US3892681A - Detergent compositions containing water insoluble starch - Google Patents

Detergent compositions containing water insoluble starch Download PDF

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US3892681A
US3892681A US333103A US33310373A US3892681A US 3892681 A US3892681 A US 3892681A US 333103 A US333103 A US 333103A US 33310373 A US33310373 A US 33310373A US 3892681 A US3892681 A US 3892681A
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ppm
weight
sodium
starch
carbon atoms
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James Byrd Edwards
Francis Louvaine Diehl
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to US333103A priority Critical patent/US3892681A/en
Priority to AU65320/74A priority patent/AU480918B2/en
Priority to DE2406518A priority patent/DE2406518C2/de
Priority to CA192,287A priority patent/CA1037209A/en
Priority to PH15508A priority patent/PH10856A/en
Priority to IT7448380A priority patent/IT1002941B/it
Priority to GB693074A priority patent/GB1429911A/en
Priority to FR7405289A priority patent/FR2218381B1/fr
Priority to NLAANVRAGE7402097,A priority patent/NL188475C/xx
Priority to BE140953A priority patent/BE811082A/xx
Priority to JP49019032A priority patent/JPS5829840B2/ja
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Publication of US3892681A publication Critical patent/US3892681A/en
Priority to US05/594,909 priority patent/US4051046A/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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads

Definitions

  • Modern laundry detergent compositions, machinery and adjunct chemical additives e,g., fabric softeners, washing machines and dryers
  • benefits sought to be imposed upon the fabrics carried through an entire cycle from washing to drying are fluffiness, softness, body, reduced electrostatic charge, diminished wrinkling, and ease of ironing. No single product or machine process is presently available which will achieve all of these benefits simultaneously.
  • present day fabric softeners impart a softness to the fabric (actually this softness is best likened to a tactile sensation of lubricity, which is distinguishable from fabric softness occasioned by enhanced fabric bulkiness) and control of electrostatic charge.
  • Modern day washing machines and dryers by means of elaborate cycles and temperature control are able to markedly improve the extent of fabric wrinkling.
  • Other products such as the well-known laundry starches impart, when applied after the washing cycle, an ease of ironing benefit and impart a body to the fabric, i.e., a sizing effect.
  • the detergent compositions of this invention impart all of these benefits simultaneously through the wash. That is, the laundry compositions of this invention, by some imperfectly understood physico-chemical interaction at the fiber or yarn level, impart through the wash cycle the above enumerated benefits. These benefits are solely attributable to the presence of starch granules hereinafter defined in combination with organic surface-active agents.
  • Detergent compositions comprising starch are not new per se. It has long been known that gross quantities of starch by means of its gel-forming character impart desirable physical properties to toilet soap bars. Also, the properties of starch as a binding agent, as an agglomerating agent, as a film-forming agent, and as an inert diluent have been exploited in granulated detergent compositions. Starch and starch derivatives have also been used in gross amounts in synthetic detergent compositions to improve the efficiency of the prilling process, that is, formation of the detergent granule from the aqueous medium in which it was either synthesized or resolubilized.
  • starch granule For these prior art purposes there is no criticality as to the integrity, size or freeness (discreteness) of the starch granule. In fact, the starch for such prior art processes is typically modified by degradation or derivatization to enhance its water solu bility and film-forming propensities. In any event, prior art detergent compositions comprising some form of starch are characteristically of poor deterging power and impart a harsh stiffness to fabrics.
  • starch-containing detergent composition which impart anti-wrinkling, ease of ironing, fabric softening (herein, the term softening is related to increased bulkiness), anti-static, folding ease and enhanced fabric drapability effects to fabrics laundered therein.
  • laundry detergent compositions formulated which are capable of simultaneously cleaning the fabrics laundered therein and also imparting to these fabrics a series of desirable properties including anti-wrinkling, ease of ironing, fabric softening, anti-static, folding ease and enhanced fabric drapability properties.
  • compositions which are capable of concurrently cleansing and imparting desirable fabric properties to the fabrics laundered therein.
  • Such compositions comprise:
  • an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergent and mixtures thereof;
  • the inventive compositions contain, in addition to the essential ingredients referred to hereinbefore, from about 1% to about 50% by weight of a smectite-type clay having an ionexchange capacity of at least about 50 meg/ grams.
  • this invention relates to a method for treating fabrics to simultaneously cleanse and impart anti-wrinkling, ease of ironing, softening and anti-static properties.
  • Such a method comprises treating fabrics in an aqueous liquor comprising:
  • the present invention relates to detergent compositions capable of concurrently cleaning and imparting desirable textile properties to fabrics washed therewith.
  • compositions comprise: (1) an organic surface-active agent and (2) a particular granular starch; in a preferred embodiment, the instant compositions also contain a smectite-type clay.
  • the essential starch component for use in the compositions of the instant invention is substantially waterinsoluble, has an average particle diameter from 1.0 to about 45, preferably from about 5 to about 25 micrometers, and has a swelling power of less than about at a temperature at 65C.
  • the starch component is to be incorporated in an amount from 0.1% to about 6%, preferably from 0.2% to about 4%.
  • Above the upper limit the previously enumerated benefits derivable from the compositions of this invention are diminished to the extent that an undesirable stiffness to textiles laundered with the instant compositions occurs. This stiffness negative is attributable to high levels of starch, i.e., exceeding about the limits as claimed.
  • the starch granules and fractures must be substantially structurally intact for properly performing their function within the compositions of the invention.
  • the swelling power is determined according to the method set forth in Cereal Chem, 36, pp. 534-544 (1959) Harry W. Leach, et al.
  • Ten grams of starch is suspended in 180 ml. of distilled water in a tared 250- ml. centrifuge bottle.
  • the suspension is mechanically stirred with a small stainless-steel paddle (0.75-inch wide, 1.5-inches high) at a rate just sufficient to keep the starch completely suspended (i.e., 200 rpm.) This low speed avoids shearing the fragile swollen granules and consequent solubilization of the starch.
  • the bottle is lowered into a thermostatted water bath maintained at a temperature of 65C (i0.lC.) and held for 30 minutes, slow stirring being continued during this period.
  • the bottle is then removed, wiped dry, and placed on the torsion balance.
  • the stirrer is removed and rinsed into the bottle with sufficient distilled water to bring the total weight of water present to 200.0 g. (including the moisture in the original starch).
  • the bottle is stoppered, mixed by gentle shaking, and then centrifuged for 15 minutes at 2200 rpm. (i.e., 700 times gravity). The clear supernate is carefully drawn off by suction to within one-quarter inch of the precipitated paste.
  • Starches having a swelling power of more than 15 at 65C are not suitable for use in the instant composition.
  • suitable starches can for example be obtained from corn, wheat, and rice.
  • Current potato and tapioca starches have a swelling power exceeding 15 at a tem perature of 65C and, therefore, are not suitable for being used in the compositions of this invention.
  • More complete information concerning water-insoluble starches, the processes for their preparation and isolation from a variety of raw materials are well known [see for example, The Starch Industry, Knight, J. W. Pergamon Press, London (1969)].
  • starch granules interact with the textile material at the fiber level to impart the above enumerated benefits to the textile fabric as a whole.
  • textile materials consist essentially of assemblies of fine flexible fibers arranged in more or less orderly geometrical arrays. Individual fibers within the assembly are usually in a bent or twisted configuration and are in various states of contact with neighboring fibers. When the assembly is deformed the fibers move relative to each other and this relative motion accounts to a large extent for the characteristic flexibility of textile materials.
  • textile fabrics treated in accordance with the present invention are characterized by having discrete starch granules intimately dispersed, in a substantive fashion, in the interstices of the fiber matrix. It is believed that these starch granules, so interfiberly positioned, act in the manner of ball bearings to reduce interfiber forces during deformation of the textile fabric as a whole. The gross effect is the enhancement of visco-elastic recovery (anti wrinkling effect) and diminution of the forces operable at interfiber contact points (ease of ironing effect). Under this conceptualization the starch granule diameter limitation is appreciated since most commercially available textile fibers have diameters which fall within the range of about 10 to about 30 micrometers. Therefore, to be effective, the starch granules of the invention must be comparable to the textile fiber diameters.
  • the starch granules as a dry powder can be admixed with a previously prepared detergent, or the starch granules as a cold water dispersion can be sprayed onto a previously prepared detergent formulation just prior to packaging. But in every case, the starch admixing step is subsequent to any moist heating step which might alter the native granular integrity of the starch granule.
  • the essential organic detergent suitable for use use in the compositions of the present invention is selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof. Said component is to be used in an amount from about 4% to about 60%, preferably from about 6% to about 40%.
  • detergent compound examples include the following:
  • Suitable soaps include the sodium, potassium, ammonium and alkanolammonium (e.g., mono-, di-, and triethanolammonium) salts by higher fatty acids (C C).
  • C C The sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps, are particularly useful.
  • Anionic synthetic detergents also include watersoluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a moiety selected from the group consisting of sulfonic acid and sulfuric acid ester moieties.
  • alkyl is the alkyl portion of higher acyl moieties.
  • examples of this group of synthetic detergents which form a part of the preferred built detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating higher alcohols (CR-C18 carbon atoms) produced by reducing glycerides of tallow or coconut oil; sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 20 carbon atoms in straight chain or branched-chain configuration, e.g., those of the type described in US. Pat. Nos.
  • 2,220,099 and 2,477,383 (especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 1 1.8 carbon atoms and commonly abbreviated as C, ,LAS); 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; sodium and potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl groups contain from about 8 to about 12 carbon atoms.
  • Anionic phosphate surfactants are also useful in the present invention. These are surface active materials having substantial detergent capability in which the anionic solubilizing group connecting hydrophobic moieties is an oxy acid of phosphorus.
  • the more common solubilizing groups are SO H and SO H.
  • Alkyl phosphate esters such as (RO) PO H and R0- PO H in which R represents an alkyl chain containing from about 8 to about 20 carbon atoms are useful herein.
  • phosphate esters can be modified by including in the molecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units.
  • Formulae for these modified phosphate anionic detergents are [R-O- (CH CH O) P-O-M or 0 ll CR CH-CHSOM where R is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group); R is alkyl of l to about 8 carbon atoms; and M is a water-soluble cation.
  • the water-soluble cation, M, in the hereinbefore described structural formula can be, for example, an alkali metal cation (e.g., sodium, potassium, lithium), ammonium or substituted-ammonium cation.
  • alkali metal cation e.g., sodium, potassium, lithium
  • substituted ammonium cations include methyl-, dimethyl-, and trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • beta-acyloxy-alkane- 1 sulfonates or alternatively 2-acyloxy-alkane- 1- sulfonates, useful herein include the sodium salt of 2- acetoxy-tridecanel-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecane-l-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecanel-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1- sulfonic acid; the sodium salt of Z-acetoxy-hexadecanel-sulfonic acid; the potassium salt of 2-octanoyloxytetradecane-l-sulfonic acid; the sodium salt of 2- acetoxy-heptadecane-l-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-l-sulfonic acid; the potassium salt of 2-acetoxy-
  • beta-acyloxy-alkane-l-sulfonate salts herein are the alkali metal salts of beta-acetoxy-alkanel-sulfonic acids corresponding to the above formula wherein R is an alkyl of about 12 to about 16 carbon atoms, these salts being preferred from the standpoints of their excellent cleaning properties and ready availability.
  • anionic detergent compounds herein both by virtue of superior cleaning properties and low sensitivity to water hardness (Ca-H- and Mg-l-lions) are the alkylated a-sulfocarboxylates, containing about to about 23 carbon atoms, and having the formula 6 wherein R is C, to C alkyl, M 18 a water-soluble cation as hereinbefore disclosed, preferably sodium ion, and R is short-chain alkyl, e.g., methyl, ethyl, propyl, and
  • alkylated a-sulfocarboxylates for use herein include:
  • lithium methyl-a-sulfolaurate as well as mixtures thereof.
  • Still another class of anionic organic detergents are the B-alkyloxy alkane sulfonates.
  • the compounds have the following formula:
  • R is a straight chain alkyl group having from 6 to 20 carbon atoms
  • R is a lower alkyl group having from 1 (preferred) to 3 carbon atoms
  • M is a watersoluble cation as hereinbefore described.
  • B-alkyloxy alkane sulfonates or alternatively 2-alkyloxy-alkane-l-sulfonates, having low hardness (calcium ion) sensitivity useful herein to provide superior cleaning levels under household wash ing conditions include:
  • anionic non-soap synthetic detergents which come within the terms of the present invention are the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil.
  • Other anionic synthetic detergents of this variety are set forth in US. Pat. Nos. 2,486,921; 2,486,922; and 2,396,278.
  • anionic, non-soap, synthetic detergents which come within the terms of the present invention, are the compounds which contain two anionic functional groups. These are referred to as dianionic detergents.
  • Suitable di-anionic detergents are the di-sulfonates, disulfates, or mixtures thereof which may be represented by the following formulae:
  • C to C dipotassium-1,2-alkyldisulfonates or disulfates disodium 1,9-hexadecyl disulfates
  • C to C disodiuml ,2-alkyldisulfonates disodium l ,9- stearyldisulfates and 6,lO-octadecyldisulfates.
  • the aliphatic portion of the disulfates or disulfonates is generally substantially linear, thereby imparting desirable biodegradable properties to the detergent compound.
  • the water-solubilizing cations include the customary cations known in the detergent art, i.e., the alkali metals, and the ammonium cations, as well as other metals in group 11A, 118, 111A, WA and IVB of the Periodic Table except for boron.
  • the preferred watersolubilizing cations are sodium or potassium.
  • Still other anionic synthetic detergents include the class designated as succinamates.
  • This class includes such surface active agents as disodium N-octadecylsulfo-succinamate; tetrasodium N-(l,2-dicarboxyethyl)- N-octadecyl-sulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.
  • the preferred surface-active agents for use in the compositions of the instant invention include alkyl ether sulfates and olefin sulfonates.
  • the preferred alkyl ether sulfates have the formula wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, an M is a salt forming cation such as alkali metal (sodium, lithium, potassium) ammonium, amines and substituted ammonium. Examples of these latter include lower C alkyl amines, and mono, di and trimethanol and ethanolamines.
  • alkyl ether sulfates wherein R has from about 14 to about 18 carbon atoms and wherein x has an average value of about 1 to about 6.
  • especially preferred species are: sodium coconut alkyl ethylene glycol ether sulfate; sodium tallow alkyl triethylene glycol ether sulfate; sodium tallow alkyl pentaoxyethylene sulfate; ammonium tetradecyl pentaoxyethylene sulfate and ammonium lauryl hexaoxyethylene sulfate.
  • Especially preferred alkyl ether sulfate components have an average (arithmetic mean) carbon chain length within the range of from about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms; and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide, preferably from about 2 to 3 moles of ethylene oxide.
  • Such mixtures comprise from about 0.05% to by weight of mixture of C 12.13 compounds, from about 55% to 70% by weight of mixture of C compounds, from about 25% to 40% by weight of mixture of C compounds and from about 0.1% to 5% by weight of mixture of C compounds.
  • such preferred alkyl ether sulfate mixtures comprise from about 15% to 25% by weight of mixture of compounds having a degree of ethoxylation of 0, from about 50% to 65% by weight of mixture of compounds having a degree of ethoxylation from 1 to 4, from about 12% to 22% by weight of mixture of compounds having a degree of ethoxylation from 5 to 8 and from about 0.5% to 10% by weight of mixture of compounds having a degree of ethoxylation greater than 8.
  • alkyl ether sulfate mixtures falling within the above-specified ranges are set forth in Table TABLE 1 MIXTURE CHARACTERISTIC ALKYL ETHER SUL- MlX- FATE TURE Average carbon chain 1 11 111 IV Length (No. C Atoms) 14.86 14.68 14.86 14.88 12-13 carbon atoms (wt. 4% 1% 1% 3% 14-15 carbon atoms (wt.%) 55% 65% 65% 57% 16-17 carbon atoms (wt.%) 36% 33% 33% 38% l819 carbon atoms (wt.%) 5% 1% 1% 2% Average degree of ethoxylation (No.
  • Said ingredients can be produced by sulfonation of a-olefins by means of uncomplexed sulfurdioxide followed by neutralization in conditions such that any sultones present are hydrolyzed to the corresponding hydroxy-alkane sulfonates.
  • the a-olefin starting materials preferably have from 14 to 16 carbon atoms.
  • Said preferred a-olefin sulfonates are described in great detail in US. Pat. specification No. 3,332,880, Adriaan Kessler et al., patented July 25, 1967, enclosed herein by reference.
  • Said a-olefin sulfonates can be represented either by individual species or by mixtures containing structurally different sulfonation products.
  • Preferred mixtures are disclosed by Kessler et 211.; one such mixture consists essentially of from about 30% to about by weight of a Component A, from about 20% to about 70% by weight of a Component B, and from about 2% to about 15% of a Component (C), wherein a.
  • said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-1- sulfonic acids containing from about 20 to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a betagamma unsaturated isomer, about 5% to about 25% of gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;
  • said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 20 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms at least of the hydroxy radical substitutions being in 3, 4, and 5 positions; and
  • said Component C is a mixture comprising from about 3095% water-soluble salts of alkene disulfonates containing from about 20 to about 24 carbon atoms, and from about 5% to about 70% water-soluble i 1 1 salts of hydroxy disulfonates containing from about 20 to about 24 carbon atoms, said alkene disulfonates containing a sulfonic group attached to a terminal carbon atom and a second sulfonate group attachedto aniniternal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atoms, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which isnot more than
  • hydroxy sulfonates include sodium salts of sodium 3-hydroxy-n-decyll -sulfonate, sodium 3--hydroxy-n-dodecyll -sulfonate,- sodium 3-hydroxy-n-tetradecyll -sulfonate, sodium 3-hydroxy-n-hexadecyll-sulfonate, sodium 3-hydroxy-n-octadecyl-l-sulfonate, sodium 3-hydroxy-n-eicosyll -sulfonate, sodium 3-hydroxy-n-docosyl-l-sulfonate, Y sodium 3-hydroxy-n-tetracosyl-l-sulfonate, 1 sodium 4-hydroxy-n-decyl-l-sulfonate, sodium 4-hydroxy-n-dodecyl-l-su lfon
  • nonionic surfactants are compounds produced by the condensation. of an alkylene oxide (hydrophilic in nature) with an organic hydrophobic compound which-is usually aliphatic or alkyl aromatic in nature; The length of the hydrophilic or polyoxyalkylene moiety which is condensed with any particular hydrophobic compoundcan be readily adjusted to yield a water-soluble compound havingthe desired degree of balance between hydrophilic and hydropho-- bic elements.
  • Anothertype of nonionicsurfactants are the so-called polar nonionics derived from amine ox ides, phosphine oxides or sulfoxides. Examples of suitable nonionic surfactants include: 1
  • the polyethylene oxide condensates of alkyl.phe-: nols. These compounds include the condensation prodnets of: alkyl phenols having an alkylgroup containing from ;about.6 tor-l2 carbonatoms in either a-sgraight chain rot-branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 :to 25 moles of ethylene oxide per mole of alkyl-phenol.
  • Thealkyl substituentin such compounds may-be de'rived,for example, from polymerized propylen'e," diisobutylene, octene, or nonene.
  • Examples of compounds of this type include'de nonyl phenol condens'ed with about moles of ethylene oxide per mole of nonyl phenol, 'dodecyl phenol condensed'with about 12-moles' of ethylene oxide per mole of phenol,'dinonyl phenol' condens'ed with about 15 moles of ethylene oxide per mole of phenol, di-isooctylphenol condensed with-about 15 moles of ethylene oxide per mole of phe- "nol, Commercially available nonionic surfactants of this typei'riclude Igep'al CO-6l0'marketed by the GAP Corporation; and Triton X-45, X-l l4, X and X- 102', all 'rhar'lteted by the 'Rohm and Haas'Company.
  • the condensation products of aliphatic alcohols with ethylene'oxide may either be straight or branch ed and generally contains from about' 8'to about 22 carbon atoms.
  • ethoxylated alcohols include the condensationprod'uct of about 6 moles of ethylene oxide with 1 mole of tridecanol, myristylalcohol condensed with about l0 moles of ethylene oxide per mole of myr istyl alcohol, the condensation product of ethylene oxide with coconut fatty alcohol wherein the coconut aleohol is mixture of fatty alcohols with alkyl chains varying 'from lQ to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per .mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the abovede sc'ribed coconut alcohol.
  • v I i v The condensation products of ethyleneoxide with a hydrophobic bases formed bythe condensation of propyleneoxidewith propylene glycol.
  • the hydrophoportion of these compounds has a molecular weight of from about 1.500 to 1800 and of course exhibits water insolubility,
  • the addition of polyoxyethylene moieties 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 wherethepolyoxyethylene contentis about 50% of thetotal weight .of the condensationproduct.
  • Examples of compounds of this type include certain, of the commercially available Pluoronic surfactants marketed by the Wyandotte Chemicals Corporation.
  • the hydrophobic base of these products consists of the reaction product of ethylene diamine and excess propylene oxide, said base having amolecular weight of from about 2500 to about 3000.1
  • This bae is-condensed with ethylene oxide to the extent that the'condensation product contains from about 40% to about 80% byweight of polyoxyethylene and has'amolecular'weight of from about 5,000 to about 111,000.
  • this type of nonionic surfactant include certain of the commercially available Te- 13 tronic compounds marketed by the Wyandotte Chemicals Corporation.
  • Surfactants having the formula RR R N O (amine oxide surfactants) wherein R is an alkyl group containing from about 10 to about 28 carbon atoms, from O to about 2 hydroxy groups and from O to about 5 ether linkages, there being at least one moiety of R which is an alkyl group containing from about 10 to about 18 carbon atoms and no ether linkages, and each R and R is selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms;
  • amine oxide surfactants include: dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, bis- (Z-hydroxyethyl -3-dodecoxyl -hydroxypropylamine oxide, (2-hydroxypropyl )methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-(2- hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.
  • Surfactants having the formula RR R P O phosphine oxide surfactants
  • R is an alkyl group containing from about 10 to about 28 carbon atoms, from O to about 2 hydroxy groups and from O to about 5 ether linkages, there being at least one moiety of R which is an alkyl group containing from about 10 to about 18 carbon atoms and no ether linkages, and each R and R is selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms.
  • phosphine oxide detergents include: dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide, dipropyldodecylphosphine oxide, bis-(hydroxymethyl)- dodecylphosphine oxide, bis-(2-hydroxyethyl)- dodecyclphosphine oxide, (2-hydroxypropyl)methyltetradecylphospine oxide, dimethyloleylphosphine oxide, and dimethyl-(Z-hydroxydodecyl)phosphine oxide and the corresponding
  • sulfoxide surfactants include octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, 3-hydroxy-tridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxy- 4-dodecoxybutyl methyl sulfoxide, octadecyl-2- hydroxyethyl sulfoxide, and dodecylethyl sulfoxide.
  • nonionic surfactants include the condensation product of nonyl phenol with about 9,5 moles of ethylene oxide per mole of nonyl phenol, the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide per mole of coconut fatty alcohol, the condensation product of tallow fatty alcohol with about 1 l moles of ethylene oxide per mole of tallow fatty alcohol and the condensation product of a secondary fatty alcohol containing about 15 carbon atoms with about 9 moles of ethylene oxide per mole of fatty alcohol.
  • AMPI-IOLYTIC SYNTHESIS DETERGENTS falling within this definition are sodium 3- (dodecylamino)-propionate, sodium 3- dodecylamino )propanel-sulfonate, sodium 2- (dodecylamino)ethyl sulfate, sodium 2- (dimethylamino)octadeconoate, disodium 3-(N- carboxymethyldodecylamino)-propane-1-sulfonate, disodium octadecyl-iminodiacetate, sodium l-carboxymethyl-Z-undecylimidazole, and sodium N,N-bis(2- hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.
  • Sodium 3-(dodecylamino)-propane-l-sulfonate is preferred.
  • ZWITTERIONIC SYNTHETIC DETERGENTS can be broadly described as derivatives of secondary and tertiary amine, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
  • the cationic atom in the quaternary compound can be part of a heterocyclic ring.
  • aliphatic group straight chain or branched, containing from about 3 to 18 carbon atoms and at least one aliphatic substituent containing an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfato, phosphato, or phosphono.
  • anionic water-solubilizing group e.g., carboxy, sulfonate, sulfato, phosphato, or phosphono.
  • Preferred compounds of this class from a commercial standpoint are 3-(N,N-dimethyl-N- hexadecylammonio)-2-hydroxypropane- 1 -sulfonate; 3-(N,N-dimethyl-N-alkylammonio)-2- hydroxypropane-l-sulfonate, the alkyl group being derived from tallow fatty alcohol; 3-(N,N-dimethyl-N- hexadecylammonio)propane-l-sulfonate; 3-(N,N- dimethhyl-N-tetradecyl-ammonio)propane-1- sulfonate; 3-(N,N-dimethhyl-N-alkylammonio )-2- hydroxypropane-l-sulfonate, the alkyl group being derived from the middle cut of coconut fatty alcohol; 3- (N,N-dimethyldodecylammonio)-2
  • R is an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group containing from 10 to 20 carbon atoms
  • M is a bivalent radical selected from the group consisting of aminocarbonyl, carbonylamino, carbonyloxy, aminocarbonylamino, the corresponding thio groupings and substituted amino derivatives
  • R and R are alkylene groups containing from 1 to 12 carbon atoms
  • R is alkyl or hydroxyalkyl containing from 1 to carbon atoms
  • R is selected from the group consisting of R groups R M-R and -R COOMe wherein R R R and R are as defined above and Me is a monovalent salt-forming cation.
  • Compounds of the type include N,- N-bis(oleylamidopropyl)-N-methyl-N-carboxymethylammonium betaine; N,N-bis(stearamidopropyD-N- methyl-N-carboxymethylammonium betaine; N- (stearamidopropyl)-N-dimethyl-N-carboxymethylammonium betaine; N,N-bis(oley1amidopropyl)-N-(2- hydroxyethyl)-N-carboxymethylammonium betaine; and N-N-bis-(stearamidopropyl)-N-(2-hydroxyethyl)- N-carboxymethylammonium betaine.
  • Zwitterionic surfactants of this type are prepared in accordance with methods described in US. Pat. No. 3,265,719 and DAS No. 1,018,421.
  • R is an alkyl group, R is a hydrogen atom or an alkyl group, the total number of carbon atoms in R and R being from 8 to 16 and NR "Z wherein R is an alkarylmethylene group containing from about 8 to 24 carbon atoms in the alkyl chain; R is selected from the group consisting of R groups and alkyl and hydroxyalkyl groups containing from 1 to 7 carbon atoms; R is alkyl or hydroxyalkyl containing from 1 to 7 carbon atoms; R is alkylene or hydroxyalkylene containing from 1 to 7 carbon atoms and Z is selected from the group consisting of sulfonate, carboxy and sulfate.
  • Examples of zwitterionic surfactants of this type include 3-(N-dodecylbenzyl-N,N dimethylammonio)propanel -sulfonate; 4-(N- dodecylbenzyLN,N-dimethylammonio )butaneJ sulfonate; 3-(N-hexadecylbenzyl-N,N- dimethylammonio )propanel -sulf0nate; 3-( N- dodecylbenzyl-N,N-dimethylammonio)propionate; 4- (N-hexadecylbenzyl-N,N-dimethylammonio)butyrate; 3-(N-tetradecylbenzyl-N,N-dimethylammonio)propane- 1 -sulfate; 3-(N-dodecylbenzyl-N ,N- dimethylammonio)-2-hydroxypropanel-sulfonate; 3- [N
  • R is an alkylphenyl, cycloalkylphenyl or alkenylphenyl group containing from 8 to 20 carbon atoms, in the alkyl, cycloalkyl or alkenyl moiety;
  • R and R2" are each aliphatic groups containing from 1 to 5 carbon atoms;
  • R and R are each hydrogen atoms, hydroxyl groups or aliphatic groups containing from 1 to 3 carbon atoms and R is an alkylene group containing from 2 to 4 carbon atoms.
  • Examples of zwitterionic surfactants of this type include 3-(N-dodecylphenyl-N,N- dimethylammonio)propanel-sulfonate; 4-(N- hexadecylphenyl-N,N-dimethyl )butanel -sulfonate; 3-(N-tetradecylphenyl-N,N-dimethylammonio)-3,3- dimethylpropane-l-sulfonate and B-(N-dodecylphenyl- N ,N-dimethylammonio )-3-hydroxypropanel sulfonate.
  • Compounds of this type are described more fully in British Pats. Nos. 970,883 and 1,046,252, incorporated herein by reference.
  • preferred compounds include 3(N,N- dimethyl-N-alkylammonio)-propanel -sulfonate and 3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropanel-sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl- N-hexadecylammonio)propane-1-sulfonate; 3(N,N- dimethyl-N-hexadecylammonio)-2-hydroxypropane-lsulfonate; 3-(N-dodecylbenzyl-N,N- dimethylammonio )-propanel -sulfonate; (N- dodecylbenzyl-N,N-dimethylammonio)acetate; 3-(N- dodecylbenzyl-N,N-dimethylammonio)
  • the clay component for use in the preferred compositions of the instant invention consists of particular smectite clay materials. These smectite clays are present in the detergent compositions at levels from about 1% to about 50%, preferably from 5% to 20% of the total compositions.
  • Such clay minerals used to enhance the beneficial properties of the instant compositions can be described as expandable, three-layer clays, i.e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least 50 meq/lOO 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-type clays There are two distinct classes of smectite-type clays; in the first, aluminum oxide is present in the silicate crystal lattice; in the second class of smectites, magnesium oxide is present in the silicate crystal lattice.
  • the general formulas of these smectites are Al (Si O OH) and Mg (Si O (Oi-U for the aluminum and magnesium oxide type clay, respectively. It is to be recognized that the range of the water of hydration in the above formulas can vary with the processing to which the clay has been subjected. This is immaterial to the use of the smectite clays in the present invention in that the expandable characteristics of the hydrated clays are dictated by the silicate lattice structure.
  • the three-layer, expandable alumino-silicates useful herein are further characterized by a dioctahedral crystal lattice, while the expandable three-layer magnesium silicates have a trioctahedral crystal lattice.
  • the clays employed in the compositions of the instant invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ion, magnesium ion, and the like. 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.
  • a typical exchange reaction involving a smectite-type clay is expressed by the following equation: smectite caly (Na) Nl-LOH 2 smectite clay (NI-1,) +NaOH Since in the foregoing equilibrium reaction, one equivalent weight of ammonium ion replaces an equivalent weight of sodium, it is customary to measure cation exchange capacity (sometimes termed base exchange capacity) in terms of milliequivalents per g. of clay (meq./l00 g.).
  • 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, lnterscience (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 about 2 meq/ 100 g.
  • Illite clays 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.
  • illite and kaolinite clays are not useful in the preferred embodiments of the instant compositions. Indeed, such illite and kaolinite clays constitute a major component of clay soils and, as noted above, are removed from fabric surfaces by means of the instant compositions.
  • smectites such as nontronite, having an ion exchange capacity of approximately 50 meq/lOO g.
  • saponite which has an ion exchange capacity of around 70 meq/lOO g.
  • montmorillonite which has an ion exchange capacity greater than 70 meq/ 100 g.
  • clay minerals useful herein can be characterized as expandable, three-layer smectite-type clays having an ion exchange capacity of at least about 50 meq/lOO g.
  • Said clay component reinforces the beneficial properties of fabrics laundered therewith, particularly the softening (lubricity) characteristics, by reference to what is obtained from compositions of the instant invention which do not contain said smectite-type clay.
  • Said additional benefits can be ascribed without being limited by this theory to the physical characteristics and ion-exchange properties of the clay used. That is to say, experiments have shown that nonexpandable clays such as the kaolinites and the illites, which are both classes of clays having ion exchange capacities below 50 meq/ 100 g., do not provide the beneficial aspects of the clays employed in the instant compositions.
  • the unique physical and electrochemical properties of the smectite clays apparently cause their interaction with, and dispersion by, the additional components of the instant compositions.
  • the smectite clays used in the preferred compositions herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite.
  • the clays herein are available under various tradenames, for example, Thixogel No. l and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volclay No. 325, from American Colloid Co., Skokie, Illinois; Black Hills Bentonite BH450,
  • smectite-type minerals obtained under the foregoing tradenames can comprise mixtures of the various discreet mineral entities. Such mixtures of the smectite minerals are suitable for use herein.
  • smectite-type clays having a cation exchange capacity of at least about 50 meq/ 100 g. are useful herein, certain clays are preferred.
  • Gelwhite GP is an extremely white form of smectite clay and is therefore preferred when formulating white granular detergent compositions.
  • Volclay BC which is a smectite-type clay mineral containing at least 3% of iron (expressed as Fe O in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in laundry compositions and is preferred from the standpoint of product performance.
  • certain smectite clays marketed under the name bentonite are sufficiently contaminated by other silicate minerals that their ion exchange capacity falls below the requisite range, and such clays are of no use in the instant compositions.
  • Appropriate clay minerals for use herein can be selected by virtue of the fact that smectites exhibit a true 14A x-ray diffraction pattern. This characteristic pattern, taken in combination with exchange capacity measurements performed in the manner noted above, provides a basis for selecting particular smectite-type minerals for use in the granular detergent compositions disclosed herein.
  • Detergent builder salts can also advantageously be employed in the compositions of the present invention.
  • Said component can be inorganic or organicin nature and can. be selected from a wide variety of known builder salts; said builders are used in an amount from about 10% to about preferably from about 10% to about 40%.
  • the weight ratio of organic surfaceactive agent to detergent builder salt is from 20:1 to 1:20, and preferably from 10:1 to 1:10.
  • Suitable alkaline, inorganic builder salts include thealkali metal carbonates, aluminates, phosphates, polyphosphates and silicates. Specific examples of these salts are sodium or potassium tripolyphosphates, aluminates, carbonates, phosphates and hexametaphosphates.
  • Suitable organic builder salts include the alkali metal, ammonium and substituted ammonium polyphosphonates, polyacetates, and polycarboxylates.
  • the polyphosphonates specifically include the sodium and potassium salts of ethylene diphosphonic acid, sodium and potassium salts of ethane-l-hydroxy- 1,1-diphosphonic acid and sodium and potassium salts of ethane-1,1 ,2-triphosphonic acid.
  • Examples of these polyphosphonic compounds are disclosed in British Pat. Nos. 1,026,366; 1,035,913; 1,129,687; 1,136,619; and 1,140,980.
  • the polyacetate builder salts suitable for use herein include the sodium, potassium lithium, ammonium, and substituted ammonium salts of the following acids; ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)- ethylenediarninetriacetic acid, N-(2.-hydroxyethyl)- nitrilodiacetic acid, diethylenetriaminepentaacetic acid, l,2-diaminocyclohexanetetraacetic acid and nitrilotriacetic acid.
  • the trisodium salts of the above acids are generally preferred.
  • polycarboxylate builder salts suitable for use herein consist of water soluble salts of polymeric aliphatic polycarboxylic acids as, for example, described inU.S. Pat. No. 3,308,067 to F. L. Diehl, patented Mar. 7, 1967; this patent being hereby incorporated by reference. 7
  • Preferred detergent builder salts for use in the compositions of the instant invention include the watersoluble salts of: (1) amino polycarboxylates; (2) ether polycarboxylates; (3) citric acid; and (4) aromatic polycarboxylates derived from benzene. These preferred detergent builder salts are preferably used in an amount from about 10% to about 40%.
  • the water-soluble amino-polycarboxylate pounds have the structural formula COIl'l- COOM CH COOM and each M is selected from hydrogen and a saltforming cation.
  • These materials include the water-soluble aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N- (Z-hydroxyethyl)nitrilodiacetates.
  • water-soluble salts of nitrilotriacetic acid e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N- (Z-hydroxyethyl)nitrilodiacetates.
  • water-soluble aminopolycarboxylates e.g., sodium and potassium ethylenediaminetetraacetates
  • nitrilotriacetates e.g., sodium and potassium ethylenediaminetetraacetates
  • nitrilotriacetates e.g., N- (Z-hydroxyethyl)nitrilodiacetates.
  • the water-soluble ether polycarboxylates have the formula:
  • R is selected from -CH COOM7 CH CH COOM
  • R is selected from CH2COOM7 CH -CH COOM,' (2H (3H 7 COOM COOM COOM .COOM COOM I I CH C C and COOM COOM COOH I I' -CH 'CH 7 whereby R and R from a closed ring structure in the event said moieties are selected from COOM COOM COOM COOM c a C and CH CH- each M is selected from hdrogen and a salt-forming cation.
  • the salt-forming cation M can be represented, for example, by alkali metal cations such as potassium, lithium and sodium and also ammonium and ammonium derivatives.
  • Citric acid also known as '2- hydroxy-propane-l,2,3-tricarboxylic acid, has the formula CH COOM C (OH) COOM CH2'COOM Citric acid while it occurs in free state in nature, large quantities of it are produced, for example, as byproduct of sugar departing from sugar beets.
  • the neutralizing cation is preferably selected from alkali metal ions such as sodium, potassium, lithium and from ammonium and substituted ammonium such as mono-, di-, and trimethylolammonium and also mono-, di-, and triethanolammonium cations.
  • Water-soluble salts of mellitic acid, benzenepentacarboxylic acid and mixtures thereof constitute another class of preferred polycarboxylate builders for use in the subject compositions.
  • a particular aspect of the present invention encompasses a method for treating fabrics for concurrently cleansing and imparting beneficial characteristics to fabrics.
  • the fabrics are treated in an aqueous liquor comprising as an essential component, from about 10 ppm to about 5000 ppm, preferably from about 100 ppm to about 3000 ppm of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergent and mixtures thereof.
  • Suitable and preferred detergents for use in the instant method are the same as those which do fit the composition aspect of this invention; these species have been described in great detail hereinbefore.
  • Another essential ingredient for use in the aqueous liquor is represented by granular substantially waterinsoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about at a temperature of 65C.
  • Said starch ingredient is used to the extent from about 0.1 ppm to 900 ppm, preferably from about 2 ppm to about 200 ppm.
  • Starch species suitable for being used are identical to those which fit the requirements of the composition aspects of this invention; said species are described in great detail hereinbefore.
  • fabrics are treated in an aqueous liquor comprising, in addition to the essential organic surface-active agents and starch referred to hereinbefore, as well from about 50 ppm to about 5000 ppm, preferably from about 50 ppm to 2500 ppm of a smectite-type clay having an ion-exchange capacity of at least about 50 meg/ g.
  • the aqueous washing liquor used for carrying out the method of this invention can for example be prepared by adding to a substantially aqueous medium, laundry formulations corresponding to the detergent compositions encompassed in this invention. Similar results are obtained, however, by adding the individual ingredients to the aqueous medium. As an example thereof, one may consider adding to the aqueous medium a granular detergent compositions containing all ingredients except starch which is to be added separately. It is also possible to prepare a detergent composition containing actives and other usual ingredients whereas the starch is added in combination with fillers like sodium sulfate or with builders like sodium carbonate. Another possiblity resides in preparing a combination of the starch together with clay and other suitable additives; said mixture is than added to the aqueous solution containing, for example, the additional essential components.
  • the peroxy bleach compound can be represented by all usual inorganic and organic ingredients which are known to be satisfactory for being incorporated for that purpose in detergent compositions.
  • inorganic peroxy bleach compounds are the alkaline metal salts of perborates, percarbonates, persilicate's, persulfates, and perphosphates.
  • the perborates can have different degrees of hydration. Although frequently the tetra hydrate form is used, it is for certain purposes desirable to incorporate perborates having a lower degree of hydration water, for example, one mole, two moles, or three moles.
  • Organic peroxy bleach agents may be used as well.
  • the like ingredients can be incorporated as such, i.e., they have been prepared perviously or they may be prepared in situ through the addition of, for example, any peroxy bleach agents suitable for being used in combination with an organic peroxy bleach activator.
  • organic peroxy bleach compounds are the water-soluble salts of monoand diperoxy acids such as perazelaic acid, monoperoxy phthalic acid, diperoxy terephthalic acid, 4- chlorodiperoxyphthalic acid.
  • Preferred aromatic peracids include the water-soluble salts of diperiosphthalic 25 acid, m-chloroperbenzoic acid and p-nitroperbenzoic acid.
  • peroxy bleach compound In the event the peroxy bleach compound is to be prepared in situ, then its precursors, ie the peroxy bleach agent and peroxygen activators are to be added separately to the detergent composition.
  • the peroxy gen bleach can be represented by all oxygen bleaching agents which are commonly used in detergent technology, i.e. organic and inorganic species, as mentioned hereinbefore.
  • the activating agents can be represented by all the oxygen activators known as being suitable for use in detergent technology. Specific examples of the preferred activators include acylated glycoluriles, tetra-acetyl methylene diamine, tetra-acetyl ethylene diamine, triacetyl isocyanurate and benzoylimidazole.
  • Acid anhydride activators which bear at least one double bond between carbon atoms in :,a' to the carbonyl group of the anhydride radical can be used as well.
  • Examples thereof are phthalic and maleic anhydrides.
  • Especially preferred bleach activators are based on aldehydes, ketones, and bisulfite adducts of aldehydes and ketones.
  • Examples of these especially preferred activators include: 1,4-cyclohexanedione; cyclohexanone; 3-oxo-cyclohexylacetic acid; 4-tertbutylcyclohexanone; 5-diethylmethylammonio-Z-pentanone nitrate; N-methylmorpholinioacetophenone nitrate; acetone; methyl ethyl ketone; 3-pentanone; methyl-pyruvate; N-methyl-4-oxopiperidine oxide; l,4-bis(N-methyl-4- oxopiperidiniomethyl) benzene chloride; N- methyltropinonium nitrate; l-methyl-4-oxo-tetrahydrothiapyranonium nitrate; N-benzyl; N-methyl-4-oxopiperidinium nitrate; N,N-dimethyl-4-oxo-piperidinium nitrate; di-2-pyridy
  • the peracid is prepared in situ, then the molar ratio of peroxygen bleach agent to bleach activator shall preferably be in the range from about 5:1 to 1:2, especially from 2:1 to 1:12.
  • detergent composition ingredients used herein include suds regulating agents such as suds boosters and suds suppressing agents, tarnish inhibitors, soil suspending agents, buffering agents, additional enzymes, brighteners, fluorescers, perfumes, dyes and mixture.
  • the suds boosters can, e.g. be represented by die-.
  • Silicones, hydrogenated fatty acid, and hydrophobic alkylene oxide condensates can be used in the like compositions for sudes suppressing purposes or, more generally, for suds regulating purposes.
  • Benzotriazole and ethylenethiourea can be used as tarnish inhibitors.
  • Carboxymethyl cellulose is a well-known soil suspending agent.
  • different enzymes such as amylase can be added as well.
  • the above additional ingredients, when used in the instant compositions are employed in the usual conventional concentrations.
  • the starch component ultimately be represented in discrete, unmodified granular form in the environment of the laundering liquor.
  • the starch granules are merely admixed in dry form or sprayed on from a non-heated aqueous dispersion.
  • detergent compositions of liquid form the starch granules are likewise merely added in proper proportion.
  • the presence of conventional dispersing agents are desirable in order to prevent settling of the starch granules within the packaging container.
  • ANTI-STATIC TEST A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35 polyester/cotton blend; 17% nylon; 18% Dacron) is washed for 10 minutes in a miniature agitator washer containing 2 gallons of aqueous washing liquor containing the test laundry compositions (as set forth below).
  • the laundering temperature is 100F; water hardness 7 grains/gallon artificial hardness.
  • the bundle comprises 5% by weight of the washing liquor.
  • the bundle is spun dry and rinsed for 2 minutes in 2 gallons of water at 100F and 7 grains/gallon hardness.
  • the fabrics are then dried in a commercial dryer.
  • the static charge on each fabric is then measured by a standard electrostatic technique within a Faraday cage.
  • the sum of the absolute values of the charges on all fabrics in the bundle, divided by the sum of the area (yards") of the total fabric surface (2sides of the fabric) is then computed.
  • This so-called static value (volt s/yard correlates with gross observations of the effects of static charges on fabric surfaces, i.e., electrical shocks, sparks, fabric clinging, etc.
  • no static clinging is exhibited by fabrics having a static value less than about 1.5 volts/yards substantial static clinging is noted in fabrics having a static value above 4.5 volts/yard.
  • ANTI-WRINKLING TEST A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35 polyester/cotton blends; 17% nylon; 18% Dacron) is washed for 10 minutes in a miniature agitator washer containing 2 gallons of aqueous washing liquor containing the test laundry compositions (as set forth below). The laundering temperature is 100F; water hardness 7 grains/gallon artificial hardness. The bundle is spun dried and rinsed for 2 minutes in 2 gallons of water at 100F and 7 grains/gallon hardness. The fabrics are then dried in a commercial dryer.
  • the extent of wrinkling on a given piece of fabric is then measured by mounting the fabric on a flat, movable surface within a light-tight box.
  • a fine beam of light from a source above the fabric impinges upon the fabric at an angle of
  • a miniature photocell affixed adjacent to the stationary light source responds to scattered light at an angle of 45 to the fabric surface.
  • a plot of the light intensity measured by the photocell versus the length of the fabric path traversed gives a profile (curve) which is in all practical respects a facsimile of the surface of the test fabric.
  • a smooth, unwrinkled fabric gives essentially a straight line of constant light intensity; whereas a wrinkled fabric gives a series of peaks and minima.
  • the ratio of the absolute distance through which the fabric was moved to the length of the plotted curve is quantitatively related to the extent of wrinkling.
  • a bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35 polyester/cotton blends; 17% nylon; 18%-Dacron) is washed for minutes in a miniature agitatori washer containing 2 gallons of aqueous washing liquor containing the test laundry compositions (as set forth below).
  • the laundering temperature is 100F; water hardness 7 grains/gallon artificial hardness.
  • the bundle comprises5% by weight of the washing liquor.
  • composition A is replaced at concentration levels of 0.1 1.5, 2.0, 3.0, and 4.0 wt. respectively.
  • Composition B Components by Weight Anionic Surfactant* 20.0 Sodium Tripolyphosphate 47.0 Sodium Silicate v 4.5 Sodium-Sulfate i 10.8 Rice Granular Starch I 1.2 Miscellaneous Minors & Moisture** Balance 1.22:1 Sodium tallow alkyl sulfatezsodium C linear alkylbenzene sulfonate carboxymethyl cellulose and coconut hexaethoxylate, ca. 0.6%. Y
  • test fabrics are laundered in an aqueous bathcontaining Composition B (0.13 wt. and exhibit superior properties with respect to antiwrinkling, ease of ironing, softness and anti-static in comparison with untreated c ontrols.
  • Substantially equivalent softening, anti-wrinkling, ease of ironing and anti-static benefits are obtained when the particular anionic surfactant in Compositions A and B is replaced with an equivalent amount of a condensation product of ,nonylphenol with about 9.5 moles-pf ethylene oxide per mole of nonylphenol; the condensation product of coconut fatty alcohol with about 6 moles of ethyleneoxide per mole of cocount fatty alcohol; the condensation product of tallow fatty alcohol with about 1 1 moles of ethyleneoxide per mole of tallow fatty alcohol; and the condensation product of a secondary fatty alcohol'containing about 15 carbon atoms with about'9 moles of ethyleneoxide per mole of fatty alcohol,respectively.
  • the foregoing ingredients except the cornstarch, are mixed in a crutcher and spray dried to provide a granular, soap based composition.
  • To this soap based composition is added 1.0 wt. of cornstarch having an average particle diameter of micrometers.
  • the foregoing composition is added to an aqueous laundering liquor at 100F at a concentration of about 0.12 wt.
  • the composition rapidly dissolves and the starch granules are uniformly and independently dispersed throughout the laundering liquor. Fabrics laundered in said luqior are concurrently cleansed, and benefited with respect to wrinkling, ease of ironing, softness and anti-static finish as determined by the beformentioned tests against control fabrics laundered exactly as above except in the absence of the starch component.
  • composition D A laundry detergent product is prepared having the following composition:
  • Water -Continued Components Wt Granular Wheat Starch 2.0 Miscellaneous Balance "'Soap mixtures comprise 90% tallow and 10% coconut soaps.
  • the foregoing ingredients except the wheat starch, are mixed in a crutcher and spray dried to provide a granular, soap based composition.
  • To this composition is added 2.0 wt. of a granular wheat starch having an average particle diameter of 27 micrometers.
  • composition is a stable laundry detergent formulation having excellent water dispersibility and providing excellent fabric laundering, fabric softening, ease of ironing, anti-wrinkling and anti-static characteristics when added to laundering liquors to the extent of about 0.12% by weight.
  • composition E A laundry detergent product is prepared having the following composition:
  • a laundry detergent product is prepared having the following composition:
  • Miscellaneous Balance 'A mixture of tallow and coconut soaps comprising 80% tallow soap and 20% coconut soap.
  • the foregoing ingredients except the granular sweet potato starch, are mixed in a crutcher and spray dried to provide a granular, soap based composition. To this composition is added 1.0 wt. of a granular sweet potato starch.
  • composition is added to an aqueous laundry bath at 100F at a concentration of 0.5% by weight.
  • Said laundering bath provides excellent fabric laundering and imparts desirable fabric softening, ease of ironing, anti-wrinkling and anti-static characteristics to nylon, cotton, polyester and polyester/cotton blends laundered therein.
  • compositions E and F are replaced with an equivalent amount of sodium citrate, sodium carbonate, sodium mellitate, or sodium nitrilotriacetate, respectively.
  • This additive is used for treating textiles in combination with a detergent base granule having the following composition.
  • a laundry detergent product is prepared having the following composition:
  • said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-lsulfonic acids containing from about 20 to about 24 carbon atoms, said mixture of positional isomers including about 20% of an alpha-beta unsaturated isohydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hy droxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms at least 90% of the hydroxy radical substitutions being in 3, 4, and positions; and
  • said Component C is a mixture comprising from about 70% water-soluble salts of alkene disulfonates 1 containing from about to about 24 carbon atoms, and from about water-soluble salts of hydroxy disulfonates containing from about 20 to about 24 carbon atoms, said alkene disulfonates containing a sulfonic group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon 2 atom and about the seventh carbon atoms, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of
  • a laundry detergent composition comprising:
  • an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof;
  • alkyl ether sulfates having the formula RO(C H,O),SO M
  • R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is l to 30 and M is a salt forming cation; and ii. olefin sulfonates having from about 12 to about 24 carbon atoms.
  • a detergent composition in accordance with claim 4 which contains also a detergent builder salt to the extent of from about 10% to about by weight; the
  • a laundry detergent composition comprising a. from about 4% to about 60% by weight of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof;
  • smectite-type clay having an ion-exchange capacity of at least about 50 meg/ g.
  • alkyl ether sulfates having the formula wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is l to 30 and M is a salt forming cation; and
  • olefin sulfonates having from about 12 to about 24 carbon atoms.
  • a detergent composition in accordance with claim 9 which contains also a detergent builder salt to the extent of from about 10% to about 60% by weight; the weight ratio of said builder to the organic surfaceactive agent being in the range of from about 20:1 to 1:20.
  • a method for treating fabrics to simultaneously cleanse and impart anti-wrinkling, ease of ironing, softening and anti-static properties comprising treating fabrics in an aqueous liquor comprising:
  • an organic surface active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof;
  • component (a) organic surface active agent is present to the extent of from about 100 ppm to about 3,000 ppm; and the component (b) starch is used to the extent of from about 2 ppm to about 200 ppm.
  • a method for treating fabrics to simultaneously cleanse and impart anti-wrinkling, ease of ironing, softening and anti-static properties comprising treating fabrics in an aqueous liquor comprising:
  • an organic surface active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof;

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US333103A 1973-02-16 1973-02-16 Detergent compositions containing water insoluble starch Expired - Lifetime US3892681A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US333103A US3892681A (en) 1973-02-16 1973-02-16 Detergent compositions containing water insoluble starch
AU65320/74A AU480918B2 (en) 1973-02-16 1974-02-07 Detergent compositions having fabric conditioning properties
DE2406518A DE2406518C2 (de) 1973-02-16 1974-02-12 Teilchenförmiges Waschmittel mit einem Gehalt an einem gewebekonditionierenden Mittel
CA192,287A CA1037209A (en) 1973-02-16 1974-02-12 Detergent compositions having fabric conditioning properties
IT7448380A IT1002941B (it) 1973-02-16 1974-02-14 Composizioni detergenti con carat teristiche di condizionatura dei tessuti
PH15508A PH10856A (en) 1973-02-16 1974-02-14 Detergent compositions having fabric conditioning properties
GB693074A GB1429911A (en) 1973-02-16 1974-02-15 Detergent compositions having fabric conditioning properties
FR7405289A FR2218381B1 (enrdf_load_stackoverflow) 1973-02-16 1974-02-15
NLAANVRAGE7402097,A NL188475C (nl) 1973-02-16 1974-02-15 Werkwijze voor het bereiden van een wasmiddel.
BE140953A BE811082A (fr) 1973-02-16 1974-02-15 Compositions detergentes possedant des proprietes de conditionnement d'etoffes
JP49019032A JPS5829840B2 (ja) 1973-02-16 1974-02-16 フハクノ コンデイシヨニングトクセイオモツ センザイソセイブツ
US05/594,909 US4051046A (en) 1973-02-16 1975-07-10 Detergent compositions containing insoluble particulate materials having fabric conditioning properties

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US333103A US3892681A (en) 1973-02-16 1973-02-16 Detergent compositions containing water insoluble starch
US35712873A 1973-05-04 1973-05-04

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JP (1) JPS5829840B2 (enrdf_load_stackoverflow)
BE (1) BE811082A (enrdf_load_stackoverflow)
CA (1) CA1037209A (enrdf_load_stackoverflow)
DE (1) DE2406518C2 (enrdf_load_stackoverflow)
FR (1) FR2218381B1 (enrdf_load_stackoverflow)
GB (1) GB1429911A (enrdf_load_stackoverflow)
IT (1) IT1002941B (enrdf_load_stackoverflow)
NL (1) NL188475C (enrdf_load_stackoverflow)
PH (1) PH10856A (enrdf_load_stackoverflow)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051046A (en) * 1973-02-16 1977-09-27 The Procter & Gamble Company Detergent compositions containing insoluble particulate materials having fabric conditioning properties
US4116854A (en) * 1977-02-14 1978-09-26 The Procter & Gamble Company Detergent compositions containing starch
US4162983A (en) * 1978-03-13 1979-07-31 The Procter & Gamble Company Fabric care composition containing starch and surfactant
US4169064A (en) * 1977-12-23 1979-09-25 The Procter & Gamble Company Detergent compositions containing starch
US4178254A (en) * 1978-03-13 1979-12-11 The Procter & Gamble Company Fabric care compositions containing smectite clay and starch
US4308151A (en) * 1980-05-12 1981-12-29 The Procter & Gamble Company Detergent-compatible fabric softening and antistatic compositions
US4488981A (en) * 1983-09-06 1984-12-18 A. E. Staley Manufacturing Company Lower alkyl glycosides to reduce viscosity in aqueous liquid detergents
US4714479A (en) * 1984-07-23 1987-12-22 Henkel Kommanditgesellschaft Auf Aktien Washing process for sensitive fabrics
US5062989A (en) * 1988-01-12 1991-11-05 Kao Corporation Detergent composition
US5290325A (en) * 1990-02-28 1994-03-01 Union Oil Company Of California Hydrocarbon fuel composition containing alpha-ketocarboxylate additive
GB2357523A (en) * 1999-12-22 2001-06-27 Unilever Plc Treatment of textile fabrics with clay minerals
US20020107169A1 (en) * 2000-12-06 2002-08-08 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric treatment compositions
US20040107504A1 (en) * 2002-12-05 2004-06-10 Blangiforti Anna Carner Leather therapy treatment
US20040127392A1 (en) * 2002-04-04 2004-07-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric treatment compositions
US6797688B2 (en) 1996-09-19 2004-09-28 The Procter & Gamble Company Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US20050015888A1 (en) * 1999-10-27 2005-01-27 The Procter & Gamble Company Wrinkle resistant composition
US20050192356A1 (en) * 2004-02-27 2005-09-01 Babish John G. Synergistic anti-inflammatory pharmaceutical compositions and methods of use
US7135451B2 (en) 2003-03-25 2006-11-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US11766496B2 (en) 2019-07-29 2023-09-26 The Procter & Gamble Company Antimicrobial fabric freshening compositions containing octenidine dihydrochloride

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076633A (en) * 1974-10-18 1978-02-28 The Procter & Gamble Company Fabric treating articles with improved conditioning properties
GB1519178A (en) * 1975-09-17 1978-07-26 Ciba Geigy Ag Detergent compositions
US4155870A (en) 1976-04-19 1979-05-22 Minnesota Mining And Manufacturing Company Skin cleaning compositions containing water-insoluble glass bubbles

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565939A (en) * 1967-06-09 1971-02-23 Standard Chem Products Inc Partial neutralization of sulfates of ethoxylated alcohols
US3665000A (en) * 1969-12-23 1972-05-23 Fmc Corp Tricarboxystarch derivatives
US3786003A (en) * 1971-11-04 1974-01-15 Shell Oil Co Liquid detergent compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3606989A (en) * 1967-10-19 1971-09-21 Purex Corp Ltd Fabric-treating composition and method
DE2055423A1 (en) * 1970-11-11 1972-05-18 Chemische Fabrik Budenheim, Rudolf A. Oetker, 6501 Budenheim Washing compositions - containing water-insoluble crosslinked cation -exchange polymers especially crosslinked polystyrene,polyacrylic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565939A (en) * 1967-06-09 1971-02-23 Standard Chem Products Inc Partial neutralization of sulfates of ethoxylated alcohols
US3665000A (en) * 1969-12-23 1972-05-23 Fmc Corp Tricarboxystarch derivatives
US3786003A (en) * 1971-11-04 1974-01-15 Shell Oil Co Liquid detergent compositions

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051046A (en) * 1973-02-16 1977-09-27 The Procter & Gamble Company Detergent compositions containing insoluble particulate materials having fabric conditioning properties
US4116854A (en) * 1977-02-14 1978-09-26 The Procter & Gamble Company Detergent compositions containing starch
US4169064A (en) * 1977-12-23 1979-09-25 The Procter & Gamble Company Detergent compositions containing starch
US4162983A (en) * 1978-03-13 1979-07-31 The Procter & Gamble Company Fabric care composition containing starch and surfactant
EP0004109A1 (en) * 1978-03-13 1979-09-19 THE PROCTER & GAMBLE COMPANY Liquid fabric care composition containing gelatinized vegetable starch, surfactant and electrolyte
US4178254A (en) * 1978-03-13 1979-12-11 The Procter & Gamble Company Fabric care compositions containing smectite clay and starch
US4308151A (en) * 1980-05-12 1981-12-29 The Procter & Gamble Company Detergent-compatible fabric softening and antistatic compositions
US4488981A (en) * 1983-09-06 1984-12-18 A. E. Staley Manufacturing Company Lower alkyl glycosides to reduce viscosity in aqueous liquid detergents
US4714479A (en) * 1984-07-23 1987-12-22 Henkel Kommanditgesellschaft Auf Aktien Washing process for sensitive fabrics
US5120464A (en) * 1988-01-12 1992-06-09 Kao Corporation Detergent composition
US5062989A (en) * 1988-01-12 1991-11-05 Kao Corporation Detergent composition
US5290325A (en) * 1990-02-28 1994-03-01 Union Oil Company Of California Hydrocarbon fuel composition containing alpha-ketocarboxylate additive
US6797688B2 (en) 1996-09-19 2004-09-28 The Procter & Gamble Company Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US6939844B2 (en) 1996-09-19 2005-09-06 The Procter & Gamble Company Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US20050130872A1 (en) * 1996-09-19 2005-06-16 The Procter & Gamble Company Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US20040235707A1 (en) * 1996-09-19 2004-11-25 The Procter & Gamble Company Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US20050015888A1 (en) * 1999-10-27 2005-01-27 The Procter & Gamble Company Wrinkle resistant composition
GB2357523A (en) * 1999-12-22 2001-06-27 Unilever Plc Treatment of textile fabrics with clay minerals
US7105476B2 (en) 2000-12-06 2006-09-12 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Fabric treatment compositions comprising organically modified particles
US20020107169A1 (en) * 2000-12-06 2002-08-08 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric treatment compositions
US20040127392A1 (en) * 2002-04-04 2004-07-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric treatment compositions
US20060040842A1 (en) * 2002-04-04 2006-02-23 Unilever Home & Personal Care Usa, Division Of Conopco., Inc. Fabric treatment compositions
US7012055B2 (en) 2002-04-04 2006-03-14 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric treatment compositions comprising organically modified particles
US20040107504A1 (en) * 2002-12-05 2004-06-10 Blangiforti Anna Carner Leather therapy treatment
US6797011B2 (en) * 2002-12-05 2004-09-28 Anna Carner Blangiforti Leather therapy treatment
US7135451B2 (en) 2003-03-25 2006-11-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US20070027059A1 (en) * 2003-03-25 2007-02-01 Corona Alessandro Iii Fabric care compositions comprising cationic starch
US20050192356A1 (en) * 2004-02-27 2005-09-01 Babish John G. Synergistic anti-inflammatory pharmaceutical compositions and methods of use
US11766496B2 (en) 2019-07-29 2023-09-26 The Procter & Gamble Company Antimicrobial fabric freshening compositions containing octenidine dihydrochloride

Also Published As

Publication number Publication date
DE2406518C2 (de) 1985-05-15
NL7402097A (enrdf_load_stackoverflow) 1974-08-20
JPS5029610A (enrdf_load_stackoverflow) 1975-03-25
CA1037209A (en) 1978-08-29
DE2406518A1 (de) 1974-08-22
IT1002941B (it) 1976-05-20
JPS5829840B2 (ja) 1983-06-24
PH10856A (en) 1977-09-13
GB1429911A (en) 1976-03-31
AU6532074A (en) 1975-08-07
FR2218381B1 (enrdf_load_stackoverflow) 1977-09-30
FR2218381A1 (enrdf_load_stackoverflow) 1974-09-13
BE811082A (fr) 1974-08-16
NL188475B (nl) 1992-02-03
NL188475C (nl) 1992-07-01

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