US3144412A - Solid detergent compositions - Google Patents

Solid detergent compositions Download PDF

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US3144412A
US3144412A US66443A US6644360A US3144412A US 3144412 A US3144412 A US 3144412A US 66443 A US66443 A US 66443A US 6644360 A US6644360 A US 6644360A US 3144412 A US3144412 A US 3144412A
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detergent
weight
water
soil
alkyl
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US66443A
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Inamorato Jack Thomas
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Colgate Palmolive Co
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Colgate Palmolive Co
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Priority to GB931438D priority Critical patent/GB931438A/en
Priority to NL270825D priority patent/NL270825A/xx
Priority to CA688539A priority patent/CA688539A/en
Priority to BE609040D priority patent/BE609040A/xx
Priority to US66443A priority patent/US3144412A/en
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to DEC25157A priority patent/DE1293378B/en
Priority to CH1154461A priority patent/CH414047A/en
Priority to FR875438A priority patent/FR1302897A/en
Application granted granted Critical
Publication of US3144412A publication Critical patent/US3144412A/en
Priority to MY1966100A priority patent/MY6600100A/en
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753Polyvinylalcohol; Ethers or esters thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • the present invention relates to a detergent composition
  • a detergent composition comprising a substantially homogeneous mixture in solid form of a water-soluble non-ionic alkyl phenol polyalkylene oxide detergent, a water-soluble alkyl aryl sulfonate detergent, and a mixture of Water-soluble cellulosic and polyvinyl alcohol soil-suspending agents, as hereinafter described and claimed.
  • compositions containing an organic detergent and a soil-suspending or anti-redeposition agent which inhibits the deposition of soil onto the fabric during the washing operation.
  • the detergent content has included various anionic and non-ionic detergents including mixtures thereof.
  • soilsuspending agents including natural and synthetic gums, cellulose derivatives such as carboxymethylcellulose, protein materials and various synthetic polymers including polyvinyl alcohol.
  • the soil-suspending agent which has received Wide acceptance in the art has been sodium carboxymethylcellulose.
  • the present invention relates to a detergent composition
  • a detergent composition comprising a substantially homogeneous mixture in solid form of a water-soluble higher alkyl phenol polyalkylene oxide detergent and a water-soluble higher alkyl aryl sulfonate detergent in a ratio from about 90:10 to 30:70 by weight, and a minor proportion of a mixture of a water-soluble cellulosic soil-suspending agent and a water-soluble polyvinyl alcohol soil-suspending agent effective to enhance the soil-suspension properties thereof.
  • a feature of this invention relates to a heat-treated composition in particulate form comprising about to 50% by weight of said mixture of non-ionic and sulfonate detergents with a mixture of carboxyalkylcellulose and polyvinyl alcohol suspending agents in amounts from 0.05 to 1% each by weight, and the balance being primarily water-soluble inorganic salts, preferably with 10 to 80% by weight of inorganic alkaline builder salts.
  • Other features of the present invention will be apparent in the following description.
  • compositions exhibit desirable detersive properties, particularly in soil-suspension effects during washing operations.
  • a synergistic or enhanced improvement in soil-suspension is achieved by this combination as evideuced by a superior whiteness of washed fabrics such as cottons in the presence of carbonaceous soil compared to the effects achieved with an equivalent amount of said soil-suspending agents when employed individually.
  • a high level of soil-suspension power is obtained with a Wide variety of fabrics in addition to cotton, including synthetic materials such as nylon, Dacron, resin-treated cottons and the like.
  • the over-all effects are superior to the properties of compositions containing said detergents when employed individually and combinations thereof containing one of said soil-suspending agents.
  • the water-soluble alkyl phenol alkylene oxide condensate detergents are known in the art.
  • the degree or proportion of the hydrophilic alkyleneoxy groups present in a particular condensate will vary with the specific hydrophobic alkyl phenol group therein, generally increasing as the number of carbons in the hydrophobic group increases so as to be sufiicient to confer the desired watersolubility and detersive properties on the final product.
  • the determination of a specific hydrophiliczhydrophobic relationship for each type is not the essential novelty of the 3,144,412 Patented Aug. 11,1964
  • the condensates will possess at least about 5 and usually from 5 to 50 alkylene oxide groups.
  • the number of ethenoxy groups per molecule of condensate may average about 7.5, 8.5, 9.5, 11.5, 20.5 or 30, with the preferred range being about 8 to 20 moles of ethylene oxide.
  • the hydrophobic alkyl phenol portion has an alkyl group of at least about five, and usually about 8 to 20 carbons.
  • the alkyl substituent or the aromatic nucleus may be diisobutylene, diamyl, iso-octyl, nonyl, ethyl hexyl, polymerized propylene, dimerized C -C olefin, and the like.
  • the preferred alkyl substituents contain 8 to 12 carbons.
  • the water-soluble higher alkyl aryl sulfonate detergents are known in the art and will usually have an average of about 8 to 15 carbon atoms in the alkyl group. It is preferred to use the higher alkyl benzene sulfonate detergent, though other similar detergents having a mononuclear aryl group, such as toluene, xylene or phenol may be used also.
  • the higher alkyl substituent on the aromatic nucleus may be branched or straight chain in structure.
  • branched-chain substituents are nonyl, dodecyl and pentadecyl groups derived from polymers of lower monoolefins including mixtures thereof and examples of straight chain alkyl groups are decyl, keryl and the like. It is preferred that the alkyl group has an average of 12-15 carbons.
  • sulfonated detergents are used preferably in the form of their alkali metal salts such as the sodium and potassium salts.
  • alkali metal salts such as the sodium and potassium salts.
  • Other water-soluble salts such as the nitrogen-containing salts may be used also, examples being the ammonium, mono-, di-, and tri-ethanolamine salts, and isopropanolamine salts of said detergents.
  • the water-soluble cellulosic soil-suspending agents are cellulose having a purity from about 60 to on a dry basis and which are of low, medium or high viscosity may be employed.
  • the degree of substitution of the carboxymethyl group per anhydroglucose unit in the cellulose molecule is variable, but is Within the range from about 0.5 to 2, andusually up to 1.25 substitution. It is preferred to employ carboxylated cellulose having about 0.5 to 0.9 substitution, and particularly about 0.5 to 0.7.
  • Other cellulosic salts are sodium carboxyethylcellulose, the cellulose sulfates and suitable lower alkyl and hydroxyalkyl ethers of cellulose.
  • the soil-suspending agent used in admixture with the carboxyalkylcellulose or the like is Water-soluble polyvinyl alcohol.
  • the specific or exact degree of polymerization is variable so that it may be of low, medium or high viscosity provided the material has the desired water-solubility and soil-suspending power to produce the enhanced effects in said mixtures.
  • Suitable polyvinyl tains minor amounts of polyvinyl acetate such as up to about 30% by weight, and preferably from about to ester content.
  • a suitable example is polyvinyl alcohol having a viscosity of 4 to 6 cps. with about 12% ester (88-89% hydrolysis).
  • Other known polyvinyl alcohols are those with a viscosity of 21-25 cps. or 3545 cps. and about 12% ester.
  • polyvinyl alcohol having a viscosity of 1.8 to 3 centipoises and a polyvinyl acetate content of about 10 to 30% by weight.
  • This material exhibits maximum stability in heat-treatment of the composition resulting in maximum soil-suspending power for the composition. It may be prepared by any suitable manner such as by control of the degree of polymerization and alcoholysis of the polyvinyl acetate to produce a product of the above characteristics.
  • the above viscosity range corresponds to an approximate weight average degree of polymerization of about to 100. Examples thereof are polyvinyl alcohols having a viscosity of 2.34 cps. and 22.3% polyvinyl acetate; 1.88 cps. and 19.6% ester; 1.98 cps. and 29.4% ester; 2.38 cps. and 12.8% ester; and the like.
  • the non-ionic detergent and the alkyl aryl sulfonate detergent are employed in a ratio from about 90:10 to about 30:70 by weight, and preferably from 90:10 to :50. It has been found that maximum detersive effects are achieved in combination with the soil-suspending agents when employing the detergents within these ranges. There is achieved a synergistic increase in soil-suspension power of the composition in the washing of certain fabrics, and the over-all effects are superior to the use of the detergents individually.
  • the mixture of detergents is important in the preparation of heat-treated solidified compositions.
  • the heating of an aqueous slurry of an alkyl benzene sulfonate detergent with inorganic salts and a particular grade of polyvinyl alcohol (such as having a viscosity of 4-6 centipoises) in a crutcher for up to about one hour at an elevated temperature, e.g., 160180 F., followed by spray-drying results in a product having reduced soil-suspending power.
  • this defect is due primarily to such factors as the nature of the polyvinyl alcohol in combination with said detergent in the aqueous slurry when it is subjected or aged at elevated temperatures prior to drying of the slurry to a solid composition.
  • the presence of the alkyl phenol alkylene oxide detergent in said heated aqueous mixtures tends to stabilize the polyvinyl alcohol and insure that a high level of soilsuspension power is exhibited by the composition even after said heat-treatment.
  • the maximum stabilizing effects are obtained where the detergent content is a major proportion of the non-ionic detergent and a minor proportion of the alkyl aryl sulfonate, the preferred ratios being from about :4O to 90:10 by weight.
  • These detergents are present 1n any suitable amount in the composition and W111 be in an amount greater than the amount of the soilsuspendrng agents and usually at least about 5% by weight of total solids.
  • the detergent content will be usually from about 5 to 50%, and preferably from 10 to 45% by weight.
  • the amount of the combined soil-suspending agents is a minor proportion of the composition. While amounts of 0.05 to 5% by weight of each of the soil-suspending agents may be used if desired, it is a feature of the present invention to use a total amount of 0.1 to 2% by weight of the solids in a ratio from about 20:1 to 1:20 by weight, preferably within the range of about 10:1 to 1:10, of the cellulosic compound to polyvinyl alcohol and sufficient to exert the desired increase in soil-suspending power.
  • the use of up to 2% of the soil-suspending agents has advantages in the manufacture of heat-dried compositions and particularly in soil-suspension effects.
  • each soil-suspending agent so 4 that the total is not in excess of 2%, and preferably not in excess of 1.5% by weight of total solids. It is preferred that each agent be employed in an amount from about 0.05-1% and sufficient to achieve a high level of soil-suspension effects in the washing of both natural and synthetic fabrics.
  • water-soluble inorganic salts there is present usually various amounts of watersoluble inorganic salts in the composition.
  • Water-soluble neutral builder salts such as sodium sulfate may be present in admixture with the sulfonate detergent since such sulfate salts are formed in the manufacture of the alkyl aryl sulfonate by certain commercial methods. Additional amounts of such inorganic sulfates may be added as desired.
  • a substantial amount of water-soluble alkaline inorganic builder salts such as about 10 to by weight of total solids, preferably 20 to 60%.
  • These salts are preferably the alkali metal polyphosphate salts which have the property of inhibiting precipitation of calcium and magnesium material in aqueous solution and of contributing to the heavyduty performance of the detergent product. They may be considered as derived from orthophosphoric acid or the like by the removal of molecularly-bound water, though any suitable means of manufacture may be employed if desired.
  • Such complex or molecularly dehydrated polyphosphate salts may be used in the form of the normal or completely neutralized salt, e.g., pentasodium tripolyphosphate, or partially neutralized salt, e.g., sodium acid tripolyphosphate.
  • phosphate salts are pentapotassium tripolyphosphate, tetrasodium and tetrapotassium pyrophosphate, sodium tetraphosphate, sodium hexametaphosphate and the like including any desired mixtures thereof.
  • alkaline builder salts may be employed also such as the water-soluble alkali metal silicates. These silicates may be employed as the sole builder salt if desired or in combination with the polyphosphates. Suitable silicates are those having an alkali oxide to silica ratio within the range of about 1:1 to 1:4, and preferably from about 1:2 to 1:3. Examples are sodium silicates having an Na O to SiO ratio of 1:2.35, 1:25, 1:32, 122.0, 121.6 and 1:1. Other materials are borax and sodium carbonate.
  • the ingredients are to be admixed so as to form a substantially homogeneous product in solid form.
  • Any suitable method may be employed including mechanical blending of the ingredients thoroughly to produce a uniform mixture.
  • the preferred method comprises forming a fluid aqueous slurry containing the organic detergents in a conventional soap crutcher or any other suitable mixing apparatus such as a ribbon blender.
  • the other ingredients are then added in any suitable order and form.
  • the polyvinyl alcohol and cellulose compounds are added usually as fine white powders with stirring.
  • the slurry should be sufiiciently fluid at elevated temperatures to insure adequate mixing and formation of a uniform product.
  • the aqueous mixture is subjected to a heat-treatment at an elevated temperature such as within the range of about to 200 F., and usually from about to 180 F.
  • the slurry is heated by external means or even by exothermic heat of reaction of certain ingredients when added to the slurry depending upon the desired temperature.
  • the addition of hydratable inorganic salts such as the anhydrous forms of sodium tripolyphosphate and sodium pyrophosphate results in exothermic reactions as hydration occurs.
  • the elevated temperature of the slurry aids in the mixing of the ingredients and in solubilization or hydration effects of specific ingredients in the slurry.
  • the time interval of the mixing operation should be sufiicient to insure adequate mixing which will be usually at least a few minutes, e.g., 5 minutes.
  • the aqueous mixture prior to drying is aged at the elevated temperature for a time sufiicient to insure adequate solubilization or hydration of certain ingredients.
  • Such aging period may be for a number of hours, such as up to about 8 hours.
  • time intervals of less than three hours prior to heat-drying, and preferably less than one hour. It is understood that excessively high temperatures or unduly long aging periods will be avoided to prevent decomposition and insure efficient processing.
  • the solids content of the aqueous slurry is determined by the type of drying operation to be employed and will be usually within the range from about 20 to 90% total solids. In the manufacture of heat-dried products involving vaporization of the water, the solids content will be usually within the range of about 40 to 65% by weight, the remainder being substantially free water content. It is usually maintained at a temperature from about 160 to 180 F.
  • the slurry may be subjected to any suitable heat-drying operation and converted to particle form. For example, the material from the crutcher or mixing vessel may be sent into a drop tank from where it may be added or pumped to a drying zone such as a spray tower.
  • This mixture may be subjected to the conventional spraydrying, roll-drying or drum-drying operations utilizing temperatures above about 212 F. to produce the detergent composition in particulate form.
  • the detergent composition is obtained in the form of heat-dried homogeneous particles, such as beads, granules, flakes, chips, powders, etc. 4
  • composition is produced thereby in the form of hollow thin-walled spheres or beads, characterized by excellent solubility in water and uniformity of particles having a small residual moisture content usually of about 3 to by weight.
  • the aqueous slurry may be solidified or dried by other suitable methods which do not involve vaporization of the water content.
  • the slurry can contain sufficient water for adequate mixing and hydration of the hydratable inorganic salts to the extent desired Without any significant excess water content so that a dry and solidified mass is formed upon suitable aging at room temperature or slightly elevated temperatures such as up to about 120 F.
  • the solidified mass may be granulated to form particles or granules of desired size.
  • Various other materials may be added in known manner to the aqueous slurry or after solidification.
  • higher fatty acid amides such as coconut or lauric monoethanolamide, isopropanolamide and diethanolamide
  • fatty alcohols such as lauryl alcohol, coconut fatty alcohols or cetyl alcohol
  • lower alkyl aryl sulfonates such as xylene or toluene sulfonates
  • coloring agents corrosion inhibiting agents, bleaching agents, foam stabilizers or inhibitors as desired, detergency improving additives, and the like.
  • suitable amounts of other detersive materials may be incorporated in the composition, such as suitable non-ionic and sulfated organic detergents.
  • Examples thereof are the normal and secondary higher alkyl sulfate detergents, particularly those having 8 to 15 carbons in the alkyl residue such as lauryl (or coconut fatty alcohol) sulfate, the higher alkyl ether sulfates, higher alkyl glyceryl ether sulfonates, higher alkyl aryl polyethylene oxide sulfates, polyoxyethylene ethers of fatty alcohols, and polyethylene condensates with hydrophobic polypropylene glycols.
  • lauryl or coconut fatty alcohol
  • Example I A detergent composition is prepared according to the following formulation.
  • the polyvinyl alcohol has a viscosity of 4-6 cps. and 11-12% polyvinyl acetate;
  • the alkyl group of the sulfonate detergent is derived from a mixture containing propylene pentamer and tetramer benzene sulfonate corresponding on the average to a tridecyl group, and the carboxymethylcellulose is a commercial grade of about 67% purity, and the non-ionic detergent is nonyl phenol ethylene oxide having an average of about 9.5 moles ethylene oxide.
  • This formulation is prepared in particulate form by mixing all of the solid ingredients except the non-ionic detergent and water in powdered form to form a homogeneous powder.
  • the non-ionic detergent is a liquid and is slowly added with stirring followed by addition of the water and the composition gradually forms a dry granular mass which is passed through a 20 mesh screen (U.S. Sieve).
  • the resulting product in particulate form is added to the washing machine and exhibits a high degree of washing power, particularly in soil-suspension power on cotton fabrics.
  • Example 11 The formulation of Example I is repeated using polyvinyl alcohol of 2.34 centipoises and 22.3% polyvinyl acetate content. The resulting solid detergent composi-. tion exhibits high soil-suspension power also.
  • Example III A solid detergent composition is prepared according to the following formulation.
  • the non-ionic detergent is nonyl phenol condensed with an average of about 9.5 moles ethylene oxide
  • the carboxymethylcellulose is a commercial grade (Du Pont 10D)
  • the polyvinyl alcohol has a viscosity of 46 centipoises and 11-12% polyvinyl acetate.
  • the composition is added to. a washing bath and exhibits superior washing properties on a variety of fabrics including cottons, Dacron-cotton mixtures, and resin-treated cottons. More particularly, this formulation has markedly superior soil-suspension properties on washing of cotton fabrics in soil anti-redeposition tests using carbon soil in soft water compared.
  • Example IV A heat-dried composition is prepared according to the following formulation.
  • the balance being small amounts of fluorescent dye, corrosion inhibitor and the like.
  • the product is prepared by adding to a crutcher a 60% solids aqueous solution of the sulfonate detergent described in Example I admixed with some sodium sulfate formed in its manufacture.
  • the non-ionic detergent having about 9.5 moles of ethylene oxide and the fatty alcohol are added as a liquid to the crutcher at 120 F.
  • the tripolyphosphate in powder form is added with agitation and there is formed a smooth, pumpable mixture within a few minutes having a total solids content of about 55-60%. It is then pumped into a spray tower where it is spray-dried with air heated to about 600 F. to yield a product in the form of beads. The product exhibits high soil-suspension power in washing tests.
  • a detergent composition comprising a substantially homogeneous mixture in solid form of (a) a water-soluble non-ionic higher alkyl phenol ethylene oxide detergent having about to 20 carbon atoms in the alkyl grou and about 5 to 50 mols of ethylene oxide and (b) a watersoluble higher alkyl mononuclear aryl sulfonate detergent having about 8 to carbon atoms in said alkyl group, the ratio of said non-ionic detergent to alkyl aryl sulfonate detergent being from about 90: 10 to 30:70 by weight and said detergents being in a total amount from about 5 to 50% by weight of the composition, and a mixture of (c) an alkali metal carboxymethylcellulose and (d) water-soluble polyvinyl alcohol soil-suspending agent having a viscosity within the range of about 1.8 to 65 centipoises, said carboxymethylcellulose and polyvinyl alcohol soil-suspending agents being from about 0.05 to 5% by weight of each in said
  • a detergent composition comprising a substantially homogeneous mixture in solid form of a water-soluble higher alkyl phenol ethylene oxide detergent having about 5 to carbon atoms in the alkyl group and about 5 to 50 moles of ethylene oxide and alkali metal higher alkyl benzene sulfonate detergent having about 8 to 15 carbons in said alkyl group, the total amount of said non-ionic and said sulfonate detergents being from about 5 to 50% by weight of the composition in a ratio from about 90: 10 to :70 by weight, and in minor proportion to said detergents about 0.1 to 2% by weight of a mixture of alkali metal carboxymethylcellulose soil-suspending agent and water-soluble polyvinyl alcohol soil-suspending agent having a viscosity from about 1.8 to centipoises in a ratio from about 20:1 to 1:20 parts by weight, the balance being primarily water-soluble inorganic builder salts.
  • a heateated detergent composition in particulate form comprising about 5 to 50% by weight of higher alkyl phenol ethylene oxide detergent having about 8 to 12 carbon atoms in the alkyl group and about 5 to 50 moles of ethylene oxide and alkali metal higher alkyl benzene sulfonate having about 8 to 15 carbons in the alkyl group in a ratio from about 90:10 to 50:50 by weight, about 0.1 to 2% by weight of a mixture of alkali metal carboxymethylcellulose and water-soluble polyvinyl alcohol soil-suspending agent having a viscosity from about 1.8 to about 6 centipoises in a ratio from about 20:1 to 1:20 parts by weight, the balance being primarily water-soluble inorganic builder salts with about 10 to by weight of alkali metal phosphate.
  • a spray-dried detergent composition in particulate form comprising about 5 to 50% of a mixture of watersoluble higher alkyl phenol ethylene oxide having 8 to 12 carbons in the alkyl group and about 8 to 20 moles of ethylene oxide and sodium higher alkyl benzene sulfonatc detergent having an average of about 12 to 15 carbons in said alkyl group in a ratio from about :10 to 50:50 by weight, about 0.1 to 2% by weight of a mixture of sodium carboxymethylcellulose and water-soluble polyvinyl alcohol in a ratio from about 20:1 to about 1:20 by weight, said polyvinyl alcohol having a viscosity of 1.8 to 3 centipoises and a polyvinyl acetate content of 10 to 30% by weight, and the balance being primarily water-soluble inorganic builder salts.
  • a process for preparing a substantially homogeneous detergent composition in solid form which comprises preparing an aqueous mixture having a solids content of about 20 to 90% by weight containing a water-soluble higher alkyl phenol ethylene oxide detergent having about 5 to 20 carbon atoms in the alkyl group and about 5 to 50 mols of ethylene oxide and a water-soluble higher alkyl mononuclcar aryl sulfonate detergent having about 8 to 15 carbons in said alkyl group in a ratio from about 90: 10 to 30:70 by weight, the total amount of said detergents being from about 5 to 50% by weight of solids, about 0.05 to 5% each by weight of solids of alkali metal carboxymethyl cellulose and water-soluble polyvinyl alcohol soil-suspending agent having a viscosity from about 1.8 to 65 centipoises in a ratio from about 20:1 to 1:20 by weight, the balance of total solids being primarily water-soluble inorganic builder salts, and forming
  • a process for manufacturing a heat-dried detergent composition in particulate form which comprises forming an aqueous slurry having a solids content from about 20 to 90% by weight containing a Water-soluble higher alkyl phenol ethylene oxide detergent containing about 5 to 20 carbon atoms in the alkyl group and 5-50 ethylene oxide groups and an alkali metal higher alkyl benzene sulfonate detergent having an average of about 8 to 15 carbons in the alkyl group in a ratio from about 90:10 to 30:70 by weight, alkali metal carboxymethylcellulose and Water-soluble polyvinyl alcohol having a viscosity of from about 1.8 to 6 centipoises, the proportions on a solids basis being about 5 to 50% by Weight of said detergents, and 0.1 to 2% by weight of a mixture of the cellulose compound and polyvinyl alcohol in a ratio from about 20:1 to 1:20 by Weight, the balance of solids being primarily Water-soluble inorganic builder salts with about 10
  • a process for manufacturing a spray-dried detergent composition in particulate form which comprises forming an aqueous slurry having a solids content from about 40 to 65% by Weight, containing a Water-soluble higher alkyl phenol ethylene oxide detergent containing 8 to 12 carbons in the alkyl group and 8 to 20 moles of ethylene oxide and a sodium higher alkyl benzene sulfonate detergent having an average of about 12 to 15 carbons in the alkyl group in a ratio from about 90:10 to 30:70 by Weight, sodium polyphosphate salt, sodium carboxymethylcellulose and Water-soluble polyvinyl alcohol having a viscosity of 1.8 to 3 centipoises and a polyvinyl acetate content of 10 to 30% by weight, the proportions of said ingredients on a solids basis being about 5 to by Weight of said detergents, 10 to by Weight of said polyphosphate and 0.05 to 1% each by Weight of the carboxymethylcellulose and polyvinyl alcohol, heating said mixture at a temperature from about

Description

United States Patent 3,144,412 SOLID DETERGENT COMPOSITIONS Jack Thomas Inamorato, Flushing, N.Y., assignor to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Nov. 1, 1960, Ser. No. 66,443 9 Claims. (Cl. 252138) The present invention relates to a detergent composition comprising a substantially homogeneous mixture in solid form of a water-soluble non-ionic alkyl phenol polyalkylene oxide detergent, a water-soluble alkyl aryl sulfonate detergent, and a mixture of Water-soluble cellulosic and polyvinyl alcohol soil-suspending agents, as hereinafter described and claimed.
It is known in the detergent art to prepare compositions containing an organic detergent and a soil-suspending or anti-redeposition agent which inhibits the deposition of soil onto the fabric during the washing operation. The detergent content has included various anionic and non-ionic detergents including mixtures thereof. A large variety of chemical materials has been proposed as soilsuspending agents including natural and synthetic gums, cellulose derivatives such as carboxymethylcellulose, protein materials and various synthetic polymers including polyvinyl alcohol. The soil-suspending agent which has received Wide acceptance in the art has been sodium carboxymethylcellulose.
The present invention relates to a detergent composition comprising a substantially homogeneous mixture in solid form of a water-soluble higher alkyl phenol polyalkylene oxide detergent and a water-soluble higher alkyl aryl sulfonate detergent in a ratio from about 90:10 to 30:70 by weight, and a minor proportion of a mixture of a water-soluble cellulosic soil-suspending agent and a water-soluble polyvinyl alcohol soil-suspending agent effective to enhance the soil-suspension properties thereof. A feature of this invention relates to a heat-treated composition in particulate form comprising about to 50% by weight of said mixture of non-ionic and sulfonate detergents with a mixture of carboxyalkylcellulose and polyvinyl alcohol suspending agents in amounts from 0.05 to 1% each by weight, and the balance being primarily water-soluble inorganic salts, preferably with 10 to 80% by weight of inorganic alkaline builder salts. Other features of the present invention will be apparent in the following description.
The compositions exhibit desirable detersive properties, particularly in soil-suspension effects during washing operations. A synergistic or enhanced improvement in soil-suspension is achieved by this combination as evideuced by a superior whiteness of washed fabrics such as cottons in the presence of carbonaceous soil compared to the effects achieved with an equivalent amount of said soil-suspending agents when employed individually. A high level of soil-suspension power is obtained with a Wide variety of fabrics in addition to cotton, including synthetic materials such as nylon, Dacron, resin-treated cottons and the like. The over-all effects are superior to the properties of compositions containing said detergents when employed individually and combinations thereof containing one of said soil-suspending agents.
The water-soluble alkyl phenol alkylene oxide condensate detergents are known in the art. The degree or proportion of the hydrophilic alkyleneoxy groups present in a particular condensate will vary with the specific hydrophobic alkyl phenol group therein, generally increasing as the number of carbons in the hydrophobic group increases so as to be sufiicient to confer the desired watersolubility and detersive properties on the final product. The determination of a specific hydrophiliczhydrophobic relationship for each type is not the essential novelty of the 3,144,412 Patented Aug. 11,1964
desired water-solubility and detersive properties and is. dependent upon the character of the hydrophobic group,
the condensates will possess at least about 5 and usually from 5 to 50 alkylene oxide groups. For example, the number of ethenoxy groups per molecule of condensate may average about 7.5, 8.5, 9.5, 11.5, 20.5 or 30, with the preferred range being about 8 to 20 moles of ethylene oxide.
The hydrophobic alkyl phenol portion has an alkyl group of at least about five, and usually about 8 to 20 carbons. For example, the alkyl substituent or the aromatic nucleus may be diisobutylene, diamyl, iso-octyl, nonyl, ethyl hexyl, polymerized propylene, dimerized C -C olefin, and the like. The preferred alkyl substituents contain 8 to 12 carbons.
The water-soluble higher alkyl aryl sulfonate detergents are known in the art and will usually have an average of about 8 to 15 carbon atoms in the alkyl group. It is preferred to use the higher alkyl benzene sulfonate detergent, though other similar detergents having a mononuclear aryl group, such as toluene, xylene or phenol may be used also. The higher alkyl substituent on the aromatic nucleus may be branched or straight chain in structure. Examples of branched-chain substituents are nonyl, dodecyl and pentadecyl groups derived from polymers of lower monoolefins including mixtures thereof and examples of straight chain alkyl groups are decyl, keryl and the like. It is preferred that the alkyl group has an average of 12-15 carbons.
These sulfonated detergents are used preferably in the form of their alkali metal salts such as the sodium and potassium salts. Other water-soluble salts such as the nitrogen-containing salts may be used also, examples being the ammonium, mono-, di-, and tri-ethanolamine salts, and isopropanolamine salts of said detergents.
. The water-soluble cellulosic soil-suspending agents are cellulose having a purity from about 60 to on a dry basis and which are of low, medium or high viscosity may be employed. The degree of substitution of the carboxymethyl group per anhydroglucose unit in the cellulose molecule is variable, but is Within the range from about 0.5 to 2, andusually up to 1.25 substitution. It is preferred to employ carboxylated cellulose having about 0.5 to 0.9 substitution, and particularly about 0.5 to 0.7. Other cellulosic salts are sodium carboxyethylcellulose, the cellulose sulfates and suitable lower alkyl and hydroxyalkyl ethers of cellulose.
The soil-suspending agent used in admixture with the carboxyalkylcellulose or the like is Water-soluble polyvinyl alcohol. The specific or exact degree of polymerization is variable so that it may be of low, medium or high viscosity provided the material has the desired water-solubility and soil-suspending power to produce the enhanced effects in said mixtures. Suitable polyvinyl tains minor amounts of polyvinyl acetate such as up to about 30% by weight, and preferably from about to ester content. A suitable example is polyvinyl alcohol having a viscosity of 4 to 6 cps. with about 12% ester (88-89% hydrolysis). Other known polyvinyl alcohols are those with a viscosity of 21-25 cps. or 3545 cps. and about 12% ester.
It is a feature of this invention to employ polyvinyl alcohol having a viscosity of 1.8 to 3 centipoises and a polyvinyl acetate content of about 10 to 30% by weight. This material exhibits maximum stability in heat-treatment of the composition resulting in maximum soil-suspending power for the composition. It may be prepared by any suitable manner such as by control of the degree of polymerization and alcoholysis of the polyvinyl acetate to produce a product of the above characteristics. The above viscosity range corresponds to an approximate weight average degree of polymerization of about to 100. Examples thereof are polyvinyl alcohols having a viscosity of 2.34 cps. and 22.3% polyvinyl acetate; 1.88 cps. and 19.6% ester; 1.98 cps. and 29.4% ester; 2.38 cps. and 12.8% ester; and the like.
The non-ionic detergent and the alkyl aryl sulfonate detergent are employed in a ratio from about 90:10 to about 30:70 by weight, and preferably from 90:10 to :50. It has been found that maximum detersive effects are achieved in combination with the soil-suspending agents when employing the detergents within these ranges. There is achieved a synergistic increase in soil-suspension power of the composition in the washing of certain fabrics, and the over-all effects are superior to the use of the detergents individually.
The mixture of detergents is important in the preparation of heat-treated solidified compositions. For example, the heating of an aqueous slurry of an alkyl benzene sulfonate detergent with inorganic salts and a particular grade of polyvinyl alcohol (such as having a viscosity of 4-6 centipoises) in a crutcher for up to about one hour at an elevated temperature, e.g., 160180 F., followed by spray-drying, results in a product having reduced soil-suspending power. Further research has shown that this defect is due primarily to such factors as the nature of the polyvinyl alcohol in combination with said detergent in the aqueous slurry when it is subjected or aged at elevated temperatures prior to drying of the slurry to a solid composition.
The presence of the alkyl phenol alkylene oxide detergent in said heated aqueous mixtures tends to stabilize the polyvinyl alcohol and insure that a high level of soilsuspension power is exhibited by the composition even after said heat-treatment. The maximum stabilizing effects are obtained where the detergent content is a major proportion of the non-ionic detergent and a minor proportion of the alkyl aryl sulfonate, the preferred ratios being from about :4O to 90:10 by weight. These detergents are present 1n any suitable amount in the composition and W111 be in an amount greater than the amount of the soilsuspendrng agents and usually at least about 5% by weight of total solids. In laundering compositions, the detergent content will be usually from about 5 to 50%, and preferably from 10 to 45% by weight.
The amount of the combined soil-suspending agents is a minor proportion of the composition. While amounts of 0.05 to 5% by weight of each of the soil-suspending agents may be used if desired, it is a feature of the present invention to use a total amount of 0.1 to 2% by weight of the solids in a ratio from about 20:1 to 1:20 by weight, preferably within the range of about 10:1 to 1:10, of the cellulosic compound to polyvinyl alcohol and sufficient to exert the desired increase in soil-suspending power. The use of up to 2% of the soil-suspending agents has advantages in the manufacture of heat-dried compositions and particularly in soil-suspension effects. The maximum improvement in such effects can be obtained by suitable proportions of each soil-suspending agent so 4 that the total is not in excess of 2%, and preferably not in excess of 1.5% by weight of total solids. It is preferred that each agent be employed in an amount from about 0.05-1% and sufficient to achieve a high level of soil-suspension effects in the washing of both natural and synthetic fabrics.
There is present usually various amounts of watersoluble inorganic salts in the composition. Water-soluble neutral builder salts such as sodium sulfate may be present in admixture with the sulfonate detergent since such sulfate salts are formed in the manufacture of the alkyl aryl sulfonate by certain commercial methods. Additional amounts of such inorganic sulfates may be added as desired. In compositions designed for laundering of heavily soiled articles, it is preferred to add a substantial amount of water-soluble alkaline inorganic builder salts, such as about 10 to by weight of total solids, preferably 20 to 60%. These salts are preferably the alkali metal polyphosphate salts which have the property of inhibiting precipitation of calcium and magnesium material in aqueous solution and of contributing to the heavyduty performance of the detergent product. They may be considered as derived from orthophosphoric acid or the like by the removal of molecularly-bound water, though any suitable means of manufacture may be employed if desired. Such complex or molecularly dehydrated polyphosphate salts may be used in the form of the normal or completely neutralized salt, e.g., pentasodium tripolyphosphate, or partially neutralized salt, e.g., sodium acid tripolyphosphate. Other phosphate salts are pentapotassium tripolyphosphate, tetrasodium and tetrapotassium pyrophosphate, sodium tetraphosphate, sodium hexametaphosphate and the like including any desired mixtures thereof.
Other alkaline builder salts may be employed also such as the water-soluble alkali metal silicates. These silicates may be employed as the sole builder salt if desired or in combination with the polyphosphates. Suitable silicates are those having an alkali oxide to silica ratio within the range of about 1:1 to 1:4, and preferably from about 1:2 to 1:3. Examples are sodium silicates having an Na O to SiO ratio of 1:2.35, 1:25, 1:32, 122.0, 121.6 and 1:1. Other materials are borax and sodium carbonate.
In the manufacture of the composition, the ingredients are to be admixed so as to form a substantially homogeneous product in solid form. Any suitable method may be employed including mechanical blending of the ingredients thoroughly to produce a uniform mixture. It is a feature of the present invention to prepare heat-treated solidified compositions in particulate form from an aqueous mixture of the ingredients in substantially homogeneous form. The preferred method comprises forming a fluid aqueous slurry containing the organic detergents in a conventional soap crutcher or any other suitable mixing apparatus such as a ribbon blender. The other ingredients are then added in any suitable order and form. The polyvinyl alcohol and cellulose compounds are added usually as fine white powders with stirring. The slurry should be sufiiciently fluid at elevated temperatures to insure adequate mixing and formation of a uniform product.
The aqueous mixture is subjected to a heat-treatment at an elevated temperature such as within the range of about to 200 F., and usually from about to 180 F. The slurry is heated by external means or even by exothermic heat of reaction of certain ingredients when added to the slurry depending upon the desired temperature. For example, the addition of hydratable inorganic salts such as the anhydrous forms of sodium tripolyphosphate and sodium pyrophosphate results in exothermic reactions as hydration occurs. The elevated temperature of the slurry aids in the mixing of the ingredients and in solubilization or hydration effects of specific ingredients in the slurry. The time interval of the mixing operation should be sufiicient to insure adequate mixing which will be usually at least a few minutes, e.g., 5 minutes. In certain techniques known in the art, the aqueous mixture prior to drying is aged at the elevated temperature for a time sufiicient to insure adequate solubilization or hydration of certain ingredients. Such aging period may be for a number of hours, such as up to about 8 hours. In gen-- eral, it is preferred to employ time intervals of less than three hours prior to heat-drying, and preferably less than one hour. It is understood that excessively high temperatures or unduly long aging periods will be avoided to prevent decomposition and insure efficient processing.
The solids content of the aqueous slurry is determined by the type of drying operation to be employed and will be usually within the range from about 20 to 90% total solids. In the manufacture of heat-dried products involving vaporization of the water, the solids content will be usually within the range of about 40 to 65% by weight, the remainder being substantially free water content. It is usually maintained at a temperature from about 160 to 180 F. The slurry may be subjected to any suitable heat-drying operation and converted to particle form. For example, the material from the crutcher or mixing vessel may be sent into a drop tank from where it may be added or pumped to a drying zone such as a spray tower. This mixture may be subjected to the conventional spraydrying, roll-drying or drum-drying operations utilizing temperatures above about 212 F. to produce the detergent composition in particulate form. As a result, the detergent composition is obtained in the form of heat-dried homogeneous particles, such as beads, granules, flakes, chips, powders, etc. 4
It is preferred to spray-dry the aqueous slurry whereby it is atomized or forced through spray nozzles into towers, with the small liquid particles becoming solidified and drying as they fall through a stream or vortex of heated air or products of combustion. The composition is produced thereby in the form of hollow thin-walled spheres or beads, characterized by excellent solubility in water and uniformity of particles having a small residual moisture content usually of about 3 to by weight.
Alternatively, the aqueous slurry may be solidified or dried by other suitable methods which do not involve vaporization of the water content. The slurry can contain sufficient water for adequate mixing and hydration of the hydratable inorganic salts to the extent desired Without any significant excess water content so that a dry and solidified mass is formed upon suitable aging at room temperature or slightly elevated temperatures such as up to about 120 F. The solidified mass may be granulated to form particles or granules of desired size.
Various other materials may be added in known manner to the aqueous slurry or after solidification. Examples thereof are higher fatty acid amides such as coconut or lauric monoethanolamide, isopropanolamide and diethanolamide; fatty alcohols such as lauryl alcohol, coconut fatty alcohols or cetyl alcohol; lower alkyl aryl sulfonates such as xylene or toluene sulfonates; coloring agents, corrosion inhibiting agents, bleaching agents, foam stabilizers or inhibitors as desired, detergency improving additives, and the like. If desired, suitable amounts of other detersive materials may be incorporated in the composition, such as suitable non-ionic and sulfated organic detergents. Examples thereof are the normal and secondary higher alkyl sulfate detergents, particularly those having 8 to 15 carbons in the alkyl residue such as lauryl (or coconut fatty alcohol) sulfate, the higher alkyl ether sulfates, higher alkyl glyceryl ether sulfonates, higher alkyl aryl polyethylene oxide sulfates, polyoxyethylene ethers of fatty alcohols, and polyethylene condensates with hydrophobic polypropylene glycols.
It is to be understood that the following examples are further illustrative of the present invention and that they are not intended to limit the scope thereof. All proportions are by weight unless otherwise specified.
Example I A detergent composition is prepared according to the following formulation.
Ingredients: Percent Alkyl phenol-ethylene oxide condensate 12.25 Sodium tridecyl benzene sulfonate 1.75 Sodium carboxymethylcellulose 0.25 Polyvinyl alcohol 0.25 Sodium tripolyphosphate 40.0 Sodium sulfate 35.0 Fluorescent dye 0.2 Moisture 10.3
In the above formulation, the polyvinyl alcohol has a viscosity of 4-6 cps. and 11-12% polyvinyl acetate; the alkyl group of the sulfonate detergent is derived from a mixture containing propylene pentamer and tetramer benzene sulfonate corresponding on the average to a tridecyl group, and the carboxymethylcellulose is a commercial grade of about 67% purity, and the non-ionic detergent is nonyl phenol ethylene oxide having an average of about 9.5 moles ethylene oxide.
This formulation is prepared in particulate form by mixing all of the solid ingredients except the non-ionic detergent and water in powdered form to form a homogeneous powder. The non-ionic detergent is a liquid and is slowly added with stirring followed by addition of the water and the composition gradually forms a dry granular mass which is passed through a 20 mesh screen (U.S. Sieve). The resulting product in particulate form is added to the washing machine and exhibits a high degree of washing power, particularly in soil-suspension power on cotton fabrics.
Example 11 The formulation of Example I is repeated using polyvinyl alcohol of 2.34 centipoises and 22.3% polyvinyl acetate content. The resulting solid detergent composi-. tion exhibits high soil-suspension power also.
Example III A solid detergent composition is prepared according to the following formulation.
Ingredients: Percent Alkyl phenol-ethylene oxide condensate 6 Sodium tridecyl benzene sulfonate 8 Sodium tripolyphosphate 40 Sodium sulfate 35 Sodium carboxymethylcellulose 0.25 Polyvinyl alcohol 0.25 Moisture 10.5
These ingredients are mixed and blended thoroughly for four hours in a blender to form a homogeneous solid mixture. As described in Example I, the non-ionic detergent is nonyl phenol condensed with an average of about 9.5 moles ethylene oxide, the carboxymethylcellulose is a commercial grade (Du Pont 10D) and the polyvinyl alcohol has a viscosity of 46 centipoises and 11-12% polyvinyl acetate. The composition is added to. a washing bath and exhibits superior washing properties on a variety of fabrics including cottons, Dacron-cotton mixtures, and resin-treated cottons. More particularly, this formulation has markedly superior soil-suspension properties on washing of cotton fabrics in soil anti-redeposition tests using carbon soil in soft water compared.
particulate form by spray-drying an aqueous slurry of the ingredients in Examples I-III as described.
Example IV A heat-dried composition is prepared according to the following formulation.
Ingredients: Percent Sodium tridecyl benzene sulfonate 4.0 Nonyl phenol-ethylene oxide condensate 10.0 Sodium tripolyphosphate 35.0 Cetyl alcohol 0.8 Sodium silicate 3.0 Sodium sulfate 37.8 Sodium carboxymethylcellulose 0.3 Polyvinyl alcohol 0.13 Moisture 8.5
the balance being small amounts of fluorescent dye, corrosion inhibitor and the like.
The product is prepared by adding to a crutcher a 60% solids aqueous solution of the sulfonate detergent described in Example I admixed with some sodium sulfate formed in its manufacture. The non-ionic detergent having about 9.5 moles of ethylene oxide and the fatty alcohol are added as a liquid to the crutcher at 120 F. There is added the sodium silicate solids in the form of an aqueous solution at 130140 F,, the remainder of the sodium sulfate, the carboxymethylcellulose powder of about 67% purity and the polyvinyl alcohol (2.34 cps. and 22.3% polyvinyl acetate) with stirring to form a uniform slurry. The tripolyphosphate in powder form is added with agitation and there is formed a smooth, pumpable mixture within a few minutes having a total solids content of about 55-60%. It is then pumped into a spray tower where it is spray-dried with air heated to about 600 F. to yield a product in the form of beads. The product exhibits high soil-suspension power in washing tests.
Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted for various ingredients without departing from the principles and true spirit of the invention.
What is claimed is:
1. A detergent composition comprising a substantially homogeneous mixture in solid form of (a) a water-soluble non-ionic higher alkyl phenol ethylene oxide detergent having about to 20 carbon atoms in the alkyl grou and about 5 to 50 mols of ethylene oxide and (b) a watersoluble higher alkyl mononuclear aryl sulfonate detergent having about 8 to carbon atoms in said alkyl group, the ratio of said non-ionic detergent to alkyl aryl sulfonate detergent being from about 90: 10 to 30:70 by weight and said detergents being in a total amount from about 5 to 50% by weight of the composition, and a mixture of (c) an alkali metal carboxymethylcellulose and (d) water-soluble polyvinyl alcohol soil-suspending agent having a viscosity within the range of about 1.8 to 65 centipoises, said carboxymethylcellulose and polyvinyl alcohol soil-suspending agents being from about 0.05 to 5% by weight of each in said composition, the balance being primarily water-soluble inorganic builder salts.
2. A detergent composition comprising a substantially homogeneous mixture in solid form of a water-soluble higher alkyl phenol ethylene oxide detergent having about 5 to carbon atoms in the alkyl group and about 5 to 50 moles of ethylene oxide and alkali metal higher alkyl benzene sulfonate detergent having about 8 to 15 carbons in said alkyl group, the total amount of said non-ionic and said sulfonate detergents being from about 5 to 50% by weight of the composition in a ratio from about 90: 10 to :70 by weight, and in minor proportion to said detergents about 0.1 to 2% by weight of a mixture of alkali metal carboxymethylcellulose soil-suspending agent and water-soluble polyvinyl alcohol soil-suspending agent having a viscosity from about 1.8 to centipoises in a ratio from about 20:1 to 1:20 parts by weight, the balance being primarily water-soluble inorganic builder salts.
3. A heateated detergent composition in particulate form comprising about 5 to 50% by weight of higher alkyl phenol ethylene oxide detergent having about 8 to 12 carbon atoms in the alkyl group and about 5 to 50 moles of ethylene oxide and alkali metal higher alkyl benzene sulfonate having about 8 to 15 carbons in the alkyl group in a ratio from about 90:10 to 50:50 by weight, about 0.1 to 2% by weight of a mixture of alkali metal carboxymethylcellulose and water-soluble polyvinyl alcohol soil-suspending agent having a viscosity from about 1.8 to about 6 centipoises in a ratio from about 20:1 to 1:20 parts by weight, the balance being primarily water-soluble inorganic builder salts with about 10 to by weight of alkali metal phosphate.
4. A detergent composition in accordance with claim 3 wherein said polyvinyl alcohol has a viscosity from 1.8 to 3 centipoises and a polyvinyl acetate content of 10 to 30% by Weight,
5. A detergent composition in accordance with claim 3 wherein said polyvinyl alcohol has a viscosity of 4 to 6 centipoises and a polyvinyl acetate content of about 12% by weight.
6. A spray-dried detergent composition in particulate form comprising about 5 to 50% of a mixture of watersoluble higher alkyl phenol ethylene oxide having 8 to 12 carbons in the alkyl group and about 8 to 20 moles of ethylene oxide and sodium higher alkyl benzene sulfonatc detergent having an average of about 12 to 15 carbons in said alkyl group in a ratio from about :10 to 50:50 by weight, about 0.1 to 2% by weight of a mixture of sodium carboxymethylcellulose and water-soluble polyvinyl alcohol in a ratio from about 20:1 to about 1:20 by weight, said polyvinyl alcohol having a viscosity of 1.8 to 3 centipoises and a polyvinyl acetate content of 10 to 30% by weight, and the balance being primarily water-soluble inorganic builder salts.
7. A process for preparing a substantially homogeneous detergent composition in solid form which comprises preparing an aqueous mixture having a solids content of about 20 to 90% by weight containing a water-soluble higher alkyl phenol ethylene oxide detergent having about 5 to 20 carbon atoms in the alkyl group and about 5 to 50 mols of ethylene oxide and a water-soluble higher alkyl mononuclcar aryl sulfonate detergent having about 8 to 15 carbons in said alkyl group in a ratio from about 90: 10 to 30:70 by weight, the total amount of said detergents being from about 5 to 50% by weight of solids, about 0.05 to 5% each by weight of solids of alkali metal carboxymethyl cellulose and water-soluble polyvinyl alcohol soil-suspending agent having a viscosity from about 1.8 to 65 centipoises in a ratio from about 20:1 to 1:20 by weight, the balance of total solids being primarily water-soluble inorganic builder salts, and forming a substantially homogeneous mixture thereof at a temperature from about F. to 200 F., drying said mixture and forming a substantially homogeneous detergent composition in solid form.
8. A process for manufacturing a heat-dried detergent composition in particulate form which comprises forming an aqueous slurry having a solids content from about 20 to 90% by weight containing a Water-soluble higher alkyl phenol ethylene oxide detergent containing about 5 to 20 carbon atoms in the alkyl group and 5-50 ethylene oxide groups and an alkali metal higher alkyl benzene sulfonate detergent having an average of about 8 to 15 carbons in the alkyl group in a ratio from about 90:10 to 30:70 by weight, alkali metal carboxymethylcellulose and Water-soluble polyvinyl alcohol having a viscosity of from about 1.8 to 6 centipoises, the proportions on a solids basis being about 5 to 50% by Weight of said detergents, and 0.1 to 2% by weight of a mixture of the cellulose compound and polyvinyl alcohol in a ratio from about 20:1 to 1:20 by Weight, the balance of solids being primarily Water-soluble inorganic builder salts with about 10 to 80% by weight of alkaline inorganic salts, maintaining said mixture at a temperature from about 100 to 200 F. with agitation and forming a substantially homogeneous mixture, heat-drying said mixture at a temperature above about 212 F., and recovering a heatdried detergent composition in particulate form.
9. A process for manufacturing a spray-dried detergent composition in particulate form which comprises forming an aqueous slurry having a solids content from about 40 to 65% by Weight, containing a Water-soluble higher alkyl phenol ethylene oxide detergent containing 8 to 12 carbons in the alkyl group and 8 to 20 moles of ethylene oxide and a sodium higher alkyl benzene sulfonate detergent having an average of about 12 to 15 carbons in the alkyl group in a ratio from about 90:10 to 30:70 by Weight, sodium polyphosphate salt, sodium carboxymethylcellulose and Water-soluble polyvinyl alcohol having a viscosity of 1.8 to 3 centipoises and a polyvinyl acetate content of 10 to 30% by weight, the proportions of said ingredients on a solids basis being about 5 to by Weight of said detergents, 10 to by Weight of said polyphosphate and 0.05 to 1% each by Weight of the carboxymethylcellulose and polyvinyl alcohol, heating said mixture at a temperature from about to F. and forming a substantially homogeneous aqueous mixture, and spray-drying said mixture at a temperature above about 212 F., and recovering a spraydried detergent composition in particulate form.
References Cited in the file of this patent UNITED STATES PATENTS 2,755,252 Fong et a1 July 17, 1956 2,798,047 Touey et a1 July 2, 1957 2,870,093 Rufl Jan. 20, 1959 2,874,123 Schaafsma et a1 Feb. 17, 1959 2,877,187 Henderson et al Mar. 10, 1959 2,897,155 McNaught et a1 July 28, 1959 OTHER REFERENCES Textile Research Journal, vol. 23, No. 11, November 1953, pp. 769-775.

Claims (1)

1. A DETERGENT COMPOSITION COMPRISING A SUBSTANTIALLY HOMOGENEOUS MIXTURE IN SOLID FORM OF (A) A WATER-SOLUBLE NON-IONIC HIGHER ALKYL PHENOL EHTYLENE OXIDE DETERGENT HAVING ABOUT 5 TO 20 CARBON ATOMS IN THE ALKYL ROUP AND ABOUT 5 TO 50 MOLS OF ETHYLENE OXIDE AND (B) A WATERSOLUBLE HIHER ALKYL MONONUCLEAR ARYL SULFONATE DETERGENT HAVING ABOUT 8 TO 15 CARBON ATOMS IN SAID ALKYL GROUP, THE RATIO OF SAID NON-IONIC DETERGENT TO ALKYL ARYL SULFONATE DETERGENT BEING FROM ABOUT 90:10 TO 30:70 BY WEIGHT AND SAID DETERGENTS BEING IN A TOTAL AMOUNT FROM ABOUT 5 TO 50% BY WEIGHT OF THE COMPOSITION AND A MIXTURE OF (C) AN ALKALI METAL CARBOXYMETHYCELLULOSE AND (D) WATER-SOLUBLE POLYVINYL ALCOHOL SOIL-SUSPENDING AGENT HAVING A VISCOSITY WITHIN THE RANE OF ABOUT 1.8 TO 65 CENTIPOISES, SAID CARBOXYMETHYLCELLULOSE AND POLYVINYL ALCOHOL SOIL-SUSPENDING AGENTS BEING FROM ABOUT 0.05 TO 5% BY WEIGHT OF EACH IN SAID COMPOSISTION, THE BALANCE BEING PRIMARILY WATER-SOLUBLE INORGANIC BUILDER SALTS.
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US3284364A (en) * 1963-01-25 1966-11-08 American Cyanamid Co Soil anti-redeposition agents
US3325414A (en) * 1963-10-01 1967-06-13 Colgate Palmolive Co Heavy duty detergent composition containing a quaternary ammonium salt
US3288859A (en) * 1965-03-30 1966-11-29 Procter & Gamble Reactions of alkali metal salts of sulfinyl carbanions and alkanesulfenates with epoxy compounds and novel compounds derived therefrom
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US3350319A (en) * 1966-01-18 1967-10-31 Mo Och Domsjoe Ab Aqueous detergent-inorganic builder concentrates
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US3959165A (en) * 1972-09-15 1976-05-25 Colgate-Palmolive Company Biodegradable, non-polluting, heavy duty synthetic organic detergent composition
US3970594A (en) * 1975-03-18 1976-07-20 The Procter & Gamble Company Hard surface cleaning compositions
US4235735A (en) * 1979-07-30 1980-11-25 Milliken Research Corporation Laundry detergent containing cellulose acetate anti-redeposition agent
US4487710A (en) * 1982-03-01 1984-12-11 The Procter & Gamble Company Granular detergents containing anionic surfactant and ethoxylated surfactant solubility aid
US6730722B1 (en) * 1998-06-19 2004-05-04 Wacker-Chemie Gmbh Cross-linkable polymer powder compositions
WO2001007551A1 (en) * 1999-07-26 2001-02-01 Henkel Kommanditgesellschaft Auf Aktien Use of polyvinyl alcohols as detergent additives capable of removing soiling
US20060035801A1 (en) * 2003-02-10 2006-02-16 Josef Penninger Bleach-containing laundry detergents or cleaning compositions comprising water-soluble builder system and soil release-capable cellulose derivative
US7375072B2 (en) 2003-02-10 2008-05-20 Henkel Kommanditgesellschaft Auf Aktien Bleach-containing laundry detergents or cleaning compositions comprising water-soluble builder system and soil release-capable cellulose derivative
WO2004069973A1 (en) * 2003-02-10 2004-08-19 Henkel Kommanditgesellschaft Auf Aktien Intensification of the cleaning power of detergents using a cellulose derivative and a hygroscopic polymer
US20060035804A1 (en) * 2003-02-10 2006-02-16 Josef Penninger Use of cellulose derivatives as foam regulators
US20060035805A1 (en) * 2003-02-10 2006-02-16 Josef Penninger Bleach-containing laundry detergent comprising cotton-active soil release-capable cellulose derivative
US20060035806A1 (en) * 2003-02-10 2006-02-16 Josef Penninger Increase in the water absorption capacity of textiles
US20060046951A1 (en) * 2003-02-10 2006-03-02 Josef Penninger Enhancement of the cleaning performance of laundry detergents by a combination of cellulose derivatives
US20060046950A1 (en) * 2003-02-10 2006-03-02 Josef Penninger Enhancement of the cleaning performance of laundry detergents by cellulose derivative and hygroscopic polymer
US7316995B2 (en) 2003-02-10 2008-01-08 Henkel Kommanditgesellschaft Auf Aktien Detergents or cleaning agents comprising a water-soluble building block system and a cellulose derivative with dirt dissolving properties
US20060030504A1 (en) * 2003-02-10 2006-02-09 Josef Penninger Detergents or cleaning agents comprising a water-soluble building block system and a cellulose derivative with dirt dissolving properties
US20080196221A1 (en) * 2007-02-15 2008-08-21 Oscar Merlin Madrigal Fastening device for securing flexible sheet material
US20080234169A1 (en) * 2007-03-20 2008-09-25 Jean Pol Boutique Detergent composition
US7713921B2 (en) * 2007-03-20 2010-05-11 The Procter & Gamble Company Detergent composition
CN104459014A (en) * 2014-11-27 2015-03-25 华南理工大学 Method for determining degree of substitution of sodium carboxymethylcellulose
CN104458611A (en) * 2014-11-27 2015-03-25 华南理工大学 Method for determining degree of substitution of water soluble food grade sodium carboxymethylcellulose
CN104459013A (en) * 2014-11-27 2015-03-25 华南理工大学 Method for testing degree of substitution of low-sodium sodium carboxymethylcellulose
CN110913864A (en) * 2018-08-17 2020-03-24 邦泰生物工程(深圳)有限公司 Stable nicotinamide riboside composition and preparation method thereof
CN110913864B (en) * 2018-08-17 2022-12-13 邦泰生物工程(深圳)有限公司 Stable nicotinamide ribose composition and preparation method thereof

Also Published As

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BE609040A (en)
DE1293378B (en) 1969-04-24
CH414047A (en) 1966-05-31
CA688539A (en) 1964-06-09
MY6600100A (en) 1966-12-31
NL270825A (en)
GB931438A (en)

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