US2994665A - Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents - Google Patents

Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents Download PDF

Info

Publication number
US2994665A
US2994665A US806429A US80642959A US2994665A US 2994665 A US2994665 A US 2994665A US 806429 A US806429 A US 806429A US 80642959 A US80642959 A US 80642959A US 2994665 A US2994665 A US 2994665A
Authority
US
United States
Prior art keywords
groups per
mole
sulfonate
anhydroglucose unit
plus
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US806429A
Inventor
Reich Irving
Hans R Dallenbach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lever Brothers Co
Original Assignee
Lever Brothers Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lever Brothers Co filed Critical Lever Brothers Co
Priority to US806429A priority Critical patent/US2994665A/en
Application granted granted Critical
Publication of US2994665A publication Critical patent/US2994665A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D73/00—Packages comprising articles attached to cards, sheets or webs
    • B65D73/0007—Packages comprising articles attached to cards, sheets or webs the articles being attached to the plane surface of a single card
    • B65D73/0014—Packages comprising articles attached to cards, sheets or webs the articles being attached to the plane surface of a single card by means of separate fixing elements, e.g. clips, clamps, bands
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/655—Mixtures of sulfonated products with alkylolamides of carboxylic acids
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • the present invention relates to detergent compositions, and more particularly to concentrated heavy duty liquid detergent compositions which are uniform stable suspensions showing no separation into layers at room temperature and which are highly effective in preventing soil redeposition when used at washing concentrations.
  • Powdered detergent compositions are generally prepared by spray drying or drum drying, which are costly operations. When used in washing, the powdered detergent compositions must be dissolved to form dilute aqueous washing solutions. This step of dissolving or dispersing the powdered detergent compositions in the wash water is time consuming. Frequently, the powdered detergent compositions are difficultly dispersed, since they may tend to form lumps. Powdered detergent compositions, moreover, tend to vary greatly in density unless particular care is taken in their preparation. Such a variation in density makes it diflicult to determine the exact amount thereof to be employed during washing.
  • powdered deteregnt compositions may be difiicult to dispense, since they sometimes clog the orifices of a dispenser.
  • powdered detergent compositions have a tendency to cake at high humidities upon standing in their open containers.
  • powdered detergent compositions being normally sold in cardboard containers, are subject to spilling and waste in the event an open container is accidentally knocked over. Furthermore, their dustiness may be bothersome, particularly to persons who suffer from dust allergies.
  • a highly effective heavy duty liquid detergent composition has been fully described in US. Patent No. 2,859,182 issued November 4, 1958.
  • This homogeneous heavy duty liquid detergent composition consists essentially of an aqueous solution of a potassium alkylaryl sulfonate, an alkali metal aryl sulfonate, tetrapotassium pyrophosphate or pentapotassium tripolyphosphate, and at least one alkylolamide or an ethylene oxide condensation product thereof.
  • the composition may also have present therein alkali metal silicates, alkalies, perfumes, dyes, brighteners, and other compatible adjuvants. Complete details concerning this homogeneous heavy duty liquid detergent composition may readily be obtained by reference to said patent.
  • This composition could be further improved, if it were possible to incorporate therein soil suspending agents which would prevent or inhibit the redeposition of soil ice upon fabrics Washed repeatedly in diluted wash solutions thereof and thereby avoid greying of the fabrics.
  • Various cellulose derivatives have been used heretofore as soil suspending agents in powdered detergent compositions.
  • the incorporation of a cellulose derivative into a powdered detergent composition presents no particular problem, since the detergent composition is in powdered form.
  • the incorporation of cellulosic soil suspending agents in the above described heavy duty liquid detergent compositions is not a simple matter.
  • the cellulosic component separated out within a few hours and the composition became stratified into two or more layers, one being a clear liquid and the others being milky or cloudy.
  • the following representative heavy duty liquid detergent formulation were prepared.
  • Calcofluor MR and Tinopal RBS are optical brighteners which are respectively disodium N:N'-bis-(2,4-diphenylamino-1:3:5-triazyl [6]) 4:4-diamino stilbene 2:2-disulfonate and sodium-2- (stilbyl-4)-(naphtho-l':2':4:5) 1:2:3 triazole-2"-sulfonate.
  • cellulose derivatives in the separate samples was made up as follows: (1) 100% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit, (2) 100% low viscosity methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule, (3) 100% sodium carboxymethylethylcellulose having 0.22 mole of carboxymethyl groups and 1.0 mole of ethyl groups per anhydroglucose unit, (4) 100% ethylcellulose having 1.26 moles of ethyl groups per anhydroglucose unit, (5) 100% sodium carboxymethylmethylcellulose having 0.150.2 mole of carboxymethyl groups per anhydroglucose unit and 14-22% of methoxyl groups per cellulose molecule (0.25% total cellulose derivatives), (6) 100% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50
  • the potassium alkylaryl sulfonates have the general formula R,-@SO:K
  • R is an alkyl group, which may be saturated or unsaturated and straight or branched chain, having from 1 to carbon atoms, at least one R having 8 to 15 carbon atoms, x is a number from 1 to 5, and may be an average number.
  • Suitable potassium alkylaryl sulfonates include,
  • the amount of water in the detergent composition was raised a corresponding amount.
  • Containers of the detergent compositions would have to be shaken prior to use in order to resuspend the separated cellulosics as best as possible and insure that a dosage poured from the containers had the correct amount of cellulosics therein. Moreover, the flecks of cellulosics ultimately combined to form a viscous layer which was hard to resuspend even with vigorous shaking.
  • a concentrated heavy duty liquid detergent composition could be prepared containing cellulose derivatives as soil suspending agents which would be highly efiective in preventing soil redeposition and greying of fabrics and which would be a stable uniform suspension showing no separation into layers at room temperature over extended periods, provided the cellulose derivative soil suspending agents were incorporated in the heavy duty liquid detergent composition in particular pairs.
  • the heavy duty liquid detergent compositions of'the invention which are stable uniform suspensions showing no separation into layers 'at room temperature and which are highly eifective in preventing soil redeposition when used at washing concentrations consist essentially of an aqueous solution of from about 7% to about 10% of a potassium alkylaryl sulfonate, from about 5% to about 8% total of one or more alkali metal aryl sulfonates,
  • R and R' taken together with the remainder of the polypropylene radical form an alkyl group having an i average molecular weight corresponding to from about 12 to about 15 carbon atoms.
  • the potassium alkylaryl sulfonate anionic detergent is used in the composition to supply a portion of the foaming and wetting action necessary in a heavy duty liquid detergent product designed for household use.
  • the polyphosphate i.e., tetrapotassium pyrophosphate or pentapotassium tripolyphosphate, is employed in the composition to supply the heavy duty detergent feature of the liquid, and impart good soil removal properties thereto.
  • the amount of polyphosphate is increased, the amount of potassium alkylaryl sulfonate is decreased.
  • Suitable alkali metal aryl sulfonate or mixtures thereof totaling from about 5% to about 8% include the following sodium orv potassium aryl sulfonates; toluene sulfonate, tetraliu sulfonate, ethylbenzene sulfonate, isopropylof 15% ortho-xylene sulfonate, 70% meta-xylene sulfonate, and-15% para-xylene sulfonate, a mixture of 47% toluenesulfonate plus 53% of a mixture of 15% ortho-xylene sulfonate, 70% meta-xylene sulfonate, and 15% para-xylene.sulfonate, a mixture of 22% orthoxylene sulfonate,. 53% meta-xylene sulfonate, 5% parafrom about 27% to about 10%, preferably about 20%,
  • the alkali metal aryl sulfonate is employed in the heavy duty liquid detergent composition to aid in solubilizing the potassium. alkylaryl sulfonate in the presence of a considerable amount of the polyphosphate and other inorganic materials.
  • the alkali .metal aryl sulfonate also solubilizes the alkylolamides which are either insoluble in water or incompatible with aqueous solutions of polyphosphates. Ihere is no advantage in adding more of the alkali metal aryl sulfonate 'than is necessary for its solubilizing eliect,--since this material appears to contribute nothing to the detergent and dishwashing characteristics of the heavy duty liquid detergent composition.
  • the alkylolamide may be either a monoalkylolamide or a dialkylolamide.
  • Typical examples of siutable alkylolamides are lauric isopropanolamide, lauric diethanolamide, coconut monoethanolamide, capric diethanolamide, tallow diethanolamide, and the monoethanolamide of a 1:1 mixture of caprylic and capric acids.
  • the alkylolamides act as solubilizers in conjunction with the alkali metal aryl sulfonate to prevent the separating out from solution of the potassium alkylaryl sulfonate.
  • alkylolamides which may also be employed include ethylene oxide condensation products thereof, for example, the condensation product of one mole of lauric monoethanolamide with one mole of ethylene oxide and the condensation product of one mole of lauric isopropanolamide with one mole of ethylene oxide. All of the above alkylolamides may be used either singly or in suitable mixtures.
  • the heavy duty liquid detergent composition also contains a total of from about 0.1% to about 3%, and preferably from about 0.25% to about 1%, and more preferably from about 0.5% to about 0.7%, of a pair of soil suspending cellulose derivatives which are simple or mixed lower alkyl, hydroxyalkyl, or carboxyalkyl ethers of cellulose and form a uniform stable suspension in the aqueous solution.
  • pairs of cellulosic soil suspending agents include the following: (1) about 9% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit plus about 91% sodium carboxymethylmethylcellulose having 0.15-0.2 mole of carboxymethyl groups per anhydroglucose unit and 14-22% of methoxyl groups per cellulose molecule, (2) about 8% sodium carboxymethylcellulose having 1.94 moles of carboxymethyl groups per anhydroglucose unit plus about 92% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule, (3) about 16% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus about 84% methylcellulose having 3536% methoxyl groups per cellulose molecule, (4) about 20% sodium carboxymethylcellulose having 0.76 mole of carboxymethyl groups per
  • the sodium cation on the carboxymethyl group is equivalent to other cations, such as potassium or ammonium or organic amine cations, such as mono-, di-, or vtri-ethanolamine.
  • cations such as potassium or ammonium or organic amine cations, such as mono-, di-, or vtri-ethanolamine.
  • the substituent contents given above for the cellulose derivatives are expressed in average values.
  • the liquid detergent composition may contain minor portions of an alkali, such as potassium hydroxide, to neutralize any excess acid impurities present in the components of the composition.
  • minor portions of compatible perfumes, dyes, optical brighteners, alkali metal silicates, and other desirable adjuvants may be added to the composition.
  • a water-soluble alkali metal silicate is added to the composition, the pH thereof must be adjusted to about 11.4 or above by the addition of free alkali, such as potassium hydroxide, to keep the silicate in solution.
  • Typical alkali metal silicates include the sodium or potassium silicates having the following alkali to silica ratios 1:3.92, 1:3.45, 122.4, 1:1.8, 1:25, and 1:20. An amount up to about 6% on a solids basis of the silicate may be employed.
  • the concentrated heavy duty liquid detergent compo sition of the invention may be prepared by mixing the components thereof together in the aqueous medium. Heat may be conveniently utilized during the mixing of the components to increase the rate of dissolution thereof.
  • a preferred method for the preparation of the stable and uniform heavy duty liquid detergent composition is the addition of the pair of cellulose derivatives to hot Water followed by cooling to form an aqueous solution thereof and the addition to the cellulose solution of an aqueous solution of the potassium alkylaryl sulfonate, alkali metal aryl sulfonate, alkylolamide or ethylene oxide condensation product thereof, and any optical brighteners, dyes, alkali, and alkali metal silicates.
  • composition is completed by the addition thereto of the tetrapotassium pyrophosphate or pentapotassium tripolyphosphate to give a composition having a pH of about 12.
  • the heavy duty liquid detergent composition of the invention will be further illustrated by the following examples.
  • a representative heavy duty liquid detergent composition was prepared having the following formula:
  • Example 1 In this example the 0.5% total cellulosics of the representative formula consisted of 8% sodium carboxymethylcellulose (70 centipoise viscosity in a 2% aqueous dispersion) having 1.94 moles of carboxymethyl groups per anhydroglucose unit plus 92% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule.
  • Example 3 In this example the 0.5 total cellulosics of the representative formula consisted of 16% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 moles of carboxymethyl groups per anhydroglucose unit plus 84% methylcellulose having 35-36% methoxyl groups per cellulose molecule.
  • Example 4 the 0.5 total cellulosics of the representative formula consisted of 20% sodium carboxymethylcellulose (3600 centipoise viscosity in a 1% aqueous dispersion) having 0.76 moles of carboxymethyl groups per anhydroglucose unit plus 80% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule.
  • Example 5 In this example the 0.5 total cellulosics of the representative formula consisted of 22.6% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups 'per anhydroglucose unit plus 77.4% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule.
  • Example 6 the total cellulosics of the representative formula was 0.32% and consisted of 43.7% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus 56.3% sodium car- 'boxymethylmethylcellulose having 0.25 mole of carboxymethyl groups per anhydroglucose unit and 10-14% methoxyl groups per cellulose molecule.
  • the water in the formula was increased in an amount correspond ing to the decrease in cellulosic content.
  • Example 7 In this example the 0.5% total cellulosics consisted of 28.6% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl, groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit plus 71.4% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule.
  • Example 8 In this example the 0.5% total cellulosics of the representative formula consisted of 44% sodium carboxymethylhydroxyethylcellulose having 0.36 mole of carboxymethyl groups and 1.07 moles of hydroxyethyl groups per anhydroglucose unit plus 56% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule.
  • Example 9 In this example the 0.5 total cellulosics in the representative formula consisted of 44% sodium carboxymethylhydroxyethylcellulose having 0.73 mole of carboxymethyl groups and 0.87 mole of hydroxyethyl groups per anhydroglucose unit plus 56% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5- 32% methoxyl groups per cellulose molecule.
  • Example 10 In this example the total cellulosics in the above representative heavy duty liquid detergent formulation was increased to 0.7% with a decrease of 0.2% in the water content.
  • the 0.7% total cellulosics consisted of 30% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule.
  • Example 11 In this example the 0.5% total cellulosics in the repre sentative formula consisted of 62% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5% hydroxypropyl groups per cellulose molecule plus 38% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups per anhydroglucose unit.
  • Example 12 In this example the 0.5 total cellulosics in the representative formula consisted of 72% methylhydroxypropylcellulose (50 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5% hydroxypropyl groups per cellulose molecule plus 28% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups per anhydro-' glucose unit.
  • Example 13 In this example the 0.5 total cellulosics in the representative formula consisted of 54% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dis persion) having 2830% methoxyl groups per cellulose molecule and 7-12% hydroxypropyl groups per cellulose molecule plus 46% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 07 mole of carboxymethyl groups per anhydroglucose unit.
  • 54% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dis persion) having 2830% methoxyl groups per cellulose molecule and 7-12% hydroxypropyl groups per cellulose molecule plus 46% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 07 mole of carboxymethyl groups per anhydroglucose unit.
  • Example 14 In this example the 0.5 total cellulosics in the repre- 'Teu-apotassium Pyrophosphate sentative formula consisted of 42% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5 hydroxypropyl groups per cellulose molecule plus 58% dihydroxypropylcellulose (6100 centipoise viscosity at 25 C. in a 2% solution in 5% aqueous sodium hydroxide) having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit.
  • 42% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5 hydroxypropyl groups per cellulose molecule plus 58% dihydroxypropylcellulose (6100 centipoise vis
  • Example 15 In this example the 0.5% total cellulosics in the representative formula consisted of 64% methylhydroxypropylcellulose (50 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7 .5-% hydroxypropyl groups per cellulose molecule plus 36% dihydroxypropylcellulose (6100 centipoise viscosity at 25 C. in a 2% solution in 5% aqueous sodium hydroxide) having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit.
  • Example 16 In this example the 0.5 total cellulosics in the representative formula consisted of 70% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule plus 30% dihydroxypropylcellulose 6100 centipoise viscosity at 25 C. in a 2% solution in 5% aqueous sodium hydroxide) having 0.3 mole of dihydroxypropyl groups per .anhydroglucose unit.
  • Example 17 In this example the 0.5% total cellulosics in the repre-. sentative formula consisted of 90% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule plus dihydroxypropylcellulose (6100 centipoise viscosity at 25 C. in a 2% solution in 5% aqueous sodium hydroxide having 0.3 moles of dihydroxypropyl groups per anhydroglucose unit.
  • the reflectance values of the test cloths were read with a General Electric reflectometer, since this apparatus uses a narrow band of the visible spectrum only and accordingly the presence of optical brighteners or fluorescent whitening agents in the tested detergent formulations does not affect the measured reflectance values.
  • the detergent compositions were as follows:
  • compositions B and C The higher reflectance values for the cloth washed 10 or 20 times in the compositions of the invention (compositions B and C) compared with composition A clearly show the compositions of the invention are highly effective in preventing soil redeposition and greying of fabrics, since they show a significant improvement even at the low levels of total soil available from naturally soiled cloth.
  • the heavy duty liquid detergent compositions of the invention contain pairs of cellulose derivatives as soil suspending agents, and yet the compositions remain as stable uniform suspensions without separation into layers at the end of one weeks storage at room temperature (7075 F.). Moreover, the compositions are highly effective in preventing the redeposition of soil from soiled fabrics as measured by repeat soil redeposition tests. It will be appreciated that in the above examples potassium alkylaryl sulfonates, alkali metal aryl sulfonates, polyphosphates, and alkylolamides other than those specifically given in the examples may be used in lieu thereof as specified hereinabove with the same results. In addition, the optional optical brighteners, dyes, silicates, and alkalies may be readily omitted from the formulations without destroying the essential properties thereof.
  • the different particles merge or react with one another in the aqueous solution to form a network or inter-linking aggregation of particles of one cellulose derivative dispersed within the other, thereby forming a combination of particles which act as a single entity in producing a stable cellulosic suspension.
  • This network of particles having one type of particle dispersed within the other naturally was absent in the case of individual cellulosics and in the case of the cellulosic pairs which formed unstable suspensions.
  • a concentrated heavy duty liquid detergent composition which remains uniform without separation into layers at room temeprature and which is highly effective 1 1 in preventing soil redeposition when used at washing concentrations consisting essentially of an aqueous solution of (1) from about 7% to about 10% of a potassium alkylaryl sulfonate having the general formula Rr-GSOSK where R is an alkyl group containing from 1 to 15 carbon atoms, at least one R having 8 to 15 carbon atoms, and x is a number from 1 to (2) from about 5% to about 8% total of alkali metal aryl sulfonate selected from the group consisting of toluene sulfonate, tetralin sulfonate, ethylbenzene sulfonate, isopropylbenzene sulfonate, ortho-xylene sulfonate, meta-xylene sulfonate, a mixture of 80% toluene sulfonate and 20%
  • a concentrated heavy duty liquid detergent composition which remains uniform without separation into layers at room temperature and which is highly efiective in preventing soil redeposition when used at washing concentrations consisting essentially of an aqueous solution of (1) from about 7% to about 10% of a potassium alkylaryl sulfonate having the general formula where R is an alkyl group containing from 1 to carbon atoms, at least one R having 8 to 15 carbon atoms, and x is a number from 1 to 5; (2) from about 5% to about 8% total'of alkali metal aryl sulfonate selected from the group consisting of toluene sulfonate, tetralin sulfonate, ethylbenzene sulfonate, isopropylbenzene sulfonate, orthoxylene sulfonate, meta-xylene sulfonate, a mixture of 80% toluene sulfonate and ethylbenzen

Description

United States Patent HEAVY DUTY LIQUID DETERGENT COL [POSI- TIONS CONTAINING A PAIR OF CELLULOSIC SOIL SUSPENDING AGENTS Irving Reich, New York, N.Y., and Hans R. Dallenbach,
Coytesville, N.J., assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Filed Apr. 15, 1959, Ser. No. 806,429
9 Claims. (Cl. 252-137) The present invention relates to detergent compositions, and more particularly to concentrated heavy duty liquid detergent compositions which are uniform stable suspensions showing no separation into layers at room temperature and which are highly effective in preventing soil redeposition when used at washing concentrations.
Many detergent compositions have heretofore been prepared, but they have primarily been in a powdered form and thereby have many disadvantages enumerated below. Powdered detergent compositions are generally prepared by spray drying or drum drying, which are costly operations. When used in washing, the powdered detergent compositions must be dissolved to form dilute aqueous washing solutions. This step of dissolving or dispersing the powdered detergent compositions in the wash water is time consuming. Frequently, the powdered detergent compositions are difficultly dispersed, since they may tend to form lumps. Powdered detergent compositions, moreover, tend to vary greatly in density unless particular care is taken in their preparation. Such a variation in density makes it diflicult to determine the exact amount thereof to be employed during washing. In addition, powdered deteregnt compositions may be difiicult to dispense, since they sometimes clog the orifices of a dispenser. Also powdered detergent compositions have a tendency to cake at high humidities upon standing in their open containers. Moreover, powdered detergent compositions, being normally sold in cardboard containers, are subject to spilling and waste in the event an open container is accidentally knocked over. Furthermore, their dustiness may be bothersome, particularly to persons who suffer from dust allergies.
All of these disadvantages of powdered detergent compositions can be obviated by employing concentrated liquid detergent compositions. While light duty liquid detergent compositions have been prepared heretofore, they have proved to be suitable only for dishwashing and the cleaning of fine fabrics. Light duty liquid detergent compositions are unsatisfactory for washing heavily soiled cotton fabrics, since such compositions have inadequate soil removal characteristics. Heavy duty liquid detergent compositions, on the other hand, have excellent soil removal characteristics and are ideally suited for the washing of heavily soiled cotton fabrics and other fabrics.
A highly effective heavy duty liquid detergent composition has been fully described in US. Patent No. 2,859,182 issued November 4, 1958. This homogeneous heavy duty liquid detergent composition consists essentially of an aqueous solution of a potassium alkylaryl sulfonate, an alkali metal aryl sulfonate, tetrapotassium pyrophosphate or pentapotassium tripolyphosphate, and at least one alkylolamide or an ethylene oxide condensation product thereof. The composition may also have present therein alkali metal silicates, alkalies, perfumes, dyes, brighteners, and other compatible adjuvants. Complete details concerning this homogeneous heavy duty liquid detergent composition may readily be obtained by reference to said patent.
This composition could be further improved, if it were possible to incorporate therein soil suspending agents which would prevent or inhibit the redeposition of soil ice upon fabrics Washed repeatedly in diluted wash solutions thereof and thereby avoid greying of the fabrics. Various cellulose derivatives have been used heretofore as soil suspending agents in powdered detergent compositions. The incorporation of a cellulose derivative into a powdered detergent composition presents no particular problem, since the detergent composition is in powdered form. The incorporation of cellulosic soil suspending agents in the above described heavy duty liquid detergent compositions, however, is not a simple matter.
Thus, when one or a mixture of various cellulose derivatives were incorporated in the detergent composition, the cellulosic component separated out within a few hours and the composition became stratified into two or more layers, one being a clear liquid and the others being milky or cloudy. For example, separate samples of the following representative heavy duty liquid detergent formulation were prepared.
In the above formulation Calcofluor MR and Tinopal RBS are optical brighteners which are respectively disodium N:N'-bis-(2,4-diphenylamino-1:3:5-triazyl [6]) 4:4-diamino stilbene 2:2-disulfonate and sodium-2- (stilbyl-4)-(naphtho-l':2':4:5) 1:2:3 triazole-2"-sulfonate.
The 0.5% total (except where otherwise indicated) cellulose derivatives in the separate samples was made up as follows: (1) 100% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit, (2) 100% low viscosity methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule, (3) 100% sodium carboxymethylethylcellulose having 0.22 mole of carboxymethyl groups and 1.0 mole of ethyl groups per anhydroglucose unit, (4) 100% ethylcellulose having 1.26 moles of ethyl groups per anhydroglucose unit, (5) 100% sodium carboxymethylmethylcellulose having 0.150.2 mole of carboxymethyl groups per anhydroglucose unit and 14-22% of methoxyl groups per cellulose molecule (0.25% total cellulose derivatives), (6) 100% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit, (7) 57.1% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit plus 42.9% sodium carboxymethylmethylcellulose having 0.l5-0.2 mole of carboxymethyl groups per auhydroglucose unit and 14-22% of methoxyl groups per cellulose molecule (0.35% total cellulose derivatives), (8) 40% sodium carboxymethylcellulose having 1.94 moles of carboxymethyl groups per anhydroglucose unit plus 60% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% of methoxyl groups per cellulose molecule, (9) sodium carboxymethylhydroxyethylcellulose having 0.36 mole of carboxymethyl and 1.07 moles of hydroxyethyl groups per anhydroglucose unit plus 20% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% of meth- 3 oxyl groups per cellulose molecule, (10) 57.1% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus 42.9% sodium 'ca'rboxymethylmethylcellulose having 0.25 mole of carboxymethyl groups per anhydroglucose unit and 10- 14% of methoxyl groups per cellulose molecule (0.35% total cellulose derivatives), (11) 60% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus 40% sodium carboxymethylethylcellulose having 0.22 mole of carboxymethyl groups and 1.0 mole of ethyl groups per anhydroglucose unit, (12) 80% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus 20% ethylcellulose having 1.26 moles of ethyl groups per anhydroglucose unit, (13) 60% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit plus 40% of sodium carboxymethylethylcellulose having 0.68 mole of carboxymethyl groups and 0.65 mole of ethyl groups per anhydroglucose unit, (14) 100% methylhydroxypropylcellulose having 27-29% methoxyl groups per cellulose molecule and 5.57.5% hydroxypropyl groups per cellulose molecule, (15) 100% methylhydroxypropylcellulose having 2830% methoxyl groups per cellulose molecule and 7-12% hydroxypropyl groups per cellulose molecule, and (16) 100% dihydroxypropylcellulose (6100 centipoise viscosity at 25 I C. in a 2% solution in aqueous sodium hydroxide) having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit. In the three instances where the total cellulose derivatives were lowered below '4 least one alkylolamide or an ethylene Oxide condensation product thereof, and a pair of cellulose derivatives as further described below.
The potassium alkylaryl sulfonates have the general formula R,-@SO:K
where R is an alkyl group, which may be saturated or unsaturated and straight or branched chain, having from 1 to carbon atoms, at least one R having 8 to 15 carbon atoms, x is a number from 1 to 5, and may be an average number. Suitable potassium alkylaryl sulfonates include,
0.5%, the amount of water in the detergent composition was raised a corresponding amount.
' Each of these heavy duty liquid detergent compositions containing either one or a mixture of cellulose derivatives was allowed to age for one week at room temperature (70-75 F.) Within only one to twenty-four hours, v
contained cellulose derivatives, they were completely unsuitable because they were unstable and separated into layers, thereby presenting an unattractive appearance which would be completely unacceptable to a consumer, such as a housewife. Containers of the detergent compositions would have to be shaken prior to use in order to resuspend the separated cellulosics as best as possible and insure that a dosage poured from the containers had the correct amount of cellulosics therein. Moreover, the flecks of cellulosics ultimately combined to form a viscous layer which was hard to resuspend even with vigorous shaking.
' It was found quite surprisingly, however, that a concentrated heavy duty liquid detergent composition could be prepared containing cellulose derivatives as soil suspending agents which would be highly efiective in preventing soil redeposition and greying of fabrics and which would be a stable uniform suspension showing no separation into layers at room temperature over extended periods, provided the cellulose derivative soil suspending agents were incorporated in the heavy duty liquid detergent composition in particular pairs. Accordingly, the heavy duty liquid detergent compositions of'the invention which are stable uniform suspensions showing no separation into layers 'at room temperature and which are highly eifective in preventing soil redeposition when used at washing concentrations consist essentially of an aqueous solution of from about 7% to about 10% of a potassium alkylaryl sulfonate, from about 5% to about 8% total of one or more alkali metal aryl sulfonates,
where R and R' taken together with the remainder of the polypropylene radical form an alkyl group having an i average molecular weight corresponding to from about 12 to about 15 carbon atoms. The potassium alkylaryl sulfonate anionic detergent is used in the composition to supply a portion of the foaming and wetting action necessary in a heavy duty liquid detergent product designed for household use.
The polyphosphate, i.e., tetrapotassium pyrophosphate or pentapotassium tripolyphosphate, is employed in the composition to supply the heavy duty detergent feature of the liquid, and impart good soil removal properties thereto. As the amount of polyphosphate is increased, the amount of potassium alkylaryl sulfonate is decreased.
Suitable alkali metal aryl sulfonate or mixtures thereof totaling from about 5% to about 8% include the following sodium orv potassium aryl sulfonates; toluene sulfonate, tetraliu sulfonate, ethylbenzene sulfonate, isopropylof 15% ortho-xylene sulfonate, 70% meta-xylene sulfonate, and-15% para-xylene sulfonate, a mixture of 47% toluenesulfonate plus 53% of a mixture of 15% ortho-xylene sulfonate, 70% meta-xylene sulfonate, and 15% para-xylene.sulfonate, a mixture of 22% orthoxylene sulfonate,. 53% meta-xylene sulfonate, 5% parafrom about 27% to about 10%, preferably about 20%,
of tetrapotassium pyrophosphate or pentapotassium trixylene sulfonate, 18% ethylbenzene sulfonate, and 2% toluene sulfonate, and a mixture of from about 1% to about 10% toluene sulfonate plus from about 99% to about of a mixture of 22% ortho-xylene sulfonate, 53% meta-xylene sulfonate, 5% para-xylene sulfonate, 18% ethylbenzene sulfonate, and 2% toluene sulfonate. The alkali metal aryl sulfonate is employed in the heavy duty liquid detergent composition to aid in solubilizing the potassium. alkylaryl sulfonate in the presence of a considerable amount of the polyphosphate and other inorganic materials. The alkali .metal aryl sulfonate also solubilizes the alkylolamides which are either insoluble in water or incompatible with aqueous solutions of polyphosphates. Ihere is no advantage in adding more of the alkali metal aryl sulfonate 'than is necessary for its solubilizing eliect,--since this material appears to contribute nothing to the detergent and dishwashing characteristics of the heavy duty liquid detergent composition.
The alkylolamide may be either a monoalkylolamide or a dialkylolamide. Typical examples of siutable alkylolamides are lauric isopropanolamide, lauric diethanolamide, coconut monoethanolamide, capric diethanolamide, tallow diethanolamide, and the monoethanolamide of a 1:1 mixture of caprylic and capric acids. The alkylolamides act as solubilizers in conjunction with the alkali metal aryl sulfonate to prevent the separating out from solution of the potassium alkylaryl sulfonate.
Other suitable alkylolamides which may also be employed include ethylene oxide condensation products thereof, for example, the condensation product of one mole of lauric monoethanolamide with one mole of ethylene oxide and the condensation product of one mole of lauric isopropanolamide with one mole of ethylene oxide. All of the above alkylolamides may be used either singly or in suitable mixtures.
The heavy duty liquid detergent composition also contains a total of from about 0.1% to about 3%, and preferably from about 0.25% to about 1%, and more preferably from about 0.5% to about 0.7%, of a pair of soil suspending cellulose derivatives which are simple or mixed lower alkyl, hydroxyalkyl, or carboxyalkyl ethers of cellulose and form a uniform stable suspension in the aqueous solution. These pairs of cellulosic soil suspending agents include the following: (1) about 9% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit plus about 91% sodium carboxymethylmethylcellulose having 0.15-0.2 mole of carboxymethyl groups per anhydroglucose unit and 14-22% of methoxyl groups per cellulose molecule, (2) about 8% sodium carboxymethylcellulose having 1.94 moles of carboxymethyl groups per anhydroglucose unit plus about 92% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule, (3) about 16% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus about 84% methylcellulose having 3536% methoxyl groups per cellulose molecule, (4) about 20% sodium carboxymethylcellulose having 0.76 mole of carboxymethyl groups per anhydroglucose unit plus about 80% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule, (5) about 22% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus about 78% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5- 32% methoxyl groups per cellulose molecule, (6) about 44% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus about 56% sodium carboxymethylmethylcellulose having 0.25 mole of carboxymethyl groups per anhydroglucose unit and -14% methoxyl groups per cellulose molecule, (7) about 29% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit plus about 71% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% of methoxyl groups per cellulose molecule, (8) about 44% sodium carboxymethylhydroxyethylcellulose having 0.36 mole of carboxymethyl groups per anhydroglucose unit plus about 56% methylcellulose (25 centipoise Viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule, (9) about 44% sodium carboxymethylhydroxyethylcellulose having 0.73 mole of carboxymethyl groups and 0.87 mole of hydroxyethyl groups per anhydroglucose unit plus about 56% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule, (10) about 62% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5 hydroxypropyl groups per cellulose molecule plus about 38% sodium carboxymethyl cellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit, (11) about 72% methylhydroxypropylcellulose (50 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellu-. lose molecule and 5.57.5% hydroxypropyl groups per 'cellulose molecule plus about 28% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit, (12) about 54% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dispersion) having -2830% methoxyl groups per cellulose molecule and 712% hydroxypropyl groups per cellulose molecule plus about 46% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit, (13) about 42% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dispersion) having 2729% methoxyl groups per cellulose molecule and 5.57.5% hydroxypropyl groups per cellulose molecule plus about 58% dihydroxypropylcellulose having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit, (14) about 64% methylhydroxypropylcellulose (50 centipoise viscosity in a 2% aqueous dispersion) having 2729% methoxyl groups per cellulose molecule and 5.57.5% hydroxypropyl groups per cellulose molecule plus about 36% dihydroxypropylcellulose having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit, and (15) from about 70% to about methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 2-7.532% methoxyl groups per cellulose molecule plus from about 30% to about 10% dihydroxypropylcellulose having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit. It will be appreciated that the sodium cation on the carboxymethyl group is equivalent to other cations, such as potassium or ammonium or organic amine cations, such as mono-, di-, or vtri-ethanolamine. The substituent contents given above for the cellulose derivatives are expressed in average values.
The remaining component of the heavy duty liquid detergent composition in water which serves as a solvent for the components thereof.
If desired, the liquid detergent composition may contain minor portions of an alkali, such as potassium hydroxide, to neutralize any excess acid impurities present in the components of the composition. In addition, minor portions of compatible perfumes, dyes, optical brighteners, alkali metal silicates, and other desirable adjuvants may be added to the composition. When a water-soluble alkali metal silicate is added to the composition, the pH thereof must be adjusted to about 11.4 or above by the addition of free alkali, such as potassium hydroxide, to keep the silicate in solution. Typical alkali metal silicates include the sodium or potassium silicates having the following alkali to silica ratios 1:3.92, 1:3.45, 122.4, 1:1.8, 1:25, and 1:20. An amount up to about 6% on a solids basis of the silicate may be employed.
The concentrated heavy duty liquid detergent compo sition of the invention may be prepared by mixing the components thereof together in the aqueous medium. Heat may be conveniently utilized during the mixing of the components to increase the rate of dissolution thereof. A preferred method for the preparation of the stable and uniform heavy duty liquid detergent composition is the addition of the pair of cellulose derivatives to hot Water followed by cooling to form an aqueous solution thereof and the addition to the cellulose solution of an aqueous solution of the potassium alkylaryl sulfonate, alkali metal aryl sulfonate, alkylolamide or ethylene oxide condensation product thereof, and any optical brighteners, dyes, alkali, and alkali metal silicates. The composition is completed by the addition thereto of the tetrapotassium pyrophosphate or pentapotassium tripolyphosphate to give a composition having a pH of about 12. The heavy duty liquid detergent composition of the invention will be further illustrated by the following examples.
A representative heavy duty liquid detergent composition was prepared having the following formula:
Components Percent by weight Potassium dodecylbenzene sulfonate 1O Tetrapotassium pyrophosphate 19.1 Sodium xylene sulfonate (commercial) 8. 15 Laurie dief'hannlm'nirio 8 Laurie isoprop 3. 2 Sodium silicate (87%) (N BaQZSlOz of 1:2.5) 7. Calcofluor MR 0. 031 Tinopal RIBS 0. 048 Water plus KOH to pH 12.1- 48.171 Total cellulose derivatives 1 0. 50
Total. 100.000
1 Except where otherwise indicated.
Example 1 In this example the 0.5% total cellulosics of the representative formula consisted of 8% sodium carboxymethylcellulose (70 centipoise viscosity in a 2% aqueous dispersion) having 1.94 moles of carboxymethyl groups per anhydroglucose unit plus 92% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule.
Example 3 In this example the 0.5 total cellulosics of the representative formula consisted of 16% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 moles of carboxymethyl groups per anhydroglucose unit plus 84% methylcellulose having 35-36% methoxyl groups per cellulose molecule.
Example 4 In this example the 0.5 total cellulosics of the representative formula consisted of 20% sodium carboxymethylcellulose (3600 centipoise viscosity in a 1% aqueous dispersion) having 0.76 moles of carboxymethyl groups per anhydroglucose unit plus 80% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule.
Example 5 In this example the 0.5 total cellulosics of the representative formula consisted of 22.6% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups 'per anhydroglucose unit plus 77.4% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule.
Example 6 In this example the total cellulosics of the representative formula was 0.32% and consisted of 43.7% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus 56.3% sodium car- 'boxymethylmethylcellulose having 0.25 mole of carboxymethyl groups per anhydroglucose unit and 10-14% methoxyl groups per cellulose molecule. The water in the formula was increased in an amount correspond ing to the decrease in cellulosic content.
Example 7 In this example the 0.5% total cellulosics consisted of 28.6% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl, groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit plus 71.4% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule.
Example 8 In this example the 0.5% total cellulosics of the representative formula consisted of 44% sodium carboxymethylhydroxyethylcellulose having 0.36 mole of carboxymethyl groups and 1.07 moles of hydroxyethyl groups per anhydroglucose unit plus 56% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5-32% methoxyl groups per cellulose molecule.
Example 9 In this example the 0.5 total cellulosics in the representative formula consisted of 44% sodium carboxymethylhydroxyethylcellulose having 0.73 mole of carboxymethyl groups and 0.87 mole of hydroxyethyl groups per anhydroglucose unit plus 56% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.5- 32% methoxyl groups per cellulose molecule.
Example 10 In this example the total cellulosics in the above representative heavy duty liquid detergent formulation was increased to 0.7% with a decrease of 0.2% in the water content. The 0.7% total cellulosics consisted of 30% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule.
Example 11 In this example the 0.5% total cellulosics in the repre sentative formula consisted of 62% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5% hydroxypropyl groups per cellulose molecule plus 38% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups per anhydroglucose unit.
Example 12 In this example the 0.5 total cellulosics in the representative formula consisted of 72% methylhydroxypropylcellulose (50 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5% hydroxypropyl groups per cellulose molecule plus 28% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 0.7 mole of carboxymethyl groups per anhydro-' glucose unit.
Example 13 In this example the 0.5 total cellulosics in the representative formula consisted of 54% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dis persion) having 2830% methoxyl groups per cellulose molecule and 7-12% hydroxypropyl groups per cellulose molecule plus 46% sodium carboxymethylcellulose (27 centipoise viscosity in a 2% aqueous dispersion) having 07 mole of carboxymethyl groups per anhydroglucose unit.
Example 14 In this example the 0.5 total cellulosics in the repre- 'Teu-apotassium Pyrophosphate sentative formula consisted of 42% methylhydroxypropylcellulose (4000 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5 hydroxypropyl groups per cellulose molecule plus 58% dihydroxypropylcellulose (6100 centipoise viscosity at 25 C. in a 2% solution in 5% aqueous sodium hydroxide) having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit.
Example 15 In this example the 0.5% total cellulosics in the representative formula consisted of 64% methylhydroxypropylcellulose (50 centipoise viscosity in a 2% aqueous dispersion) having 27-29% methoxyl groups per cellulose molecule and 5.5-7 .5-% hydroxypropyl groups per cellulose molecule plus 36% dihydroxypropylcellulose (6100 centipoise viscosity at 25 C. in a 2% solution in 5% aqueous sodium hydroxide) having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit.
Example 16 In this example the 0.5 total cellulosics in the representative formula consisted of 70% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule plus 30% dihydroxypropylcellulose 6100 centipoise viscosity at 25 C. in a 2% solution in 5% aqueous sodium hydroxide) having 0.3 mole of dihydroxypropyl groups per .anhydroglucose unit.
Example 17 In this example the 0.5% total cellulosics in the repre-. sentative formula consisted of 90% methylcellulose (25 centipoise viscosity in a 2% aqueous dispersion) having 27.532% methoxyl groups per cellulose molecule plus dihydroxypropylcellulose (6100 centipoise viscosity at 25 C. in a 2% solution in 5% aqueous sodium hydroxide having 0.3 moles of dihydroxypropyl groups per anhydroglucose unit.
At the end of one weeks storage at room temperature (70-75 F.) all of the compositions in Examples 1 through 17 were still uniform stable suspensions and showed no evidence of separation into layers. Some of these compositions were stored for several months at room temperature and at the end of this period they were still uniform stable suspensions. Repeat soil redeposition tests showed that all of these compositions were highly etfective in preventing soil redeposition and greying of fabrics. There is reproduced below the data pertaining to a home laundry repeat washing test utilizing two typical heavy duty liquid detergent compositions of the invention containing pairs of cellulose derivatives and a composition without the presence of a pair of cellulose derivatives as a basis of comparison. In this test broadcloth was subjected to a large number of repeat washings in the presence of naturally soiled cloth. The reflectance values of the test cloths were read with a General Electric reflectometer, since this apparatus uses a narrow band of the visible spectrum only and accordingly the presence of optical brighteners or fluorescent whitening agents in the tested detergent formulations does not affect the measured reflectance values. The detergent compositions were as follows:
bat
Potassium Dodeeylbenzene Sulfonate Sodium Xylene Sulfonate (Commercial) Laurie Diethanolamide Laurie Isoptopanolamide" Sodium Silicate. (37%) (NazOZSiOz of 1:2.5)- Calcofluor MR Tlno RBS Water-l-KOH to pH 12.1-.- Total Cellulose Derivatives Reflectance Values Composition 5 Washes 10 Washes 20Washes A i 84. 5 80. 3 78. 4 B 84. 2 81. 7 80. 4 O 85. 0 83. 5 81. 2
The higher reflectance values for the cloth washed 10 or 20 times in the compositions of the invention (compositions B and C) compared with composition A clearly show the compositions of the invention are highly effective in preventing soil redeposition and greying of fabrics, since they show a significant improvement even at the low levels of total soil available from naturally soiled cloth.
The above examples clearly illustrate that the heavy duty liquid detergent compositions of the invention contain pairs of cellulose derivatives as soil suspending agents, and yet the compositions remain as stable uniform suspensions without separation into layers at the end of one weeks storage at room temperature (7075 F.). Moreover, the compositions are highly effective in preventing the redeposition of soil from soiled fabrics as measured by repeat soil redeposition tests. It will be appreciated that in the above examples potassium alkylaryl sulfonates, alkali metal aryl sulfonates, polyphosphates, and alkylolamides other than those specifically given in the examples may be used in lieu thereof as specified hereinabove with the same results. In addition, the optional optical brighteners, dyes, silicates, and alkalies may be readily omitted from the formulations without destroying the essential properties thereof.
It is not clearly understood at this time why individual cellulose derivatives do not form stable suspensions in. the heavy duty liquid detergent composition nor why certain pairs of cellulose derivatives do form stable suspensions in the heavy duty liquid detergent composition while other pairs of cellulose derivatives are unstable in the heavy duty liquid detergent composition and cause undesirable stratification. It is apparent from photomicrographic studim, however, that the heavy duty liquid detergent compositions of the invention have the cellulosic particles present therein in a distinctive form. It was observed that in the cellulose derivative pairs of the invention, the different particles merge or react with one another in the aqueous solution to form a network or inter-linking aggregation of particles of one cellulose derivative dispersed within the other, thereby forming a combination of particles which act as a single entity in producing a stable cellulosic suspension. This network of particles having one type of particle dispersed within the other naturally was absent in the case of individual cellulosics and in the case of the cellulosic pairs which formed unstable suspensions.
This application is a continuation-in-part of our copending application Serial No. 619,931, filed November 2, 1956, and now abandoned.
Various modifications and changes may be made in the compositions of this invention without departing from the spirit thereof, and accordingly it will be understood that the invention is to be limited only Within the scope of the appended claims.
We claim:
1. A concentrated heavy duty liquid detergent composition which remains uniform without separation into layers at room temeprature and which is highly effective 1 1 in preventing soil redeposition when used at washing concentrations consisting essentially of an aqueous solution of (1) from about 7% to about 10% of a potassium alkylaryl sulfonate having the general formula Rr-GSOSK where R is an alkyl group containing from 1 to 15 carbon atoms, at least one R having 8 to 15 carbon atoms, and x is a number from 1 to (2) from about 5% to about 8% total of alkali metal aryl sulfonate selected from the group consisting of toluene sulfonate, tetralin sulfonate, ethylbenzene sulfonate, isopropylbenzene sulfonate, ortho-xylene sulfonate, meta-xylene sulfonate, a mixture of 80% toluene sulfonate and 20% ethylbenzene sulfonate, a mixture of 61% ortho-xylene sulfonate and 39% isopropylbenzene sulfonate, a mixture of 15% orthoxylene sulfonate, 70% meta-xylene sulfonate, and 15% para-xylene sulfonate, a mixture of 47% toluene sulfonate plus 53% of a mixture of 15 ortho-xylene sulfonate, 70% meta-xylene sulfonate, and 15% para-xylene sulfonate, a mixture of 22% ortho-xylene sulfonate, 53% meta-xylene sulfonate, 5% para-xylene sulfonate, 18% ethylbenzene sulfonate, and 2% toluene sulfonate, and a mixture of from about 1% to about toluene sulfonate plus from about 99% to about 90% of a mixture of 22% ortho-xylene sulfonate, 53% meta-xylene sulfonate, 5% para-xylene sulfonate, 18% ethylbenzene sulfonate, and 2% toluene sulfonate; (3) from about 27% to about 10% of a potassium polyphosphate selected from the group consisting of tetrapo-tassium pyrophosphate and pentapotassium tripolyphosphate; (4) from about 4% to about 7% total of at least one compound selected from the group consisting of lauric isopropanolamide, lauric diethanolamide, coconut monoethanolamide, capric diethanolarnide, tallow diethanolamide, the monoethanolamide of a 1:1 mixture of caprylic and capric acids, the condensation product of one mole of lauric monoethanolamide with one mole of ethylene oxide, and the condensation product of one mole of lauric isopropanolamide with one mole of ethylene oxide; and (5 and 6) from about 0.1% to about 3% total of a pair of soil suspending cellulose ethers selected from the group consisting of simple and mixed lower alkyl, hydroxyalkyl, and carboxyalkyl ethers of cellulose, which ethers form with One another in the aqueous solution a network of particles of one cellulose ether dispersed within the other.
2. A concentrated heavy duty liquid detergent composition which remains uniform without separation into layers at room temperature and which is highly efiective in preventing soil redeposition when used at washing concentrations consisting essentially of an aqueous solution of (1) from about 7% to about 10% of a potassium alkylaryl sulfonate having the general formula where R is an alkyl group containing from 1 to carbon atoms, at least one R having 8 to 15 carbon atoms, and x is a number from 1 to 5; (2) from about 5% to about 8% total'of alkali metal aryl sulfonate selected from the group consisting of toluene sulfonate, tetralin sulfonate, ethylbenzene sulfonate, isopropylbenzene sulfonate, orthoxylene sulfonate, meta-xylene sulfonate, a mixture of 80% toluene sulfonate and ethylbenzene sulfonate, a mixture of 61% ortho-xylene sulfonate and 39% isopropylbenzene sulfonate, a mixture of 15% ortho-xylene sulfonate, 70% meta-xylene sulfonate, and 15% paraxylene sulfonate, a mixture of 47% toluene sulfonate plus 53% of a mixture of 15% ortho-xylene sulfonate, 70% meta-xylene sulfonate, and 15% paraxylene sulfonate, a mixture of 22% ortho-xylene sulfonate, 53% meta-xylene sulfonate, 5% para-xylene sulfonate, 18% ethylbenzene sulfonate, and 2% toluene sulfonate, and a mixture of -f rom about 1% to about 10% toluene su]fo (5 12 nate plus from about 99% to about 90% of a mixture of 22% ortho-xylene sulfonate, 53% meta-xylene sulfonate, 5% para-xylene sulfonate, 18% ethylbenzene sulfonate, and 2% toluene sulfonate; (3) from about 27% to about 10% of a potassium polyphosphate selected from the group consisting of tetrapotassium pyrophosphate and pentapotassium tripolyphosphate; (4) from about 4% to about 7% total of at least one compound selected from the group consisting of lauric isopropanolamide, lauric diethanolamide, coconut monoethanolamide, capric diethanolarnide, tallow diethanolamide, the monoethanolamide of a 1:1 mixture of caprylic and capric acids, the condensation product of one mole of lauric monoethanolamide with one mole of ethylene oxide, and the condensation product of one mole of lauric isopropanolamide with one mole of ethylene oxide; and (5 and 6) from about 0.1% to about 3% total of a pair of cellulose derivatives selected from the group consisting of about 9% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit plus about 91% sodium carboxymethylmethylcellulose having 0.l5-0.2 mole of carboxymethyl groups per anhydroglucose unit and 14- 22% of methoxyl groups per cellulose molecule, about 8% sodium carboxymethylcellulose having 1.94 moles of carboxymethyl groups per anhydroglucose unit plus about 92% methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.5-32% methoxyl groups per cellulose molecule, about 16% sodium carboxymethylcellulose hazving 0.7 mole of carboxymethyl groups per anhydroglucose unit plus about 84% methylcellulose having 3536% methoxyl groups per cellulose molecule, about 20% sodium carboxymethylcellulose having 0.76 mole of carboxylmethyl groups per anhydroglucose unit plus about methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.532% methoxyl groups per cellulose molecule, about 22% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus about 78% methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.5-32% methoxyl groups per cellulose molecule, about 44% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus about 56% sodium carboxymethylmethylcellulose having 0.25 mole of carboxymethyl groups per anhydroglucose unit and 1014% methoxyl groups per cellulose molecule, about 29% sodium' carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50 mole hydroxyethyl groups per anhydroglucose unit plus about 71% methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.5- 32% methoxyl groups per cellulose molecule, about 44% sodiumcarboxymethylhydroxyethylcellulose having 0.36 mole of carboxymethyl groups and 1.07 moles of hydroxyethyl groups per anhydroglucose unit plus about 56% methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.532% methoxyl groups per cellulose molecule, about 44% sodium carboxymethylhydroxyethyleellulose having 0.73 mole of carboxymethyl groups and 0.87 mole of hydroxyethyl groups per anhydroglucose unit plus about 56% methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.5-32% methoxyl groups per cellulose molecule, about 62% methylhydroxypropylcellulose of 4000 centipoise viscosity in a 2% aqueous dispersion having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5 hydroxypropyl groups per cellulose molecule plus about 38% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit, about 72% methylhydroxypropylcellulose of 50 centipoise viscosity in a 2% aqueous dispersion having 27-29% methoxyll groups per celluose molecule and 5.57.5% hydroxypropyl groups per cellulose molecule plus about 28% sodium carboxymethylcellulose having 07 mole of carboxymethyl groups per anhydroglucose unit, about 54% methylhydroxypropylcellulose of 4000 centipoise viscosity in a 2% aqueous dispersion having 28-30% methoxyl groups per cellulose molecule and 7-12% hydroxypropyl groups per cellulose molecule plus about 46% sodium carboxylmethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit, about 42% methylhydroxypropylcelluose of 4000 centipoise viscosity in a 2% aqueous dispersion having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5% hydroxypropyl groups per cellulose molecule plus about 58% dihydroxypropylcellulose having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit, about 64% methylhydroxypropylcellulose of 50 centipoise viscosity in a 2% aqueous dispersion having 27-29% methoxyl groups per cellulose molecule and 5.5-7.5% hydroxypropyl groups per cellulose molecule plus about 36% dihydroxypropylcellulose having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit and from about 70% to about 90% methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.532% methoxyl groups per cellulose molecule plus from about 30% to about 10% dihydroxypropylcellulose having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit.
3. A concentrated heavy duty liquid detergent composition as set forth in claim 2 wherein the pair of cellulose derivatives totals about 0.5%.
4. A concentrated heavy duty liquid detergent composition as set forth in claim 2 wherein the pair of cellulose derivatives totals about 0.7% and consists of about 30% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus about 70% methylcellulose having a viscosity of 25 centipoises in a 2% aqueous dispersion and having 27.532% methoxyl groups per cellulose molecule.
5. A concentrated heavy duty liquid detergent composition as set forth in claim 3 wherein the pair of cellulose derivatives is about 22% sodium carboxymethylcellulose having 0.7 mole of carboxymethyl groups per anhydroglucose unit plus about 78% methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.5- 32% methoxyl groups per cellulose molecule.
6. A concentrated heavy duty liquid detergent composition as set forth in claim 3 wherein the pair of cellulose '14 derivatives is about 8% sodium carboxymethylcellulos having 1.94 moles of carboxymethyl groups per anhydroglucose unit plus about 92% methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.5- 32% methoxyl groups per cellulose molecule.
7. A concentrated heavy duty liquid detergent composition as set forth in claim 3 wherein the pair of cellulose derivatives is about 29% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxy-methyl groups and 0.50 mole of hydroxyethyl groups per anhydroglucose unit plus about 71% methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.5- 32% methoxyl groups per cellulose molecule.
8. A concentrated heavy duty liquid detergent compo sition as set forth in claim 3 wherein the pair of cellulose derivatives is about 9% sodium carboxymethylhydroxyethylcellulose having 0.91 mole of carboxymethyl groups and 0.50 mole of hydroxyet-hyl groups per anhydroglucose unit plus about 91% sodium carboxymethylmethylcellulose having 0.150.2 mole of carboxymethyl groups per anhydroglucose unit and 14-22% methoxyl groups per cellulose molecule.
9. A concentrated heavy duty liquid detergent composition as set forth in claim 3 wherein the pair of cellulose derivatives is from about to about methylcellulose of 25 centipoise viscosity in a 2% aqueous dispersion having 27.5-32% methoxyl groups per cellulose molecule plus from about 30% to about 10% dihydroxypropylcellulose having a viscosity of 6100 centipoises at 25 C. in a 2% solution in 5% aqueous sodium hydroxide and having 0.3 mole of dihydroxypropyl groups per anhydroglucose unit.
References Cited in the file of this patent UNITED STATES PATENTS Re. 23,840 Vitale et a1. June 15, 1954 2,581,677 Machlis et a1 Jan. 8, 1952 2,618,632 Klug Nov. 18, 1952 2,733,214 Vitale et a1. Jan. 31, 1956 2,860,107 Lamberti et a1 Nov. 11, 1958 FOREIGN PATENTS 678,445 Great Britain Sept. 3, 1952

Claims (1)

1. A CONCENTRATED HEATY DUTY LIQUID DETERGENT COMPOSITION WHICH REMAINS UNIFORM WITHOUT SEPARATION INTO LAYERS AT ROOM TEMPERATURE AND WHICH IS HIGHLY EFFECTIVE IN PREVENTING SOIL REDEPOSITION WHEN USED AT WASHING CONCENTRATIONS CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTION OF (1) FROM ABOUT 7% TO ABOUT 10% OF A POTASSIUM ALKYLARYL SULFONATE HAVING THE GENERAL FORMULA
US806429A 1959-04-15 1959-04-15 Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents Expired - Lifetime US2994665A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US806429A US2994665A (en) 1959-04-15 1959-04-15 Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US806429A US2994665A (en) 1959-04-15 1959-04-15 Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents

Publications (1)

Publication Number Publication Date
US2994665A true US2994665A (en) 1961-08-01

Family

ID=25194025

Family Applications (1)

Application Number Title Priority Date Filing Date
US806429A Expired - Lifetime US2994665A (en) 1959-04-15 1959-04-15 Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents

Country Status (1)

Country Link
US (1) US2994665A (en)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3175978A (en) * 1962-06-01 1965-03-30 California Research Corp Light duty liquid detergent
US3211660A (en) * 1961-02-03 1965-10-12 Colgate Palmolive Co Liquid detergent composition
US3232880A (en) * 1961-04-10 1966-02-01 Ultra Chemical Works Inc Liquid detergent composition
US3254028A (en) * 1961-02-06 1966-05-31 Colgate Palmolive Co Liquid detergent composition
US3269468A (en) * 1962-07-20 1966-08-30 Continental Oil Co Foaming agents for use in air drilling of wells
US3280026A (en) * 1963-12-30 1966-10-18 Dow Chemical Co Viscous cellulose ether compositions
US3325416A (en) * 1963-10-01 1967-06-13 Colgate Palmolive Co Synthetic gum dispersions
US3354091A (en) * 1959-12-22 1967-11-21 Colgage Palmolive Company Homogeneous heavy-duty liquid detergent
US3393154A (en) * 1965-10-23 1968-07-16 Colgate Palmolive Co Pearlescent liquid detergent compositions
US3920561A (en) * 1974-07-15 1975-11-18 Procter & Gamble Composition for imparting softness and soil release properties to fabrics
US3953380A (en) * 1970-10-28 1976-04-27 Colgate-Palmolive Company Liquid detergent
US3954642A (en) * 1972-12-02 1976-05-04 Henkel & Cie Gmbh Impregnated textile fibrous structures for cleaning purposes
US3956155A (en) * 1972-12-02 1976-05-11 Henkel & Cie G.M.B.H. Textile fibrous cleaning structures
US4048433A (en) * 1976-02-02 1977-09-13 The Procter & Gamble Company Cellulose ethers having a low molecular weight and a high degree of methyl substitution
US4127495A (en) * 1978-01-19 1978-11-28 Hercules Incorporated Non-built liquid detergents
US4174305A (en) * 1975-04-02 1979-11-13 The Procter & Gamble Company Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents
US4235735A (en) * 1979-07-30 1980-11-25 Milliken Research Corporation Laundry detergent containing cellulose acetate anti-redeposition agent
US4379059A (en) * 1980-11-07 1983-04-05 Lever Brothers Company Fabric softening composition and a process for preparing it from cationic surfactant and thickener
EP0100125A2 (en) * 1982-07-27 1984-02-08 THE PROCTER & GAMBLE COMPANY Liquid detergent compositions comprising coacervate mixture of alkylcellulose and carboxymethylcellulose and method for preparing them
US4465619A (en) * 1981-11-13 1984-08-14 Lever Brothers Company Built liquid detergent compositions
US4532067A (en) * 1984-01-11 1985-07-30 Lever Brothers Company Liquid detergent compositions containing hydroxypropyl methylcellulose
US4800037A (en) * 1987-06-05 1989-01-24 Lever Brothers Company Process for making a heavy duty liquid detergent composition
CH680734A5 (en) * 1989-10-12 1992-10-30 Laredj Sekkiou
US5332528A (en) * 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
US5837666A (en) * 1994-06-30 1998-11-17 The Procter & Gamble Company Detergent compositions comprising methyl cellulose ether
WO2007098862A1 (en) * 2006-02-28 2007-09-07 Henkel Ag & Co. Kgaa Graying-inhibiting liquid washing composition
WO2012022736A1 (en) 2010-08-18 2012-02-23 Unilever Plc Fabric treatment compositions comprising targeted benefit agents
WO2013026656A1 (en) 2011-08-24 2013-02-28 Unilever Plc Benefit agent delivery particles comprising dextran
WO2013026657A1 (en) 2011-08-24 2013-02-28 Unilever Plc Benefit agent delivery particles comprising non-ionic polysaccharides
WO2015091109A1 (en) * 2013-12-19 2015-06-25 Henkel Ag & Co. Kgaa Hpmc-containing liquid laundry detergent

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2581677A (en) * 1952-01-08 Phosphate detergent composition in
GB678445A (en) * 1949-05-27 1952-09-03 Frederick Joseph Pollok Improvements in or relating to aqueous solutions containing soapless detergents
US2618632A (en) * 1949-04-05 1952-11-18 Hercules Powder Co Ltd Mixed cellulose ether and preparation thereof
USRE23840E (en) * 1950-05-03 1954-06-15 Liquid anionic-dialkylolamide
US2733214A (en) * 1956-01-31 Synthetic detergent compositions
US2860107A (en) * 1957-07-25 1958-11-11 Lever Brothers Ltd Controlled sudsing heavy duty liquid detergent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2581677A (en) * 1952-01-08 Phosphate detergent composition in
US2733214A (en) * 1956-01-31 Synthetic detergent compositions
US2618632A (en) * 1949-04-05 1952-11-18 Hercules Powder Co Ltd Mixed cellulose ether and preparation thereof
GB678445A (en) * 1949-05-27 1952-09-03 Frederick Joseph Pollok Improvements in or relating to aqueous solutions containing soapless detergents
USRE23840E (en) * 1950-05-03 1954-06-15 Liquid anionic-dialkylolamide
US2860107A (en) * 1957-07-25 1958-11-11 Lever Brothers Ltd Controlled sudsing heavy duty liquid detergent

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3354091A (en) * 1959-12-22 1967-11-21 Colgage Palmolive Company Homogeneous heavy-duty liquid detergent
US3211660A (en) * 1961-02-03 1965-10-12 Colgate Palmolive Co Liquid detergent composition
US3254028A (en) * 1961-02-06 1966-05-31 Colgate Palmolive Co Liquid detergent composition
US3232880A (en) * 1961-04-10 1966-02-01 Ultra Chemical Works Inc Liquid detergent composition
US3175978A (en) * 1962-06-01 1965-03-30 California Research Corp Light duty liquid detergent
US3269468A (en) * 1962-07-20 1966-08-30 Continental Oil Co Foaming agents for use in air drilling of wells
US3325416A (en) * 1963-10-01 1967-06-13 Colgate Palmolive Co Synthetic gum dispersions
US3280026A (en) * 1963-12-30 1966-10-18 Dow Chemical Co Viscous cellulose ether compositions
US3393154A (en) * 1965-10-23 1968-07-16 Colgate Palmolive Co Pearlescent liquid detergent compositions
US3953380A (en) * 1970-10-28 1976-04-27 Colgate-Palmolive Company Liquid detergent
US3954642A (en) * 1972-12-02 1976-05-04 Henkel & Cie Gmbh Impregnated textile fibrous structures for cleaning purposes
US3956155A (en) * 1972-12-02 1976-05-11 Henkel & Cie G.M.B.H. Textile fibrous cleaning structures
US3920561A (en) * 1974-07-15 1975-11-18 Procter & Gamble Composition for imparting softness and soil release properties to fabrics
US4174305A (en) * 1975-04-02 1979-11-13 The Procter & Gamble Company Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents
US4048433A (en) * 1976-02-02 1977-09-13 The Procter & Gamble Company Cellulose ethers having a low molecular weight and a high degree of methyl substitution
US4127495A (en) * 1978-01-19 1978-11-28 Hercules Incorporated Non-built liquid detergents
US4235735A (en) * 1979-07-30 1980-11-25 Milliken Research Corporation Laundry detergent containing cellulose acetate anti-redeposition agent
US4379059A (en) * 1980-11-07 1983-04-05 Lever Brothers Company Fabric softening composition and a process for preparing it from cationic surfactant and thickener
US4465619A (en) * 1981-11-13 1984-08-14 Lever Brothers Company Built liquid detergent compositions
EP0100125A2 (en) * 1982-07-27 1984-02-08 THE PROCTER & GAMBLE COMPANY Liquid detergent compositions comprising coacervate mixture of alkylcellulose and carboxymethylcellulose and method for preparing them
EP0100125A3 (en) * 1982-07-27 1986-09-10 The Procter & Gamble Company Liquid detergent compositions comprising coacervate mixture of alkylcellulose and carboxymethylcellulose and method for preparing them
US4532067A (en) * 1984-01-11 1985-07-30 Lever Brothers Company Liquid detergent compositions containing hydroxypropyl methylcellulose
US4800037A (en) * 1987-06-05 1989-01-24 Lever Brothers Company Process for making a heavy duty liquid detergent composition
CH680734A5 (en) * 1989-10-12 1992-10-30 Laredj Sekkiou
US5332528A (en) * 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
US5837666A (en) * 1994-06-30 1998-11-17 The Procter & Gamble Company Detergent compositions comprising methyl cellulose ether
US7883549B2 (en) * 2006-02-28 2011-02-08 Henkel Ag & Co. Kgaa Graying-inhibiting liquid washing composition
US20080313819A1 (en) * 2006-02-28 2008-12-25 Josef Penninger Graying-inhibiting liquid washing composition
WO2007098862A1 (en) * 2006-02-28 2007-09-07 Henkel Ag & Co. Kgaa Graying-inhibiting liquid washing composition
WO2012022736A1 (en) 2010-08-18 2012-02-23 Unilever Plc Fabric treatment compositions comprising targeted benefit agents
US8637445B2 (en) 2010-08-18 2014-01-28 Conopco Inc. Fabric treatment compositions comprising targeted benefit agents
US9334469B2 (en) 2010-08-18 2016-05-10 Conopco, Inc. Fabric treatment compositions comprising targeted benefit agents
WO2013026656A1 (en) 2011-08-24 2013-02-28 Unilever Plc Benefit agent delivery particles comprising dextran
WO2013026657A1 (en) 2011-08-24 2013-02-28 Unilever Plc Benefit agent delivery particles comprising non-ionic polysaccharides
US9351910B2 (en) 2011-08-24 2016-05-31 Conopco, Inc. Benefit agent delivery particles comprising dextran
WO2015091109A1 (en) * 2013-12-19 2015-06-25 Henkel Ag & Co. Kgaa Hpmc-containing liquid laundry detergent

Similar Documents

Publication Publication Date Title
US2994665A (en) Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents
US3144412A (en) Solid detergent compositions
US3843563A (en) Detergent compositions
US4255294A (en) Fabric softening composition
US3771951A (en) Improved process for washing polyester materials
US2859182A (en) Heavy duty liquid detergent composition
US3325414A (en) Heavy duty detergent composition containing a quaternary ammonium salt
US3254028A (en) Liquid detergent composition
US4605506A (en) Fabric softening built detergent composition
EP0023361A1 (en) Laundry detergent containing anti-redeposition agent
US3354091A (en) Homogeneous heavy-duty liquid detergent
US3211660A (en) Liquid detergent composition
SE430075B (en) DETERGENT COMPOSITION FOR COMPRESSION OF TRANSFER TRANSFER WHEN WASHING TEXTILES
JPH0258319B2 (en)
JP2682534B2 (en) Paste-like low-foaming phosphorus-free detergent
CA1079152A (en) Liquid laundry detergent
US3953382A (en) Detergent compositions
US3075922A (en) Prepartion of liquid detergent compositions
US4056355A (en) Detergent formulations and their use
FI81376B (en) BENTONIT INNEHAOLLANDE, TEXTILUPPMJUKANDE, FLYTANDE TVAETTMEDELSKOMPOSITION.
US3101324A (en) Liquid detergent composition
US2746932A (en) Synthetic detergent compositions
US2860107A (en) Controlled sudsing heavy duty liquid detergent
US3282852A (en) Heavy duty liquid detergents
AU596089B2 (en) Fabric softening and antistatic liquid detergent compositions