR-A-2 568 790 in the name of the Applicant.

A titre de cation, on utiliser 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 uses magnesium chloride, for example magnesium chloride hexahydrate.

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 plant 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 .

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. 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.The products described above (polysaccharides, biogums, modified gums) are used in solid form, in powder, or in aqueous solution. 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 finale de 0,05 à 10 %.For these two types of stabilizers, amounts in percentage by weight relative to the final 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.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 molecule of sucrose. , 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.

Pour ce dernier type de stabilisants, les quantités utilisées en pourcentage pondéral par rapport à la suspension finale varient entre 0,001 et 2 %.For the latter type of stabilizers, the amounts used as a 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 aqueuses à base de zéolite selon l'invention se fait en enchaînant les étapes suivantes : on introduit la quantité voulue de résine silicone, et éventuellement d'au moins un stabilisant, dans une suspension aqueuse de zéolite, et on mélange.The aqueous suspensions based on zeolite according to the invention are prepared by chaining the following steps: the desired amount of silicone resin, and optionally at least one stabilizer, is introduced into an aqueous zeolite suspension, and mixing is carried out.

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.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.

Un exemple concret va maintenant être donné.A concrete example will now be given.

EXEMPLEEXAMPLE

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

L'extrait sec de la suspension aqueuse de zéolite 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 aqueous zeolite 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.

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.The 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.

On utilise une résine dans laquelle R est un méthyle. Cette résine est utilisée ici à l'état solide. Elle est commercialisée par la demanderesse sous la référence RHODORSIL® 865 A sous la forme d'une émulsion.A resin is used in which R is methyl. This resin is used here in the solid state. It is marketed by the applicant under the reference RHODORSIL® 865 A in the form of an emulsion.

Les résultats sont donnés ci-dessous.The results are given below.

L'essai 1 se fait avec 0,17% en poids de résine par rapport à la suspension et 1% en poids d'acide oxalique. L'essai 2 est fait à titre comparatif sur la même suspension amenée au même pH avec l'acide oxalique seul dans la même quantité ; la suspension de l'essai 2 est stable mais on constate qu'elle est visqueuse. L'essai 3 est fait à titre comparatif sur une suspension contenant 49,7 % de zéolite mais ne renfermant ni résine ni acide oxalique ; on constate que la suspension de l'essai 3 n'est pas stable. Essai 1 2 comparatif 3 comparatif Zéolite anhydre % poids suspension 49,3 49,3 49,7 pH 10,87 10,86 11,57 Viscosité (en mPa.s) à 5s⁻¹ 4030 7130 5920 Sédimentation Surnageant % volume 5 jours 3 3,5 10 jours 8 6 15 jours Décantat % volume 5 jours << 1 60 10 jours << 1 90 15 jours Test 1 is carried out with 0.17% by weight of resin relative to the suspension and 1% by weight of oxalic acid. Test 2 is made for comparison on the same suspension brought to the same pH with oxalic acid alone in the same quantity; the suspension of test 2 is stable but it is found to be viscous. Test 3 is carried out for comparison on a suspension containing 49.7% of zeolite but not containing either resin or oxalic acid; it is found that the suspension of test 3 is not stable. Test 1 2 comparison 3 comparison Anhydrous zeolite% weight suspension 49.3 49.3 49.7 pH 10.87 10.86 11.57 Viscosity (in mPa.s) at 5s⁻¹ 4030 7130 5920 Sedimentation Supernatant% volume 5 days 3 3.5 10 days 8 6 15 days Decantate % volume 5 days << 1 60 10 days << 1 90 15 days

Claims (17)

  1. Aqueous suspension based on a zeolite, characterized by the following points:
    . it also contains a silicone resin which has, per molecule, at least two different units chosen from those of formulae: R₃SiO0.5 (unit M), R₂SiO (unit D), RSiO1.5 (unit T) and SiO₂ (unit Q), the radicals R, which may be identical or different, being chosen from the vinyl, phenyl and 3,3,3-trifluoropropyl radicals and straight-chain or branched alkyl radicals;
    . the zeolite represents from 40 to 51% of the weight of the said suspension and the silicone resin represents from 0.01 to 2% of the weight of the said suspension.
  2. Suspension according to claim 1, characterized in that silicone resin represents from 0.05 to 0.3% of the weight of the said suspension.
  3. Suspension according to claim 1 or 2, characterized in that the resin is hydroxylated and has a hydroxyl group content by weight of between 0.1 and 10%.
  4. Suspension according to one of the preceding claims, characterized in that the radical R is a methyl radical.
  5. Suspension according to one of the preceding claims, characterized in that it also contains at least one stabilizer.
  6. Suspension according to claim 5, characterized in that the stabilizer is a cation from the alkaline-earth group.
  7. Suspension according to claim 5, characterized in that the stabilizer is a biogum.
  8. Suspension according to claim 7, characterized in that the biogum is a xanthan gum.
  9. Suspension according to claim 5, characterized in that the stabilizer is chosen from the group comprising the macromolecular polyholosides, in particular cellulose and starch or their derivatives.
  10. Suspension according to claim 5, characterized in that the stabilizer is chosen from the group of carboxylic acids and alkali metal salts.
  11. Suspension according to claim 5, characterized in that the stabilizer is a polymer of acrylic acid crosslinked with a sucrose polyallyl ether.
  12. Process for the preparation of an aqueous suspension according to one of the preceding claims, characterized in that the desired amount of silicone resin and optionally of at least one stabilizer is introduced into an aqueous suspension of zeolite and mixed.
  13. Process according to claim 12, characterized in that, when use is made of a stabilizer consisting of a cation of the alkaline-earth group, the amount varies between 0.002 and 0.5% relative to the weight of the final suspension.
  14. Process according to claim 12, characterized in that, when use is made of a stabilizer chosen from the group formed by biogums and macromolecular polyholosides, the amount varies between 0.001 and 2% relative to the weight of the final suspension.
  15. Process according to claim 12, characterized in that, when use is made of a stabilizer chosen from the group of carboxylic acids and alkali metal salts, the amount varies between 0.05 and 10% relative to the weight of the final suspension.
  16. Process according to claim 12, characterized in that, when use is made of a stabilizer consisting of a polymer of acrylic acid crosslinked with a sucrose polyallyl ether, the amount varies between 0.001 and 2% relative to the weight of the final suspension.
  17. Detergent composition, characterized in that it contains a suspension according to any one of claims 1 to 11.
EP90402760A 1989-10-09 1990-10-05 Aqueous zeolite suspension comprising of a silicon resin Expired - Lifetime EP0427577B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8913137A FR2652818B1 (en) 1989-10-09 1989-10-09 ZEOLITE SUSPENSION COMPRISING A SILICONE RESIN.
FR8913137 1989-10-09

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EP0427577A1 EP0427577A1 (en) 1991-05-15
EP0427577B1 true EP0427577B1 (en) 1996-03-27

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FR2652819B1 (en) * 1989-10-09 1994-01-07 Rhone Poulenc Chimie SUSPENSION OF ZEOLITE COMPRISING A SILICONATE.
IT1250437B (en) * 1991-07-01 1995-04-07 Paolo Colombo STABLE AND EASILY PUMPABLE ZEOLITE SUSPENSIONS
GB9315671D0 (en) * 1993-07-29 1993-09-15 Dow Corning Sa Foam control agents and their use
JP4889096B2 (en) * 2006-02-09 2012-02-29 株式会社 資生堂 Antibacterial zeolite and skin external preparation containing the same
US20150258150A1 (en) * 2014-03-14 2015-09-17 Osprey Biotechnics, Inc. Bacillus amyloliquefaciens strain

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US2702855A (en) * 1946-02-01 1955-02-22 Bess Leon Differentiating circuits
US3769222A (en) * 1971-02-09 1973-10-30 Colgate Palmolive Co Free flowing nonionic surfactants
DE2854484A1 (en) * 1978-12-16 1980-06-26 Bayer Ag STABLE AQUEOUS ZEOLITE SUSPENSIONS
US4402867A (en) * 1981-12-22 1983-09-06 Mobil Oil Corporation Silica-modified zeolite catalysts
DE3208598A1 (en) * 1982-03-10 1983-09-22 Degussa Ag, 6000 Frankfurt METHOD FOR THE PRODUCTION OF ZEOLITES MODIFIED WITH ORGANOSILANES
FR2523950B1 (en) * 1982-03-23 1985-11-22 Mizusawa Industrial Chem PROCESS FOR THE PREPARATION OF A SUSPENSION OF ZEOLITE WITH EXCELLENT STATIC AND DYNAMIC STABILITY
US4545919A (en) * 1982-08-31 1985-10-08 Ciba-Geigy Corporation Detergent composition for washing off dyeings obtained with fibre-reactive dyes and washing process comprising the use thereof
GB8401875D0 (en) * 1984-01-25 1984-02-29 Procter & Gamble Liquid detergent compositions
DE3408040A1 (en) * 1984-03-05 1985-09-12 Henkel KGaA, 4000 Düsseldorf STABILIZED, AQUEOUS ZEOLITE SUSPENSION
FR2568790B1 (en) * 1984-08-10 1990-01-12 Rhone Poulenc Chim Base PROCESS FOR OBTAINING A STABLE AND PUMPABLE AQUEOUS SUSPENSION OF ZEOLITE AND SUSPENSION THUS OBTAINED
US4639321A (en) * 1985-01-22 1987-01-27 The Procter And Gamble Company Liquid detergent compositions containing organo-functional polysiloxanes
JPS61256915A (en) * 1985-05-10 1986-11-14 Showa Koki Kk Zeolite slurry
DE3536934A1 (en) * 1985-10-17 1987-04-23 Bayer Ag ELECTROVISCOSE LIQUIDS
JPS62153116A (en) * 1985-12-24 1987-07-08 Showa Koki Kk Water-based zeolite slurry
JPS62167216A (en) * 1986-01-17 1987-07-23 Lion Corp Aqueous zeolite suspension
US4673516A (en) * 1986-09-02 1987-06-16 Integral Corporation Aqueous hydrogel lubricant
DE3805624A1 (en) * 1988-02-24 1989-08-31 Degussa POWDERED DETERGENT DEFOAMER

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ATE136054T1 (en) 1996-04-15
FR2652818A1 (en) 1991-04-12
DE69026198D1 (en) 1996-05-02
NO904360D0 (en) 1990-10-08
JPH03207797A (en) 1991-09-11
NO177189B (en) 1995-04-24
FR2652818B1 (en) 1994-04-01
EP0427577A1 (en) 1991-05-15
PT95532A (en) 1991-08-14
YU188690A (en) 1993-10-20
BR9005012A (en) 1991-09-10
CA2027013A1 (en) 1991-04-10
KR910008122A (en) 1991-05-30
FI904946A0 (en) 1990-10-08

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