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 suspensions of zeolite.
• zeolite suspensions 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 silicone resin.
• the 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 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.
• a silicone resin is used in the suspensions of the type described above.
• silicone resins are branched organopolysiloxane polymers which are well known and commercially available. They have, per molecule, at least two different units chosen from those of formula R3SiO 0.5 (unit M), R2SiO (unit D), RSiO 1.5 (unit T) and SiO2 (unit Q).
• radicals R are identical or different and are chosen from linear or branched alkyl radicals, vinyl, phenyl, trifluoro-3,3,3 propyl radicals.
• the alkyl radicals have 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 solid products; more particularly between 0.05 and 0.3 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 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. 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, Na2S04 and sodium pyrophosphate or tripolyphosphate.
• water-soluble polymers of acrylic acid crosslinked with a polyallylether of sucrose 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 quantities used as a 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 and mixture.
• 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.
• 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 containing neither resin nor oxalic acid; it is found that the suspension of test 3 is not stable.
• Test 1 2 comparative. 3 comparative.

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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)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Silicon Polymers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Fluid-Damping Devices (AREA)

Applications Claiming Priority (2)

Publications (2)

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Citations (8)

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• 1989
  • 1989-10-09 FR FR8913137A patent/FR2652818B1/fr not_active Expired - Fee Related
• 1990
  • 1990-09-27 JP JP2255491A patent/JPH03207797A/ja active Pending
  • 1990-10-05 DE DE69026198T patent/DE69026198D1/de not_active Expired - Lifetime
  • 1990-10-05 YU YU188690A patent/YU47378B/sh unknown
  • 1990-10-05 AT AT90402760T patent/ATE136054T1/de not_active IP Right Cessation
  • 1990-10-05 CA CA002027013A patent/CA2027013A1/fr not_active Abandoned
  • 1990-10-05 EP EP90402760A patent/EP0427577B1/de not_active Expired - Lifetime
  • 1990-10-05 BR BR909005012A patent/BR9005012A/pt not_active Application Discontinuation
  • 1990-10-08 IE IE359490A patent/IE903594A1/en unknown
  • 1990-10-08 FI FI904946A patent/FI904946A0/fi not_active IP Right Cessation
  • 1990-10-08 NO NO904360A patent/NO177189C/no unknown
  • 1990-10-08 KR KR1019900015972A patent/KR910008122A/ko not_active Application Discontinuation
  • 1990-10-08 PT PT95532A patent/PT95532A/pt not_active Application Discontinuation
  • 1990-10-09 US US07/594,558 patent/US5064562A/en not_active Expired - Fee Related

Patent Citations (8)

Non-Patent Citations (1)

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