US3422021A - Detergent composition - Google Patents

Detergent composition Download PDF

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US3422021A
US3422021A US266055A US3422021DA US3422021A US 3422021 A US3422021 A US 3422021A US 266055 A US266055 A US 266055A US 3422021D A US3422021D A US 3422021DA US 3422021 A US3422021 A US 3422021A
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acid
sodium
detergent
builder
water
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Clarence Henry Roy
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Procter and Gamble Co
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    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/367—Organic compounds containing phosphorus containing halogen
    • C11D3/368—Organic compounds containing phosphorus containing halogen containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4025—Esters of poly(thio)phosphonic 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
    • C11D3/36—Organic compounds containing phosphorus
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/367—Organic compounds containing phosphorus containing halogen

Definitions

  • this invention relates to a novel class of substituted methylene diphosphonic acid compounds and their water soluble salts which possess excellent detergency builder properties with a broad range of detergent surface active compounds. Novel laundering compositions whose cleaning powers are enhanced by these novel compounds are also described.
  • water soluble inorganic alkaline builder salts which are used alone or in combination.
  • alkali metal carbonates borates, phosphates, polyphosphates, bicarbonates and silicates.
  • organic builder compounds known heretofore and which also can be used alone and in combination are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g. sodium and potassium ethylenedia-minetetraacetate, sodium and potassium N-(2- hydroxyethyl)-ethylenediaminetriacetate, sodium and potassium nitrilotriacetate and sodium, potassium and triethanolammonium-N-(Z-hydroxyethyl) nitrilodiacetate.
  • Alkali metal salts of phytic acid e.g. sodium phytate are also suitable as organic builders.
  • Another object of this invention is to provide a novel class of compounds. Another object is to provide a novel class of substituted methylenediphosphonic acid compounds and their salts. Another object of this invention is to provide a novel class of compounds which are useful detergent builder compounds. Yet another object is to provide improved detergent compositions containing as the builder material a water soluble substituted methylenediphosphonate salt of the general structure described below. A yet further object is to provide improved built detergent compositions in which the builder material is a substituted methylenediphosphonate water soluble salts of this invention which built compositions are surprisingly effective in cool water washing situations. Another object is to provide detergent compositions in which the builder compound is one specified below and the detergent active is selected from a broad class of detergent surfactant materials.
  • the new class of substituted methylenediphosphonic acid compounds has the following general formula:
  • X and Y are each selected from the group consisting of a methyl radical, a benzyl radical, halogen, carboxymethylene radical, and hydrogen, at least one of X and Y being other than hydrogen.
  • water soluble derivatives of the new compounds of this invention surprisingly have been discovered to be highly efficient detergency builders. They offer as an advantage over previously known builder compounds the possibility of using proportionally smaller amounts of builder compound without sacrificing in overall cleaning performance. Other similarly valuable advantages are discussed hereinafter.
  • alkali metal or ammonium or substituted ammonium (e.g. triethanol ammonium) salt form can be prepared according to this invention
  • the alkali metal derivatives are the preferred forms. Suitable alkali metals include sodium and potassium.
  • the compounds herein are generally obtained as the tetrasodium and trisodium salts as prepared according to this invention.
  • Each of the lesser neutralized forms such as monosodium and disodium derivatives or the free acid form have comparable builder capacity to the trisodium and tetrasodium salt forms, provided, that additional alkali is added to adjust the pH of the washing solution to be within a range of from about 8 to about 12.
  • the standard alkaline materials can be used for this purpose, such as alkali metal silicates, phosphates, borates and carbonates. Free alkali materials such as sodium and potassium hydroxides can be used also.
  • reaction product is a carbanion derived from the active methylene grouping present in the parent methylene ester starting material.
  • the equation for this step is as follows:
  • This carbanion reaction product is then reacted with a suitable alkylating agent or halogenating agent in order to obtain the desired substituted methylenediphosphonate tetraalkyl ester.
  • the phosphonate esters so derived can usually be purified by simple distillative means, if desired, after removal of by-product salts. More often, the crude product is converted directly to the free phosphonic acid by methods kwnown to those skilled in the art, namely, by hydrolyzing with concentrated hydrochloric acid or in the case of isopropyl esters, by pyrolysis.
  • An excellent novel pyrolytic process is described in a copending application Ser. No. 218,863, filed Aug. 23, 1962, by Clarence H. Roy. Addition of base such as sodium hydroxide and potassium hydroxide to the acids results in formation of the corresponding salts.
  • the tetraalkyl ester of methylene diphosphonic acid used as a starting material for preparing the novel compounds of this invention can be prepared according to the following method.
  • a Barrett distilling receiver which had been modified by the addition of a thermometer well and thermometer was connected to the top of the fractionating column; and to the top of the Barrett receiver was fitted a Dewar condenser cooled with Dry Ice and protected from atmospheric moisture by a drying tube.
  • the temperature of the reaction mixture was quickly brought to reflux at 143 C.
  • the temperature of the circulating water in the packed reflux condenser was maintained at 65 C. This temperature was suflicient to return unreacted starting material and allow the by-product isopropyl bromide to be distilled.
  • the heat input to the reaction was such that vigorous refluxing continued as the tem erature of the mixture slowly increased. After about two hours of heating the first distillate was observed, and after five hours a total of 33 gm. of isopropyl bromide had been collected.
  • the temperature of the reaction mixture was allowed to increase to 185 C. over a twelve hour period, and b means of an electronic temperature controller it was held there for the remainder of the reaction.
  • the reaction mixture was transferred to a distilling flask and the low boiling materials (excess phosphite, etc.) were removed through a short one-piece still under a vacuum of 0.1 mm. of mercury and head temperatures up to 50 C. At this point the contents of the flask weighed approximately 330 gm. and was 93% to 95% tetraisopropyl methylenediphosphonate. The purity of this material was suflicient to proceed in the synthesis of the novel compounds of this invention.
  • the low boiling materials excess phosphite, etc.
  • a high capacity vacuum pump can be introduced into the system and the pressure reduced to 0.005 mm. of mercury.
  • the material boiling between C. and 116 C. is collected and redistilled through an electrically heated 24-inch Vigreaux column.
  • Trisodium ethylidenediphosphonate A practical preparation of the title salt was accomplished by refluxing 154 gm. of crude tetraisopropyl ethylidenediphosphonate prepared according to Example 1(A) in 500 ml. of concentrated hydrochloric acid for five hours. The reaction mixture was concentrated to a constant volume and seeded with a few crystals of acid from a previous preparation. The seeded viscous product was then rotated in a flash evaporator under high vacuum until the entire mass had crystallized. The crystalline product was removed from the flask with acetone washes, and an almost theoretical yield of crude ethylidenediphosphonic acid product (M.P. l59163 C.) was obtained. Addition of three equivalents of sodium hydroxide to an aqueous solution of this acid resulted in formation of the trisodium salt which could be used directly in a laundering composition.
  • reaction mixture was then concentrated to a constant volume in vacuo; and the remaining material dissolved in 700 ml. of hexane and extracted with water until halide free. Reduction of the hexane solution to constant in vacuo volume gave 260 gm. of crude tetraisopropyl benzyl-methylenediphosphonate,
  • EXAMPLE VII (A) Preparation of tetraisopropyl dibrornomethylenediphosphonate The dibrominated methylenediphosphonate was obtained from the repeated refractionations of the mixture of monobromo, BrCH[PO(OC H -i) and dibrominated products, Br C[PO(OC H -i) mentioned in Example V. The tetraisopropyl dibromomethylenediphosphonate, Br C[PO(OC H -i) had an N of 1.4710.
  • Each of the acids prepared above is very easily converted to a salt form by reacting with a base such as sodium hydroxide, as illustrated for instance in Example VI.
  • the resulting compounds perform as excellent detergency builder materials as mentioned previously and also as exemplified hereinafter.
  • detergent compositions consisting essentially of an organic detergent surfactant compound and, as a builder, an organic water soluble salt of one of the new compounds identified above, the ratio by weight of the builder to the detergent surfactant compound being in the range of about 1:3 to about 10:1 said composition providing in solution a pH of between about 8 to about 12.
  • the preferred ratio of builder to said detergent surfactant compound is in the range of about 1:2 to about 5:1 and the optimum pH range is between 9.5 to 11.5.
  • organic detergent surfactant compounds which can be successfully built by compounds prepared according to this invention are anionic, nonionic, ampholytic and zwitterionic detergent surfactants, and mixtures thereof.
  • the anionic organic detergents include both soap and non-soap detergents.
  • Suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • the non-soap anionic synthetic detergents can be broadly described as the water soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • alkyl are higher acyl radicals.
  • the synthetic detergents which form a part of the preferred compositions of the present invention are the sodium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkylbenzenesulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, especially those of the types described in United States Letters Patent Nos.
  • sodium alkylglycerylethersulfonates especially those ethers of the higher alcohols derived from tallow and coconut oil
  • sodium coconut oil fatty acid monoglyceride sulfates and sulfonates so-
  • Nonionic synthetic detergents This class of synthetic detergents may be broadly defined as compounds aliphatic or alkyl aromatic in nature which do not ionize in water solution.
  • Pluronic a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with an hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1200 to 2500.
  • the addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.
  • nonionic synthetic detergents include:
  • the polyethylene oxide condensates of alkylphenols, e.g. the condensation products of alkylphenols or dialkylphenols wherein the alkyl group contains from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, said ethylene oxide being present in amounts equal to 8 to 25 moles of ethylene oxide per mole of alkylphenol.
  • the alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, n-octene, or nnonene, for example.
  • Those nonionic compounds derived from the condensation of ethylene Oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are satisfactory.
  • compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylenediamine and excess propylene oxide, said base having a molecular weight on the order of 2,500 to 3,000 are satisfactory.
  • R is an alkyl radical of from about 8 to 18 carbon atoms, and R and R are each methyl or ethyl radicals.
  • the arrow in the formula is a conventional representation of a semi-polar bond.
  • amine Oxides suitable for use in this invention include dimethyldodecylamine oxide, dirncthyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide.
  • dimethyldodecylphosphine oxide dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide,
  • Ampholytic synthetic detergents This class of synthetic detergents can be broadly described as derivatives of aliphatic amines which contain a long chain of about 8 to 18 carbon atoms, and an anionic water solubilizing group, e.g. carboxy, sulfo, or sulfato. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium-3-dodecylaminopropanesulfonate.
  • Zwitterionic synthetic detergents This class of synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium compounds, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g. carboxy, sulfo, or sulfato.
  • Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylammonio)-propane-l-sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate.
  • anionic, nonionic, ampholytic and zwitterionic detergent surfactants mentioned above can be used singly or in combination in the practice of the present invention.
  • the above lists of examples are not intended to be complete but merely specific illustrations of the numerous detergents which can find application within the scope of this invention.
  • organic synthetic detergent compounds and the novel builder compounds of this invention can be formulated according to any of the several commercially desirable composition forms, for example, granular, flake, liquid and tablet form.
  • Granular detergent compositions according to one embodiment of this invention can contain a representative builder and the detergent active in the ratio of about 1:3 to about 10:1.
  • the preferred ratio of builder to detergent active in a granular product is about 1:2 to about 5:1.
  • Another special embodiment of this invention is a liquid detergent composition also containing a builder and a detergent active in the ratio of about 1:3 to about 10:1.
  • the preferred ratios and optimum detergency results with liquid compositions obtain when the builder and the detergent active are mixed in ratios by weight of about 1:2 to about 3:1, respectively.
  • the potassium salt form of the builder compounds is preferred for use in built liquid compositions.
  • the detergent compositions employing the builder compounds of this invention have special and unusually outstanding applicability in the area of built liquid detergents.
  • This area presents special problems to the formulator in view of the peculiarities inherent in aqueous systems and the special requirements of solubility of the ingredients and, more especially, their stability in such mediums.
  • sodium tripolyphosphate which is outstanding in its behavior in granular compositions, is generally regarded as being unsuited for built liquid detergents. It has a fairly strong propensity to hydrolyze into lower forms of phosphates.
  • a sample built liquid detergent composition of this invention can consist essentially of a substituted methylenediphosphonic acid builder compound of this invention and a detergent surfactant in the ratios above described and the balance being a vehicle medium, for example, water, a water-alcohol mixture, etc.
  • a finished detergent formulation of this invention there can be added in minor amounts materials which make the product more effective or more attractive.
  • materials which make the product more effective or more attractive.
  • a soluble sodium carboxymethyl cellulose can be added in minor amounts to inhibit soil redeposition.
  • a tarnish inhibitor such as benzotriazole or ethylenethiourea can also be added in amounts up to about 2%.
  • Fluorescers, perfume, and color while not essential in the compositions of the invention, can be added in amounts up to about 1%.
  • An alkaline materials or alkali such as sodium hydroxide or potassium hydroxide can be added in minor amounts as supplementary pH adjusters.
  • suitable additives water, brightening agents, sodium sulfate, and sodium carbonate.
  • Corrosion inhibitors generally are added also.
  • Soluble silicates are highly effective inhibitors and can be added to certain formulas of this invention at levels of from about 3% to about 8%.
  • Alkali metal, preferably potassium or sodium, silicates having a weight ratio of SiO :M O of from 1.011 to 2.8:1 can be used. M in this ratio refers to sodium or potassium.
  • a sodium silicate having a ratio of SiO :Na O of about 1.6:1 to 2.45:1 is especially preferred for economy and effectiveness.
  • a hydrotropic agent may at times be found desirable.
  • Suitable hydrotropes are water soluble alkali metal salts of toluenesulfonate, benzenesulfonate, and xylenesulfonate.
  • Preferred hydrotropes are the potassium or sodium toluenesulfonates.
  • the hydrotrope salt may be added, if desired, at levels of 0% to about 12%. While a hydrotrope will not ordinarily be found necessary it can be added, if so desired, for any reason such as to produce a product which retains its homogeneity at a low temperature.
  • compositions in which the percentages are by weight, will serve to illustrate but not limit this invention.
  • Each of the compositions in the examples gives in solution a pH within the desired range of from about 8 to about 12.
  • An excellent built liquid detergent formulation according to this invention has the following composition.
  • Percent Sodium dodecylbenzenesulfonate (the dodecyl radical being a polypropylene, predominantly tetrapro- Performance of this detergent composition is excellent in laundry tests as well as dishwashing evaluations. Its resistance to hydrolysis makes possible cleaner washes as well as longer shelf life since the novel builder compound remains in its active form throughout the complete washing cycle notwithstanding the large amounts of water present.
  • a granular detergent composition prepared according to this invention has the following formulations:
  • Washing performance characteristics of this composition are exceptionally good from the point of view of general cleaning and whiteness maintenance performance.
  • EXAMPLE XII Another highly effective granular detergent composition offering equally good laundering performance in the area of whiteness, cleaning and whiteness maintenance has the following formulation:
  • EXAMPLE XIII An effective cool water built liquid detergent which also performs exceptionally well as a heavy duty detergent composition especially in the areas of cleaning and white ness maintenance, has the following composition:
  • cleaning means the ability of a built laundering composition to remove deeply embedded soil lines or deposits such as occur on collars and cuffs.
  • whiteness is a more general term which is a measurement of the ability of a built laundering composition to whiten areas which are only slightly or moderately soiled.
  • Whiteness maintenance is a term used to describe the ability of a built laundering composition of preventing the soil which has been removed from the fabrics during the washing cycle from redepositing back upon the fabrics. Specific test methods are described below.
  • the detergent compositions consisted of a detergent surfactant and a builder.
  • concentration of the surfactant in the washing solution was constant at .03% by weight.
  • the builders also were used in the washing solution at .03% concentration by weight.
  • the washing solutions had a pH of 10.
  • the water contained seven grains (equivalent CaCO per gallon hard- 3 (N,N dimethyl N hexadecylammonio)propane 1- sulfonate, a 1:1 mixture of hexadecyl-Z-hydroxythiosulfate and octadecyl-2-hydroxythiosulfate and Tergitol-IZ- P-12, which is a commercially available dodecyl phenyl polyethyleneglycol ether product prepared by condensing 12 moles of ethylene oxide with one mole of dodecyl phenol.
  • Trisodium ethylidenediphosphonate (EDP) and sodium tripolyphosphate (STP) were used as builders.
  • EDP Trisodium ethylidenediphosphonate
  • STP sodium tripolyphosphate
  • the temperature of the Washing solution was 80 F. and was adjusted to a pH of 11 with sodium hydroxide. Again, the water hardness was seven grains per gallon and the washing cycle lasted ten minutes. The results are presented in Table 11 below:
  • Whiteness measurements were made on the backs of the laundered naturally soiled cuffs with a commercially available photoelectric reflectometer, i.e. a Hunter Color and Color Difference Meter, manufactured by Gardner Laboratory, Inc., Bethesda, Maryland.
  • This instrument is designed to distinguish color dilferences and operates on the tristimulus colorimeter principle wherein the 45 diffuse reflectance of an incident light beam on a test specimen is measured through a combination of green, blue and amber filters.
  • the electrical circuitry of the instrument is so designed that lightness and chromaticity values for the test specimen are read directly.
  • the departure from white (MgO taken as a standard white) of the test specimen is calculated by introducing the lightness and chromaticity values so obtained into a complex mathematical formula supplied by the manufacturer. An evaluation of relative performance compared to a standard detergent composition is thus obtained for the test formulations. These are later compared with other values obtained from other samples.
  • EDP whiteness values are either comparable of with Tergitol as the detergent surfactant or are very sub- (a) fatty acid soaps, and stantially better, as with the second and third detergent (b) water-soluble alkali metal salts of organic sulfuric surfactants in Table III.
  • This type of regroup consisting of the water-soluble salts of ethyldidenedeposited soil on the fabrics is of serious concern and diphosphonic acid, isopropylidenediphosphonic acid, benimprovements in this area are constantly being sought.
  • water-soluble salts being selected from the group consist- TABLE IV.WIIITENESS MAINTENANCE EVALUATION RELATIVE TO %TA1lq ⁇ gARD DETERGENT COMPOSITION; TEMPERATURE 80 F. (NBS Detergent surfactants CoLA, Col.B, 001.0, STP/03% EDP/.03% STP/06% National Bureau of Standards.
  • the whiteness maintenance results obtained with EDP ing of sodium, potassium, ammonium and substituted amat .03% are substantially superior to the whiteness mainmonium salts, wherein the ratio by weight of said builder tenance results attained by STP at .03% with each of to said detergent is in the range of from about 1:3 to the two different surfactants tested. Even more surprisabout 10:1, said composition providing in an aqueous ing, however, are the better whiteness maintenance values solution a pH of from about 8 to about 12. of EDP at .03%, Column B, over the results using STP 2.
  • the ratio by weight of said builder to said deterpecting this superior performance by EDP over STP in gent is within the range of from about 1:2 to about 5:1, such an important detergency area as whiteness mainand provides in aqueous solution a pH of about 9.5 to tenance. 11.5.
  • a detergent composition according to claim 1 whereover-all detergency results attained with the novel builder in the anionic detergent is a watersoluble alkali metal salt compounds of this invention based on comparisons with of an organic sulfuric reaction product having in its moleca sodium tripolyphosphate builder.
  • an alkyl radical having 8 to 22 carbon good performance results in areas of cleaning, whiteness atoms and a radical selected from the group consisting Of and whiteness maintenance are obtained when the subu n c id a d sulfuric acid ester radicals. stituted methylenediphosphonate compounds of this in- 4.
  • a detergent composition according to claim 1 wherevention are employed to build other detergent surfactants in the anionic deters is an alkali metal yl Sulfatfl besides those for which performance d ta i r t d compound in which the alkali metal is selected from soabove. While not complete, a list of suitable soap and syndium and potassium and in which the alkyl substituent thetic non-soap detergent compounds which can be used contains from about 8 to 18 carbon atoms, appears above.
  • novel compounds de- A detergent Composition accol'dng to Claim 1 Wherescribed herein can be used alone as detergent builders, in the anionic detergent is an alkali metal alkylbenezeneor they can be used in admixtures with other organic a d sulfonate in which the alkali metal is selected from sodium inorganic builder materials. and potassium and in which the alkyl group contains from Though the principles of this invention have been illusabout 9 to about 15 carbon atoms.

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US266055A 1963-03-18 1963-03-18 Detergent composition Expired - Lifetime US3422021A (en)

Applications Claiming Priority (5)

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US26605563A 1963-03-18 1963-03-18
DE1793768A DE1793768C3 (de) 1963-03-18 1964-03-17 Substituierte Methylendiphosphonsäuren und deren wasserlösliche Salze
US493925A US3404178A (en) 1963-03-18 1965-10-07 Substituted methylene diphosphonic acids and their salts
NL6514133A NL6514133A (enExample) 1963-03-18 1965-11-01
BE672205A BE672205A (enExample) 1963-03-18 1965-11-10

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US493925A Expired - Lifetime US3404178A (en) 1963-03-18 1965-10-07 Substituted methylene diphosphonic acids and their salts

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BE (1) BE672205A (enExample)
CA (1) CA777769A (enExample)
CH (1) CH465745A (enExample)
DE (2) DE1467655C3 (enExample)
FI (1) FI42559B (enExample)
FR (1) FR1457272A (enExample)
GB (1) GB1026366A (enExample)
NL (1) NL6514133A (enExample)
SE (1) SE300479B (enExample)

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US3639281A (en) * 1966-12-16 1972-02-01 Monsanto Co Built detergent compositions containing tris(methyl phosphonic acid) phosphine oxide and its salts
US3624188A (en) * 1968-10-25 1971-11-30 Procter & Gamble Hypohalogenation of tetramethyl and tetraethyl methylenediphosphonates and trihydrocarbyl phosphonoacetates
US4071456A (en) * 1973-10-23 1978-01-31 Lever Brothers Company Fabric-softening compositions
US3966628A (en) * 1974-08-21 1976-06-29 Westvaco Corporation Solid cleaning compositions containing C21 dicarboxylic acid
US3962100A (en) * 1975-08-18 1976-06-08 The Procter & Gamble Company Fabric softening agents
US4025444A (en) * 1975-08-18 1977-05-24 The Procter & Gamble Company Fabric softening agents
US4478761A (en) * 1980-04-28 1984-10-23 University Of Iowa Research Foundation Method for preparing fluorine-containing phosphonates
US4330486A (en) * 1980-04-28 1982-05-18 University Of Iowa Reseach Foundation Bis(phosphonic acid) difluoromethane
EP0150532A1 (en) 1983-12-22 1985-08-07 The Procter & Gamble Company Peroxygen bleach activators and bleaching compositions
US4814326A (en) * 1985-05-24 1989-03-21 Istituto Gentili S.P.A. Pharmaceutical compositions based on diphosphonates for the treatment of arthrosis and osteoarthritis
US5658954A (en) * 1994-03-17 1997-08-19 Targosz; Eugene F. Whitefly insecticide
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EP0679714A2 (en) 1994-04-28 1995-11-02 The Procter & Gamble Company Detergent compositions containing cellulase enzyme and selected perfumes for improved odor and stability
EP0693549A1 (en) 1994-07-19 1996-01-24 The Procter & Gamble Company Solid bleach activator compositions
WO1996025478A1 (en) 1995-02-15 1996-08-22 The Procter & Gamble Company Detergent composition comprising an amylase enzyme and a nonionic polysaccharide ether
EP0753559A1 (en) 1995-07-13 1997-01-15 The Procter & Gamble Company Method of cleaning textile fabrics
EP0753557A1 (en) 1995-07-13 1997-01-15 The Procter & Gamble Company Packaged foaming composition
EP0763594A1 (en) 1995-09-18 1997-03-19 The Procter & Gamble Company Process for making granular detergents
EP0771785A1 (en) 1995-11-02 1997-05-07 The Procter & Gamble Company Beta-amino ester compounds of perfume alcohols and their use in cleaning or laundry compositions
WO1997042282A1 (en) 1996-05-03 1997-11-13 The Procter & Gamble Company Detergent compositions comprising polyamine polymers with improved soil dispersancy
US6660711B1 (en) 1999-07-16 2003-12-09 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines and mid-chain branched surfactants
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US6790814B1 (en) 1999-12-03 2004-09-14 Procter & Gamble Company Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
US6617300B2 (en) 2000-08-30 2003-09-09 Procter & Gamble Company Granular bleach activators having improved solubility profiles
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US6953587B2 (en) 2000-09-13 2005-10-11 Proacter & Gamble Company Process for making a water-soluble foam component
US20030206965A1 (en) * 2000-09-29 2003-11-06 The Procter & Gamble Company Allergen neutralization compositions
US20030203035A1 (en) * 2000-09-29 2003-10-30 The Procter & Gamble Company Allergen neutralization compositions
US6387864B1 (en) 2000-12-15 2002-05-14 Ecolab Inc. Composition and method for prevention of discoloration of detergents using nonionic surfactants and an alkaline source
US20110053824A1 (en) * 2001-02-28 2011-03-03 Chandrika Kasturi Liquid detergent composition exhibiting enhanced alpha-amylase enzyme stability
US20100022434A1 (en) * 2001-02-28 2010-01-28 Chandrika Kasturi Liquid detergent composition exhibiting enhanced alpha-amylase enzyme stability
US6858570B2 (en) 2001-03-03 2005-02-22 Clariant Gmbh Laundry detergents and laundry treatment compositions comprising one or more dye-transfer-inhibiting dye fixatives
US7091167B2 (en) 2001-03-03 2006-08-15 Clariant Gmbh Laundry detergents and laundry treatment compositions comprising dye-transfer-inhibiting dye fixatives
US20040204590A1 (en) * 2001-12-03 2004-10-14 Ogidigben Miller J. Ep4 receptor agonist, compositions and methods thereof
US20050148521A1 (en) * 2002-01-24 2005-07-07 Yissum Research Development Company Of The Hebrew University Anti-cancer combination and use thereof
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Also Published As

Publication number Publication date
FR1457272A (fr) 1966-01-24
US3404178A (en) 1968-10-01
BE672205A (enExample) 1966-05-10
AU4194564A (en) 1966-09-08
DE1793768A1 (de) 1974-02-28
DE1467655C3 (de) 1975-09-25
CA777769A (en) 1968-02-06
DE1793768B2 (de) 1978-10-05
FI42559B (enExample) 1970-06-01
GB1026366A (en) 1966-04-20
NL6514133A (enExample) 1967-05-02
AU289589B2 (en) 1969-03-17
SE300479B (enExample) 1968-04-29
DE1467655B2 (de) 1973-11-08
DE1793768C3 (de) 1979-06-07
DE1467655A1 (de) 1969-09-25
CH465745A (de) 1968-11-30

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