EP0011333B1 - Teilchenförmiger Reinigungsmittel-Zusatz, welcher einen unlöslichen anionisch-kationischen Weichmacher-Komplex enthält, und Reinigungsmittel, welche den Zusatz enthalten - Google Patents

Teilchenförmiger Reinigungsmittel-Zusatz, welcher einen unlöslichen anionisch-kationischen Weichmacher-Komplex enthält, und Reinigungsmittel, welche den Zusatz enthalten Download PDF

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Publication number
EP0011333B1
EP0011333B1 EP19790200647 EP79200647A EP0011333B1 EP 0011333 B1 EP0011333 B1 EP 0011333B1 EP 19790200647 EP19790200647 EP 19790200647 EP 79200647 A EP79200647 A EP 79200647A EP 0011333 B1 EP0011333 B1 EP 0011333B1
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EP
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Prior art keywords
anionic
additive
quaternary ammonium
particulate
detergent additive
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EP19790200647
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English (en)
French (fr)
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EP0011333A1 (de
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Kenneth Lee Jones
Ellsworth Robert Draper Jr.
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from US06/064,955 external-priority patent/US4265772A/en
Priority claimed from US06/071,424 external-priority patent/US4272386A/en
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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds

Definitions

  • This invention relates to compositions which provide static control benefits in fabric laundering operations. More particularly, it relates to providing these benefits at reduced antistatic agent levels while simultaneously cleansing fabrics by means of conventional detergent compositions and detergency builders.
  • quaternary ammonium compounds are known in the art to possess antistatic properties. These quaternary ammonium compounds are also known to be generally incompatible with anionic surfactants commonly employed in laundering compositions. The anionic surfactants attack and inactivate the quaternary ammonium compounds in the wash-water environment. Thus, larger amounts than desired of the fairly expensive quaternary ammonium compounds must be added to detergent compositions in order to avoid total inactivation in wash solution. It therefore would be highly beneficial, from a performance and economic standpoint, to be able to shield the quaternary ammonium compounds in the wash water, without disturbing their effectiveness as static control agents in the subsequent machine drying process.
  • Some of the quaternary ammonium compound continued to be inactivated by the anionic surfactants, and some of the prills continued to be broken up and dispersed in the wash water, preventing the efficient deposition of antistatic materials of an effective size range onto the fabrics to be treated.
  • the above-described techniques still required the addition of larger quantities of the quaternary ammonium compound than necessary to achieve good static control in the absence of the detergent.
  • the conventional organic agglomerating agents, such as dextrin glue solutions required in US-A-4141841 to agglomerate the prills with the salts could cause poor caking characteristics and flowability problems in the detergent product under certain conditions, making handling and packaging difficult at times.
  • the present invention by contrast, teaches the deliberate pre-wash-water complexing of certain anionic components with the quaternary ammonium compounds to deliver superior static control at significantly reduced levels of antistatic material.
  • U.S. Patent Nos. 3,936,537 and 4,141,841 attempted to avoid the interaction of anionic components with the quaternary ammonium compound upon which the present invention is based.
  • water can act as the agglomerating agent and/or the complexing medium, while producing a product with at least equivalent caking characteristics, and even superior caking qualities under certain conditions.
  • the organic agglomerating agents required in US-A-4141841 have been eliminated in the present invention, reducing material costs and eliminating extra processing and handling steps.
  • the present invention encompasses a particulate detergent additive for preventing static buildup on textiles and for softening fabrics when applied thereto from a laundry solution, the additive comprising a quaternary ammonium compound of formula [R l R 2 R 3 R 4 N]'Y - wherein at least one, but not more than two, of R,, R 2 , R 3 , and R 4 is an organic radical containing a group selected from a C,e-C 12 aliphatic radical, or an alkyl phenyl or alkyl benzyl radical having 10 to 16 carbon atoms in-the alkyl chain, the remaining group or groups being selected from C l -C 4 alkyl, C 2 -C 4 hydroxyalkyl, and cyclic structures in which the nitrogen atom forms part of the ring, Y constituting an anionic radical selected from the group consisting of hydroxide, halide, sulfate, methylsulfate, ethylsulfate and phosphate
  • the complex constitutes 5096-100% of the surface of the particulate additive and most preferably tha anionic complexing component complexes substantially all of the quaternary ammonium compound.
  • the quaternary ammonium compound and optionally the dispersion inhibitor are in admixture with a particulate anionic complexing component, which preferably is sodium tripolyphosphate.
  • the invention also embraces a detergent composition incorporating from 3% to 50.% by weight of the particulate detergent additive together with from 5% to 85% by weight surfactant selected from the group consisting of anionic, nonionic, ampholytic, and zwitterionic surfactants, and mixtures thereof, and from 5% to 85% by weight of detergency builder material.
  • This invention comprises the deliberate, pre-wash-water complexing of quaternary ammonium compounds with certain anionic complexing components to deliver superior static control at significantly reduced levels of antistatic material.
  • the antistatic particles of the present invention are formed by the at least partial complexing of the cationic quaternary ammonium compound with the anionic complexing components.
  • the complex formed should constitute at least 25% of the surfaces of the antistatic particles. More preferably, the complex constitutes at least 50% of the surfaces, and most preferably the complex constitutes substantially all the surfaces of the antistatic particles.
  • the reaction can also result in the complexation of substantially all of the quaternary ammonium compound, although it is preferred that the complexing be limited to the surfaces of the antistatic particles.
  • the present antistatic particles deliver static control advantages because they are less susceptible to wash-water penetration and breakup than the uncomplexed quaternary ammonium particles, thereby allowing for a more efficient deposition of anti- static material of an effective size range and composition onto the laundered fabrics.
  • the complexed material which is relatively water-impermeable and water-insoluble, separates unreacted quaternary ammonium antistatic material from the wash-water environment and thus hinders the inactivation of this antistatic material by anionic surfactants.
  • the complex itself may provide some additional static control of its own to the system.
  • the anionic complexing component should be chosen, in view of the particular cationic antistatic agent used, to achieve such a water-impenetrable and insoluble complex.
  • the complexing components should also be chosen to maximize the antistatic properties of the complex itself.
  • the antistatic particles additionally contain an organic dispersion inhibitor which is intimately mixed with the quaternary ammonium compound and formed into a prill prior to the compiexing reaction.
  • the dispersion inhibitor adds to the water-impenetrability and insolubility of the complex formed and thus enhances the antistatic benefits realized from the present invention.
  • a mixture of anionic complexing components is used.
  • anionic complexing components which are Water-soluble neutral or alkaline salts, especially STP, can absorb excess moisture making the particulate detergent additive stronger and more free-flowing.
  • the additive products of the present invention can be admixed or agglomerated with smectite clays to enhance fabric softening, and the detergent composition of this invention can additionally contain water-soluble detergency compounds and detergency builder salts.
  • the quaternary ammonium compound provides antistatic benefits on the fabrics and also adds an increment of softening benefit to the fabrics, while the detergent surfactant and builder components provide known cleansing and building benefits.
  • the individual particle size of the particulate detergent additive lies in the range from 10 microns to 500 microns, and most preferably from 25 microns to 250 microns, and most preferably from 50 microns to 100 microns. Further, the particulate additive should not have a solubility in water at 25°C of greater than 50 ppm (parts per million), preferably less than 10 ppm.
  • the softening or melting point of the particulate additive should lie in the range from 38°C to 122°C, preferably from 38°C to 93°C, more preferably from 66°C to 79°C.
  • the anionic complexing component required to form the complex is selected from the group consisting of anionic synthetic surfactants; soaps; nonsurfactant electrolytes selected from the group consisting of alkali metal orthophosphates, polyphosphates, borates, tetraborates, silicates, sulfates, and citrates; and mixtures thereof.
  • the anionic component represents from 1% to 90% by weight, more preferably from 5% to 60% by weight, of the particulate detergent additive.
  • the anionic component is preferably reacted with the quaternary ammonium antistatic agent, or antistatic agent/dispersion inhibitor mixture, as a solution (preferably a water solution) which comprises from 196 to 80% by weight, preferably from 5% to 50% by weight of the anionic component.
  • the anionic complexing component is present in such a solution at a concentration close to its saturation point.
  • the anionic complexing solution is preferably sprayed onto the quaternary ammonium compound itself, or onto prills, agglomerates or admixes containing it.
  • a fluidized bed reactor can also be used to contact the anionic solution with the quaternary compound particles or prills.
  • the anionic complexing component can optionally be admixed as a solid with the quaternary ammonium compound before being complexed, preferably by being sprayed with a complexing medium, such as water or an aqueous complexing solution.
  • Nonsurfactant electrolytes suitable as the anionic complexing component include alkali metal phosphates, borates, carbonates, silicates, sulfates, citrates, and mixtures thereof.
  • alkali metal phosphates borates, carbonates, silicates, sulfates, citrates, and mixtures thereof.
  • Preferred are sodium tetraborate, potassium tetraborate, sodium tripolyphosphate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium sulfate, potassium sulfate, sodium citrate, potassium citrate, and mixtures thereof.
  • sodium tripolyphosphate, sodium sulfate, and mixtures thereof are especially preferred.
  • Water-soluble salts of the higher fatty acids are useful as the anionic complexing component herein.
  • Suitable are ordinary alkali metal soaps such as the sodium, potassium, ammonium, and alkanolammonium salts of higher fatty acids containing from 8 to 24 carbon atoms and preferably from 10 to 20 carbon atoms.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soaps.
  • Anionic synthetic surfactants useful as a complexing component herein include water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 8 to 22 carbon atoms and a sulfonic acid or sulfuric acid ester-group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants which can be used in the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Ca-C,a carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium C a -C 2o paraffin sulfonates; and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from 9 to 15 carbon atoms in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
  • anionic surfactant compounds useful herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide either sulfate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 13 carbon atoms.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of alpha- sulfonated fatty acids containing from 6 to 20 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkene sulfonates containing from 10 to 20 carbon atoms in the alkane group; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
  • olefin sulfonates having 12 to 24 carbon atoms.
  • the term "olefin sulfonates” is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxyalkane sulfonates.
  • the sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents for example by liquid S0 2 , chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO 2 , etc., when used in the gaseous form.
  • the alpha-olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 24 carbon atoms preferably 14 to 16 carbon atoms. Preferably they are straight chain olefins.
  • suitable 1-olefins include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and 1- . tetracosene.
  • the olefin sulfonates can contain minor amount of other materials, such as alkene disulfonates depending upon the reaction conditions, proportions of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
  • Preferred anionic synthetic surfactants are alkali and alkaline earth metal, ammonium and alkanol ammonium salts of linear and branched C 10 -C 14 alkyl benzene sulfonates, C 10 -C 20 alpha-sulfo carboxylic acid salts and esters in which the alkyl group has 1-8 carbon atoms, C 10 -C 20 alkane sulfonates, C 14 -C 18 olefin sulfonates, C 10 -C 18 alkyl sulfates and mixtures thereof.
  • the preferred group of anionic complexing components for use herein includes sodium tetraborate, potassium tetraborate, sodium tripolyphosphate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium sulfate, potassium sulfate, sodium citrate, potassium citrate, C 10 -C 14 linear and branched alkyl benzene sulfonates, C 10 -C 18 alkyl sulfates, and mixtures thereof.
  • Especially preferred anionic complexing components are sodium tripolyphosphate, sodium sulfate, C 10 -C 14 linear and branched alkylbenzene sulfonates, and mixtures thereof.
  • the cationic component of the present invention is a quaternary'ammonium antistatic agent, which will be employed in the particulate detergent additive in an amount from 10% to 99% by weight, preferably from 20% to 75% by weight, more preferably from 30% to 60% by weight.
  • Suitable quaternary ammonium antistatic agents are included in U.S. Patent 3,936,537.
  • the quaternary ammonium antistatic agent will normally be employed at a level of from 90% to 20% by weight, and more preferably from 80% to 50% by weight, of the intimate mixture.
  • the antistatic agents useful herein are quaternary ammonium salts of the formula [R 1 R 2 R 3 R 4 N] + Y - wherein R, and preferably R 2 represent an organic radical containing a group selected from a C, 6- C 22 aliphatic radical or an alkyl phenyl or alkyl benzyl radical having 10-16 atoms in the alkyl chain, R 3 and R 4 represent hydrocarbyl groups containing from 1 to 4 carbon atoms, or C 2 -C 4 hydroxy alkyl groups and cyclic structures in which the nitrogen atom forms part of the ring, and Y is an anion such as halide, methylsulfate, or ethylsulfate.
  • the hydrophobic moiety i.e., the C 16 -C 22 aliphatic, C 10 -C 16 alkyl phenyl or alkyl benzyl radical
  • the organic radical R may be directly attached to the quaternary nitrogen atom or may be indirectly attached thereto through an amide, esters, alkoxy, ether, or like grouping.
  • the quaternary ammonium antistatic agents used in this invention can be prepared in various ways well known in the art. Many such materials are commercially available.
  • the quaternaries are often made. from alkyl halide mixtures corresponding to the mixed alkyl chain lengths in fatty acids.
  • the "ditallow" quaternaries are made from alkyl halides having mixed C 14 -C 18 chain lengths. Such mixed di-long chain quaternaries are useful herein and are preferred from a cost standpoint.
  • disallow is intended to refer to the above-described ditallowalkyl. quaternaries.
  • the quaternary ammonium antistatic compounds useful herein include both water-soluble and substantially water-insoluble materials. Imidazolinium compounds enumerated in the US-A-3936537 possess appreciable water solubility and can be utilized in the present invention by mixing with the appropriate type and level of organic dispersion inhibitor and complexing component to give ultimate particle solubility in water of less than 50 ppm (parts per million) at 25°C. Relatively water-soluble quaternary ammonium antistatic agents may also be of the nonring variety, such as diisostearyl dimethyl ammonium chlorides disclosed in U.S. Patent 3,395,100 to Fisher et al.
  • Exemplary quaternary ammonium imidazolinium compounds are specifically methyl-1-alkylamido- ethyl-2-alkyl imidazolinium methyl sulfates, specifically 1-methyl-1-[(tallowamido)ethyl]-2-tallow- imidazolinium methyl sulfate.
  • the most-useful quaternary ammonium antistatic agents are characterized by relatively limited solubility in water.
  • substantially water-insoluble quaternary ammonium antistatic agents suitable for use in the compositions of the instant invention. All of the quaternary ammonium compounds listed can be formulated with the detergent compositions herein, but the compilation of suitable quaternary compounds hereinafter is only by way of example and is not intended to be limiting of such compounds.
  • Dioctadecyldimethyl ammonium chloride is an especially preferred quaternary antistatic agent for use herein by virtue of its high antistatic activity; ditallow dimethyl ammonium chloride is equally preferred because of its ready availability and its good antistatic activity; other useful di-long chain quaternary compounds are dicetyl dimethyl ammonium chloride; bis- docosyl dimethyl ammonium chloride; didodecyl dimethyl ammonium chloride; ditallow dimethyl ammonium bromide; dioleoyl dimethyl ammonium hydroxide; ditallow dimethyl ammonium chloride; ditallow dipropyl ammonium bromide; ditallow dibutyl ammonium fluoride; cetyldecylmethylethyl ammonium chloride; bis-[ditallow dimethyl ammonium] sulfate; tris-[ditallow dimethyl ammonium] phosphate; and the like.
  • the particulate detergent additive contains an organic dispersion inhibitor which is intimately mixed with the quaternary ammonium compound in the form of a prill prior to the complexing reaction.
  • the organic dispersion inhibitor adds to the water-impenetrability and insolubility of the complex formed and thus enhances the antistatic benefits realized from the present invention.
  • the organic dispersion inhibitor represents from 10% to 80% by weight, more preferably from 20% to 50% by weight, of the intimate mixture.
  • the intimate mixture represents from 10% to 99%, preferably from 20% to 90%, most preferably from 30% to 70% by weight of the particulate detergent additive.
  • the dispersion inhibitor should have a solubility in water of 50 ppm maximum at 25°C and a softening point in the range of 38°C-93°C, preferably 52°C-93°C, and is preferably selected from the group consisting of paraffinic waxes, cyclic and acyclic mono-and polyhydric alcohols, substituted and unsubstituted aliphatic carboxylic acids, esters of the foregoing alcohols and acids, C 3 -C 4 alkylene oxide condensates of any of the foregoing materials and mixtures thereof.
  • Tallow alcohol is preferred because of ready availability, but useful dispersion inhibitors include other fatty alcohols in the C, 4 -C ze range, such as myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and mixtures thereof.
  • Saturated fatty acids having 12 to 24 carbon atoms in the alkyl chain can be used, such as: lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, as well as mixtures of these, particularly those derived from naturally occurring sources such as tallow, coconut, and marine oils.
  • Esters of the aliphatic alcohols and fatty acids are useful dispersion inhibitors, provided they have a total of more than 22 carbon atoms in the acid and alkyl radicals. Long chain C 22 -C 3 . paraffinic hydrocarbon materials such as the saturated hydrocarbon octacosane having 28 carbon atoms can also be used.
  • the anionic complexing component may not include soaps, which are more fully described above.
  • sorbitan esters which comprise the reaction product of C, 2 -C ze fatty acyl halides or fatty acids and the complex mixtures of cyclic anhydrides of sorbitol collectively known as "sorbitan".
  • the reaction sequence necessary to produce such sorbitan esters from sorbitol is set out in the Baskerville patent incorporated by reference.
  • the sorbitan esters are, in turn, complex mixtures of mono,- di-, tri-, and tetra-ester forms, of which the tri- and tetra- are the least water-soluble and hence the most preferred for the purposes of the present invention.
  • Typical fatty acids that are suitable for the alkyl portion of the ester are palmitic, stearic, docosanoic, and behenic acids and mixtures ⁇ of any of these.
  • These sorbitan esters, particularly the tri- and tetra-esters, provide a degree of fabric softening in addition to their function as dispersion inhibitors.
  • mixtures of anionic complexing components are used in forming the particulate detergent additives. These mixtures can be formed into a solution and sprayed onto the quaternary ammonium compound forming the desired complex, or, one of the complexing components, preferably a water-soluble neutral or alkaline salt, is added to the system as a solid prior to complexing with a solution of the remaining complexing component.
  • the salt can assist in the formation of the complex, thus enhancing the benefits realized from its formation, and it can itself complex with the quaternary ammonium compound. Further, the salt can absorb excess moisture, making the particulate detergent additive stronger and more free-flowing.
  • a neutral or alkaline salt has a pH in solution of seven or greater.
  • This salt can be either organic or inorganic.
  • the water-soluble, neutral or alkaline salt will be employed in the particulate detergent additive in an amount from 5% to 75% by weight, preferably from 5% to 40% by weight, and more preferably from 10% to 30% by weight of the particulate detergent additive.
  • the dispersion inhibitor/static control agent intimate mixture is admixed with the water-soluble neutral or alkaline salts described herein and this mixture is sprayed with water.
  • the resulting product which is free of conventional agglomerating agents (such as dextrin glues), is a very effective static control product, providing performance, cost and physical property benefits over similar agglomerates which utilize conventional agglomerating agents.
  • water-soluble neutral or alkaline salts examples include alkali metal chlorides such as sodium chloride and potassium chloride, alkali metal fluorides such as sodium fluoride and potassium fluoride, alkali metal carbonates such as sodium carbonates, alkali metal silicates, and mixtures thereof.
  • alkali metal chlorides such as sodium chloride and potassium chloride
  • alkali metal fluorides such as sodium fluoride and potassium fluoride
  • alkali metal carbonates such as sodium carbonates
  • alkali metal silicates alkali metal silicates
  • Any conventional water-soluble, neutral or alkaline inorganic salts such as the alkali metal sulfates, notably sodium sulfate, can be employed in the present invention.
  • Water-soluble, neutral or alkaline salts also include the variety commonly known as detergency builder salts, especially alkaline, polyvalent anionic builder salts.
  • Suitable detergency builder salts include polyvalent inorganic or organic salts or mixtures thereof.
  • Suitable water-soluble, preferred inorganic alkaline detergency builder salts include alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates, and sulfates. Specific examples of such salts include the sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates and hexametaphosphates.
  • suitable organic alkaline detergency builder salts are: water-soluble amino- polyacetates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)nitrilodiacetates; water-soluble salts of phytic acid, e.g., sodium and potassium phytates; water-soluble polyphosphonates, including sodium, potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium and lithium salts of methylene diphosphonic acid and comparable examples.
  • water-soluble amino- polyacetates e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)nitrilodiacetates
  • water-soluble salts of phytic acid e.g., sodium and potassium phytates
  • water-soluble polyphosphonates including sodium, potassium and lithium salt
  • the particulate detergent additive may optionally contain smectite clay as an ingredient.
  • smectite clays may be admixed with the particulate detergent additive of this invention at levels from 5% to 70% by weight, preferably from 20% to 60% by weight, and most preferably from 25% to 50% by weight of the resulting admixture, to form compositions which provide laundered fabrics with outstanding fabric softening and static control benefits.
  • the clays used herein are "impalpable", i.e., have a particle size which cannot be perceived tactilely. Impalpable clays have particle sizes below 50 microns; the clays used herein have a particle size range of from 5 microns to 50 microns.
  • the clay minerals can be described as expandable, three-layer clays, i.e., aluminosilicates and magnesium silicates, having an ion exchange capacity of at least 50 meq/100 g. of clay and preferably at least 60 meq/100 g. of clay.
  • expandable as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water.
  • the three-layer expandable clays used herein are those materials classified geologically as smectites.
  • smectite clays There are two distinct classes of smectite clays that can be broadly differentiated on the basis of the number of octahedral metal-oxygen arrangements in the central layer for a given number of silicon- oxygen atoms in the outer layers.
  • the clays employed in the compositions of the instant invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions.
  • cation exchange capacity (sometimes termed “base exchange capacity") in terms of milliequi- valents per 100 g. of clay (meq/100 g.).
  • base exchange capacity cation exchange capacity
  • the cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971).
  • the cation exchange capacity of a clay mineral relates to such factors as the expandable properties of the clay, the charge of the clay, which, in turn, is determined at least in part by the lattice structure, and the like.
  • the ion exchange capacity of clays varies widely in the range from 3 meq/100 g. of kaolinites to 150 meq/100 g., and greater, for certain smectite clays.
  • Illite clays although having a three layer structure, are of a nonexpanding lattice type and have an ion exchange capacity somewhere in the lower portion of the range, i.e. around 26 meq/100 g. for an average illite clay.
  • Attapulgites another class of clay minerals, have a spicular (i.e. needle-like) crystalline form wilth a low cation exchange capacity (25-30 meq/100 g).
  • Their structure is composed of chains of silica tetrahedrons linked together by octahedral groups of oxygens and hydroxyl containing AI and Mg atoms.
  • illite, attapulgite, and kaolinite clays are not useful in the instant compositions. Indeed, illite and kaolinite clays constitute a major component of clay soils which are removed from fabric surfaces by means of the instant compositions.
  • the alkali metal montmorillonites, saponites, and hectorites, and certain alkaline earth metal varieties of these minerals such as calcium montmorillonites have.been found to show useful fabric-softening benefits when incorporated in compositions in accordance with the present invention.
  • smectite clay minerals include: sodium montmorillonite, sodium hectorite, sodium saponite, calcium montmorillonite, and lithium hectorite. Accordingly, smectite clays useful herein can be characterized as montmorillonite, hectorite, and saponite clay minerals having an ion exchange capacity of at least 50 meq/100 g., and preferably at least 60 meq/100 g.
  • the smectite clays are preferably admixed with the particulate detergent additive after the additive has been aged for a time sufficient for the complexing reaction to have been substantially completed.
  • the particulate detergent additive of the present invention can be further incorporated in a detergent composition, by, for example, dry mix addition, with a surfactant selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic surfactants, and mixtures thereof. From 5% to 85% by weight, preferably from 5% to 50% by weight, and most preferably from 10% to 25% by weight of the final detergent composition can comprise the organic surfactant component.
  • organic surfactants useful herein have been described above as possible anionic complexing components, and are further described in U.S. Patent 3,579,454, from column 11, line 45 through column 13, line 64. An extensive discussion of surfactants is contained in U.S. Patent 3,936,537 from column 11, line 39 through column 13, line 52.
  • detergent compositions of the present invention can be included in the detergent compositions of the present invention.
  • detergency builders such as those enumerated in the US-A-3936537 from column 13, line 54 through column 16, line 17, as well as color speckles, bleaching agent and bleach activators, suds boosters or suds suppressors, anti- tarnish and anti-corrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, alkalinity sources, hydrotropes, enzymes, enzyme- stabilizing agents, perfumes, alkyl polyethoxylate nonionic surfactants, and other optional detergent compounds.
  • the detergent compositions of the instant invention can contain a detergency builder in an amount from 5% to 85% by weight, preferably from 15% to 60% and most preferably from 20% to 40% by weight of the entire detergent composition.
  • a solution containing from 1 % to 80% by weight, preferably from 5% to 50% by weight of an anionic complexing component is prepared.
  • the anionic complexing component is present in solution at a concentration close to its saturation point.
  • the anionic complexing component represents from 1% to 90% by weight, preferably from 10% to 60% by weight, of the particulate detergent additive.
  • the anionic complexing component is selected from the group consisting of anionic synthetic surfactants; soaps, non-surfactant electrolytes selected from the group consisting of alkali metal phosphates, borates, carbonates, silicates, sulfates, and citrates; and mixtures thereof.
  • water alone is the solvent of the complexing solution.
  • the solution is sprayed onto the quaternary ammonium compound, resulting in the at least partial complexing of the quaternary ammonium compound with the anionic complexing component.
  • the complex formed should constitute at least 25% of the surfaces of the anti-static particles. More preferably, the complex constitutes at least 50% of the surfaces, and most preferably the complex constitutes substantially all the surfaces of the antistatic particles.
  • the reaction can also result in the complexation of substantially all of the quaternary ammonium compound, although it is preferred that the complexing be limited to the surfaces of the antistatic particles.
  • the anionic complexing component can optionally be admixed as a solid with the quaternary ammonium compound prior to being complexed, preferably by being sprayed with a complexing medium. This complexing medium is preferably water or, with further improvement, a solution of anionic complexing component in water.
  • the quaternary ammonium antistatic compound is intimately mixed with an organic dispersion inhibitor and formed into particulates, or prills, according to methods more fully described in U.S. Patent 3,936,537.
  • a water-soluble neutral or alkaline salt preferably sodium tripolyphosphate
  • Water-soluble neutral or alkaline salts agglomerated with these prills are described in European published Application No. A1-0000416.
  • the agglomerates can also result in the formation of stable agglomerates consisting of the anionic complexing component and the prilled particles.
  • the agglomerates are substantially free of organic agglomerating agents, and preferably, water alone acts as the agglomerating agent.
  • Smectite clay is optionally admixed or agglomerated into the additive product to provide an additional fabric-softening benefit.
  • the complexing medium can be sprayed onto the quaternary ammonium antistatic compound particles, prills, agglomerates, and other complexing components, in a mixer, such as the Schugi mixer (Flexomix 160, 250, 335 or 400), the O'Brien mixer, the Littleford mixer, the Patterson-Kelly mixer, ribbon mixers, a fluidized bed, and/or virtually any of the conventionally-known pan agglomerators.
  • the optional smectite clays can be admixed with the additive product in a conventional pan agglomerator.
  • the resulting particulate detergent additive composition is aged for approximately one hour, optionally mixed with silica if increased flowability is desired, and admixed with conventional detergent granules.
  • a particulate detergent additive composition is prepared as follows:
  • the dimethyl di-hydrogenated tallow ammonium chloride (DTDMAC) and tallow alcohol were melted together to form a clear solution at 122°C.
  • This molten solution was atomized at 11032 kPa into a chamber with ambient temperature air passing through the chamber.
  • the atomized droplets froze into solid particles in the size range of 20 microns to 150 microns.
  • the softening point of the DTDMAC/tallow alcohol mixture was 74°C.
  • the DTDMAC/tallow alcohol mixture had a solubility of substantially less than 10 ppm in 25°C water.
  • the prills in all the subsequent examples have essentially the same characteristics.
  • Sodium tripolyphosphate (STP) and the DTDMAC/tallow alcohol prills, in a 7:4 ratio of priII:STP were fed into a Schugi mixer (Flexomix 160) where they were thoroughly admixed.
  • the sodium tripolyphosphate was a dry, anhydrous, powder with at least 90% passing through a 100-mesh Tyler sieve.
  • the 7:4 ratio priii:STP mixture was sprayed with an anionic complexing solution comprising 0.7 parts sodium citrate, per 1 part water.
  • the particulate detergent additive product was discharged from the. Schugi Flexomix 160 mixer onto a pan agglomerator and there mixed with sodium montmorillonite clay of good fabric softening performance and having an ion exchange capacity of 63 meq/100 g. (available from Georgia Kaolin Co. USA under the trade name Brock), which was also discharged onto the pan agglomerator.
  • the resulting mix was aged for approximately one hour, mixed with silica to increase flowability, and then admixed, by dry mix addition, with a conventionul detergent composition comprising surfactants, builders and other optional detergent ingredients.
  • the particulate detergent additive product provided increased static control performance and softening benefits relative to uncomplexed DTDMAC particles and to uncomplexed DTDMAC/tallow alcohol prills, either alone, when merely admixed with anionic complexing components or salts, or when agglomerated with anionic complexing components or salts, using conventional organic agglomerating agents.
  • sodium citrate and/or the STP are replaced with other anionic complexing components, such as: sodium tetraborate, potassium tetraborate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium sulfate, potassium sulfate, potassium citrate, anionic surfactants such as Cl,7-Cl4 linear and branched alkylbenzene sulfonates and C 16 -C 18 alkyl sulfates, and mixtures thereof.
  • anionic complexing components such as: sodium tetraborate, potassium tetraborate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium sulfate, potassium sulfate, potassium citrate, anionic surfactants such as Cl,7-Cl4 linear and branched al
  • sodium tripolyphosphate is replaced with other water-soluble neutral or alkaline salts, such as: sodium tetraborate, potassium tetraborate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium sulfate, potassium sulfate, sodium citrate, potassium citrate, and mixtures thereof.
  • sodium tetraborate potassium tetraborate
  • potassium tripolyphosphate sodium pyrophosphate
  • potassium pyrophosphate sodium hexametaphosphate
  • potassium hexametaphosphate sodium sulfate
  • potassium sulfate sodium citrate, potassium citrate, and mixtures thereof.
  • the organic dispersion inhibitor is a mixture of C 10 -C 22 alkyl sorbitan esters, the major component of which is one or more esters selected from the group consisting of sorbitan trilaurate, sorbitan trimyristate, sorbitan tripalmitate, sorbitan tristearate, sorbitan tetralaurate, sorbitan tetramyristate, sorbitan tetrapalmitate, sorbitan tetrastearate, and mixtures thereof.
  • esters selected from the group consisting of sorbitan trilaurate, sorbitan trimyristate, sorbitan tripalmitate, sorbitan tristearate, sorbitan tetralaurate, sorbitan tetramyristate, sorbitan tetrapalmitate, sorbitan tetrastearate, and mixtures thereof.
  • the silica is an optional additive, and substantially similar results are achieved without its inclusion.
  • the particulate detergent additive of Example I was incorporated into a detergent composition as follows:
  • the particulate detergent additive of Example t is incorporated into a detergent composition as follows:
  • compositions of Examples II and III provide the static control advantages at reduced antistatic ,agent levels, as described in Example I.
  • a particulate detergent additive composition was prepared as follows:
  • the particulate detergent additive provided stable agglomerates and increased static control performance and softening benefits relative to STP/prill agglomerates formed using conventional agglomerating agents, such as dextrin glues. Also, material costs were reduced and extra processing and handling steps were eliminated due to the elimination of conventional agglomerating agents.
  • sodium tripolyphosphate is replaced with other water-soluble neutral or alkaline salts, such as: sodium tetraborate, potassium tetraborate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium sulfate, potassium sulfate, sodium citrate, potassium citrate, and mixtures thereof.
  • sodium tetraborate sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium sulfate, potassium sulfate, sodium citrate, potassium citrate, and mixtures thereof.
  • the organic dispersion inhibitor is a mixture of C 10 -C 22 alkyl sorbitan esters, the major component of which is one or more esters selected from the group consisting of sorbitan trilaurate, sorbitan trimyristate, sorbitan tripalmitate, sorbitan tristearate, sorbitan tetralaurate, sorbitan tetramyristate, sorbitan tetrapalmitate, sorbitan tetrastearate, and mixtures thereof.
  • esters selected from the group consisting of sorbitan trilaurate, sorbitan trimyristate, sorbitan tripalmitate, sorbitan tristearate, sorbitan tetralaurate, sorbitan tetramyristate, sorbitan tetrapalmitate, sorbitan tetrastearate, and mixtures thereof.
  • the silica is an optional additive, and substantially similar results are achieved without its inclusion.
  • a particulate detergent additive composition was prepared as follows:
  • composition of the admix was as follows:
  • Example IV The above-described mix was admixed on a 31 part basis, by dry mix addition, with the base detergent granule composition described in Example II.
  • the detergent composition demonstrated the benefits described in Example IV.
  • a 7:4 ratio prill:STP mixture was prepared according to the procedure of Example I. The mixture was sprayed with an anionic complexing solution in a Schugi mixer. This procedure was repeated with other anionic complexing solutions being sprayed onto other samples of 7:4 prill:STP mixtures. As a control composition, a 7:4 prill:STP mixture was sprayed with a dextrin-water organic agglomerating agent solution. The reaction of the anionic complexing components (the STP and the anionic component contained in the solution) with the DTDMAC in the prills resulted in the formation of a relatively insoluble complex which constituted at least 10% of the surfaces of the prills.
  • Sodium montmorillonite clay was admixed with the complexed prills and/or the complexed prill agglomerates in a pan agglomerator. The resulting admix was incorporated into a conventional detergent composition, by dry mix addition, with the base detergent granules of Example II.
  • a series of fabrics were washed in these respective compositions, including the control composition, at a wash water temperature of 38°C and at a water hardness of 34.2 ppm and then dried under ordinary machine drying conditions and at a dew point of 5°C. These were full-scale washer and dryer loads using conventional fabric bundles. The fabrics were then measured for average volts per square yard using a Faraday cage apparatus and for number of clings.
  • the admix compositions and the percent usage of the admix (equivalent to 5.0% DTDMAC in the finished product) in the final detergent compositions were as follows: The results were as follows:

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Claims (10)

1. Teilchenförmiger Waschmittel-Zusatz zur Verhinderung der statischen Aufladung von Textilien und zum Weichmachen von Geweben wenn er aus einer Waschlösung auf dieselben aufgebracht wird, enthaltend eine quaternäre Ammoniumverbihdung der Formel [R1R2R3R4N]+Y-, worin mindestens einer, jedoch nicht mehr als 2 der Reste R" R2, R3 und R4 ein organischer Rest ist, der einen aliphatischen C16-C22-Rest oder einen Alkylphenyl- oder Alkylbenzylrest mit 10 bis 16 C-Atomen in der Alkylkette enthält, wobei die restliche(n) Gruppe(n) C1-C4-Alkyl, C2-C4-Hydroxyalkyl oder cyclische Strukturen sind, worin das Stickstoff-atom einen Teil des Ringes bildet, und Y einen anionischen Rest bedeutet und zwar Hydroxid-, Halogenid-, Sulfat-, Methylsulfat-, Ethylsulfat- oder Phosphationen, und gegebenenfalls einen organischen Dispersionsinhibitor, der ein organischer Feststoff ist mit einer Löslichkeit in Wasser von maximal 50 ppm bei 25°C und einem Erweichungspunkt von 24 bis 122°C, wobei dieser Stoff ein Paraffinwachs, cyclischer oder acyclischer ein- oder zweiwertiger Alkohol, eine substituierte oder nicht substituierte aliphatische Carbonsäure, ein Ester der vorstehenden Alkohole und Säuren, C3-C4-Alkylenoxidkondensat einer der vorstehenden Stoffe und Gemische davon ist, wobei im wesentlichen alle Teilchen eine Größe von 10,um bis 500 jum, eine Löslichkeit in Wasser von maximal 50 ppm bei 25°C und einen Erweichungspunkt von 24 bis 122°C aufweisen, dadurch gekennzeichnet, daß der teilchenförmige Zusatz einen Komplex enthält, enthaltend
(a) 10 bis 99 Gew.-%, bezogen auf den Zusatz der quaternären Ammoniumverbindung und
(b) 1 bis 90 Gew.-% eines anionischen Komplexbildners in Form von anionischen synthetischen oberflächenaktiven Stoffen, Seifen, nicht-oberflächenaktiven Electrolyten in Form von Alkalimetallphosphaten, -boraten, -carbonaten, -silikaten, -sulfaten und -citraten und Gemischen der vorstehenden Stoffe, worin der Komplex mindestens 25% der Oberfläche des teilchenförmigen Zusatzes darstellt.
2. Teilchenförmiger Waschmittelzusatz nach Anspruch 1, worin der Komplex 50 bis 100% der Oberfläche des teilchenförmigen Zusatzes darstellt.
3. Teilchenförmiger Waschmittelzusatz nach Anspruch 2, worin der anionische Komplexbildner im wesentlichen die gesamte quaternäre Ammoniumverbindung komplexiert.
4. Teilchenförmiger Waschmittelzusatz einer der Ansprüche 1 bis 3, enthaltend 5 bis 60Gew.-% des anionischen Komplexbildners.
5. Teilchenförmiger Waschmittelzusatz einer der Anspüche 1 bis 4, worin der anionische Komplexbildner Natrium- oder Kaliumtetraborat, -tripolyphosphat, -pyrophosphat, -hexametaphosphat, -sulfat, -citrat, C10-C14-lineares oder verzweigtes Alkylbenzolsulfonat, C10-C18-Alkylsulfat oder Gemische davon ist.
6. Teilchenförmiger Waschmittelzusatz einer der Ansprüche 1 bis 5, enthaltend 20 bis 75 Gew.-% der quaternären Ammoniumverbindung.
7. Teilchenförmiger Waschmittelzusatz einer der Ansprüche 1 bis 6, worin die quaternäre ammoniumverbindung gegebenenfalls mit einem Dispersionsinhibitor mit einer wäßrigen Lösung, die den anionischen Komplexbildner enthält, versprüht ist.
8. Teilchenförmiger Waschmittelzusatz nach Anspruch 7, worin die quaternäre Ammoniumverbindung und gegebenenfalls der Dispersionsinhibitor im Gemisch mit einem teilchenförmigen anionischen Komplexbildner vorliegen.
9. Teilchenförmiger Waschmittelzusatz nach Anspruch 8, worin der mit der quaternären Ammoniumverbindung vermischte anionische Komplexbildner Natriumtripolyphosphat ist.
10. Waschmittel zur Verhinderung des statischen Aufladens von Textilien und zum Weichmachen von damit gewaschenen Geweben, dadurch gekennzeichnet, daß er enthält:
(1) 5 bis 85 Gew.-% eines anionischen, nichtionischen, ampholytischen oder zwitterionischen oberflächenaktiven Stoffes oder Gemische davon,
(2) 5 bis 85 Gew.-% eines Detergensgerüststoffs und
(3) 3 bis 50 Gew.-% des teilchenförmigen Waschmittelzusatzes gemäß einem der Ansprüche 1 bis 9.
EP19790200647 1978-11-16 1979-11-06 Teilchenförmiger Reinigungsmittel-Zusatz, welcher einen unlöslichen anionisch-kationischen Weichmacher-Komplex enthält, und Reinigungsmittel, welche den Zusatz enthalten Expired EP0011333B1 (de)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US96144578A 1978-11-16 1978-11-16
US96144678A 1978-11-16 1978-11-16
US06/064,955 US4265772A (en) 1978-11-16 1979-08-08 Antistatic, fabric-softening detergent additive
US64955 1979-08-08
US06/071,424 US4272386A (en) 1978-11-16 1979-08-30 Antistatic, fabric-softening detergent additive
US71424 1979-08-30
US961445 1997-10-30
US961446 1997-10-30

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DE3271167D1 (en) * 1981-09-11 1986-06-19 Procter & Gamble Fabric softening detergent additive products and use thereof in detergent compositions
US4786422A (en) * 1986-10-06 1988-11-22 Colgate-Palmolive Co. Fabric softening and antistatic particulate wash cycle laundry additive containing cationic/anionic surfactant complex on bentonite
DE69424551T3 (de) † 1994-12-02 2005-12-29 The Procter & Gamble Company, Cincinnati Kationisches Tensid enthaltende Waschmittelzusammensetzungen sowie deren Herstellung
CN1216660C (zh) * 1995-02-14 2005-08-31 联合泡沫技术公司 稳定的和防水的含水泡沫组合物
GB0207483D0 (en) 2002-03-28 2002-05-08 Unilever Plc Fabric conditioning compositions
US8097580B2 (en) 2008-06-26 2012-01-17 The Procter & Gamble Company Liquid laundry treatment composition comprising an asymmetric di-hydrocarbyl quaternary ammonium compound
US8163690B2 (en) 2008-06-26 2012-04-24 The Procter & Gamble Company Liquid laundry treatment composition comprising a mono-hydrocarbyl amido quaternary ammonium compound

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US3959155A (en) * 1973-10-01 1976-05-25 The Procter & Gamble Company Detergent composition
US3936537A (en) * 1974-11-01 1976-02-03 The Procter & Gamble Company Detergent-compatible fabric softening and antistatic compositions
IT7828107A0 (it) * 1977-09-26 1978-09-26 Procter & Gamble Composizione detergente antistatica a effetto ammorbidente sui tessuti e procedimento per produrre tale composizione.

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