Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—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
  • C11D3/3738—Alkoxylated 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
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions

Definitions

• the present invention relates to liquid detergent formulations containing clay as a component.
• Most liquid detergent formulations are aqueous based, Conventionally these formulations have primarily performed the function of cleansing the fabrics washed whereas the softening of the washed fabric has been performed by a separate formulation introduced usually during the rinse cycle of the wash.
• Another set of well known fabric softening agents are the tetra-alkyl quaternary ammonium halides, especially the di(hydrogenated tallow)- and distearyl-dialkyl ammonium halides.
• these are cationic softeners and are not compatible with liquid detergents which contain an anionic component.
• a further set of compounds which is believed to have a softening effect on fabrics are clays, especially the smectite type clays.
• clays especially the smectite type clays.
• Several recent publications notably GB-A-2201172, GB-A-1400898, GB-A-1462484, GB-A-2132629 and EP 225142 describe the use of smectite type clays in various formulations.
• these clays are well known for their ability to increase in volume by several fold and to form a gelatinous/thixotropic substance when in contact with water. Since, in general, liquid detergent formulations are aqueous based and may already contain suspended solids, this results in considerable changes in viscosity of the formulation upon storage for any length of time.
• the present invention is an aqueous based liquid detergent formulation comprising in a homogenous dispersion or suspension water, one or more surfactants, a builder salt and a clay characterised in that the clay is pretreated with one or more barrier materials selected from a siloxane, a polysiloxane, a polyacrylate, dialkyl citrate, alkoxylated dialkyl citrate, alkoxylated glycerol mono- and distearates, and alkoxylated N-alkyl alkanolamides prior to incorporation of the clay in the formulation.
• barrier materials selected from a siloxane, a polysiloxane, a polyacrylate, dialkyl citrate, alkoxylated dialkyl citrate, alkoxylated glycerol mono- and distearates, and alkoxylated N-alkyl alkanolamides prior to incorporation of the clay in the formulation.
• carrier material as used herein and throughout the specification is meant one or more materials listed herein whenever used to pretreat a clay by coating, impregnating or otherwise having incorporated therein or on the surface thereof one or more of the materials listed whether or not such treatment results in the material acting as a protective barrier on the clay so treated.
• any of the well known surfactants can be used in the detergent compositions of the present invention.
• a typical list of these surfactants can be found in EP-A-225142 and in EP-A-11340.
• water soluble anionic surfactants include the salts of alkyl benzene sulphonates and paraffin sulphonates.
• salts of alkyl sulphates, alkyl polyalkoxy ether sulphates, fatty acid monoglyceride sulphates and sulphonates and alkyl phenol polyalkoxy ether sulphates may also be used.
• Suitable examples of the above surfactants are linear straight chain alkyl benzene sulphonates having alkyl groups with 8-16 carbon atoms and methyl branched alkyl sulphates having 8-16 carbon atoms which are also effective.
• anionic detergent compounds suitable for use herein include the sodium fatty acid monoglyceride sulphonates and sulphates derived from coconut oil; and sodium or porassium salts of C8-C12 alkyl phenol alkylene oxide ether sulphate containing up to 10 alkylene oxide units per molecule. Mixtures of anionic surfactants may also be used. A substantial list of such compounds can be found in e.g. McCutcheon's Dictionary of Emulsifiers and Detergents, International Edition (1981), published by the Manufacturing Confectioner Publishing Co. and in "Surfactants Europa: A Directory of Surface Active Agents available in Europe", Ed. Gordon L. Hollis, Vol 1 (1982), published by George Goodwin.
• the nonionic surfactants which may be used in the present invention are condensates of an alkylene oxide e.g. ethylene oxide with a hydrophobic group to form a surfactant having an appropriate hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, suitably from 9.5 to 13.5, preferably from 10 to 12.5.
• HLB hydrophilic-lipophilic balance
• the hydrophobic group may be an aliphatic or aromatic type and the length of the polyoxyethylene group condensed therewith can be readily adjusted to yield a water-soluble compound having the desired degree of HLB.
• Suitable nonionic surfactants include:
• nonionic surfactants useful for the purposes of the invention include the various grades of Dobanol (Registered Trade Mark, supplied by Shell) Lutensol (Registered Trade Mark, supplied by BASF) and Synperonics (Registered Trade Mark, supplied by ICI).
• the amount of surfactant in the formulation is suitably from 2-30% w/w, preferably from 6-15% w/w of the total formulation.
• An essential component of detergent compositions in accordance with the invention is one or more detergent builder salts which may comprise up to 35% of the composition, more typically from 5 to 25% by weight thereof.
• Suitable detergent builder salts useful herein can be of the polyvalent inorganic and polyvalent organic types or mixtures thereof.
• suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, phosphates, pyrophosphates, tripolyphosphates and bicarbonates.
• Suitable organic alkaline detergency builder salts are water-soluble polycarboxylates such as the salts of nitrilotriacetic acid, lactic acid, glycollic acid and ether derivatives thereof; succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid; citric acid, aconitic acid, citraconic acid, carboxymethyloxysuccinic acid, lactoxysuccinic acid, and 2-oxy-1,1,3-propane tricarboxylic acid; oxydisuccinic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,1,3,3-propane tetracarboxylic acid and 1,1,2,3-propane tetracarboxylic acid; cyclopentane-cis, cis,cis-tetracarboxylic acid, cyclopentadiene penta
• Water-insoluble detergent builders can also be used.
• a specific example of such builders are the zeolites especially the sodium type A zeolite typified by SASIL (Registered Trade Mark).
• Mixtures of organic and/or inorganic builders can also be used.
• builder salts are the alkali metal pyrophosphates and alkali metal tripolyphosphates.
• the builder salts are suitably present in an amount from 1-35% w/w, preferably from 5-25% w/w based on the total formulation. In some cases it may be necessary to add buffering agents in order to control the pH value of the formulation within the desired range. Buffering agents of this type will be well known to those skilled in the art. Examples include a combination of borax and glycerol.
• the feature of the invention is the use of a clay component which has been pretreated with a barrier material prior to incorporation in the detergent formulation.
• clays may be used any aluminosilicate type material which has the ability to impart softening to fabrics laundered with a formulation containing the same.
• Clays having an ion-exchange capacity of at least 50 meq/100g of clay (milliequivalents per 100g of clay) are preferred.
• Specific examples of such clays include smectite type clays. These latter clays are multi-layered clays which layered structure is capable of increasing the volume thereof several-fold by their ability to swell or expand when in contact with water and thereby form a thixotropic gelatinious substance.
• Such clays are well known in the art and are described for example in GB-A-2201172, GB-A-1400898, GB-A-1462484, GB-A-2132629 and EP-A-225142 which are incorporated herein by reference.
• Specific examples of clays that may be used in the present invention include bentonite, montmorillonite, nontronite, volchonskite, saponite, hectorite, sanconite and vermiculite, and mixtures thereof.
• the clays used may be hydrophilic or organophilic provided that pre-treatment thereof with the barrier materials is carried out prior to incorporation in the detergent formulation.
• the barrier material used is one or more of siloxanes, polyacrylates, dialkyl citrate, alkoxylated dialkyl citrate, alkoxylated glycerol mono- and distearates, and alkoxylated N-alkyl alkanolamides. Of these siloxanes are preferred.
• the siloxanes (I) used as barrier materials are derivable by the reaction of a siloxane with an olefin and excess alkylene oxide.
• the product of this reaction may be used directly as the barrier material even though such a product may be a mixture of (I) and some unreacted or partially reacted materials.
• the siloxane (I) is the predominant component.
• the value of r can be 0 in formula (I) because this will represent the absence of any unreacted -OSi(R10)(H)- groups in the siloxane used.
• the amount of clay present in the formulation is suitably from 1 to 50%, preferably from 2 to 30% by weight of the total formulation.
• the clay may be, for instance, pre-treated with the barrier material by any one of the following methods.
• it may be spray coated neat or from a suitable solvent, coated from eg. a fluidised bed, dry-milled or by admixture of clay, barrier material and a solvent followed by evaporation of the solvent.
• the clay may be coated, impregnated or otherwise have incorporated therein or on the surface thereof some or all of the barrier material used for the treatment.
• the barrier material used for the treatment.
• the clay suitably has from 0.1 to 50%w/w, preferably from 1 to 30% w/w of the polysiloxane based on the total treated clay.
• the detergent formulation is a liquid.
• the formulations can be a heavy duty type liquid detergent (HDLD) and the detergent formulation can be formed by thoroughly mixing the treated clay with the other ingredients of the detergent using a high speed mixer.
• HDLD heavy duty type liquid detergent
• the amount of treated clay present in the detergent formulation is suitably that which is sufficient to maintain the desired viscosity without loss of stability.
• the detergent formulations disclosed herein can contain other materials commonly used in such compositions.
• various soil-suspending agents such as carboxymethyl-cellulose, corrosion inhibitors, dyes, optical brightners, suds-boosters, suds-depressants, germicides, anti-tarnishing agents such as sodium silicate, and enzymes, well known in the art for use in detergent formulations can also be employed herein.
• Bound water can also be present in said detergent formulations.
• the detergent formulations of the present invention can be prepared in several ways. For instance, a portion of the builder salt can initially be added to water before additon of the pre-treated clay and the surfactant. Such a method gives a homogeneousdispersion having uniform rheological properties. Also, it is possible to add the necessary amount of water at a temperature of e.g. 40-50°C to a mixer provided with a stirrer; thereafter between 25 and 5% of the builder salt is added thereto with stirring; the pre-treated clay is then added and formed into a homogeneous dispersion with stirring and the mixture is then cooled.
• a portion of the builder salt can initially be added to water before additon of the pre-treated clay and the surfactant.
• Such a method gives a homogeneousdispersion having uniform rheological properties.
• the formulations of the present invention initially have a viscosity of less than 3000 CPS, preferably less than 1500 CPS at 20°C and more preferably lie in the range of 600-1000CPS, and a shear rate of 21 Sec ⁇ 1. Viscosities below 600 CPS can result in loss of stability.
• the treated clays used in the formulations of the present invention not only give softness to the fabric washed therewith but also have the effect of maintaining the stability of the formulation.
• the fabrics so treated can also facilitate ironing of the washed fabrics.
• the clay tested in these Examples was Texas bentonite clay.
• cloths were treated in a beaker at typical Wisk concentrations (eg. 10g/l) at 60°C. After drying and conditioning for 24 hours at 20°C and 60% relative humidity, the cloths were ranked for softness by panel assessment.
• typical Wisk concentrations eg. 10g/l
• Wisk was stable to a 0.5% inclusion of Pruduct Y.
• a 1% level of Product Y caused phase separation when mixed directly into Wisk liquid or when formulated into a typical Wisk-type structured liquid detergent formulation.
• the viscosity of Wisk was approximately 740 cP at a shear rate of 20s ⁇ 1 at 25°C.
• Wisk + 5% clay 1140 cP
• Wisk + 10% clay 1410 cP Wisk plus 10% clay exhibited phase separation after one freeze-thaw cycle; Wisk plus 5% clay separated after two cycles.
• the initial method of coating was designed to give a surface coating of siloxane on sodium montmorillonite.
• 20g siloxane was dissolved (or dispersed) in approximately 200 cm3 chloroform and 180 g Texas bentonite clay was added. The solvent was evaporated, followed by oven drying of the clay for 2 hours at 70°C. Any lumps of clay were ground to a fine powder.
• Wisk plus clay/Product Y appears to outperform both the currently used powders and liquid detergents combined with fabric conditioners.
• the increased softening due to both siloxane and clay at the cloth surface came from a pre-treated clay according to the invention.
• the coating with product Y therefore enables a softening clay to be incorporated into Wisk liquid whilst maintaining freeze-thaw stability.

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• Chemical & Material Sciences (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Citations (5)

• 1989
  • 1989-02-02 GB GB898902286A patent/GB8902286D0/en active Pending
• 1990
  • 1990-02-01 JP JP2052590A patent/JPH02245098A/ja active Pending
  • 1990-02-01 EP EP90301039A patent/EP0381487A1/de not_active Ceased

Patent Citations (5)

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