US3816321A - Laundering aid - Google Patents

Laundering aid Download PDF

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Publication number
US3816321A
US3816321A US00249810A US24981072A US3816321A US 3816321 A US3816321 A US 3816321A US 00249810 A US00249810 A US 00249810A US 24981072 A US24981072 A US 24981072A US 3816321 A US3816321 A US 3816321A
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percent
sodium
potassium
laundering
water
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D Kleinschmidt
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to US00249810A priority Critical patent/US3816321A/en
Priority to DE2321724A priority patent/DE2321724C2/de
Priority to AU55072/73A priority patent/AU5507273A/en
Priority to CA170,217A priority patent/CA997244A/en
Priority to IT23638/73A priority patent/IT986991B/it
Priority to FR7315750A priority patent/FR2183178B1/fr
Priority to NLAANVRAGE7306084,A priority patent/NL178980C/xx
Priority to GB2107573A priority patent/GB1393508A/en
Priority to BE130677A priority patent/BE799022A/xx
Priority to JP48050177A priority patent/JPS4954407A/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B11/00—Wrapping, e.g. partially or wholly enclosing, articles or quantities of material, in strips, sheets or blanks, of flexible material
    • B65B11/06—Wrapping articles, or quantities of material, by conveying wrapper and contents in common defined paths
    • B65B11/08—Wrapping articles, or quantities of material, by conveying wrapper and contents in common defined paths in a single straight path
    • B65B11/10—Wrapping articles, or quantities of material, by conveying wrapper and contents in common defined paths in a single straight path to fold the wrappers in tubular form about contents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B51/00—Devices for, or methods of, sealing or securing package folds or closures; Devices for gathering or twisting wrappers, or necks of bags
    • B65B51/10—Applying or generating heat or pressure or combinations thereof
    • B65B51/18—Applying or generating heat or pressure or combinations thereof by endless bands or chains
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions

Definitions

  • a laundering aid comprising a water-1nsoluble, polyur- [58] Field of Search 252/89 90 91 134 l 17 1 0lyalky1eneimine material releasably comd 3 bined with a detergent composition, said aid providing a means of introducing a detergent composition into a [56] References Cited laundry bath and at the same time serving to adsorb dirt and vagrant anionic dyes from the aqueous laun- UNITED STATES PATENTS dry media, thereby providing an improved laundering 2,813,775 11/1957 Steuber 260/775 C process 3.165566 1/1965 Murphy....
  • This invention encompasses laundering aids comprising a chemically modified polyurethane material in combination with a soap or synthetic organic detergent composition.
  • the invention comprises the use of the chemically modified polyurethane material in aqueous laundry baths to scavenge dirt and anionic dyes released from the fabrics being laundered.
  • U.S. Patent No. 3,424,545, Jan 28, 1969, to R. A. Bauman discloses a phosphorylated cloth which is added to laundry baths to remove inorganic cations but which does not remove organic anions and dirt as is accomplished with the present invention.
  • U.S. Pat. No. 3,694,364, Sept. 26, 1972, to .l. B. Edwards relates to the use of cellulosic materials coated with alkanoylated polyalkyleneimines in laundering baths. While the laundering aids of Edwards are effective, their manufacture requires a three-step processinvolving formation of the fabric, its surface modification and a final surface treatment.
  • polyurethane substrates to which are chemically affixed various polyalkyleneimine materials during the polyurethane polymerization, all as hereinafter detailed, can be added to aqueous laundering solutions to scavenge or trap dirt and vagrant anionic dyes from the solution.
  • the polyurethane-polyalkyleneimine material also contains a detergent composition which is released into the bath.
  • the user can add a predetermined amount of detergent to the bath in conjunction with the dye and dirt trapper material.
  • the dirt and anionic dye trapper material can be removed from the aqueous laundry bath, together with the dirt and anionic dyes adsorbed thereon, and discarded.
  • the polyurethane-polyalkylenimine material employed in the present invention is known in the art.
  • U.S. Pat. No. 3,165,566 discloses a process for curing polyurethane by passing urethane prepolymer through a polyamine. The resulting filaments can be woven into trapper cloths of the type used herein.
  • Foamed polyurethanes of the type suitable for use herein are disclosed in Belgian Patent No. 665,293; U.S. Pat. No. 2,813,775 discloses polyisocyanates containing polyamides.
  • the use of the foregoing polyalkyleneimine-polyurethane materials in combination with detergent components or as anionic dirt and dye trappers has not been suggested heretofore.
  • It is a primary and major object of the present invention tO provide an improved laundering aid capable of performing a fabric cleansing function and at the same time adsorbing negatively charged particulate matter (especially dirt) and dissolved organic anionic matter (especially dyes) on its surface. Another object is to provide an improved laundering process.
  • the invention comprises a detergent composition in releasable combination with a water-insoluble substrate consisting of polyurethane in chemical combination with a polyalkyleneimine material.
  • the invention encompasses adding a waterinsoluble polyurethane-polyalkyleneimine substrate to an aqueous washing solution containing a detergent composition to trap dirt and organic anionic materials.
  • the laundering aids herein comprise: (I) a waterinsoluble substrate consisting of polyurethane which is chemically combined with at least about 0.1 percent, more preferably from about 1 percent to about 10 percent, by weight of substrate of a polyalkyleneimine material containing the moiety 1 wherein y is an integer of from I to 4, z is an integer greater than I, R is selected from the group consisting of hydrogen and alkyl and alkanoyl substituents containing from about I to about 22 carbon atoms, each R is an alkyl group containing from I to about 22 carbon atoms, and X is an anion such as methylsulfate, halogen, sulfate, hydroxide and the like; and (2) a water-soluble detergent composition in releasable combination with said substrate.
  • alkylated or alkanoylated polyalkyleneimines are used herein, from about 5 percent to about 100 percent, more preferably 10 percent to 50 percent, of the nitrogen atoms in the polyalkyleneimine are substituted with alkyl or alkanoyl groups containing 1 to 22 carbon atoms.
  • polyalkyleneimines including alkylated and alkanoylated polyalkyleneimines, of any degree of polymerization, especially those in the I range of 2 to 50,000, especially 20 to 10,000, monomer units per molecule, are preferred.
  • the polyurethane-polyalkyleneimine substrate materials are used herein to scavenge, or trap, dirt and anionic dyes released during a laundering process, they are referred to herein as trapper materials or trappers". While any of the materials prepared in the manner described in U.S. Pat. Nos. 3,165,566 and 2,813,775 and in Belgian Patent 665,293, incorporated herein by reference, are suitable for use herein as the trapper material, polyurethane-polyethylene-imine materials are preferred. Especially preferred for use in the present invention are trappers comprising waterinsoluble, foamed polyurethane in chemical combination with from about 0.5 percent to about 10 percent by weight of polyethyleneimine.
  • the trapper materials herein are prepared by forming polyurethane (from an isocyanate and a polyol) in the presence of a polyalkyleneimine.
  • the polyalkyleneimine compounds used to prepare the water-insoluble polyalkyleneiminc-polyurethane materials herein comprise a polyalkyleneimine backbone having pendant hydrogen, or alkyl or alkanoyl groups on the nitrogen atoms. These polymers are difiicult to describe in other than a qualitative manner.
  • the preferred polyalkyleneimine used herein is polyethyleneimine. It is believed that.the structural formula of polyethyleneimine is:
  • N- cmcmi r wherein 2 represents a whole number greater than 1, usually about 2 to l00,000.
  • the degree of polymerization, 1, is not critical for the purposes of this invention. Branched chains occur along the polymeric backbone and the relative proportions of primary, secondary and tertiary amino groups present in the polymer will vary, depending on the manner of preparation. The distribution of amino groups in a typical polyethyleneimine is approximately as follows:
  • the polyethyleneimine can only be characterized in terms of molecular weight.
  • Such polymers can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods are described in U.S. Pat. Nos. 2,182,306; 3,033,746; 2,208,095; 2,806,839; and 2,552,696, incorporated herein by reference.
  • Alkylated and alkanoylated polyethyleneimines are obtained by heating alkyl halides, organic acids or acid halides with the polyethyleneimine in the manner described in U.S. Pat. Nos. 2,296,226; 2,272,489; and 2,l85,480, incorporated herein by reference.
  • the other polyalkyleneimines useful herein are prepared in like fashion.
  • Various ratios of alkylating or alkanoylating agent to polyethyleneimine can be employed so that varying percentages of the nitrogen atoms are thereby substituted. The percentage of nitrogen substitution can be determined, for example, by examination of the proton resonance or the infrared spectrum of the polymer.
  • alkylated polyalkyleneimine polyurethanes can be further substituted to yield polyalkyleneimines having the nitrogen substituents quaternarized with alkyl groups R.
  • the resulting alkylated and alkanoylated polyethyleneimines which have molecular weights in the range of about 1,000 to about I million. are useful herein.
  • the trapper substrate prepared in the foregoing manner is preferably used in releasable combination with a detergent composition, and, in a preferred embodiment, is in bag conformation releasably containing said detergent composition.
  • the container is added to the laundry water and the laundering process is carried out in standard fashion.
  • the trapper bag releases the detergent composition and remains to scavenge dirt and anionic dyes.
  • a trapper in sponge form is impregnated or coated with a detergent composition which is released on contact with water. The released trapper sponge then performs its anionic dye and dirt adsorbing function.
  • Still another article comprises a detergent formulation in tablet form having a trapper substrate incorporated in the interior which is released when the tablet dissolves in water.
  • Exemplary detergent and presoak compositions suitable for use with the trapper material in the practice of this invention are those typical commercial products comprising a mixture of about 10 percent to about 100 percent by weight of a water-soluble organic detergent compound; preferred compositions contain from about 10 percent to about percent by weight of a water-soluble detergency builder and from about l0 percent to about 90 percent by weight of the aforesaid organic detergent compounds. Minor amounts of common laundry additive ingredients, as hereinafter detailed, can also be present. lncluded in this definition of detergent compositions are built and unbuilt soap compositions and detergent compositions containing enzymes.
  • the trapper material is compatible with all manner of those compositions and successfully accomplishes its dirt and organic anionic dye trapping function in their presence. Surprisingly, although many of the most useful organic detergent compounds commonly employed in modern laundry detergent compositions are organic anionic materials, the trapper material does not interfere with their cleaning properties.
  • Non-limiting examples of typical water-soluble synthetic organic detergents, enzymes, soaps and builders, along with typical compositions containing them, which are suitably employed in conjunction with the trapper material to provide a laundering aid are more fully described below.
  • typical compositions containing them which are suitably employed in conjunction with the trapper material to provide a laundering aid are more fully described below.
  • organic detergent compounds which can be utilized with the trapper material in the laundering aids encompassed by this invention include the following:
  • Anionic Soap and Non-Soap Synthetic Detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkanol-ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about to about 20 carbon atoms.
  • Suitable fatty acids can be obtained from natural sources such as, for instance, plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof).
  • the fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process).
  • Resin acids are suitable such as rosin and those resin acids in tall oil.
  • Naphthenic acids are also suitable.
  • Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • This class of detergents also includes water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical.
  • alkyl is the alkyl portion of higher acyl radicals.
  • this group of synthetic detergents which form a part of the preferred built detergent compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C C carbon atoms produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about carbon atoms in straight chain or branched chain configuration, e.g., those of the type described in U.S. 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 12 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; sodiumcoconut oil fatty acid monoglyceride' sulfonates and sulfates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about I to 6 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 8 to about 12 carbon atoms.
  • C LAS linear straight chain alkyl benzene sulfonates
  • 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 l-l, SO H, and --CO H.
  • Alkyl phosphate esters such as (RO) PO H and ROPO l-l in which R represents an alkyl chain containing from about 8 to about carbon atoms are useful.
  • esters can be modified by including in the mol ecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units.
  • Formulae for these modified phosphate anionic detergents are in which R represents an alkyl group containing from about 8 to 20 carbon atoms, or an alkylphenyl group in which the alkyl group contains from about 8 to 20 carbon atoms, and M represents a water-soluble cation such as hydrogen, sodium, potassium, ammonium or substituted ammonium; and in which n is an integer from 1 to about 40.
  • Suitable anionic organic detergents particularly useful in this invention includes salts of 2-acyloxyalkane-l-sulfonic acids. These salts have the formula ii (1)0112 R1C H-CHzS03M 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 trimethylammonium 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.
  • B-acyloxy-alkane-l-sulfonates or alternatively 2-acyloxy-alkane-l-sulfonates, useful herein to provide superior cleaning levels under substantially neutral washing conditions include the sodium salt of 2-acetoxy-tridecane-l-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecane-lsulfonic acid; the lithium salt of 2-butanoyloxytetradecane-l-sulfonic acid; the sodium salt of 2- pentanoyloxy-pentadecane-l-sulfonic acid; the sodium salt of Z-acetoxy-hexadecane-l-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-l-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-lsulfonic acid; the lithium salt of 2-acetoxy-octadecanel-sulfonic acid; the sodium salt of
  • B-acyloxy-alkane-l-sulfonate salts herein are the alkali metal salts of B-acetoxy-alkane-l-sulfonic acids corresponding to the above formula wherein R is 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-1+ and Mg-H' ions) are the alkylated a-sulfocarboxylates, containing about 10 to about 23 carbon atoms, and having the formula where 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, and M is a watersoluble cation as hereinbefore described.
  • B-alkyloxy alkane sulfonates or alternatively 2-a1ky1oxy-alkane-l-sulfonates, having low hardness (calcium ion) sensitivity useful herein to provide superior cleaning levels under household washing conditions include:
  • alkyl ether sulfates Other synthetic anionic detergents useful herein are alkyl ether sulfates. These materials have the formula RO(C H O),SO M wherein R is alkyl or alkenyl of about to about 20 carbon atoms, x is 1 to 30, and M is a water-soluble cation as defined hereinbefore.
  • the alkyl ether sulfates useful in the present invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms. Preferably, R has 14 to 18 carbon atoms.
  • the alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from tallow are preferred herein. Such alcohols are reacted with 1 to 30, and especially 6, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 6 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
  • alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulfate; lithium tallow alkyl triethylene glycol ether sulfate; and sodium tallow alkyl hexaoxyethylene sulfate.
  • alkali metal coconutand tallow-alkyl oxyethylene ether sulfates having an average of about 1 to about 10 oxyethylene moieties.
  • the alkyl ether sulfates of the present invention are known compounds and are described .in U.S. Pat. No. 3,332,876, incorporated herein by reference.
  • 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 U.S. 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 disulfonates, disulfates, or mixtures thereof which may be represented by the following formulae:
  • R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example, the C to C disodium 1,2- alkyldisulfates, C to C dipotassium-l,2-alkyldisulfonates or disulfates, disodium 1,9-hexadecy1 disulfates, C to C disodium-1 ,2-alkyldisulfonates, disodium 1 ,9- stearyldisulfates and 6,10-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, 11B, 111A, IVA and [VB 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-( 1,2-dicarboxyethyl)- N-octadecylsulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.
  • olefin sulfonates having about 12 to about 24 carbon atoms.
  • olefin sulfonates is used herein to mean compounds which can be produced by the sulfonate of a-olefms by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkane-sulfonates.
  • the sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid S chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 etc., when used in the gaseous form.
  • inert diluents for example by liquid S chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 etc., when used in the gaseous form.
  • the a-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 l-olefins include l-dodecene; l-tetradecene; l-hexadecene; 1- octadecene; l-eicosene and l-tetracosene.
  • the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonate process.
  • Nonionic Synthetic detergents may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Pluronic a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic portion of the molecule which, of course, exhibits water insolubility, has a molecular weight of from about 1500 to 1800.
  • the addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50 percent of the total weight of the condensation product.
  • nonionic synthetic detergents include:
  • the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to to 25 moles of ethylene oxide per mole of alkyl phenol.
  • alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.
  • ethylene oxide e.g., a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
  • Nonionic detergents include nonyl phenol condensed with about 10 to about 30 moles of ehtylene oxide per mole of phenol; the condensation products of ethylene alcohol with an average of either about 5.5 or about 15 moles of ethylene oxide per mole of alcohol, and, the condensation product of about 15 moles of ethylene oxide with one mole of tridecanol.
  • a detergent having the formula R R R N O (amine oxide detergent) wherein R is an alkyl group containing from about 10 to about 28 carbon atoms,-
  • R which is an alkyl group containing from about 10 to about 18 carbon atoms and 0 ether linkages, and each R and R are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.
  • amine oxide detergents 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 )-34iodecoxyl -hydroxypropylamine oxide, (2-hydroxypropyl )methyltetradecylamine oxide, dimethyloleyamine oxide, dimethyl-(2- hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.
  • a detergent having the formula RR R P O phosphine oxide detergent
  • R is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to hydroxymethyl)dodecylphosphine oxide, bis-(2- hydroxyethyl)dodecylphosphine oxide, (2- hydroxypropyl)methyltetradecylphosphine oxide,
  • dimethyloleylphosphine oxide and dimethyl-(2- hydroxydodecyl)phosphine oxide and the corresponding decyl, hexadecyl, and octadecyl homologs of the above compounds.
  • Ampholytic Synthetic Detergents falling within this definition are sodium 3- (dodecylamino)propionate, sodium 3- (dodecylamino)propane-l -sulfonate, sodium 2- (dodecylamino)ethyl sulfate, sodium 2- (dimethylamino)octadecanoate, disodium 3-(N- carboxymethyldodecylamin0)propanel -sulfonate, disodium octadecyl-iminodiazetate, sodium l-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2- hyd roxyethyl )-2-sulfato-3-dodecoxypropylamine.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium and phosphonium or tertiary sulfonium compounds, in which the cationic atom may be part of a heterocyclic ring, and in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 3 to 18 carbon atoms, and at least one aliphatic substituent contains 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.
  • Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylammonio)-2- hydroxypropanel -sulfonate, 3-( N ,Ndimethyl-N- hexadecylammonio )propanel -sulfonate, 2-( N,N- dimethyl-N-dodecylammonio)acetate, 3-(N,N- dimethyl N-dodecylammonio)-propionate, 2-(N,N-
  • ammoniopropane sulfonates containing about 8 to about 21 carbon atoms are one class of detergent compounds preferred herein by virtue of their relatively low calcium ion (hardness) sensitivity.
  • pholytic and Zwitterionic detergent compounds either 7 singly or in various well-known combinations, can be used herein.
  • the above examples are merely illustrations of the numerous detergents suitable for use herein and it is to be understood that other organic soaps and detergent compounds can also be used in conjunction with trapper materials to provide laundering aids.
  • Non-limiting examples of suitable water-soluble, inorganic alkaline detergency builder salts are the alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates and sulfates. Specific examples of such salts are sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates and hexametaphosphates.
  • organic alkaline detergency builder salts examples include: (l) water-soluble aminopolyacetates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)- nitrilodiacetates', (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates see US. Pat. No. 2,739,942; (3) water-soluble polyphosphonates, including, specifically, sodium, potassium and lithium salts of methylene diphosphonic acid; sodium, potassium and lithium salts of ethylene diphosphonic acid; and sodium potassium and lithium salts of ethane-1,1,2-triphosphonic acid.
  • aconitic acid, mellitic acid and the pentaand 7 :fi ykeuulose tetra-carboxylic acids prepared by the malonic acid 10 010 additive? p synthesis can be employed herein as builders.
  • the mmswre water-soluble alkali metal salts of these materials are Including perfumes and optical brighteners. also suitable.
  • Mixtures of organic and/or inorganic builders can be used and are generally desirable.
  • One such mixture of builders is disclosed in Canadian Patent 755,038, e.g., Detergent Composition D ternary mixtures of sodium tripolyphosphate, trisodium weigh, nitrilotriacetate and trisodium ethane-l-hydroxy-l,l- Percent diphosphonate.
  • the above described builders can also 5 dimelhyldodecylphosphine oxide be utilized singly in this invention.
  • Preferred builders herein include: the sodium and pogfiy i z with 1 mole of coconut O tassium salts of the tripolyphosphates, nitr lotriac- 10 melhylenediphosphonm etates, mellitates (benzenehexacarboxylates), silicates, 8 5 2m pg g l so ium car oxymet yce uose citrates, carbonates, oxydisuccinates, phloroglucinol- 10 Sodium memmc trisulfonates, and (ethylenedioxy)diacetates. bal.
  • compositions suitable for use in combination :9 sodium suig ehl H h r J potassium ic orocyanurate eac with the trapper materials employed in the present in- 005 perfume vention to provide laundering aids.
  • the compositions bal. moisture listed are for the purposes of illustration and are not intended to be limiting of the types of formulations used 40 with the trapper materials to provide the laundering aids of this invention.
  • Detergent Composition F (Liquid) Weight Percent Detergent Composition A Weight 6 sodium-3-dodecylaminopropionate Percent 6 sodium linear dodecylbenzenesulfonate 20 potassium pyrophosphate 7.8 sodium linear dodecylbenzenesulfonate 8 P na 9.5 sodium tallowalkyl sulfate SOdlum slllcale 49 4 Sodium mpolyphosphme 50 0.3 carboxymethylhydroxyethylcellulose 5 9 Sodium Smcme 0.05 addmves (optional) 13 10 50 bal. water 0.2 sodium carhoxymcthylcellulose 2,2 nqninnic suds controlling agents lncluding perfumes and optical brighteners.
  • Detergent Composition H Detergent Composition L (For Cool Water Use) Weight Weight Percent Percent 40 sodium salt of SO;,-sulfonated tetradecene H5) zzmaz ggg g $8 ii'i'sii'iiiii'iillfi il '2-"i?o; .e 40 sodium 10 Sodium carbon Y P [0 sodium silicate (N a,O:SiO 125 ha! moisture 0.3 sod um oxydlsuccinate 10 sodium (ethylenedroxfidtacetate l 0 bal.
  • compositions with the exception of Detergent composition l Compositions E and G since these contain enzymeweigm destroying bleaches) a minor amount, i.e., from about Percent 0.001 percent to about 2 percent, by weight, of an enzyme such as an amylase, a protease or a lipase, can be 7.5 tetradecyl-B-methoxyfitlfonatc added to provide the cleansing advantages of said en- 2.2 o i l l'atty acid suds depressant zymes'
  • the temperature of the aqueous medium employed in any of the various stages of laundering processes employing the laundering aids of this invention is not critical in that said aids function well at temperatures from about 32F to about 212F, preferably from about 75F to about 160F. It is well established that certain laundry detergents and additives are suitable for use at the weigh Cmpomm lower temperatures within this range while others per- Percent form more effectively at higher temperatures. It is further recognized that certain whitening agents such as 10 Sodium near dodecylbenzenesuifonm 35 perborate are suitable for use only at the higher tem- 10 condensation Product of 1 mole 0f nonyl peratures within this range.
  • the practitioner l0 g 'f f ggggfi gz jf of this invention can select a commercial detergent, 30 trisodium ethane-l-hydroxyd,l-diphosphonate bleach, whitener or presoak composition which funcg z gg z ii gf z b tions at any desired temperature, combine it with the [0 fgisoziium phosphate 2 2 40 trapper material and thereby provide a laundering aid 0.5 sodium carboxymethylcellulose designed to meet the needs of various laundering situa- 0. l 3-phenyl-2,S-diphenylthiophene tions.
  • the laundering aids of this invention can be prepared baL ggfljfj' bnghtener) using a variety of trapper materials prepared in the manner of the art and a variety of detergent compositions much like those available commercially.
  • the examples herein are intended to illustrate the present invention but are not intended to be limiting thereof.
  • the terms, 100 percent SPEI, percent SPEI, etc., 5O relate to the percent of the nitrogen atoms in polyethylweigm K (Fm use) eneimine which are alltylated or alkanoylated.
  • polyurethanes used in the instant invention are the well-known polymeric substances produced by the 5 sodium salt of sorsulfonaied -tri n condensation of a polyisocyanate and a polyhydroxylg8 containing material such as a polyol.
  • P y e foam y be a sq idi "a p n perfume foam prepared by reacting a polyether, such as polymoislurc propylene glycol, or polyesters having free hydroxyl g gzfi mgfggm fgigfiz groups, with a di-isocyanate in the presence of some l, lf t water and a catalyst.
  • a polyether such as polymoislurc propylene glycol, or polyesters having free hydroxyl g gzfi mgfggm fgigfiz groups
  • the water reacts with isocyanate groups partly to cause cross-linking and partly to cause the formation of ethyleneimine is quaternized prior to being added, to
  • the polyurethane-polyalkyleneimine substrates herein are formed by the addition of a polyalkyleneimine of the type noted above during the urethane polymerization process.
  • the polyalkyleneimine is thereby incorporated in the polymer by covalent bonds.
  • the polyurethane used herein is one made from a polypropylene glycol and either toluene or naphthalene diisocyanate.
  • the polyurethane can alternatively be derived from other di-isocyanates with other alkylene oxides or with polyesters having free hydroxyl groups.
  • polyurethane foam containing about 3 percent by weight polyethyleneimine is prepared as follows: 100 parts polypropylene glycol (avg. mol. wt. 2000), 50 parts toluene di-isocyanate, 5 parts polyethyleneimine (avg. mol. wt. 2000), 5 parts fluorotrichloromethane and 0.l part stannous octanoate are intimately mixed and allowed to react at about 50C 70C for about two hours. The resulting foam mass is then cured by bringing the mass to a temperature of about 90C 100C for two minutes. The foam is then washed thoroughly with agitation to remove any excess polyethyleneimine and air dried. The resulting polyurethanepolyethyleneimine copolymeric foam is suitable for use in the articles and processes of this invention without further treatment.
  • polyethyleneimine is replaced by an equivalent amount of 50 percent SPEI and copolymers of polyurethane 50 percent SPEI suitable for use herein are secured.
  • a polyurethane foam containing about 3 percent by weight of polyethyleneimine wherein 25 percent of the nitrogen atoms are quaternized with methyl groups is prepared as follows: 100 parts polypropyleneglycol (avg. mol. wt. 2,000), 50 parts toluene di-isocyanate, 5 parts polyethyleneimine (avg. mol. wt. 2,000), 5 parts fluorotrichloromethane and 0.1 stannous octanoate are intimately mixed and allowed to react at about 50C for about 2 hours. The resulting foam mass is then treated with 2 parts dimethylsulfate at 70C for a period of two hours.
  • the resulting foam mass is cured by bringing the mass to a temperature of about IC for 2 minutes.
  • the foam is then washed thoroughly with agitation to remove any excess polyethyleneimine and dimethylsulfate; the mass is air dryed.
  • the resulting polyurethane-25 percent methyl quaternized polyethyleneimine copolymeric foam is suitable for use in the articles and processes of this invention without further treatment.
  • the dimethylsulfate is replaced by an equivalent amount of decyl iodide and s s a zsdiqy q m s ans-tfi Percent decyl polyethyleneimine suitable for use herein are secured.
  • polyethyleneimine is replaced by an equivalent amount of polybutyleneimine and polypropyleneimine, respectively, and equivalent compositions containing the respective quaternized polyalkyleneimine-polyurethane foams are secured.
  • Foamed polyurethane-polyalkyleneimine copolymer prepared in the manner of Foam 1, above, is fashioned into cloths (about 8 inches square) weighing about 2 g., folded into bag-like containers, filled with about 2 oz. of detergent composition A, above, and sealed, thereby providing a laundering aid.
  • the detergent composition dissolves from the trapper cloth container and is released into said bath. Dirt and anionic dyes released from fabrics laundered in the bath are trapped in the surface of the trapper cloth bag, which is then discarded.
  • the trapper cloth bag is prepared containing about 2 oz. of detergent compositions B, C, D, E, H, I, J, K and L, above, respectively, in place of detergent composition A, and equivalent laundering and dye and dirt trapping results are obtained.
  • a 4 in. X 4 in. X 1 in. Foam I sponge is soaked in detergent composition F and detergent composition G, above, respectively, and provides a laundering aid comprising a trapper sponge impregnated with a detergent composition.
  • the sponge is soaked in 20 percent (wt.) aqueous solutions of detergent compositions A, B, C, D, E, H, I, J, K, and L, respectively, and dried, and trapper sponges impregnated with these detergent compositions are secured.
  • Said trapper sponges impregnated with detergents are added to aqueous laundry baths 50 and release therein the respective detergent compositions while trapping dirt and anionic dyes.
  • the polyurethane Foam l is replaced by an equivalent amount of the methyl quaternized polyethyleneimine Foam 2, described above, and equivalent results are secured.
  • detergent formulations A, B, C, D, F, H, I, J, K and L, above are each modified by adding a lipase, an amylase and a protease, respectively, in about 0.05 percent concentration of said enzymes based on weight of detergent. Equivalent results are obtained in that the fabrics are cleansed while the trapper adsorbs dirt and anionic dyes released into the laundry bath.
  • tergent tablet is prepared as follows.
  • a polyurethane prepolymer mix is formed from 100 parts polypropylene glycol (avg. mol. wt. 2,500), 25 parts toluene diisocyanate, 25 parts naphthalene di-isocyanate, and 0.05 parts stannous octanoate.
  • the pre-polymer mix is extruded through a bath of polyethyleneimine and the resulting filaments cured at 90C-100C for 3 minutes.
  • the resulting filaments which contain about 5 percent by weight of the polyethyleneimine copolymerized with the polyurethane, are woven into trapper cloths.
  • the detergent tablet containing said trapper cloth is added to an aqueous laundry bath at a temperature of about 1 10F; the detergent composition dissolves and releases the trapper cloth which scavenges dirt and anionic dyes and substantially decreases dye transfer between the fabrics being laundered.
  • detergent compositions B, C, D, E, H, l, J, K and L, above, respectively, are used to form said tableted detergent object containing the trapper.
  • the polyethyleneimine is replaced by an equivalent amount of polybutyleneimine and by 25 percent stearylated polyethyleneimine in which percent of the total nitrogen atoms are quaternized with methyl bromide and equivalent results are secured.
  • the above laundering aids comprising detergent compositions and trappers are prepared using the following trapper materials, all prepared by forming poly urethane from toluene di-isocyanate and a propyleneglycol in the presence of polyalkyleneimines and alkylated and alkanoylated polyalkyleneimines and quaternized polyalkyleneimines: polyurethane to which is chemically affixed about 10% by weight of the following polyalkyleneimines, respectively: 50 percent stearoylated di-ethyleneimine, 70 percent methylated triethyleneimine, 10 percent stearoylated dipropyleneimine, 50 percent methylated dibutyleneimine, 15 percent stearoylated polypropyleneimine (avg.
  • mol. wt. 20,000 percent diethylated polymethyleneimine hydroxide (quaternarized; mol. wt. 100,000), 10 percent methylated polybutyleneimine (avg. mol. wt. 2,000), 15 percent hexanoylated polymethyleneimine (avg. mol. wt. 25,000), 50 percent docosanoylated-50 percent ethylated polybutyleneimine (avg. mol. wt. 50,000), 5 percent octanoylated-5 percent methanoylated polymethyleneimine (avg. mol. wt.
  • the released trapper cloth scavenges dirt and anionic dyes from aqueous laundry baths and substantially inhibits dye transfer.
  • the laundering aids of the present invention are suitable for use inall manner of aqueous laundering processes. It is well-known that such laundering processes can involve additional steps such as bleaching with hypohalite solutions and fabric softening and antistatic treatments involving quater nary ammonium salts. Such laundering, bleaching and treating processes are commonly carried out over a pH range of from about 3 to about 14. Such considerations are immaterial to the practice of this invention in that the laundering aids perform their cleaning and trapping function under all such conditions and in the presence of any of these common laundry additives.
  • the quantity of trapper required to remove substantially all the dirt and dye from an aqueous laundry bath will vary with the amount of dirt and dye released from the laundered cloths. Assuming a moderate-to-heavy dirt load and dye release, about a 2 02. mass of the foamed trapper will remove substantially all dirt and dye released from one 6 pound laundry bundle washed in about 8 gallons of water. More or less trapper can be employed, as desired.
  • a laundering aid consisting essentially of 1 a water-insoluble substrate consisting of polyurethane chemically combined with from about 0.1 percent to about 10 percent by weight of said substrate of a polyalkyleneimine material containing the moiety wherein y is an integer of from 1 to 4, z is an integer greater than 1, R is selected from the group consisting of hydrogen and alkyl and alkanoyl substituents containing from about 1 to about 22 carbon atoms, R is an alkyl group containing from 1 to about 22 carbon atoms and X is an anion; and (2) a water-soluble detergent composition in releasable combination with said substrate in an amount sufficient to provide good fabric cleansing.
  • a laundering aid according to claim 1 wherein the water-insoluble substrate consists of polyurethane chemically combined with from about 1 percent to about 10 percent by weight of polyethyleneimine.
  • a laundering aid according to claim 1 wherein the detergent composition comprises from about 10 percent to about percent by weight of a water-soluble organic detergent compound and from about 10 percent to about 90 percent by weight of a water-soluble detergency builder.
  • a laundering aid according to claim 3 wherein the organic detergent compound is a member selected from the group consisting of alkali metal soaps and water-soluble organic sulfonic acid reaction products having in their molecular structure an alkyl substituent containing from about 8 to about 22 carbon atoms and a sulfuric acid or sulfonic ester substituent and wherein the detergency builder is a member selected from the group consisting of sodium nitrilotriacetate, potassium nitrilotriacetate, sodium mellitate, potassium mellitate, sodium citrate, potassium citrate, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium oxydisuccinate, potassium oxydisuccinate, sodium phloroglucinoltrisulfonate, potassium phloroglucinoltrisulfonate, sodium (ethylenedioxy)diacetate and potassium (ethylenedioxy)diacetate.
  • the organic detergent compound is a member selected from the group consisting of alkali metal
  • a process for trapping dirt and anionic dyes in laundering baths comprising adding to said bath a detergent composition in an amount sumcient to provide good fabric cleansing and a water-insoluble substrate consisting of polyurethane chemically combined with from about 0.1 percent to about percent by weight of said substrate of a polyalkyleneimine material containing the moiety

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  • Chemical Kinetics & Catalysis (AREA)
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US00249810A 1972-05-03 1972-05-03 Laundering aid Expired - Lifetime US3816321A (en)

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Application Number Priority Date Filing Date Title
US00249810A US3816321A (en) 1972-05-03 1972-05-03 Laundering aid
DE2321724A DE2321724C2 (de) 1972-05-03 1973-04-28 Hilfsmittel zum Waschen
AU55072/73A AU5507273A (en) 1972-05-03 1973-05-01 Laundering aid
IT23638/73A IT986991B (it) 1972-05-03 1973-05-02 Prodotto coadiuvante per lavan deria
CA170,217A CA997244A (en) 1972-05-03 1973-05-02 Laundering aid
FR7315750A FR2183178B1 (en, 2012) 1972-05-03 1973-05-02
NLAANVRAGE7306084,A NL178980C (nl) 1972-05-03 1973-05-02 Voorwerp voor gebruik in een wassop en wasproces, waarbij men een dergelijk voorwerp gebruikt.
GB2107573A GB1393508A (en) 1972-05-03 1973-05-03 Laundering article
BE130677A BE799022A (fr) 1972-05-03 1973-05-03 Auxiliaire de blanchisserie,
JP48050177A JPS4954407A (en, 2012) 1972-05-03 1973-05-04

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CA (1) CA997244A (en, 2012)
DE (1) DE2321724C2 (en, 2012)
FR (1) FR2183178B1 (en, 2012)
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US4095946A (en) * 1977-03-25 1978-06-20 The Procter & Gamble Company Article for cleaning and conditioning fabrics
US4118525A (en) * 1977-03-25 1978-10-03 The Procter & Gamble Company Article and method for fabric softening and static control
US4156604A (en) * 1978-09-15 1979-05-29 Minnesota Mining And Manufacturing Company Controlled delivery of corrosion inhibitors for silver recovery cartridges
US4170565A (en) * 1977-03-25 1979-10-09 The Procter & Gamble Company Substrate article for cleaning fabrics
US4188304A (en) * 1977-05-18 1980-02-12 Lever Brothers Company Detergent composition in a water-insoluble bag having a water-sensitive seal
US4294576A (en) * 1979-06-23 1981-10-13 Basf Aktiengesellschaft Removal of oligomer deposits from textile materials
US4648510A (en) * 1985-01-14 1987-03-10 Henkel Kommanditgesellschaft Auf Aktien Easily dispensable detergency booster cloths and dispenser therefor
US4761249A (en) * 1985-12-23 1988-08-02 Henkel Kommanditgesellschaft Auf Aktien Soil-collecting cleaning enhancers in aqueous surfactant laundering and cleaning solutions
US4773939A (en) * 1986-02-22 1988-09-27 Henkel Kommanditgesellschaft Auf Aktien Use of insoluble soil collectors for at least partial regeneration of laundering and cleaning solutions
US4830784A (en) * 1986-03-01 1989-05-16 Henkel Kommanditgesellschaft Auf Aktien Laundry detergents and cleaners with reduced requirement for conventional chemicals
US5055215A (en) * 1989-03-03 1991-10-08 Fabritec International Corporation Unit-dose drycleaning product and method
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US5269952A (en) * 1992-12-21 1993-12-14 E. I. Du Pont De Nemours And Company Antistatic finish for dyeable surfactant-containing poly(m-phenylene isophthalamide) fibers
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ITBO20080721A1 (it) * 2008-11-28 2010-05-29 Dylas Italia S R L Articolo per il lavaggio di tessuti colorati e confezione che lo comprende
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US20100275384A1 (en) * 2007-05-31 2010-11-04 Colgate-Palmolive Company Fabric softening compositions comprising polymeric materials
ITMI20100789A1 (it) * 2010-05-05 2011-11-06 Ica Spa Compressa polifunzionale per tessuti e relativo processo di fabbricazione
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CN106917233A (zh) * 2017-03-09 2017-07-04 无锡小天鹅股份有限公司 用于洗衣机的护色装置和洗衣机
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US3963649A (en) * 1972-09-11 1976-06-15 The Procter & Gamble Company Liquid detergent composition
US4095946A (en) * 1977-03-25 1978-06-20 The Procter & Gamble Company Article for cleaning and conditioning fabrics
US4118525A (en) * 1977-03-25 1978-10-03 The Procter & Gamble Company Article and method for fabric softening and static control
US4170565A (en) * 1977-03-25 1979-10-09 The Procter & Gamble Company Substrate article for cleaning fabrics
US4188304A (en) * 1977-05-18 1980-02-12 Lever Brothers Company Detergent composition in a water-insoluble bag having a water-sensitive seal
US4156604A (en) * 1978-09-15 1979-05-29 Minnesota Mining And Manufacturing Company Controlled delivery of corrosion inhibitors for silver recovery cartridges
US4294576A (en) * 1979-06-23 1981-10-13 Basf Aktiengesellschaft Removal of oligomer deposits from textile materials
US4648510A (en) * 1985-01-14 1987-03-10 Henkel Kommanditgesellschaft Auf Aktien Easily dispensable detergency booster cloths and dispenser therefor
US4761249A (en) * 1985-12-23 1988-08-02 Henkel Kommanditgesellschaft Auf Aktien Soil-collecting cleaning enhancers in aqueous surfactant laundering and cleaning solutions
US4773939A (en) * 1986-02-22 1988-09-27 Henkel Kommanditgesellschaft Auf Aktien Use of insoluble soil collectors for at least partial regeneration of laundering and cleaning solutions
US4830784A (en) * 1986-03-01 1989-05-16 Henkel Kommanditgesellschaft Auf Aktien Laundry detergents and cleaners with reduced requirement for conventional chemicals
US5055215A (en) * 1989-03-03 1991-10-08 Fabritec International Corporation Unit-dose drycleaning product and method
US5196132A (en) * 1989-03-03 1993-03-23 Fabritec International Corporation Unit-dose drycleaning product
US5196139A (en) * 1989-06-19 1993-03-23 Lever Brothers Company, Division Of Conopco, Inc. Bleach article containing polyacrylate or copolymer of acrylic and maleic
US5238587A (en) * 1991-03-20 1993-08-24 Creative Products Resource Associates, Ltd. Dry-cleaning kit for in-dryer use
US5269952A (en) * 1992-12-21 1993-12-14 E. I. Du Pont De Nemours And Company Antistatic finish for dyeable surfactant-containing poly(m-phenylene isophthalamide) fibers
US5571287A (en) * 1993-01-11 1996-11-05 Colgate-Palmolive Company Soap composition containing sodium pyrophosphate
WO1996026831A1 (en) * 1995-03-01 1996-09-06 The Clorox Company Laundry article for preventing dye carry-over and indicator therefor
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US5972041A (en) * 1995-06-05 1999-10-26 Creative Products Resource, Inc. Fabric-cleaning kits using sprays, dipping solutions or sponges containing fabric-cleaning compositions
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CA997244A (en) 1976-09-21
JPS4954407A (en, 2012) 1974-05-27
NL178980C (nl) 1986-06-16
FR2183178B1 (en, 2012) 1976-05-28
FR2183178A1 (en, 2012) 1973-12-14
NL178980B (nl) 1986-01-16
AU5507273A (en) 1974-11-07
DE2321724C2 (de) 1982-07-01
NL7306084A (en, 2012) 1973-11-06
BE799022A (fr) 1973-11-05
DE2321724A1 (de) 1973-11-15
IT986991B (it) 1975-01-30
GB1393508A (en) 1975-05-07

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