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
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
• • 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent compositions
• • 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
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
  • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
• • 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
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3776—Heterocyclic compounds, e.g. lactam
• • 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
  • C11D3/3792—Amine oxide containing polymers

Definitions

• the present invention relates to a process for making granular detergent which have a high surfactant activity and which are free-flowing and rapidly dissolving.
• the invention relates to a premixed free-flowing powder which comprises hydrophobic silica and a hygroscopic powder which comprises a polymer.
• the invention relates to high active, high bulk density granular detergent compositions.
• Granular detergent granules comprising low levels of certain polymers which provide structure or strength to the granule are known and have been made by spray drying aqueous solutions or slurries comprising the polymer.
• spray dried granules have low bulk densities (for example 350-550 g/l). Further treatment is necessary in order to increase the bulk density and various methods have been proposed to do this.
• One approach is to apply mechanical work to the spray dried powder in order to reduce its porosity and increase its bulk density.
• Another approach is to granulate a liquid or paste, typically in the presence of a powder. Polymers may be added to such a process either as a component of the liquid/paste, or as a component of the powder. Examples in the prior art of the such processes include:
• compositions comprising polymer and water soluble inorganic component.
• Compositions comprising surfactants and hydrophobic silica are not foreseen.
• EPA 513 824 published on 19th November, 1992 describes a process for making granular detergents which comprise up to 60% by weight of nonionic surfactant. It suggests that various powder components may be premixed in order to improve physical properties, but it does not indicate which powders may be advantageously premixed.
• the hygroscopic nature of many polymers presents a problem.
• the component also comprises a high level of surfactant.
• Hygroscopic powders which are bound into the surface of the detergent component cause the component to readily absorb water which encourages gel formation, caking of the detergent powder and poor dispensing and dissolution properties.
• the present invention aims to solve this problem by providing a process in which the surface of hygroscopic powders which comprise polymers is modified before the high bulk density detergent granules are formed. This surface modification effect is provided by premixing the hygroscopic powder with hydrophobic silica.
• the present invention further aims to provide a high bulk density detergent composition which comprises high levels of detergent surfactant and polymers.
• a process for making a high active granular detergent component or composition having a bulk density of at least 650 g/l which comprises the steps of:
• the first aspect of the present invention relates to a process for making a high active granular detergent component or composition having a bulk density of at least 650 g/l.
• the process comprises the steps of:
• the polymer component of the hygroscopic powder is chosen from the group consisting of polymers or co-polymers of acrylic and maleic acid, polyvinyl pyrrolidone, polyvinyl pyrridine N oxide, carboxymethyl cellulose, polyaspartate, and starch.
• the hydrophobic silica is used as a coating agent to coat, or partially coat the outer surfaces of the hygroscopic powder.
• One method of preparing the hygroscopic powder which is useful in the present invention is to use a spray drying technique, wherein a two fluid nozzle is used in the spray drying step. Most preferably compressed air is used as one of the fluids in the two fluid nozzle.
• the premixed hydrophobic silica and hygroscopic polymer is mixed with the surfactant paste prior to the fine dispersion mixing of step iii).
• One way of doing this is to use an extruder, for example a twin screw extruder.
• a high active surfactant paste is prepared.
• One or various aqueous pastes of the salts of anionic surfactants is preferred for use in the present invention, preferably the sodium salt of the anionic surfactant.
• the anionic surfactant is preferably as concentrated as possible, (that is, with the lowest possible moisture content possible that allows it to flow in the manner of a liquid) so that it can be pumped at temperatures at which it remains stable.
• an anionic surfactant should preferably be a part of the paste in a concentration of above 10% by weight, preferably from 10-95%, more preferably from 20-95%, and most preferably from 40%-95% by weight.
• the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, since low moisture leads to a higher concentration of the surfactant in the finished particle.
• the paste contains between 5 and 40% water, more preferably between 5 and 30% water and most preferably between 5 and 20% water.
• high active surfactant pastes it is preferable to use high active surfactant pastes to minimize the total water level in the system during mixing, granulating and drying.
• Lower water levels allow for: (1) a higher active surfactant to builder ratio, e.g., 1:1; (2) higher levels of other liquids in the formula without causing dough or granular stickiness; (3) less cooling, due to higher allowable granulation temperatures; and (4) less granular drying to meet final moisture limits.
• Viscosity is a function, among others, of concentration and temperature, with a range in this application from about 5,000 cps to 10,000,000 cps.
• the viscosity of the paste entering the system is from about 20,000 to about 100,000 cps. and more preferably from about 30,000 to about 70,000 cps.
• the viscosity of the paste of this invention is measured at a temperature of 70°C and at a shear rate of from 10 to 50 sec ⁇ 1, in particular, about 25 sec ⁇ 1.
• the paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 40-60°C) and its degradation point (depending on the chemical nature of the paste, e.g. alkyl sulphate pastes tend to degrade above 75-85°C).
• High temperatures reduce viscosity simplifying the pumping of the paste but result in lower active agglomerates.
• in-line moisture reduction steps e.g. flash drying
• the activity of the agglomerates is maintained high due to the elimination of moisture.
• the introduction of the paste into the mixer can be done in many ways, from simply pouring to high pressure pumping through small holes at the end of the pipe, before the entrance to the mixer. While all these ways are viable to manufacture agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste results in a better distribution in the mixer which improves the yield of particles with the desired size. Most preferably a twin screw extruder is used.
• the use of high pumping pressures prior to the entrance in the mixer results in an increased activity in the final agglomerates.
• the activity of the aqueous surfactant paste is at least 30% and can go up to about 95%; preferred activities are : 60-90% and 70-80%.
• the balance of the paste is primarily water. At the higher active concentrations, little or no builder is required for cold granulation of the paste.
• the resultant concentrated surfactant granules can be added to dry builders or powders or used in conventional agglomeration operations.
• the aqueous surfactant paste contains an organic surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. Anionic surfactants are preferred. Surfactants useful herein are listed in U.S. Pat. No.
• cationic surfactants are generally less compatible with the aluminosilicate materials herein, and thus are preferably used at low levels, if at all, in the present compositions.
• the following are representative examples of surfactants useful in the present compositions.
• Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
• Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
• Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
• Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms in a linear or branched chain and a sulfonic acid or sulfuric acid ester group.
• alkyl is the alkyl portion of acyl groups.
• these group of synthetic or natural surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383.
• Especially valuable are linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-C13 LAS.
• anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
• Suitable anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
• the acid salts are typically discussed and used, the
• the preferred anionic surfactant pastes are mixtures of linear or branched alkylbenzene sulfonates having an alkyl of 10-16 carbon atoms and alkyl sulfates having an alkyl of 10-18 carbon atoms. These pastes are usually produced by reacting a liquid organic material with sulfur trioxide to produce a sulfonic or sulfuric acid and then neutralizing the acid to produce a salt of that acid.
• the salt is the surfactant paste discussed throughout this document.
• the sodium salt is preferred due to end performance benefits and cost of NaOH vs. other neutralizing agents, but is not required as other agents such as KOH may be used.
• Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
• a particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of from about 0.01:1 to about 1:1, more preferably about 0.05:1.
• Nonionics can be used up to an equal amount of the primary organic surfactant.
• Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
• Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
• Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 4 to 25 moles of ethylene oxide per more of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 25 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
• Other preferred nonionics are polyhydroxy fatty acid amides which may be produced by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
• the preferred amine for use in the present invention is N-(R1)-CH2(CH2OH)4-CH2-OH and the preferred ester is a C12-C20 fatty acid methyl ester.
• Most preferred is the reaction product of N-methyl glucamine with C12-C20 fatty acid methyl ester.
• Methods of manufacturing polyhydroxy fatty acid amides have been described in WO 92 6073, published on 16th April, 1992. This application describes the preparation of polyhydroxy fatty acid amides in the presence of solvents.
• N-methyl glucamine is reacted with a C12-C20 methyl ester.
• alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
• RO C n H 2n O
• t Z x wherein Z is a moiety derived from glucose
• R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms
• t is from 0 to 10 and n is 2 or 3
• x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
• Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075
• Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
• Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
• Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
• Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from about 11 to 14 carbon atoms in the alkyl group; alkyl sulfates containing from about 12 to 18 carbon atoms in the alkyl group; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from about 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from about 1 to 4; olefin or paraffin sulfonates containing from about 14 to 16 carbon atoms; alkyldimethylamine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from about 14 to 18 carbon atoms; soaps of higher fatty acids containing from about 12 to 18 carbon atom
• Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5, R6 and R7 are each C1 to C7 alkyl preferably methyl; X ⁇ is an anion, e.g. chloride.
• Examples of such trimethyl ammonium compounds include C12 ⁇ 14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
• Specific preferred surfactants for use herein include: sodium linear C11-C13 alkylbenzene sulfonate; alpha-olefin sulphonates; triethanolammonium C11-C13 alkylbenzene sulfonate; alkyl sulfates, (tallow, coconut, palm, synthetic origins, e.g.
• the surfactant paste described above is formed into granules by fine dispersion mixing in the presence of a powder.
• the surfactant paste is either intimately mixed with a component which is a free-flowing mixture of a hydrophobic silica and a hygroscopic powder comprising a polymer prior to granulation, or said free-flowing mixture is added directly to the mixer/granulator as one of the powder components of the granulation step.
• the hydrophobic silica which is present at a level of from 0.5% to 10% of the component is a highly dispersed amorphous silicon dioxide. It is commercially available in many forms. Most commonly silica has a tapped density of from 50 g/l to 120 g/l.
• silica particles can be chemically modified to change their behaviour with respect to water.
• silica particles may be treated with organosilanes to make the particles predominantly hydrophobic. It has been found that silicas must be hydrophobised to be useful in the present invention.
• silica is usually prepared by one of two techniques; either by precipitation or by high temperature flame hydrolysis. Precipitated silicas generally have an agglomerate size of from 3 micrometers to 100 micrometers, whereas fumed silicas (made by flame hydrolysis) usually have primary particles which are generally spherical and have an average diameter of from 7nm to 40nm.
• Fumed silicas having an average primary particle size of from 7 to 25 nanometers are preferred in the present invention.
• silicas which are particularly useful in the present invention include those supplied by Degussa AG, Frankfurt, Germany under the Trade Name "Aerosil”. Aerosil R972 has been found to be particularly useful.
• This silica is a hydrophobic, fumed silica which has a specific surface area of about 110 square metres per gram and an average primary particle size of 16 nanometers.
• the other essential feature of the powder is a hygroscopic powder which comprises a polymer. By hygroscopic it is meant that the powder shows more than 50% moisture uptake at 80% relative humidity at 25°C.
• a 3 gram sample of the powder having an average particle size of 250 micrometers, is placed on an 80mm diameter petri dish.
• the sample is dried in a vacuum oven at 40°C for 48 hours, and the dry weight recorded.
• the sample is then placed in a relative humidity and temperature control unit. (That is, any sample chamber which has controllable % relative humidity (80+/-2%) and temperature (25+/-1°C)).
• the unit is set at 80% relative humidity and 25°C for at least 8 hours.
• the sample weight is then recorded again.
• a powder which absorbs more than 50% of its dry weight at 80% relative humidity and 25°C is considered to be hygroscopic.
• the powder may consist exclusively of a polymer, or, alternatively, the powder may further comprise other detergent ingredients such as surfactants, builders (especially zeolites) etc.
• the powder may be prepared by any suitable means including spray drying of an aqueous solution or slurry of the powder components.
• One particularly preferred method is spray drying using a two-fluid nozzle, the process of which is described in more detail below.
• Polymers which are particularly useful as components of the hygroscopic powder of the present invention include sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyvinyl pyrrolidone, polyethylene glycol, polyaspartate, polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000. Most preferred are polymeric polycarboxyate builders are set forth in U.S.
• Patent 3,308,067, Diehl, issued March 7, 1967 Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
• the hygroscopic powder and the hydrophobic silica are thoroughly premixed before the granulation step with the surfactant paste. A process for this is described in more detail below.
• other powders may be used in the process of granulating the surfactant paste. Examples of suitable powders will be described below in more detail.
• the detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula Na z [(AlO2) z ⁇ (SiO2) y ] ⁇ xH2O wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264.
• Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO2 ⁇ ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
• the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix.
• the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
• Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
• particle size diameter herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
• the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaCO3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
• the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness.
• Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
• the amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange of at least about 50 mg eq. CaCO3/g (12 mg Mg++/g) and a Mg++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
• Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
• the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
• a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference.
• Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
• the crystalline aluminosilicate ion exchange material has the formula Na12[(AlO2)12(SiO2)12] ⁇ xH2O wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about 5 microns.
• the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
• the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
• neutral water-soluble salts examples include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates.
• the alkali metal, and especially sodium, salts of the above are preferred.
• Sodium sulfate is typically used in detergent granules and is a particularly preferred salt.
• Citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
• water-soluble salts include the compounds commonly known as detergent builder materials.
• Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhydroxysulfonates.
• alkali metal especially sodium, salts of the above.
• inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
• polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
• Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
• nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
• powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. and process acids such as starch and sugars, can be used in preferred embodiments of the present invention.
• other components may be added at any one of the stages of the process of the present invention, or they may be mixed with or sprayed on to the granular detergents of the present invention.
• Another optional detergent composition ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures.
• Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms, exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
• useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
• a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m2/g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.
• a preferred silicone suds controlling agent is disclosed in Bartollota et al. US Patent 3,933,672.
• Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646,126 published April 28, 1977.
• An example of such a compound is DC0544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
• the suds suppressors described above are normally employed at levels of from 0.001% to 0.5% by weight of the composition, preferably from 0.01% to 0.1% by weight.
• the preferred methods of incorporation comprise either application of the suds suppressors in liquid form by spray-on to one or more of the major components of the composition or alternatively the formation of the suds suppressors into separate particulates that can then be mixed with the other solid components of the composition.
• the incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al US Patent No. 3,933,672.
• Another optional ingredient useful in the present invention is one or more enzymes.
• Preferred enzymatic materials include the commercially available amylases, neutral and alkaline proteases, lipases, esterases and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
• the process of fine dispersion mixing or granulation will typically be carried out in a high speed mixer.
• fine dispersion mixing and/or granulation means mixing and/or granulation of the mixture in a fine dispersion mixer at a blade tip speed of from about 5m/sec. to about 50 m/sec., unless otherwise specified.
• the total residence time of the mixing and granulation process is preferably in the order of from 0.1 to 10 minutes, more preferably 0.1-5 and most preferably 0.2-4 minutes.
• the more preferred mixing and granulation tip speeds are about 10-45 m/sec. and about 15-40 m/sec.
• Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc.
• any of a number of mixers/agglomerators can be used.
• the process of the invention is continuously carried out.
• mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are especially preferred.
• this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
• the stirrer and cutter may be operated independently of one another and at separately variable speeds.
• the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
• mixers found to be suitable for use in the process of the invention include Diosna R V series ex Dierks & Söhne, Germany; and the Pharma Matrix R ex T K Fielder Ltd., England.
• Other mixers believed to be suitable for use in the process of the invention are the Fuji R VG-C series ex Fuji Sangyo Co., Japan; and the Roto R ex Zanchetta & Co srl, Italy.
• Other preferred suitable equipment can include Eirich R , series RV, manufactured by Gustau Eirich Hardheim, Germany; Lödige R , series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lödige Machinenbau GmbH, Paderborn Germany; Drais R T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth R RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, England.
• the Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and having a residence time in the order of 0.1 to 10 minutes can be used.
• the "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred.
• the invention can be practiced as a batch or a continuous process.
• the preferred operating temperatures for the agglomeration step should also be as low as possible since this leads to a higher surfactant concentration in the finished particle.
• the temperature during the agglomeration is less than 100°C, more preferably between 10 and 90°C, and most preferably between 20 and 80°C.
• Lower operating temperatures useful in the process of the present invention may be achieved by a variety of methods known in the art such as nitrogen cooling, cool water jacketing of the equipment, addition of solid CO2, and the like; with a preferred method being solid CO2, and the most preferred method being nitrogen cooling.
• the granules formed in the high speed mixer may still have a higher moisture content than desired. In this case the desired moisture content of the free flowing granules of this invention can be adjusted to levels adequate for the intended application by drying in conventional powder drying equipment such as fluid bed dryers.
• a hot air fluid bed dryer If a hot air fluid bed dryer is used, care must be exercised to avoid degradation of heat sensitive components of the granules. It is also advantageous to have a cooling step prior to large scale storage. This step can also be done in a conventional fluid bed operated with cool air. The drying/cooling of the agglomerates can also be done in any other equipment suitable for powder drying such as rotary dryers, etc.
• the final moisture of the agglomerates needs to be maintained below levels at which the agglomerates can be stored and transported in bulk.
• the exact moisture level depends on the composition of the agglomerate but is typically achieved at levels of 1-8% free water (i.e. water not associated to any crystalline species in the agglomerate) and most typically at 2-4%. Further details of the preferred process of the present invention are given below.
• a preferred process for the preparation of the hygroscopic powder is by spray drying.
• a most preferred process uses a two fluid nozzle or spinning disk.
• nozzles are particularly useful to make polymer containing granules for use in the present invention, wherein the concentrated polymer-containing slurry or solution has a high viscosity and/or a non-Newtonian rheology.
• a slurry is difficult to spray dry through a conventional pressure nozzle.
• Suitable two fluid nozzles and disks are supplied by Delavan, and described in their "Spray Drying Manual” and by Spraying Systems Co., and described in their Technical Manual No. 402.
• the atomisation in two-fluid nozzles is derived from energy in compressed air, gas or pressurised steam.
• air-atomising nozzles are used.
• the atomisation in spinning disks is derived from the kinetic energy of the disk on to which the slurry or solution is sprayed.
• the slurry or solution may comprise other detergent ingredients, such as those described herein, as well as polymer.
• One preferred composition is polymer and aluminosilicate, especially zeolite A. Compositions of this type, as well as processes for making them have been described in DE 33 16 513, published on 8th November, 1984. When the hygroscopic powder has been prepared, it is the necessary to coat the surface with hydrophobic silica. Suitable hydrophobic silicas have been described above.
• the hygroscopic powders can be added placed in a low shear mixer or rotating drum.
• the hydrophobic silica can then be added to the drum or mixer while it is in motion.
• the hydrophobic silica coats the hygroscopic powder and makes the particles free flowing.
• the flow aid creates a hydrophobic layer which protects against moisture.
• the invention can be practised as a batch or a continuous process.
• another process which is suited to the present invention is that of fluidised bed coating.
• the extruder fulfils the functions of pumping and mixing the viscous surfactant paste on a continuous basis.
• a basic extruder consists of a barrel with a smooth inner cylindrical surface.
• the extruder screw Mounted within this barrel is the extruder screw. There is an inlet port for the high active paste which, when the screw is rotated, causes the paste to be moved along the length of the barrel.
• the detailed design of the extruder allows various functions to be carried out. Firstly additional ports in the barrel may allow other ingredients, including the chemical structuring agents to be added directly into the barrel. Secondly a vacuum pump and a seal around the shaft of the screw allows a vacuum to be drawn which enables the moisture level to be reduced. Thirdly means for heating or cooling may be installed in the wall of the barrel for temperature control. Fourthly, careful design of the extruder screw promotes mixing of the paste both with itself and with other additives.
• a preferred extruder is the twin screw extruder.
• This type of extruder has two screws mounted in parallel within the same barrel, which are made to rotate either in the same direction (co-rotation) or in opposite directions (counter-rotation).
• the co-rotating twin screw extruder is the most preferred piece of equipment for use in this invention.
• An extruder is particularly useful in a preferred embodiment of the present invention because the hygroscopic powder/hydrophobic silica can be added to the surfactant paste via an inlet port in the extruder and can be considered as chemical structuring agents.
• the extruder helps to ensure thorough and intimate mixing of the paste and the powder.
• the extruder conveys the conditioned paste which now comprises polymer and hydrophobic silica into the mixer where fine dispersion and granulation takes place. Suitable mixers have been defined above.
• Suitable twin screw extruders for use in the present invention include those supplied by : APV Baker, (CP series); Werner and Pfleiderer, (Continua Series); Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR Series).
• the extruder allows the paste to be conditioned by moisture and temperature reduction. Moisture may be removed under vacuum, preferably between 0 mmHg (gauge) and -55 mmHg (gauge), (0 - 7.3 kPa below atmospheric pressure).
• Temperature may be reduced by the addition of solid carbon dioxide or liquid nitrogen directly into the extruder barrel.
• liquid nitrogen is used at up to 30% by weight of the paste.
• An aqueous surfactant paste comprising: 62.5% by weight sodium alkyl sulphate having substantially C14 and C15 alkyl chains; 15.5% by weight sodium alkyl ester sulphate having substantially C13 to C15 alkyl chains and an average of 3 ethoxy groups per molecule; 17% by weight of water and the balance being mainly comprised of unreacted alcohol and sulphates.
• a powder premix was prepared by mixing the sodium salt of a co-polymer of maleic and acrylic acid with 2% by weight of hydrophobic silica (Aerosil R972, trade name, supplied by Degussa) in a Loedige FM130D (trade name) mixer for 30 seconds.
• aqueous surfactant paste and the premixed co-polymer / hydrophobic silica were then intimately mixed in a twin screw extruder with a barrel in 6 sections (manufactured by Werner & Pfleiderer, C58).
• the resulting viscous paste was then placed in a Loedige FM130D (trade name) batch ploughshare mixer containing a mixture of 2 parts zeolite A to 1 part finely divided light carbonate. The mixer is operated until granulation takes place.
• the resulting agglomerates were transferred to a fluid bed drier and then classified through mesh sieves to remove oversize and fine particles.
• the agglomerates formed had a surfactant content of 40% by weight, a polymer level of 12% by weight, a silica level of 0.24% by weight and an equilibrium relative humidity level of 10% at room temperature.
• the granules formed have excellent flow and handling properties.
• example 1 The process of example 1 was repeated, except that the co-polymer of maleic and acrylic acid was not mixed with 2% of hydrophobic silica.
• the silica level in the finished agglomerates was 0%, and the agglomerates after granulation, drying and classification showed poor handling and flow properties.
• An aqueous surfactant paste comprising: 62.5% by weight sodium alkyl sulphate having substantially C14 and C15 alkyl chains; 15.5% by weight sodium alkyl ester sulphate having substantially C13 to C15 alkyl chains and an average of 3 ethoxy groups per molecule; 17% by weight of water and the balance being mainly comprised of unreacted alcohol and sulphates.
• a powder premix was prepared by mixing the sodium salt of a co-polymer of maleic and acrylic acid with 2% by weight of hydrophobic silica (Aerosil R972, trade name, supplied by Degussa) batchwise in a ribbon blender.
• the aqueous surfactant paste and the premixed co-polymer / hydrophobic silica were then intimately mixed in a twin screw extruder (manufactured by Werner & Pfleiderer, C170).
• the resulting viscous paste was extruded directly into a Loedige CB30 (trade name) high speed mixer containing a mixture of 1 part zeolite A to 1 part finely divided light carbonate.
• the mixer operates on a continuous basis and discharges directly into a Loedige KM (trade name) continuous ploughshare mixer.
• the resulting agglomerates were transferred to a fluid bed drier, cooled in a fluid bed cooler and then classified through mesh sieves to remove oversize and fine particles.
• the agglomerates formed had a surfactant content of 40% by weight, a polymer level of 11.2% by weight, a silica level of 0.22% by weight and an equilibrium relative humidity level of 10% at room temperature.
• the granules formed have excellent flow and handling properties.
• An Eirich RVO2 high shear mixer was charged with a mixture of 32 parts Zeolite A to 32 parts finely divided carbonate.
• a mixture of 10 parts PVP and 1 part hydrophobic silica (Aerosil R972, trade name, supplied by Degussa) was premixed and added to the mixer.
• 25 parts of a nonionic surfactant paste of containing GA and C25E3 in a 25/75 ratio were also added to the mixer.
• the mixer is operated at a speed of 2500 rpm until granulation takes place.
• the mixer is then stopped and the agglomerates are cooled in a fluid bed and classified through mesh sieves.
• the resulting agglomerates have excellent physical properties including flowability and have a bulk density of 750 g/l.
• This example describes the process in batch mode in a lab scale high shear mixer (food processor).
• the sodium salt of the copolymer of maleic and acrylic acid is premixed with the hydrophobic silica.
• the mixer is first charged with a mixture of powders to be used, in this case: percent by weight sodium salt of the copolymer of maleic and acrylic acid 10 hydrophobic silica (Aerosil R972) 1 Carbonate 32 Zeolite A 32 total 75 ⁇
• a nonionic surfactant paste containing a GA/C25E3 mixture at a ratio of 50/50 was added at 25 percent by weight before starting the mixer.
• the mixer was then operated until granulation took place.
• the mixer was then stopped and the agglomerates were cooled in a fluid bed and classified through mesh sieves.
• the resulting agglomerates had excellent physical properties including flowability and had a bulk density of 700 g/l.

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• 1993
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