US3853779A - Low foaming detergent compositions - Google Patents

Low foaming detergent compositions Download PDF

Info

Publication number
US3853779A
US3853779A US00410502A US41050273A US3853779A US 3853779 A US3853779 A US 3853779A US 00410502 A US00410502 A US 00410502A US 41050273 A US41050273 A US 41050273A US 3853779 A US3853779 A US 3853779A
Authority
US
United States
Prior art keywords
detergent
percent
amine
nonionic
compositions
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
US00410502A
Inventor
J Inamorato
R Hunter
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.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive 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
Priority to AU55033/73A priority Critical patent/AU5503373A/en
Priority to DE2323326A priority patent/DE2323326A1/en
Priority to CA172,998A priority patent/CA992833A/en
Priority to FR7320299A priority patent/FR2187898B1/fr
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US00410502A priority patent/US3853779A/en
Application granted granted Critical
Publication of US3853779A publication Critical patent/US3853779A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0026Low foaming or foam regulating compositions
    • 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
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines

Definitions

  • ABSTRACT non-foaming detergent compositions which include nonionic or mixtures of nonionic and anionic detergent, builder salt, and higher alkyl amine, the amine being present in sufficient proportion to make a combination of synthetic detergent and builder non-foaming or essentially non-foaming in wash waters of usual dilutions for washing machine use.
  • the invention relates to compositions in which the nonionic synthetic detergent is a higher alkoxy polyethoxy ethanol, the anionic synthetic detergent is a higher alkyl benzene sulfonate, the builder is or includes an alkali metal polyphosphate, and the amine anti-foam additive is a di-higher alkyl amine.
  • the compositions are effective laundering agents, primarily intended for use in automatic washing machines and in almost all practical uses are non-foaming, even when used in the normally foam generating horizontal tumbler type of washing machine.
  • the present invention relates to new synthetic detergent compositions and more particularly to compositions based on anionic detergents, nonionic detergents, and mixtures thereof having improved properties.
  • Aqueous solutions of these detergent compositions are characterized by a very low degree of foam formation under conditions of vigorous and continuous agitation.
  • compositions of the present invention not only do not foam excessively, but they also have superior detersive properties.
  • the presence of certain dialkylamines in detergent compositions consisting essentially of anionic sulfated and sulfonated and nonionic surfactants is effective to achieve a significant enhancement in surface-active properties and a reduction in foaming.
  • the improved detergent compositions include water-soluble anionic and nonionic surfactants and mixtures thereof, alkaline builder salts, and a minor proportion of a dialkylamine effective to suppress the formation of foam in the detergent compositions.
  • the new detergent compositions generate less foam than current available products, and prevent overfoaming in soft water areas.
  • the new detergent compositions permit the consumer to use higher levels of detergent before over-foaming occurs.
  • Illustrative of the foam suppressing additives of the present invention are the dialkyl amines wherein the alkyl substituents have between 8 and 18 carbon atoms. Suitable examples of such compounds include dicocoamine, di hydrogenated tallow amine, di soya amine, and di (2 ethyl hexyl) amine.
  • compositions of the present invention contain as the active ingredient the anionic sulfated and sulfonated detergents, nonionic detergents, and mixtures thereof.
  • the anionic sulfated and sulfonated detergents include the aliphatic sulfated or sulfonated compounds, such as the aliphatic acyl-containing compounds wherein the acyl radical has between 8 and 22 carbon atoms, and more particularly, the aliphatic carboxylic ester type, containing at least about 10 and preferably between 12 and 26 carbon atoms in the molecule.
  • the aliphatic detersive compounds it is preferred to use the sulfonated aliphatic compounds having between 12 and 22 carbon atoms.
  • aliphatic detergents may be found the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e.g. coconut oil monoglyceride monosulfate; the long chain pure or mixed higher alkyl sulfates, e.g., lauryl sulfate, cetyl sulfate, and higher fatty alcohol sulfates derived from coconut oil; the hydroxy sulfonated higher fatty acid esters, e.g., higher fatty acid esters of 2, 3 dihydroxy propane sulfonic acid; the higher fatty acid esters of low molecular weight alkylol sulfonic acids, e.g., oleic ester of isethionic acid; the higher fatty acid ethanolamide sulfates; the higher fatty acid amides of amino alkyl sulfonic acids, e.g., lauric amide of taurine, and the like.
  • higher fatty acids e.g
  • the foamsuppressing effects are particularly enhanced when the synthetic detergent comprises primarily a nonionic detergent.
  • the preferred class of nonionic detergents includes the ethoxylation products of hydrophobic hydroxyl compounds such as long chain aliphatic compounds and alkyl aromatic compounds.
  • hydrophobic hydroxyl compounds such as long chain aliphatic compounds and alkyl aromatic compounds.
  • .Other nonionic detergents are the polyethylene oxide condensates of alkyl phenols, having, for example, an alkyl group of about 6 to 12 carbon atoms (e.g., nonyl phenol) in which there are a plurality of ethylene oxide units (up to 30) per mole of alkyl phenol.
  • Another class of nonionic detergents includes the polyethylene oxide condensates of higher glycols, which may be made, for example, by condensing ethylene oxide with a polypropylene glycol made by reacting propylene oxide and propylene glycol, said polypropylene glycol having a molecular weight of l,500l,800.
  • the nonionic detergent may be made by condensing ethylene oxide with a water-insoluble reaction product (e.g., of molecular weight about 3,000) of a diamine (e.g., ethylene diamine) and excess propylene oxide, to incoporate about 40-80 percent of ethylene oxide in the final condensation product.
  • a water-insoluble reaction product e.g., of molecular weight about 3,000
  • a diamine e.g., ethylene diamine
  • propylene oxide e.g., propylene oxide
  • nonionic compounds are the polyoxyalkylene esters of organic acids such as higher fatty acids, rosin acids, tall oil acids, acids from petroleum oxidation products, etc. These esters will usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 12 to about 30 moles of ethylene oxide or its equivalent.
  • alkylene oxide condensates with higher fatty acid amides.
  • the fatty acid group will generally contain from about 8 to about 22 carbon atoms, and this will be condensed with about 10 to about 50 moles of ethylene oxide as the preferred illustration.
  • the corresponding carboxamides and sulfonamides may also be used as substantial equivalents.
  • the active ingredient should preferably be in the form of a highly watersoluble salt, e.g., ammonium, mono, di-, and triethanol amine salts.
  • the liquid detergent composition may be prepared in dilute or concentrated aqueous solution with or without the presence of a lower molecular weight aliphatic alcohol such as ethyl alcohol, propylene glycol, etc.
  • the amount of nonionic surfactant that can be present in compositions of the present invention ranges from about 2 to about 30 percent, preferably from about 5 to about 15 percent, by weight based on the final composition.
  • an anionic detergent may be incorporated in the formulation.
  • the preferred anionic detergents are the alkyl aryl sulfonate detergents, which may be mononuclear or polynuclear in structure. More particularly, the aromatic nucleus may be derived from benzene, toluene, xylene, phenol, cresols, naphthalene, etc.
  • the alkyl substituent on the aromatic nucleus may vary widely, as long as the desired detergent power of the active ingredient is preserved.
  • alkyl aromatic sulfonate detergents are the higher alkyl aromatic sulfonates.
  • the higher alkyl substituent may be branched or straight chain in structure; it comprises such groups as octyl, decyl, dodecyl, tridecyl, keryl, pentadecyl, and hexadecyl, mixed long-chain alkyls derived from longchain fatty acid materials, cracked paraffin wax olefins, polymers of monoolefins, etc.
  • Preferred examples of this class are the higher alkyl mononuclear aryl sulfonates wherein the alkyl group has about 8 to 22, and preferably between 12 and 18 carbon atoms.
  • the higher alkyl benzene sulfonates wherein the higher alkyl group averages between 12 and 16 carbon atoms.
  • propylene may be polymerized to the tetramer and condensed with benzene in the presence of a Friedel-Crafts catalyst to yield essentially the dodecyl benzene derivative which is suitable for sulfonation to the desired sulfonate compounds.
  • anionic detergents are generally used in the form of their water-soluble salts, such as the alkali metal, alkaline earth metal, ammonium, amine, and alkylolamine salts. While the sodium, potassium, ammonium, and alkylolamine (e.g., mono-, di-, and triethanolamine) salts are preferred ordinarily, other salts such as the lithium, calcium, and magnesium salts may be used if desired. For general use, it is ordinarily preferred to use the sodium and potassium salts. For certain specialized uses, it may be preferred to select the ammonium and alkylolamine salts in view of their generally greater solubility in aqueous solution.
  • the sodium, potassium, ammonium, and alkylolamine salts e.g., mono-, di-, and triethanolamine
  • other salts such as the lithium, calcium, and magnesium salts may be used if desired.
  • the concentration of these water-soluble salts (including suitable mixtures thereof) in the detergent compositions of the present invention is preferably from about -50 percent. With built compositions, particularly in particulate form, an active ingredient content of 5-50 percent, and preferably about -40 percent, yields highly satisfactory results. Compositions with very high concentrations of these active ingredients are prepared for specialized use generally. Thus in liquid detergent compositions, any suitable concentrations may be employed, e.g., from about 5 to about 50 percent of the weight of the total liquid detergent composition.
  • inorganic salt detergent builders such as various water-soluble inorganic polyphosphates, sulfates, silicates, borates, and carbonates, does not adversely affect the foaming and detergent properties of the present composition.
  • These builders the total amount of which may range by weight, based on finished composition, from about l0 to about 90 percent, but more usually between 45 to about 85 percent, contribute their different specific effect toward a more satisfactory washing treatment of soiled clothing, dishes, etc.
  • the most common alkaline builder salts are the phosphates, which inhibit the precipitation of alkaline earth materials, such as calcium and magnesium compounds, in aqueous media.
  • alkali metal salts, and, most particularly, the sodium and potassium salts, of the chain polyphosphates are usually employed. Examples of such compounds include: sodium tripolyphosphate, p0- tassium acid tripolyphosphate, tetrapotassium pyrophosphate, sodium hexametaphosphate, potassium tetraphosphate, and the like.
  • the phosphates are either crystalline substances or glassy, amorphous products.
  • These phosphates may be the sole builder salts or may be used in combination with any of the aforementioned builder salts.
  • compositions of the present invention include soil suspending agents, brighteners, thickening agents, coloring materials, and perfumes. These additives are generally present in amounts of less than 5 percent of the total detergent composition.
  • the soil suspending agents are generally water soluble or hydrophilic polymeric substances such as the lower alkyl cellulose esters, e.g., methyl cellulose and ethylcellulose; hydroxyalkyl cellulose esters, e.g., hydroxyethyl cellulose, cellulose ethane sulfonic acid, cellulose glycollic acid; carboxy lower alkyl cellulose compounds, e.g., sodium carboxy methyl cellulose, potassium carboxy methyl cellulose, sodium carboxy propyl cellulose, and the like; water-soluble or dispersible synthetic polymeric materials which may be homopolymers, copolymers, graft copolymers, terpolymers, interpolymers, and the like and are illustrated by polyvinyl pyrrolidone, polyvinyl alcohol, hydrolyzed polyvinyl acetate, polyacrylic acid, polyacrylamide; maleic anhydride copolymers with alkyl vinyl esters, e.g., methyl vinyl ester;
  • the essential constituents of the present composition are the synthetic detergent, builder salts, and amine, with soap being a preferred additive to improve anti-foam properties
  • various other materials may also be present, either for their additional effects or because they are generally carried along with the essential constituents.
  • water although not required in particulate or solid compositions, is usually present therein to a minor extent. it may be a part of the soap charged or water of hydration with builder salt.
  • liquid detergent compositions it is the primary solvent and may have with it lower alkanols, diols, or polyols, such as ethanol, isopropanol, propylene glycol, to improve solubilization of the various ingredients.
  • filler salts which do not improve detergency but add bulk and sorption capacity for liquid constituents, may be utilized.
  • sodium sulfate and sodium chloride are good fillers, especially the former.
  • those which are hydratable have a capacity for sorption of any excess water which may be present, improving the free-flowing nature of the products.
  • Fluorescent brighteners are frequently used to improve the whitening effect of the detergent on the ma terials washed.
  • various cotton brighteners polyamide brighteners, polyester brighteners, and bleach-stable brighteners.
  • These may be reaction products of cyanuric chloride and the disodium salt of diaminostilbene disulfonic acid, benzidine sulfone disulfonic acid, aminocoumarins, diphenyl pyrazoline derivatives or naphthotriazolyl stilbenes.
  • Such materials are described in Stensby, Optical Brighteners and Their Evaluation, a reprint of articles published in Soap & Chemical Specialties in April, May, July, August, and September, l967, especially at pp. 3-5 thereof.
  • the fluorescent dyes or optically active brightener compounds also serve to improve the appearance of the particulate detergent compositions containing them, making such compositions appear whiter or brighter.
  • adjuvants may be present, such as hydrotropes (in the case of liquid compositions) solvents and solubilizing agents (also primarily in liquid compositions), bactericides, fungicides, dyes, water dispersible pigments, chelating agents, antioxidants, stabilizers, and perfumes.
  • hydrotropes in the case of liquid compositions
  • solubilizing agents also primarily in liquid compositions
  • bactericides in the case of liquid compositions
  • fungicides in the case of liquid compositions
  • dyes e.g., bactericides, fungicides, dyes, water dispersible pigments, chelating agents, antioxidants, stabilizers, and perfumes.
  • the proportions of such adjuvants will be maintained as low as feasible, almost always being less than 20 percent of the composition, frequently less than percent thereof, and preferably less than 5 percent thereof, in total. Normally there will be present no more than 5 percent of any such composition and preferably, in most cases, the amount of adjuvant will be
  • a small proportion of a higher fatty acid soap may be included in the detergent compositions of the present invention; both for its detersive properties and as a supplemental foam-suppressing agent.
  • the most common water-soluble soaps are the alkali metal, ammonium, and alkanolamine soaps derived from mixtures of animal and vegetable fats and oils.
  • the soaps may be considered to be derivatives of higher fatty acids having from 10 to 20, and preferably from 12 to 18, carbon atoms. These fatty acids are obtained from oils, such as coconut oil, palm kernel oil, corn oil, cottonseed oil, and olive oil; and animal fats, greases and oils such as beef tallow, mutton tallow, hog greases, and fish oils.
  • the preferred soaps for the present compositions are alkali metal soaps, for example, the sodium soaps of mixed coconut oil and tallow, preferably wherein the mixtures contain a major proportion of tallow anda minor proportion, less than 40 percent, of coconut oil.
  • the amount of dialkylamine foam suppressing additives is generally minor in proportion to the total detergent composition. Particularly effective results have been achieved when the dialkylamine is present in amounts between about 1% percent and aboutlS percent of the total detergent composition. It is generally preferred to use from about 1 to about 5 percent, of the additive.
  • the optimum amount of additive and its ratio to the active ingredients will vary according to the spe cific materials, the contemplated field of application, and manner of use. Where a soap'is present, it is preferred to use soap in the amount of from 1.5 to 5 times that of the amine.
  • detergent products in accordance with this invention one needs only to mix the various constituents thereof, with the only critical or difficult part of the manufacturing method being in addition of the nonionic material and the amine to the particulate solid material builder or the rest of the detergent product.
  • This can be accomplished by mixing the anti-foam agents with other constituents, less perfume, in an aqueous slurry or crutcher mix and spray drying the slurry (at high pressure, e.g., 200 to 2,000 lbs/sq.
  • the crutcher mix which is heated to about 60 to 90C. before spraying, will usually contain only limited proportions of the nonionic detergent and amine because of a tendency of these materials to be flashed away in the spray drying operation and to plume out the top of the spray tower, causing objectionable tower smoking.
  • the spray drying should be effected with no more than 2 percent of each. such ingredient, preferably no more than I percent of each thereof, in the spray dried product and any additional amounts of these materials should be post-added to the spray dried beads, at which time the synthetic gum or other anti-redeposition agent may also-be admixed with the product. If the detergent and the amine are not liquid'they may be melted or dissolved in water or a so]- vent for spraying onto the detergent builder and other materials. Perfumes and other volatile liquids are usually sprayed onto the particles as a last step, after cooling.
  • a flow-inducing agent such as finely divided particles of Bentonite, clays or other lubricants, of which one sold as Satintone is considered to be the best.
  • the products of this invention are used in the same manner as that in which the commercial synthetic detergents are employed. They may be added to the washing machine before or after the clothing, and the machine may be started immediately after addition or starting may be after a substantial time has passed.
  • water temperature is normally from I to 75C., pref erably about 60C. and the concentration of detergent composition is from 0.1 to 0.4 percent.
  • the product is free flowing and is readily measured out and added to the washing machine. It foams only slightly in the absence of soil in zero hardness water. When soiled laundry is used the product does not foam at all. Clothes washed are clean and of excellent whiteness. In comparison with comparable foaming detergents, especially in horizontally tumbling washing machines, reflectometer readings indicate that better washing is obtained with the compositions of this invention.
  • a detergent composition is prepared by forming about a 60 percent solids aqueous slurry containing, on a solids basis, about 10 percent sodium tridecylbenzene sulfonate, about 4 percent Neodol 451 l (a C C linear primary alcohol with 11 ethoxy groups made by Shell Chemical Co), about percent potassium tripolyphosphate, about I percent, 1, 1 di (2 ethyl hexyl)
  • foam heights were measured under simulated household-use conditions in a tumbler-type washing machine test. The washing machine test was conducted in the following manner:
  • Neodol 45 1 I07: Potassium tetrapyrophosphate 15 Sodium silicate 7.5
  • the improved detergent formulations of this invention are suitable for use in dilute aqueous solutions in a variety of washing appliances, such as rotary drum or tumbler-type washers, etc. When so employed, little or no foam is formed, with no adverse effect on the detergency characteristics in operating at temperatures from about 65 to 140F, as commonly used in washing practice.
  • This suppression of suds in accordance with the invention permits employing a larger concentration of the active detergent in the preparation of washing solutions, as compared with the concentrations theretofore considered permissible maxima for tumbler-washer operations. A greater washing efficiency can therefore be achieved.
  • the tendency to froth upon rinsing is substantially obviated.
  • the low foaming detergent formulations of the pres ent invention can be used in tumbler-type washers, as well as in any other washing equipment which utilizes conventional high foaming organic detergent materials.
  • these formulations can be used to reduce foaming in a number of solutions and emulsions which, upon agitation, produce unduly high suds levels, causing spillage and pumping difficulties, and interfering with a satisfactory filling of containers.
  • a low foaming detergent composition comprising 1. about 2 to about 30 percent ofa water soluble nonionic or anionic synthetic organic detergent,
  • composition as defined in claim 1 wherein the nonionic detergent is a polyethoxylated higher alkanol.
  • a composition as defined in claim 2 wherein the nonionic has the molecular configuration of a condensation product of a C to C alkanol with from 3 to 30 moles of ethylene oxide.
  • composition as defined in claim 3 wherein the nonionic has the molecular configuration of a condensation product of a C1445 alkanol with 1 1 moles of ethylene oxide.
  • composition as defined in claim 2 wherein the amine is dicocoamine.
  • composition as defined in claim 2 wherein the phosphate is sodium tripolyphosphate.
  • composition as defined in claim 1 wherein the anionic detergent is a C to C alkyl benzene sulfonate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

This invention relates to non-foaming detergent compositions which include nonionic or mixtures of nonionic and anionic detergent, builder salt, and higher alkyl amine, the amine being present in sufficient proportion to make a combination of synthetic detergent and builder non-foaming or essentially nonfoaming in wash waters of usual dilutions for washing machine use. More particularly, the invention relates to compositions in which the nonionic synthetic detergent is a higher alkoxy polyethoxy ethanol, the anionic synthetic detergent is a higher alkyl benzene sulfonate, the builder is or includes an alkali metal polyphosphate, and the amine anti-foam additive is a dihigher alkyl amine. The compositions are effective laundering agents, primarily intended for use in automatic washing machines and in almost all practical uses are non-foaming, even when used in the normally foam generating horizontal tumbler type of washing machine.

Description

Inamorato et a1.
[ LOW FOAMING DETERGENT COMPOSITIONS [75] Inventors: Jack T. Inamorato, Westfield, N..I.;
Robert T. Hunter, Grand Rapids, Mich. [73] Assignee: Colgate-Palmolive Company, New
York, N.Y.
[22] Filed: Oct. 29, 1973 [21] Appl. No.: 410,502
Related US. Application Data [63] Continuation of Ser. No. 260,319, June 6, 1972,
abandoned.
[52] US. Cl 252/110, 252/525, 252/DIG. l, 252/DIG. 15 [51] Int. Cl ..C11d 9/10 [58] FieldofSearch ..252/1l0,525,DIG.1, 252/DIG. 15
[56] References Cited UNITED STATES PATENTS 2,954,347 9/1960 St. John et a1. ,4 252/109 2,954,348 9/1960 Schwoeppe 252/109 3,679,608 7/1972 Aubert 252/526 3,684,723 8/1972 Best et al. 1. 252/132 3,696,056 10/1972 Inamorato..... 252/358 X 3,709,836 l/1973 lnamorato 252/110 X 1 Dec. 10, 1974 FOREIGN PATENTS OR APPLICATIONS 138,340 11/1946 Australia 252/321 Primary Examiner-Leland A. Sebastian Attorney, Agent, or Firm Herbert S. Sylvester; Murray M. Grill; Norman Blumenkopf [57] ABSTRACT This invention relates to non-foaming detergent compositions which include nonionic or mixtures of nonionic and anionic detergent, builder salt, and higher alkyl amine, the amine being present in sufficient proportion to make a combination of synthetic detergent and builder non-foaming or essentially non-foaming in wash waters of usual dilutions for washing machine use. More particularly, the invention relates to compositions in which the nonionic synthetic detergent is a higher alkoxy polyethoxy ethanol, the anionic synthetic detergent is a higher alkyl benzene sulfonate, the builder is or includes an alkali metal polyphosphate, and the amine anti-foam additive is a di-higher alkyl amine. The compositions are effective laundering agents, primarily intended for use in automatic washing machines and in almost all practical uses are non-foaming, even when used in the normally foam generating horizontal tumbler type of washing machine.
7 Claims, No Drawings LOW FOAMING DETERGENT COMPOSITIONS This is a continuation of applicantion Ser. No. 260,319 filed June 6, 1972, now abandoned.
BACKGROUND OF THE INVENTION The present invention relates to new synthetic detergent compositions and more particularly to compositions based on anionic detergents, nonionic detergents, and mixtures thereof having improved properties. Aqueous solutions of these detergent compositions are characterized by a very low degree of foam formation under conditions of vigorous and continuous agitation.
Although the formation of abundant foam has been considered a desirable property of a washing agent as an indication of lasting detergent power, it is also recognized that copious suds formation is not necessarily a measure of detergent effectiveness. In fact, with certain household and commercial appliances and apparatus, production of copious suds is a handicap rather than an advantage. Compositions of the present invention not only do not foam excessively, but they also have superior detersive properties.
SUMMARY OF THE INVENTION It has now been discovered that the presence of certain dialkylamines in detergent compositions consisting essentially of anionic sulfated and sulfonated and nonionic surfactants is effective to achieve a significant enhancement in surface-active properties and a reduction in foaming. More particularly, the improved detergent compositions include water-soluble anionic and nonionic surfactants and mixtures thereof, alkaline builder salts, and a minor proportion of a dialkylamine effective to suppress the formation of foam in the detergent compositions.
The new detergent compositions generate less foam than current available products, and prevent overfoaming in soft water areas. In addition, the new detergent compositions permit the consumer to use higher levels of detergent before over-foaming occurs.
Illustrative of the foam suppressing additives of the present invention are the dialkyl amines wherein the alkyl substituents have between 8 and 18 carbon atoms. Suitable examples of such compounds include dicocoamine, di hydrogenated tallow amine, di soya amine, and di (2 ethyl hexyl) amine.
The novel compositions of the present invention contain as the active ingredient the anionic sulfated and sulfonated detergents, nonionic detergents, and mixtures thereof. Included therein are the aliphatic sulfated or sulfonated compounds, such as the aliphatic acyl-containing compounds wherein the acyl radical has between 8 and 22 carbon atoms, and more particularly, the aliphatic carboxylic ester type, containing at least about 10 and preferably between 12 and 26 carbon atoms in the molecule. Among the aliphatic detersive compounds, it is preferred to use the sulfonated aliphatic compounds having between 12 and 22 carbon atoms. As suitable examples of aliphatic detergents may be found the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e.g. coconut oil monoglyceride monosulfate; the long chain pure or mixed higher alkyl sulfates, e.g., lauryl sulfate, cetyl sulfate, and higher fatty alcohol sulfates derived from coconut oil; the hydroxy sulfonated higher fatty acid esters, e.g., higher fatty acid esters of 2, 3 dihydroxy propane sulfonic acid; the higher fatty acid esters of low molecular weight alkylol sulfonic acids, e.g., oleic ester of isethionic acid; the higher fatty acid ethanolamide sulfates; the higher fatty acid amides of amino alkyl sulfonic acids, e.g., lauric amide of taurine, and the like.
It is a feature of this invention that the foamsuppressing effects are particularly enhanced when the synthetic detergent comprises primarily a nonionic detergent. The preferred class of nonionic detergents includes the ethoxylation products of hydrophobic hydroxyl compounds such as long chain aliphatic compounds and alkyl aromatic compounds. Among such materials are the polyethylene oxide condensates of aliphatic alcohols having, for example, 8 to 18 carbon atoms, such as lauryl or tallow alcohols, combined with, for example, 3-3O moles of ethylene oxide for each mole of the long chain alcohol.
.Other nonionic detergents are the polyethylene oxide condensates of alkyl phenols, having, for example, an alkyl group of about 6 to 12 carbon atoms (e.g., nonyl phenol) in which there are a plurality of ethylene oxide units (up to 30) per mole of alkyl phenol. Another class of nonionic detergents includes the polyethylene oxide condensates of higher glycols, which may be made, for example, by condensing ethylene oxide with a polypropylene glycol made by reacting propylene oxide and propylene glycol, said polypropylene glycol having a molecular weight of l,500l,800. Again, the nonionic detergent may be made by condensing ethylene oxide with a water-insoluble reaction product (e.g., of molecular weight about 3,000) of a diamine (e.g., ethylene diamine) and excess propylene oxide, to incoporate about 40-80 percent of ethylene oxide in the final condensation product. Ethoxylation products of compounds containing mercapto, rather than hydroxy],
groups may also be used.
Other suitable nonionic compounds are the polyoxyalkylene esters of organic acids such as higher fatty acids, rosin acids, tall oil acids, acids from petroleum oxidation products, etc. These esters will usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 12 to about 30 moles of ethylene oxide or its equivalent.
Still other useful nonionic surfactants are the alkylene oxide condensates with higher fatty acid amides. The fatty acid group will generally contain from about 8 to about 22 carbon atoms, and this will be condensed with about 10 to about 50 moles of ethylene oxide as the preferred illustration. The corresponding carboxamides and sulfonamides may also be used as substantial equivalents.
In liquid detergents, the active ingredient (surfactant) should preferably be in the form of a highly watersoluble salt, e.g., ammonium, mono, di-, and triethanol amine salts. The liquid detergent composition may be prepared in dilute or concentrated aqueous solution with or without the presence of a lower molecular weight aliphatic alcohol such as ethyl alcohol, propylene glycol, etc.
The amount of nonionic surfactant that can be present in compositions of the present invention ranges from about 2 to about 30 percent, preferably from about 5 to about 15 percent, by weight based on the final composition.
If the detersive action of an anionic detergent is desired, an anionic detergent may be incorporated in the formulation. The preferred anionic detergents are the alkyl aryl sulfonate detergents, which may be mononuclear or polynuclear in structure. More particularly, the aromatic nucleus may be derived from benzene, toluene, xylene, phenol, cresols, naphthalene, etc. The alkyl substituent on the aromatic nucleus may vary widely, as long as the desired detergent power of the active ingredient is preserved.
More specific examples of suitable alkyl aromatic sulfonate detergents are the higher alkyl aromatic sulfonates. The higher alkyl substituent may be branched or straight chain in structure; it comprises such groups as octyl, decyl, dodecyl, tridecyl, keryl, pentadecyl, and hexadecyl, mixed long-chain alkyls derived from longchain fatty acid materials, cracked paraffin wax olefins, polymers of monoolefins, etc. Preferred examples of this class are the higher alkyl mononuclear aryl sulfonates wherein the alkyl group has about 8 to 22, and preferably between 12 and 18 carbon atoms. More particularly, it is preferred to use the higher alkyl benzene sulfonates wherein the higher alkyl group averages between 12 and 16 carbon atoms. For example, propylene may be polymerized to the tetramer and condensed with benzene in the presence ofa Friedel-Crafts catalyst to yield essentially the dodecyl benzene derivative which is suitable for sulfonation to the desired sulfonate compounds.
These various anionic detergents are generally used in the form of their water-soluble salts, such as the alkali metal, alkaline earth metal, ammonium, amine, and alkylolamine salts. While the sodium, potassium, ammonium, and alkylolamine (e.g., mono-, di-, and triethanolamine) salts are preferred ordinarily, other salts such as the lithium, calcium, and magnesium salts may be used if desired. For general use, it is ordinarily preferred to use the sodium and potassium salts. For certain specialized uses, it may be preferred to select the ammonium and alkylolamine salts in view of their generally greater solubility in aqueous solution. The concentration of these water-soluble salts (including suitable mixtures thereof) in the detergent compositions of the present invention is preferably from about -50 percent. With built compositions, particularly in particulate form, an active ingredient content of 5-50 percent, and preferably about -40 percent, yields highly satisfactory results. Compositions with very high concentrations of these active ingredients are prepared for specialized use generally. Thus in liquid detergent compositions, any suitable concentrations may be employed, e.g., from about 5 to about 50 percent of the weight of the total liquid detergent composition.
The presence of conventional amounts of inorganic salt detergent builders, such as various water-soluble inorganic polyphosphates, sulfates, silicates, borates, and carbonates, does not adversely affect the foaming and detergent properties of the present composition. These builders, the total amount of which may range by weight, based on finished composition, from about l0 to about 90 percent, but more usually between 45 to about 85 percent, contribute their different specific effect toward a more satisfactory washing treatment of soiled clothing, dishes, etc.
The most common alkaline builder salts are the phosphates, which inhibit the precipitation of alkaline earth materials, such as calcium and magnesium compounds, in aqueous media. The alkali metal salts, and, most particularly, the sodium and potassium salts, of the chain polyphosphates are usually employed. Examples of such compounds include: sodium tripolyphosphate, p0- tassium acid tripolyphosphate, tetrapotassium pyrophosphate, sodium hexametaphosphate, potassium tetraphosphate, and the like. The phosphates are either crystalline substances or glassy, amorphous products. Any water-soluble glassy polyphosphate with mole ratios of alkali oxide to phosphorous oxide of between about 5:3 and about 1:1, and an average chain length of from 3 to several thousands, is suitable for use as a builder in the compositions of the present invention. These phosphates may be the sole builder salts or may be used in combination with any of the aforementioned builder salts.
Other functional materials which optionally may be present in the compositions of the present invention include soil suspending agents, brighteners, thickening agents, coloring materials, and perfumes. These additives are generally present in amounts of less than 5 percent of the total detergent composition.
The soil suspending agents are generally water soluble or hydrophilic polymeric substances such as the lower alkyl cellulose esters, e.g., methyl cellulose and ethylcellulose; hydroxyalkyl cellulose esters, e.g., hydroxyethyl cellulose, cellulose ethane sulfonic acid, cellulose glycollic acid; carboxy lower alkyl cellulose compounds, e.g., sodium carboxy methyl cellulose, potassium carboxy methyl cellulose, sodium carboxy propyl cellulose, and the like; water-soluble or dispersible synthetic polymeric materials which may be homopolymers, copolymers, graft copolymers, terpolymers, interpolymers, and the like and are illustrated by polyvinyl pyrrolidone, polyvinyl alcohol, hydrolyzed polyvinyl acetate, polyacrylic acid, polyacrylamide; maleic anhydride copolymers with alkyl vinyl esters, e.g., methyl vinyl ester; natural products such as starch and the like.
Although the essential constituents of the present composition are the synthetic detergent, builder salts, and amine, with soap being a preferred additive to improve anti-foam properties, various other materials may also be present, either for their additional effects or because they are generally carried along with the essential constituents. For example, water, although not required in particulate or solid compositions, is usually present therein to a minor extent. it may be a part of the soap charged or water of hydration with builder salt. In liquid detergent compositions it is the primary solvent and may have with it lower alkanols, diols, or polyols, such as ethanol, isopropanol, propylene glycol, to improve solubilization of the various ingredients.
Various filler salts, which do not improve detergency but add bulk and sorption capacity for liquid constituents, may be utilized. Thus, sodium sulfate and sodium chloride are good fillers, especially the former. Of the filler salts, those which are hydratable have a capacity for sorption of any excess water which may be present, improving the free-flowing nature of the products.
Fluorescent brighteners are frequently used to improve the whitening effect of the detergent on the ma terials washed. Among these are various cotton brighteners, polyamide brighteners, polyester brighteners, and bleach-stable brighteners. These may be reaction products of cyanuric chloride and the disodium salt of diaminostilbene disulfonic acid, benzidine sulfone disulfonic acid, aminocoumarins, diphenyl pyrazoline derivatives or naphthotriazolyl stilbenes. Such materials are described in Stensby, Optical Brighteners and Their Evaluation, a reprint of articles published in Soap & Chemical Specialties in April, May, July, August, and September, l967, especially at pp. 3-5 thereof. The fluorescent dyes or optically active brightener compounds also serve to improve the appearance of the particulate detergent compositions containing them, making such compositions appear whiter or brighter.
Various other adjuvants may be present, such as hydrotropes (in the case of liquid compositions) solvents and solubilizing agents (also primarily in liquid compositions), bactericides, fungicides, dyes, water dispersible pigments, chelating agents, antioxidants, stabilizers, and perfumes. Generally, the proportions of such adjuvants will be maintained as low as feasible, almost always being less than 20 percent of the composition, frequently less than percent thereof, and preferably less than 5 percent thereof, in total. Normally there will be present no more than 5 percent of any such composition and preferably, in most cases, the amount of adjuvant will be less than 1 or 2 percent.
A small proportion ofa higher fatty acid soap may be included in the detergent compositions of the present invention; both for its detersive properties and as a supplemental foam-suppressing agent. The most common water-soluble soaps are the alkali metal, ammonium, and alkanolamine soaps derived from mixtures of animal and vegetable fats and oils. The soaps may be considered to be derivatives of higher fatty acids having from 10 to 20, and preferably from 12 to 18, carbon atoms. These fatty acids are obtained from oils, such as coconut oil, palm kernel oil, corn oil, cottonseed oil, and olive oil; and animal fats, greases and oils such as beef tallow, mutton tallow, hog greases, and fish oils. The preferred soaps for the present compositions are alkali metal soaps, for example, the sodium soaps of mixed coconut oil and tallow, preferably wherein the mixtures contain a major proportion of tallow anda minor proportion, less than 40 percent, of coconut oil.
The amount of dialkylamine foam suppressing additives is generally minor in proportion to the total detergent composition. Particularly effective results have been achieved when the dialkylamine is present in amounts between about 1% percent and aboutlS percent of the total detergent composition. It is generally preferred to use from about 1 to about 5 percent, of the additive. The optimum amount of additive and its ratio to the active ingredients will vary according to the spe cific materials, the contemplated field of application, and manner of use. Where a soap'is present, it is preferred to use soap in the amount of from 1.5 to 5 times that of the amine.
To make detergent products in accordance with this invention one needs only to mix the various constituents thereof, with the only critical or difficult part of the manufacturing method being in addition of the nonionic material and the amine to the particulate solid material builder or the rest of the detergent product. This can be accomplished by mixing the anti-foam agents with other constituents, less perfume, in an aqueous slurry or crutcher mix and spray drying the slurry (at high pressure, e.g., 200 to 2,000 lbs/sq. inch), into a tower at an elevated temperature, e.g., 150 to 300C, so as to reduce the moisture content thereof to about 10 percent or less and to produce beads which are generally globular in shape and are in the 6 to 200, preferably 6 to 140 and most preferably, 8 to 100 mesh particle size range (US. Standard Sieve Series). When such a procedure is followed, the crutcher mix, which is heated to about 60 to 90C. before spraying, will usually contain only limited proportions of the nonionic detergent and amine because of a tendency of these materials to be flashed away in the spray drying operation and to plume out the top of the spray tower, causing objectionable tower smoking. To avoid such pluming of the high pressure sprayed and atomized droplets it is often desirable to post-add any larger amounts of these materials, and sometimes it is even preferred to spray the crutcher mix without either the nonionic detergent or the amine and to post-add both of them to the spray dried mixture. Of course, where spray drying is not employed the various granular constituents may be admixed and the liquid ingredients, amine and nonionic, in solid forms may be admixed with the mixture, taking care to distribute them evenly. In such manufacturing methods the particle sizes of the products resulting may be finer and the very fine particles may be removed by screening. Yet, such losses will not be great because the presence of the nonionic detergent and the amine help to prevent excessive dusting. Thus, such materials will usually also be in the 6 to 200 mesh particle size range. lf desired, all particulate detergents may be screened so as to keep the sizes of particles in the ranges mentioned.
Together with post-additions of liquid ingredients, it is sometimes also desirable to post-add the sodium carboxymethyl cellulose or other gum products which have been found to counter the satisfactory sorption of liquids, such as solutions or melts of the nonionic detergent or higher alkyl amine type, and thereby cause excessive lumping. Thus, in the manufacturing methods, summarized, when small proportions of alkyl amine and nonionic detergent are used all ingredients may be spray dried together and there will be no objectionable smoking of the spray tower. When powders are used, all ingredients may be mixed together in a blender, such as a Day mixer or ribbon blender and, if desired, may be micropulverized together. When spray dried beads are to be used and the proportions of detergent and amine are greater than 2 percent of each or greater than a 4 percent total, the spray drying should be effected with no more than 2 percent of each. such ingredient, preferably no more than I percent of each thereof, in the spray dried product and any additional amounts of these materials should be post-added to the spray dried beads, at which time the synthetic gum or other anti-redeposition agent may also-be admixed with the product. If the detergent and the amine are not liquid'they may be melted or dissolved in water or a so]- vent for spraying onto the detergent builder and other materials. Perfumes and other volatile liquids are usually sprayed onto the particles as a last step, after cooling. if flow of the finished product is not as good as desired there may be addedto the detergent composition a flow-inducing agent, such as finely divided particles of Bentonite, clays or other lubricants, of which one sold as Satintone is considered to be the best.
The products of this invention are used in the same manner as that in which the commercial synthetic detergents are employed. They may be added to the washing machine before or after the clothing, and the machine may be started immediately after addition or starting may be after a substantial time has passed. The
water temperature is normally from I to 75C., pref erably about 60C. and the concentration of detergent composition is from 0.1 to 0.4 percent. The product is free flowing and is readily measured out and added to the washing machine. It foams only slightly in the absence of soil in zero hardness water. When soiled laundry is used the product does not foam at all. Clothes washed are clean and of excellent whiteness. In comparison with comparable foaming detergents, especially in horizontally tumbling washing machines, reflectometer readings indicate that better washing is obtained with the compositions of this invention.
In the foam height tests described below, the following detergent compositions were used:
Table I DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examples illustrate compositions of the present invention.
EXAMPLE I A detergent composition is prepared by forming about a 60 percent solids aqueous slurry containing, on a solids basis, about 10 percent sodium tridecylbenzene sulfonate, about 4 percent Neodol 451 l (a C C linear primary alcohol with 11 ethoxy groups made by Shell Chemical Co), about percent potassium tripolyphosphate, about I percent, 1, 1 di (2 ethyl hexyl) To determine the degree of foam inhibition, foam heights were measured under simulated household-use conditions in a tumbler-type washing machine test. The washing machine test was conducted in the following manner:
To a tumbler-type washing machine was charged 26 liters of water of I ppm hardness at 120F containing O.l5 percent by weight of the test formulation. Then three pounds of clean terry towels were added. The foam height, in inches, as viewed through the door window, is measured periodically over a 10 minute wash cycle.
Theresults of the tests are tabulated in Table II, wherein composition 6 is a commercially available lowfoaming detergent composition used for comparison with the compositions of the present invention.
The results of the test indicate that the low foaming detergent compositions of the present invention develop much less foam in use than currently available low foaming detergent compositions. In addition, soiled clothes washed with the detergent composition come out clean and white, even though little or no foam is generated.
amine, about 7.5 percent sodium silicate, 0.5 percent sodium carboxymethyl cellulose, and about 32 percent sodium sulfate. This slurry is submitted to spray drying with heated air at a temperature of about 350F with a resultant moisture loss of about 40 percent. The resulting composition is recovered in the form of beads.
EXAMPLE II Using the procedure of Example I, an improved detergent composition is prepared from the following components:
Sodium dodecyl benzene sulfonate 59? Neodol 45l l 10% Sodium silicate 20% Sodium sulfate 18% l, 1 di hydrogenated tallow amine 5% Sodium carboxy methyl cellulose 2% Sodium tripolyphosphate 40% EXAMPLE III An improved liquid detergent composition is prepared from the following components:
Neodol 45! 1 I07: Potassium tetrapyrophosphate 15 Sodium silicate 7.5
, -Continued Optical brighteners 0.2 Sodium carboxy methyl cellulose 0.3 Dicoco amine l Resin stabilizer (Ethylene-maleic anhydride polymer) l.O Water 65 The detergent produced is essentially non-foaming under ordinary use conditions and is a good cleaning agent.
Changes in builders and fillers do not prevent the compositions from being essentially non-foaming. For example, when the sodium silicate contents of the described compositions are changed to 50:50 mixtures of pentasodium tripolyphosphate, soda ash, trisodium nitrilotriacetate, sodium bicarbonate, tetrasodium pyrophosphate, monosodium phosphate, trisodium phosphate or disodium phosphate, each with the described sodium silicate or a sodium silicate of an Na O:SiO ratio of about 1:1.7 or 1:2.6, products of good detergency are obtained, which are non-foaming. This is also so when such proportions are varied and the amounts of builder are increased or decreased within the described ranges. Replacement of the sodium sulfate with sodium chloride and increase in the sodium sulfate content to approximately twice its level in Example 11, at the expense of the sodium silicate, do not adversely affect the non-foaming properties of the detergent compositions.
The improved detergent formulations of this invention are suitable for use in dilute aqueous solutions in a variety of washing appliances, such as rotary drum or tumbler-type washers, etc. When so employed, little or no foam is formed, with no adverse effect on the detergency characteristics in operating at temperatures from about 65 to 140F, as commonly used in washing practice. This suppression of suds in accordance with the invention permits employing a larger concentration of the active detergent in the preparation of washing solutions, as compared with the concentrations theretofore considered permissible maxima for tumbler-washer operations. A greater washing efficiency can therefore be achieved. Furthermore, the tendency to froth upon rinsing is substantially obviated.
The low foaming detergent formulations of the pres ent invention can be used in tumbler-type washers, as well as in any other washing equipment which utilizes conventional high foaming organic detergent materials. In fact, these formulations can be used to reduce foaming in a number of solutions and emulsions which, upon agitation, produce unduly high suds levels, causing spillage and pumping difficulties, and interfering with a satisfactory filling of containers.
What is claimed is:
l. A low foaming detergent composition comprising 1. about 2 to about 30 percent ofa water soluble nonionic or anionic synthetic organic detergent,
2. from about 10 to about percent of a water soluble alkaline phosphate builder salt, and
3. from about 0.5 to about 15 percent of a C to C dialkyl or dialkenyl amine.
2. A composition as defined in claim 1 wherein the nonionic detergent is a polyethoxylated higher alkanol.
3. A composition as defined in claim 2 wherein the nonionic has the molecular configuration of a condensation product of a C to C alkanol with from 3 to 30 moles of ethylene oxide.
4. A composition as defined in claim 3 wherein the nonionic has the molecular configuration of a condensation product of a C1445 alkanol with 1 1 moles of ethylene oxide.
5. A composition as defined in claim 2 wherein the amine is dicocoamine.
6. A composition as defined in claim 2 wherein the phosphate is sodium tripolyphosphate.
7. A composition as defined in claim 1 wherein the anionic detergent is a C to C alkyl benzene sulfonate.

Claims (12)

1. A LOW FOAMING DETERGENT COMPOSITION COMPRISING
1. ABOUT 2 TO ABOUT 30 PERCENT OF A WATER SOLUBLE NIONIC OR ANIONIC SYNTHETIC ORGANIC DETERGENT,
2. FROM ABOUT 10 TO ABOUT 90 PERCENT OF A WATER SOLUBLE ALKALINE PHOSPHATE BUILDER SALT, AND
2. A composition as defined in claim 1 wherein the nonionic detergent is a polyethoxylated higher alkanol.
2. from about 10 to about 90 percent of a water soluble alkaline phosphate builder salt, and
3. from about 0.5 to about 15 percent of a C10 to C18 dialkyl or dialkenyl amine.
3. A composition as defined in claim 2 wherein the nonionic has the molecular configuration of a condensation product of a C8 to C18 alkanol with from 3 to 30 moles of ethylene oxide.
3. FROM ABOUT 0.5 TO ABOUT 15 PERCENT OF A C10 TO C18 DIALKYL OR DIALKENYL AMINE.
4. A composition as defined in claim 3 wherein the nonionic has the molecular configuration of a condensation product of a C14 15 alkanol with 11 moles of ethylene oxide.
5. A composItion as defined in claim 2 wherein the amine is dicocoamine.
6. A composition as defined in claim 2 wherein the phosphate is sodium tripolyphosphate.
7. A composition as defined in claim 1 wherein the anionic detergent is a C8 to C22 alkyl benzene sulfonate.
US00410502A 1972-06-06 1973-10-29 Low foaming detergent compositions Expired - Lifetime US3853779A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU55033/73A AU5503373A (en) 1972-06-06 1973-05-01 Low-foaming detergent composition
DE2323326A DE2323326A1 (en) 1972-06-06 1973-05-09 NON-FOAM DETERGENT AND CLEANING AGENTS
CA172,998A CA992833A (en) 1972-06-06 1973-06-01 Low-foaming detergent composition
FR7320299A FR2187898B1 (en) 1972-06-06 1973-06-05
US00410502A US3853779A (en) 1972-06-06 1973-10-29 Low foaming detergent compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US26031972A 1972-06-06 1972-06-06
US00410502A US3853779A (en) 1972-06-06 1973-10-29 Low foaming detergent compositions

Publications (1)

Publication Number Publication Date
US3853779A true US3853779A (en) 1974-12-10

Family

ID=26947925

Family Applications (1)

Application Number Title Priority Date Filing Date
US00410502A Expired - Lifetime US3853779A (en) 1972-06-06 1973-10-29 Low foaming detergent compositions

Country Status (5)

Country Link
US (1) US3853779A (en)
AU (1) AU5503373A (en)
CA (1) CA992833A (en)
DE (1) DE2323326A1 (en)
FR (1) FR2187898B1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155882A (en) * 1973-08-01 1979-05-22 Lever Brothers Company Process for preparing particulate detergent compositions containing nonionic surfactants
EP0023367A1 (en) * 1979-07-05 1981-02-04 THE PROCTER & GAMBLE COMPANY Detergent composition having textile softening property
US4332692A (en) * 1979-02-28 1982-06-01 The Procter & Gamble Company Laundering with a nonionic detergent system at a temperature between the cloud point and the phase coalescence temperatures
US4394127A (en) * 1980-02-07 1983-07-19 Lever Brothers Company Method of depositing perfume and compositions therefor
WO1996012000A1 (en) * 1994-10-13 1996-04-25 The Procter & Gamble Company Detergent compositions containing amines and anionic surfactants
WO1997000929A1 (en) * 1994-10-13 1997-01-09 The Procter & Gamble Company Detergent compositions containing amines and anionic surfactants
US5981466A (en) * 1994-10-13 1999-11-09 The Procter & Gamble Company Detergent compositions containing amines and anionic surfactants

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU138340A (en) * 1940-04-09 1940-05-14 William Goa-da Elastic band, especially belt or strap
US2954347A (en) * 1955-10-27 1960-09-27 Procter & Gamble Detergent composition
US2954348A (en) * 1956-05-28 1960-09-27 Procter & Gamble Detergent compositions
US3679608A (en) * 1968-08-02 1972-07-25 Procter & Gamble Low foaming hard surface cleaners
US3684723A (en) * 1964-04-21 1972-08-15 Lever Brothers Ltd Detergent composition
US3696056A (en) * 1970-05-28 1972-10-03 Colgate Palmolive Co Ternary foam control systems with amines or amides and detergent compositions containing same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2127077A5 (en) * 1971-02-22 1972-10-13 Colgate Palmolive Co Low-foam detergents - for drum washers,give abundant foam for handwashing
BE792005A (en) * 1971-11-30 1973-03-16 Colgate Palmolive Co NON-FOAMING DETERGENT COMPOSITIONS

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU138340A (en) * 1940-04-09 1940-05-14 William Goa-da Elastic band, especially belt or strap
US2954347A (en) * 1955-10-27 1960-09-27 Procter & Gamble Detergent composition
US2954348A (en) * 1956-05-28 1960-09-27 Procter & Gamble Detergent compositions
US3684723A (en) * 1964-04-21 1972-08-15 Lever Brothers Ltd Detergent composition
US3679608A (en) * 1968-08-02 1972-07-25 Procter & Gamble Low foaming hard surface cleaners
US3696056A (en) * 1970-05-28 1972-10-03 Colgate Palmolive Co Ternary foam control systems with amines or amides and detergent compositions containing same
US3709836A (en) * 1970-05-28 1973-01-09 Colgate Palmolive Co Built anionic detergent composition having inverse foam-to-temperature relationship and process for producing same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155882A (en) * 1973-08-01 1979-05-22 Lever Brothers Company Process for preparing particulate detergent compositions containing nonionic surfactants
US4332692A (en) * 1979-02-28 1982-06-01 The Procter & Gamble Company Laundering with a nonionic detergent system at a temperature between the cloud point and the phase coalescence temperatures
EP0023367A1 (en) * 1979-07-05 1981-02-04 THE PROCTER & GAMBLE COMPANY Detergent composition having textile softening property
US4394127A (en) * 1980-02-07 1983-07-19 Lever Brothers Company Method of depositing perfume and compositions therefor
WO1996012000A1 (en) * 1994-10-13 1996-04-25 The Procter & Gamble Company Detergent compositions containing amines and anionic surfactants
WO1997000929A1 (en) * 1994-10-13 1997-01-09 The Procter & Gamble Company Detergent compositions containing amines and anionic surfactants
US5981466A (en) * 1994-10-13 1999-11-09 The Procter & Gamble Company Detergent compositions containing amines and anionic surfactants

Also Published As

Publication number Publication date
AU5503373A (en) 1974-11-07
FR2187898A1 (en) 1974-01-18
DE2323326A1 (en) 1974-01-03
FR2187898B1 (en) 1977-07-29
CA992833A (en) 1976-07-13

Similar Documents

Publication Publication Date Title
US2486921A (en) Detergent composition
US3741911A (en) Phosphate-free detergent composition
US3325414A (en) Heavy duty detergent composition containing a quaternary ammonium salt
EP0342917B1 (en) Detergent composition
US3144412A (en) Solid detergent compositions
US7354892B2 (en) Low suds laundry detergents with enhanced whiteness retention
US2855367A (en) Detergent composition
US3619115A (en) Cool water laundering process
US3957661A (en) Fabric softening laundry detergent containing organic esters of phosphoric acid
US3285856A (en) Low foaming compositions having good detersive properties
US3649569A (en) Textile treating compounds compositions and processes for treating textiles
US4013577A (en) Heavy duty dry biodegradable detergent composition
US3539521A (en) Detergent composition
CA1082073A (en) Detergent compositions
US4049557A (en) Fabric conditioning compositions
KR900008341B1 (en) Liquid detergent composition
US4009114A (en) Non-phosphate detergent composition
CA1334919C (en) Liquid detergent compositions
US4248729A (en) Detergency booster
US3265624A (en) Detergent composition
US3853779A (en) Low foaming detergent compositions
US3776851A (en) Detergents containing tetrahydroxysuccinic acid and salts thereof
US3231508A (en) Low foaming detergent compositions
US3966649A (en) Liquid detergents containing chelidamic acids and salts thereof
JPH021800A (en) Fabrics softening additive for detergent composition