Laundering Aid

Abstract

A laundering aid comprising a water-insoluble, polyurethane-polyalkyleneimine material releasably combined with a detergent composition, said aid providing a means of introducing a detergent composition into a laundry bath and at the same time serving to adsorb dirt and vagrant anionic dyes from the aqueous laundry media, thereby providing an improved laundering process.

Description

BACKGROUND OF THE INVENTION

This invention encompasses laundering aids comprising a chemically modified polyurethane material in combination with a soap or synthetic organic detergent composition. In its method aspect, 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.

Most laundering compositions contain various synthetic materials capable of suspending dirt released from fabrics during the laundering process. Without such additives much of the dirt released during washing is redeposited on the fabric surface. Even so, washing machine manufacturers have been constrained to design machines wherein the wash water does not drain through the clothes since even the suspended soil would then be redeposited on the fabric surface. Another problem encountered during the laundering of fabrics is that of dye transfer. Dye transfer is most evident when deeply colored fabrics are laundered in the same bath with less highly colored, or white, fabrics. Heretofore, there has been no good way to combat the problem of dye transfer other than mechanically sorting the fabrics to partition said fabrics into dark and light shades for separate laundering.

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 J. 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 process involving formation of the fabric, its surface modification and a final surface treatment.

It has now been found that certain water-insoluble 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. As an article of manufacture, the polyurethane-polyalkyleneimine material also contains a detergent composition which is released into the bath. Thus, the user can add a predetermined amount of detergent to the bath in conjunction with the dye and dirt trapper material. Following the laundering operation, 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. For example, U.S. Pat. No. 3,165,566 discloses a process for curing polyurethane by passing urethane pre-polymer 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. However, 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. These and other objects are obtained by the present invention as will be seen from the following disclosure.

SUMMARY OF THE INVENTION

The invention comprises a detergent composition in releasable combination with a water-insoluble substrate consisting of polyurethane in chemical combination with a polyalkyleneimine material. In its process aspect the invention encompasses adding a water-insoluble polyurethane-polyalkyleneimine substrate to an aqueous washing solution containing a detergent composition to trap dirt and organic anionic materials.

DETAILED DESCRIPTION OF THE INVENTION

The laundering aids herein comprise: (1) a water-insoluble 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 ##SPC1## 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, each R' is an alkyl group containing from 1 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. When 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. For the purposes of this invention, polyalkyleneimines, including alkylated and alkanoylated polyalkyleneimines, of any degree of polymerization, especially those in the range of 2 to 50,000, especially 20 to 10,000, monomer units per molecule, are preferred.

Since 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 water-insoluble, foamed polyurethane in chemical combination with from about 0.5 percent to about 10 percent by weight of polyethyleneimine.

The foregoing patents relating to amine-containing polyurethanes disclose a variety of water-insoluble polyurethane substrates prepared in the presence of various polyalkyleneimines; alkylated and alkanoylated polyalkyleneimines can be employed in the same manner to provide polyurethanes chemically combined with alkylated and alkanoylated polyalkyleneimines. The resulting materials have the polyalkyleneimines (or alkylated or alkanoylated polyalkyleneimines) chemically affixed to the polyurethane, presumably by covalent bonding (urea linkages) with the monomer units of the polymer. Any excess, uncombined, polyalkyleneimines can be removed by a water wash. The chemically bound polyalkyleneimine materials in such compositions are not removed by contact with water. Any of these water-insoluble polyurethane-polyalkyleneimine trapper materials can be employed herein in combination with detergents and soaps to provide laundering aids.

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 polyalkyleneimine-polyurethane materials herein comprise a polyalkyleneimine "backbone" having pendant hydrogen, or alkyl or alkanoyl groups on the nitrogen atoms. These polymers are difficult to describe in other than a qualitative manner. For example, the preferred polyalkyleneimine used herein is polyethyleneimine. It is believed that the structural formula of polyethyleneimine is: ##SPC2##

wherein z represents a whole number greater than 1, usually about 2 to 100,000. The degree of polymerization, z, 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:

--CH.sub.2 --CH.sub.2 --NH.sub.2 30% --CH.sub.2 --CH.sub.2 --NH-- 40% --CH.sub.2 --CH.sub.2 --N-- 30%

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 2,185,480, 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. The 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 1 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. Alternatively, 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 90 percent by weight of a water-soluble detergency builder and from about 10 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. Included 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. Usually, from about 2 oz. to about 6 oz. of such compositions are used in conjunction with the trapper, but this is not critical in that any amount of such compositions sufficient to provide good fabric cleansing can be so employed.

Organic Detergents

The organic detergent compounds which can be utilized with the trapper material in the laundering aids encompassed by this invention include the following:

A. Anionic Soap and Non-Soap Synthetic Detergents

This class of 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 10 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. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Examples of 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.sub.8 - C.sub.18) 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 15 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.sub.12 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 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 1 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.

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, of course, are --SO.sub.4 H, --SO.sub.3 H, and --CO.sub.2 H. Alkyl phosphate esters such as (R--O).sub.2 PO.sub.2 H and ROPO.sub.3 H.sub.2 in which R represents an alkyl chain containing from about 8 to about 20 carbon atoms are useful.

These 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 ##SPC3##

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.

Another class of suitable anionic organic detergents particularly useful in this invention includes salts of 2-acyloxyalkane-1-sulfonic acids. These salts have the formula ##SPC4##

where R.sub.1 is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group); R.sub.2 is alkyl of 1 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. Specific examples of 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.

Specific examples of .beta.-acyloxy-alkane-1-sulfonates, or alternatively 2-acyloxy-alkane-1-sulfonates, useful herein to provide superior cleaning levels under substantially neutral washing conditions include the sodium salt of 2-acetoxy-tridecane-1-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-1-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of 2-propionyloxy-docosane-1-sulfonic acid; the isomers thereof.

Preferred .beta.-acyloxy-alkane-1-sulfonate salts herein are the alkali metal salts of .beta.-acetoxy-alkane-1-sulfonic acids corresponding to the above formula wherein R.sub.1 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.

Typical examples of the above-described .beta.-acetoxy alkanesulfonates are described in the literature: Belgium Patent 650,323 discloses the preparation of certain 2-acyloxy alkanesulfonic acids. Similarly, U.S. Pat. No. 2,094,451 and 2,086,215 disclose certain salts of .beta.-acetoxy alkanesulfonic acids. These patents are hereby incorporated by reference.

Another preferred class of anionic detergent compounds herein, both by virtue of superior cleaning properties and low sensitivity to water hardness (Ca++ and Mg++ ions) are the alkylated .alpha.-sulfocarboxylates, containing about 10 to about 23 carbon atoms, and having the formula ##SPC5##

wherein R is C.sub.8 to C.sub.20 alkyl, M is a water-soluble cation as hereinbefore disclosed, preferably sodium ion, and R' is short-chain alkyl, e.g., methyl, ethyl, propyl, and butyl. These compounds are prepared by the esterification of .alpha.-sulfonated carboxylic acids, which are commercially available, using standard techniques. Specific examples of the alkylated .alpha.-sulfocarboxylates preferred for use herein include:

ammonium methyl-.alpha.-sulfopalmitate,

triethanolammonium ethyl-.alpha.-sulfostearate,

sodium methyl-.alpha.-sulfopalmitate,

sodium ethyl-.alpha.-sulfopalmitate,

sodium butyl-.alpha.-sulfostearate,

potassium methyl-.alpha.-sulfolaurate,

lithium methyl-.alpha.-sulfolaurate,

as well as mixtures thereof.

A preferred class of anionic organic detergents are the .beta.-alkyloxy alkane sulfonates. These compounds have the following formula: ##SPC6##

where R.sub.1 is a straight chain alkyl group having from 6 to 20 carbon atoms, R.sub.2 is a lower alkyl group having from 1 (preferred) to 3 carbon atoms, and M is a water-soluble cation as hereinbefore described.

Specific examples of .beta.-alkyloxy alkane sulfonates, or alternatively 2-alkyloxy-alkane-1-sulfonates, having low hardness (calcium ion) sensitivity useful herein to provide superior cleaning levels under household washing conditions include:

potassium-.beta.-methoxydecanesulfonate,

sodium 2-methoxytridecanesulfonate,

potassium 2-ethoxytetradecylsulfonate,

sodium 2-isopropoxyhexadecylsulfonate,

lithium 2-t-butoxytetradecylsulfonate,

sodium .beta.-methoxyoctadecylsulfonate, and

ammonium .beta.-n-propoxydodecylsulfonate.

Other synthetic anionic detergents useful herein are alkyl ether sulfates. These materials have the formula RO(C.sub.2 H.sub.4 O).sub.x SO.sub.3 M wherein R is alkyl or alkenyl of about 10 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.

Specific examples of 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.

Preferred herein for reasons of excellent cleaning properties and ready availability are the alkali metal coconut- and 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.

Additional examples of 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.

Additional examples of 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 di-anionic detergents. Suitable di-anionic detergents are the disulfonates, disulfates, or mixtures thereof which may be represented by the following formulae:

R(so.sub.3).sub.2 m.sub.2, r(so.sub.4).sub.2 m.sub.2, r(so.sub.3)(so.sub.4)m.sub.2,

where R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example, the C.sub.15 to C.sub.20 disodium 1,2-alkyldisulfates, C.sub.15 to C.sub.20 dipotassium-1,2-alkyldisulfonates or disulfates, disodium 1,9-hexadecyl disulfates, C.sub.15 to C.sub.20 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 IIA, IIB, IIIA, IVA and IVB of the Periodic Table except for boron. The preferred water-solubilizing cations are sodium or potassium. These dianionic detergents are more fully described in British Letters Patent 1,151,392.

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.

Other suitable anionic detergents utilizable herein are olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonate of .alpha.-olefins 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 SO.sub.2, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO.sub.2, etc., when used in the gaseous form.

The .alpha.-olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbon atoms. Preferably, they are straight chain olefins. Examples of suitable 1-olefins include 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.

In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, 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.

A specific anionic detergent which has also been found excellent for use in the present invention is described more fully in the U.S. Pat. No. 3,332,880, incorporated herein by reference.

B. Nonionic Synthetic Detergents

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.

For example, 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.

Other suitable nonionic synthetic detergents include:

1. 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 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.

2. Compounds derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. For example, compounds containing from about 40 percent to about 80 percent polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 and 3,000, are satisfactory.

3. The condensation product of aliphatic alcohols having from 8 to 22 carbon atoms, in either straight chain or branched chain configuration with 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.

4. 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.

Other examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 15 moles of ethylene oxide per mole of phenol; dodecyl mercaptan condensed with 10 moles of ethylene oxide per mole of mercaptan; bis-(N-2-hydroxyethyl)lauramide; nonyl phenol condensed with 20 moles of ethylene oxide per mole of nonyl phenol; myristyl alcohol condensed with 10 moles of ethylene oxide per mole of myristyl alcohol; lauramide condensed with 15 moles of ethylene oxide per mole of lauramide; and di-isooctylphenol condensed with 15 moles of ethylene oxide.

5. A detergent having the formula R.sup.1 R.sup.2 R.sup.3 N.fwdarw.O (amine oxide detergent) wherein R.sup.1 is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R.sup.1 which is an alkyl group containing from about 10 to about 18 carbon atoms and 0 ether linkages, and each R.sup.2 and R.sup.3 are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.

Specific examples of 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-(2-hydroxyethyl)-3-dodecoxy-1-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.

6. A detergent having the formula R.sup.1 R.sup.2 R.sup.3 P.fwdarw.O (phosphine oxide detergent) wherein R.sup.1 is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R.sup.1 which is an alkyl group containing from about 10 to about 18 carbon atoms and 0 ether linkages, and each of R.sup.2 and R.sup.3 are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.

Specific examples of the phosphine oxide detergents include: dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide, bis(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.

7. A detergent having the formula ##SPC7##

(sulfoxide detergent) wherein R.sup.1 is an alkyl radical containing from about 10 to about 28 carbon atoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxyl substituents at least one moiety of R.sup.1 being an alkyl radical containing 0 ether linkages and containing from about 10 to about 18 carbon atoms, and wherein R.sup.2 is an alkyl radical containing from 1 to 3 carbon atoms and from one to two hydroxyl groups: e.g., octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl 2-hydroxyethyl sulfoxide, and dodecylethyl sulfoxide.

C. Ampholytic Synthetic Detergents

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfato. Examples of compounds falling within this definition are sodium 3-(dodecylamino)propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyldodecylamino)propane-1-sulfonate, disodium octadecyl-iminodiazetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.

D. Zwitterionic Synthetic Detergents

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. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate, 2-(N,N-dimethyl-N-dodecylammonio)acetate, 3-(N,N-dimethyl N-dodecylammonio)-propionate, 2-(N,N-dimethyl-N-octadecylammonio)ethyl sulfate, 2-(trimethylammonio)ethyl dodecylphosphonate, ethyl 3-(N,N-dimethyl-N-dodecylammonio)propylphosphonate, 3-(P,P-dimethyl-P-dodecylphosphonio)propane-1-sulfonate, 2-(S-methyl-S-tert-hexadecyl-sulfonio)ethane-1-sulfonate, 3-(S-methyl-S-dodecylsulfonio)propionate, sodium 2-(N,N-dimethyl-N-dodecylammonio)ethyl phosphonate, 4-(S-methyl-S-tetra-decylsulfonio)butyrate, 1-(2-hydroxyethyl)-2-undecylimidazolium-1-acetate, 2-(trimethylammonio)octadecanoate, and 3-N,N-bis-(2-hydroxyethyl-N-octadecylammonio)-2-hydroxypropane-1-sulfonate . Some of these detergents are described in the following U.S. Pat. Nos. 2,129,264; 2,178,353; 2,774,786; 2,813,898; and 2,828,332. The 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.

These soap and non-soap anionic, nonionic, ampholytic and zwitterionic detergent compounds, either 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.

Builder Salts

Many of the common detergent compositions contain water-soluble builder salts, either of the organic or inorganic type; these are wholly compatible with the trapper materials and can be used in conjunction with organic detergent compounds and 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.

Examples of suitable organic alkaline detergency builder salts are: (1) 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 U.S. 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. Other examples include these alkali metal salts of ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid, and water-soluble salts of polycarboxylate polymers and copolymers such as those described in U.S. Pat. No. 3,308,067.

The polycarboxylate materials described in U.S. Pat. No. 2,264,103, are also suitably employed herein. For example, aconitic acid, mellitic acid and the penta- and tetra-carboxylic acids prepared by the malonic acid synthesis can be employed herein as builders. The water-soluble alkali metal salts of these materials are 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., ternary mixtures of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane-1-hydroxy-1,1-diphosphonate. The above described builders can also be utilized singly in this invention.

Preferred builders herein include: the sodium and potassium salts of the tripolyphosphates, nitrilotriacetates, mellitates (benzenehexacarboxylates), silicates, citrates, carbonates, oxydisuccinates, phloroglucinoltrisulfonates, and (ethylenedioxy)diacetates.

Various polyelectrolytes such as carboxymethyl-cellulose, carboxymethylhydroxyethylcellulose, and the like, are commonly added to detergent formulations to provide a soil antiredeposition effect. Any such materials are suitable for use in the laundering aids of this invention.

Optical bleaches, such as the stilbenes, furans, thiophenes and the like, are all useful with the laundering aids and can be incorporated therein.

The following are examples of typical detergent and presoak compositions suitable for use in combination with the trapper materials employed in the present invention to provide laundering aids. The compositions listed are for the purposes of illustration and are not intended to be limiting of the types of formulations used with the trapper materials to provide the laundering aids of this invention.

______________________________________ Detergent Composition A Weight Percent ______________________________________ 7.8 sodium linear dodecylbenzenesulfonate 9.5 sodium tallowalkyl sulfate 49.4 sodium tripolyphosphate 5.9 sodium silicate 13.7 Na.sub.2 SO.sub.4 0.2 sodium carboxymethylcellulose 2.2 nonionic suds controlling agents bal. moisture ______________________________________

______________________________________ Detergent Composition B Weight Percent ______________________________________ 90 sodium soap of 20:80 coconut:tallow fatty acids 5 sodium silicate 3 tetrasodium pyrophosphate 1.5 sodium chloride 0.05 additives* (optional) bal. moisture ______________________________________ * Including perfumes and optical brighteners.

______________________________________ Detergent Composition C Weight Percent ______________________________________ 17.5 sodium linear dodecylbenzenesulfonate 50 sodium citrate 14 sodium sulfate 0.5 sodium carboxymethylcellulose 7 sodium silicate 0.10 additives* (optional) bal. moisture ______________________________________ * Including perfumes and optical brighteners.

______________________________________ Detergent Composition D Weight Percent ______________________________________ 5 dimethyldodecylphosphine oxide 10 condensation product of 11 moles of ethylene oxide with 1 mole of coconut fatty alcohol 10 tetrasodium methylenediphosphonate 60 sodium tripolyphosphate 0.5 sodium carboxymethylcellulose 10 sodium mellitate bal. moisture ______________________________________

______________________________________ Detergent Composition E Weight Percent ______________________________________ 7 sodium tallowalkyl sulfate 7 sodium linear dodecylbenzenesulfonate 50 sodium tripolyphosphate 10 sodium carbonate 10 sodium sulfate 15 potassium dichlorocyanurate (bleach) 0.05 perfume bal. moisture ______________________________________

______________________________________ Detergent Composition F (Liquid) Weight Percent ______________________________________ 6 sodium-3-dodecylaminopropionate 6 sodium linear dodecylbenzenesulfonate 20 potassium pyrophosphate 8 potassium toluenesulfonate 3.8 sodium silicate 0.3 carboxymethylhydroxyethylcellulose 0.05 additives* (optional) bal. water ______________________________________ * Including perfumes and optical brighteners.

______________________________________ Detergent Composition G (Liquid) Weight Percent ______________________________________ 6 sodium linear dodecylbenzenesulfonate 4 dimethyldodecylamine oxide 10 trisodium ethane-1-hydroxy-1,1-diphosphonate 10 tripotassium nitrilotriacetate 8 potassium toluenesulfonate 3.8 sodium silicate (ratio SiO.sub.2 :Na.sub.2 O of 2:1) 5 potassium dichlorocyanurate (bleach) 0.3 sodium carboxymethylcellulose 0.20 3-morpholino-2,5-diphenylfuran (optical brightener) 0.10 perfume bal. water ______________________________________

______________________________________ Detergent Composition H Weight Percent ______________________________________ 40 sodium salt of SO.sub.3 -sulfonated tetradecene 10 dimethyl coconutalkylammonio acetate 30 trisodium ethane-hydroxy triphosphonate 10 sodium carbonate bal. moisture ______________________________________

______________________________________ Detergent Composition I Weight Percent ______________________________________ 7.5 tetradecyl-.beta.-methoxysulfonate 2 sodium tallowalkyl sulfate 2.2 hydrogenated marine oil fatty acid suds depressant 40 sodium tripolyphosphate 20 trisodium nitrilotriacetate 10 sodium silicate (2:1 ratio SiO.sub.2 :Na.sub.2 O) 13 sodium citrate 0.20 perfume bal. water ______________________________________

______________________________________ Detergent Composition J Weight Percent ______________________________________ 10 sodium linear dodecylbenzenesulfonate 10 condensation product of 1 mole of nonyl phenol with 12 moles of ethylene oxide 10 sodium tripolyphosphate 30 trisodium ethane-1-hydroxy-1,1-diphosphonate 10 trisodium nitrilotriacetate 6 sodium silicate (2:1 ratio SiO.sub.2 :Na.sub.2 O) 10 trisodium phosphate 0.5 sodium carboxymethylcellulose 0.1 3-phenyl-2,5-diphenylthiophene (optical brightener) 0.2 3-diethanolamino-2,5-di-p-methoxyphenylfuran (optical brightener) bal. moisture ______________________________________

______________________________________ Detergent Composition K (For Cool Water Use) Weight Percent ______________________________________ 5 sodium tallowalkyl sulfate 12 3(N,N-dimethyl-N-dodecylammonio)- - 2-hydroxy-propane-1-sulfonate 5 sodium salt of SO.sub.3 -sulfonated .alpha.-tridecene 30 sodium tripolyphosphate 20 trisodium nitrilotriacetate 10 sodium silicate (SiO.sub.2 :Na.sub.2 O = 1.6:1) 10 sodium phloroglucinoltrisulfonate 0.3 sodium carboxymethylhydroxyethylcellulose 0.1 3-deca(oxyethylene)-2,5-diphenylfuran 0.05 perfume bal. moisture ______________________________________

______________________________________ Detergent Composition L (For Cool Water Use) Weight Percent ______________________________________ 5 sodium tallowalkyl sulfate 5 3(N,N-dimethyl-N-hexadecylammonio- propane-1-sulfante 10 dimethyldodecylphosphine oxide 5 trisodium ethane-1-hydroxy-1,1-diphosphonate 10 trisodium nitrilotriacetate 40 sodium tripolyphosphate 10 sodium silicate (Na.sub.2 O:SiO.sub.2 = 1:2.5) 0.3 sodium oxydisuccinate 10 sodium (ethylenedioxy)diacetate bal. moisture ______________________________________

In the above compositions (with the exception of Compositions E and G since these contain enzyme-destroying bleaches) a minor amount, i.e., from about 0.001 percent to about 2 percent, by weight, of an enzyme such as an amylase, a protease or a lipase, can be added to provide the cleansing advantages of said enzymes. The enzyme used in a given composition will depend to some extent on the pH, but this selection can be made by reference to available pH-activity tables for enzymes.

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 32.degree.F to about 212.degree.F, preferably from about 75.degree.F to about 160.degree.F. It is well established that certain laundry detergents and additives are suitable for use at the lower temperatures within this range while others perform more effectively at higher temperatures. It is further recognized that certain whitening agents such as perborate are suitable for use only at the higher temperatures within this range. Therefore, the practitioner of this invention can select a commercial detergent, bleach, whitener or presoak composition which functions at any desired temperature, combine it with the trapper material and thereby provide a laundering aid designed to meet the needs of various laundering situations.

The laundering aids of this invention can be prepared 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", "50 percent SPEI", etc., relate to the percent of the nitrogen atoms in polyethyleneimine which are alkylated or alkanoylated. Similar terminology is used with the other alkylated and alkanoylated polyalkyleneimines employed herein.

The polyurethanes used in the instant invention are the well-known polymeric substances produced by the condensation of a polyisocyanate and a polyhydroxyl-containing material such as a polyol. Though containing many free urethane or free isocyanate groups, the molecule may have a number of other constituents. A polyurethane foam may be a solid, rigid or spongy, foam prepared by reacting a polyether, such as polypropylene glycol, or polyesters having free hydroxyl groups, with a di-isocyanate in the presence of some water and a catalyst. As the polymer forms in this reaction, the water reacts with isocyanate groups partly to cause cross-linking and partly to cause the formation of amine groups, at the same time producing carbon dioxide which causes foaming. In other cases trifluoromethane or a similar volatile material can be used as the blowing agent, or additional blowing agents. 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. Preferably the polyurethane used herein is one made from a polypropylene glycol and either toluene or naphthalene di-isocyanate. The polyurethane can alternatively be derived from other di-isocyanates with other alkylene oxides or with polyesters having free hydroxyl groups. Procedures for preparing polyurethane-polyalkyleneimine copolymers are given below.

FOAM 1

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 0.1 part stannous octanoate are intimately mixed and allowed to react at about 50.degree.C - 70.degree.C for about two hours. The resulting foam mass is then "cured" by bringing the mass to a temperature of about 90.degree.C - 100.degree.C for two minutes. The foam is then washed thoroughly with agitation to remove any excess polyethyleneimine and air dried. The resulting polyurethane-polyethyleneimine copolymeric foam is suitable for use in the articles and processes of this invention without further treatment.

In the above procedure, the polyethyleneimine is replaced by an equivalent amount of 50 percent SPEI and copolymers of polyurethane - 50 percent SPEI suitable for use herein are secured.

FOAM 2

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 50.degree.C for about 2 hours. The resulting foam mass is then treated with 2 parts dimethylsulfate at 70.degree.C for a period of two hours. Following this treatment, the resulting foam mass is cured by bringing the mass to a temperature of about 100.degree.C 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.

In the above procedure, the dimethylsulfate is replaced by an equivalent amount of decyl iodide and quaternized copolymers of polyurethane-25 percent decyl polyethyleneimine suitable for use herein are secured.

In a modification of the above procedure, the polyethyleneimine is quaternized prior to being added to the polyurethane pre-polymer mix. This is accomplished as follows: 50 parts polyethyleneimine are admixed with 50 parts ethyl iodide at 25.degree.C for one hour. The resulting product is the polyethyleneimine in which approximately 30 percent of the total nitrogen atoms are quaternized with ethyl substituents; the counterion is iodide. The resulting quaternized polyethyleneimine is used to replace the polyethyleneimine in the procedure described in Foam 1 and a polyurethane foam containing the quaternized polyethyleneimine is secured.

In the foregoing procedure, the polyethyleneimine is replaced by an equivalent amount of polybutyleneimine and polypropyleneimine, respectively, and equivalent compositions containing the respective quaternized polyalkyleneimine-polyurethane foams are secured.

EXAMPLE I

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. Upon addition of the laundering aid to an aqueous laundry bath, 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.

In a modification of the above article a 4 in. .times. 4 in. .times. 1 in. Foam 1 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. Alternatively, 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 and release therein the respective detergent compositions while trapping dirt and anionic dyes. The polyurethane Foam 1 is replaced by an equivalent amount of the methyl quaternized polyethyleneimine Foam 2, described above, and equivalent results are secured.

In a modification of the above articles, 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.

EXAMPLE II

A laundering aid comprising a trapper cloth in a detergent tablet is prepared as follows. A polyurethane prepolymer mix is formed from 100 parts polypropylene glycol (avg. mol. wt. 2,500), 25 parts toluene di-isocyanate, 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 90.degree.C-100.degree.C 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.

A laundering aid comprising a trapper cloth prepared in the foregoing manner in a detergent table is prepared as follows: the trapper cloth (about 6 in. .times. 6 in. .times. 1/16 in. weighing about 5 g.) is compacted by folding into an object having the dimensions approximately 0.5 in. .times. 1 in. .times. 2 in. About 2.5 oz. of detergent formulation A, above, is molded around the folded trapper cloth and compacted in an automatic press to a tablet, said tablet containing in its interior said trapper cloth. The detergent tablet containing said trapper cloth is added to an aqueous laundry bath at a temperature of about 110.degree.F; 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. In a modification of this laundering aid, detergent compositions B, C, D, E, H, I, J, K and L, above, respectively, are used to form said tableted detergent object containing the trapper.

In the above compositions, the polyethyleneimine is replaced by an equivalent amount of polybutyleneimine and by 25 percent stearylated polyethyleneimine in which 15 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 polyurethane 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 di-propyleneimine, 50 percent methylated dibutyleneimine, 15 percent stearoylated polypropyleneimine (avg. mol. wt. 20,000), 20 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. 10,000), 20 percent dihexylated polyethyleneimine fluoride (quaternarized; mol. wt. 3,000), 5 percent docosylated polyethyleneimine (avg. mol. wt. 1,000), 100 percent docosylated polybutyleneimine (avg. mol. wt. 100,000). In each instance, the released trapper cloth scavenges dirt and anionic dyes from aqueous laundry baths and substantially inhibits dye transfer.

It is to be understood that the laundering aids of the present invention are suitable for use in all 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 quaternary 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.

Furthermore, it is recognized that 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 oz. 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.

Claims

What is claimed is:

1. 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 ##SPC8##

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.

2. 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.

3. A laundering aid according to claim 1 wherein the detergent composition comprises from about 10 percent to about 90 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.

4. 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.

5. A laundering aid according to claim 1 wherein the substrate is in bag conformation releasably containing the detergent composition.

6. A laundering aid according to claim 1 wherein the detergent composition is in tablet form and the substrate is incorporated in said tablet.

7. A laundering aid according to claim 1 wherein the substrate is in sponge form releasably containing the detergent composition.

8. A process for trapping dirt and anionic dyes in laundering baths comprising adding to said bath a detergent composition in an amount sufficient to provide good fabric cleansing and 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 ##SPC9##

wherein y is an integer of from 1 to 4, z is an integer greater than 1, and 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.sup.- is an anion.

9. A process according to claim 8 wherein the water-insoluble substrate consists of polyurethane chemically combined with from about 1 percent to about 10 percent by weight of polyethyleneimine.