US3694364A - Laundering aid - Google Patents

Abstract

A LAUNDERING AID COMPRISING AN AMINE-COATED MODIFIED CELLULOSIC SUBSTRATE IN COMBINATION WITH A DETERGENT, SAID AID PROVIDING A MEANS OF INTRODUCING A DETERGENT INTO A WASHING SOLUTION AND AT THE SAME TIME SERVING TO ADSORB DIRT AND VAGRANT ANIONIC DYES FROM THE AQUEOUS MEDIA, THEREBY PROVIDING AN IMPROVED LAUNDERING PROCESS.

Description

United States Pateflf v 3,694,364 LAUNDERING AID James B. Edwards, Cincinnati, Ohio, assignor to The Procter & Gable Company, Cincinnati, Ohio No Drawing. Filed Dec. 28, 1970, Ser. No. 102,200 Int. Cl. Clld 17/04 US. Cl. 252-90 11 Claims ABSTRACT OF THE DISCLOSURE A laundering aid comprising an amine-coated modified cellulosic substrate in combination with a detergent, said aid providing a means of introducing a detergent into a washing solution and at the same time serving to adsorb dirt and vagrant anionic dyes from the aqueous media, thereby providing an improved laundering process.

BACKGROUND OF THE INVENTION This invention encompasses laundering aids comprising a surface-modified cellulosic material for use in aqueous laundry baths to scavenge dirt and anionic dyes released from the fabrics being laundered, and a soap or synthetic organic detergent. US. Patent 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.

Generally, laundry product formulations contain various synthetic materials capable of suspending dirt released from fabrics during the laundering process. Without such additives, much of the dirt released during the 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.

It has now been found that certain surface-modified, water-insoluble cellulosic substrates, containing a detergent, all as hereinafter detailed, can be added to aqueous laundering solutions to remove soil and, at the same time, to scavenge or trap, dirt and vagrant anionic dyes from the solution. 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.

Accordingly, it is a primary and major object of the present invention to provide an article of manufacture, i.e., a laundering aid, comprising a dirt and anionic dye trapper material in combination with a detergent composition; which article releases said detergent in an aqueous medium to perform a fabric cleansing function while said trapper material adsorbs 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 become apparent from the following disclosure.

SUMMARY OF THE INVENTION The present invention encompasses an article of manufacture which provides an improved laundering process by removing dirt and organic anionic materials, especially 3,694,364 Patented Sept. 26, 1972 DETAILED DESCRIPTION OF THE INVENTION The amine-coated cellulosic dirt and anionic dye trapper materials used in the laundering aid of this invention are those materials more fully described in the concurrently filed application of James B. Edwards entitled Sur face-Modified Cellulose, Ser. No. 102,199, filed Dec. 28, 1970, incorporated herein by reference. These laundering aids comprise: 1) a water-insoluble cellulosic substrate, especially cotton, the surface of which is first made anionic by phosphorylation, carboxymethylation, sulfoethylation, sulfatoethylation, succination or phosphatoethylation and is subsequently coated with greater than about 0.1%, more preferably from about 5% to about 30%, by weight of substrate, of a polymeric amine having the formula 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 groups containing from about 1 to about 22 carbon atoms, from about 5% to about more preferably 10% to 50%, of the nitrogen atoms in said polymeric amine being substituted with alkyl or alkanoyl groups containing 6 to 22 carbon atoms; and (2). a water-soluble organic detergent in releasable combination with said substrate.

Especially preferred for use as the dirt and anionic dye trapper material in the laundering aid are the aminecoated fabrics, fibers, cloths and sponges described in the Edwards application, cited above. Since these surfacemodified materials are used herein to scavenge, or trap, dirt and anionic dyes released during a laundering process, they are sometimes referred to herein as trapper materials or trappers. While any of the materials disclosed by Edwards are suitable for use herein as the trapper material, the cotton substrates modified by phosphorylation sand chemisorption of a polymeric amine thereon are preferred herein. Especially preferred for use in the present invention are the trapper cloths comprising phosphorylated cotton, especially cotton terry, containing from about 1.1% to 5.3% phosphorus, by weight of cloth, on which is chemisorbed from about 2% to about 50% of an alkyl or alkanoyl polyamine, by weight of cloth, wherein the alkyl or alkanoyl groups contain 6 to 22 carbon atoms. Polyethylenimine which is from about 10% to 50% stearoylated is especially preferred as the polyamine. For the purposes of this invention, alkylated or alkanoylated polyamine substrate coatings of any degree of polymerization, especially those in the range of 2 to 50,000, more especially 20-10,000, monomer units per molecule, are satisfactory.

As detailed above, the laundering aid of this invention comprises a trapper material in combination with an organic detergent. In a preferred embodiment of this invention the trapper material is formed into a container for a detergent composition. The container is added to the laundry water and the laundering process is carried out in the standard fashion. The laundering aid releases the detergent composition and remains to scavenge dirt and anionic dyes. Alternatively, the trapper material, in the form of a cloth or a spongelike material, is impregnated or coated with a detergent composition which is released on contact with water. The released trapper material then performs its anionic dye and dirt absorbing function. Still another article comprises a detergent formulation in tablet form having a trapper material in its interior which is released when the tablet dissolves in water. Exemplary laundry and presoak compositions suitable for use with the trapper material in the practice of this invention can be those typical commercial products comprising a mixture of about to about 50% of a synthetic organic detergent compound and about 10% to about 90% of a water-soluble detergency builder salt along with a minor amount of common laundry additive ingredients, all as hereinafter detailed. Alternatively, built or unbuilt soap compositions can be employed; detergent compositions containing enzymes are also suitable herein. The trapper material is compatible with all manner of these 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 formulations 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 formulations are used in conjunction with the trapper, but this is not critical in that any amount of such compositions snfiicient 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) Water-soluble soaps.-Examples of suitable soaps for use in this invention are the sodium, potassium, ammonium and alkanolammonium (e.g., mono-, di-, and triethanolammonium) salts of higher fatty acids (C C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.

(b) Anionic synthetic non-soap detergents-A preferred class can be broadly described as the watersoluble salts, particularly the alkali metal salts, of organic sulfuric acid reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of these anionic synthetic detergents 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 can be a straight or branched chain and contains from about 9 to about carbon atoms, preferably about 12 to 14 carbons; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; 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 alkyl phenol ethylene oxide ether sulfates, with 1 to 10 units of ethylene oxide per molecule and wherein the alkyl radicals contain from 8 to 12 carbon atoms; 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 amide of a methyl tauride in which the fatty acids, for example, are derived from coconut oil; sodium and potassium salts of SO -sulfonated C -C a-olefins.

(c) Nonionic synthetic detergents.-One class of nonionic detergents can 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 watersoluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. A second class of nonionic detergents comprises higher fatty amides. A third class of nonionic detergents has semipolar characteristics. These three classes can be defined in further detail as follows:

(1) One class of nonionic synthetic detergents is marketed under the trade name of Pluronic. These detergent compounds are formed by condensing ethylene oxide with a hydrophobic group 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 the polyoxyethylene content is about 50% of the total weight of the condensation product.

(2) Alkylphenol-polyethylene oxide condensates are 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, 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.

(3) Nonionic synthetic detergents can be derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine and include compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000. Such compounds result from the reaction of ethylene oxide with a hydrohobic 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 to 3,000.

(4) Other nonionic detergents include condensation products 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 alcoholethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol.

(5) The ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms are useful nonionic detergents. These acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.

(6) Semi-polar nonionic detergents include long chain tertiary amine oxides corresponding to the following general formula wherein R is an alkyl radical of from about 8 to about 18 carbon atoms, R and R are each methyl, ethyl or hydroxyethyl radicals, R is ethylene, and n ranges from 0 to about 10. The arrow in the formula is a conventional representation of semi-polar bond. Specific examples of amine oxide detergents include dimethyldodecylamine oxide and bis-(Z-hydroxyethyl)dodecylamine oxide.

(7) Other semi-polar nonionic detergents include long chain tertiary phosphine oxides corresponding to the general formula RR'R"P O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical containing from 10 to 20 carbon atoms and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are found in US. Patent 3,304,263 which issued Feb. 14, 1967, and include: dimethyldodecylphosphine oxide and dimethyl-(2-hydroxydodecyl)phosphine oxide.

(8) Still other semi-polar nonionic synthetic detergents include long chain sulfoxides having the formula wherein R is an alkyl radical containing from about 10 to about 28 carbon atoms, from to about ether linkages and from 0 to about 2 hydroxyl substituents, at least one moiety of R being an alkyl radical containing 0 ether linkages and containing from about to about 18 carbon atoms, and wherein R is an alkyl radical containing from 1 to 3 carbon atoms and from one to two hydroxyl groups. Specific examples of these sulfoxides are: dodecyl methyl sulfoxide and 3-hydroxy tridecyl methyl sulfoxide.

(d) Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in Which the aliphatic radical can be straight chain or branched alkyl and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono. Examples of compounds falling within this definition are sodium-3-dodecylaminopropi0nate and sodium 3 dodecylaminopropane sulfonate.

(e) Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium phosphonium and sulfonium compounds, in which the aliphatic radical can be straight chain or branched alkyl, and wherein one of the aliphatic substituents contains from about 8 to 24 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphate or phosphono. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylammonio)propane'l-sulfonate and 3-(N,N-dimethyl- N-hexadecylammonio) -2-hydroxy propane 1 sulfonate which are preferred for their cool water detergency characteristics. See, for example, Snoddy et 211., Canadian Patent 708,148.

Various calcium ion insensitive detergents such as tallowdimethylammonio acetate, tallowdimethylammonio undecylenate, and tallowdimethylammonio propionate are especially useful herein.

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 the amine-coated modified cellulosic 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 types; these are wholly compatible with the trapper materials and can be used in conjunction with 6 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)-nitrilo diacetates; (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates-see US. Patent 2,739,942; (3) water-soluble polyphosphonates, including, specifically, sodium, potassium and lithium salts of ethane-l-hydroxy- 1,1-diphosphonic acid; 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,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-l,1,2-triphosphonic acid, ethane-2- hydroxy 1,1,2-triphosphonic acid, propane-l,l,3,3-tetraphosphonic acid, propane 1,1,2,3-tetraphosphonic acid, and propane-l,2,2,3-tetraphosphonic acid, and water-soluble salts of polycarboxylate polymers and copolymers such as those described in the patent of Francis L. Diehl, US. Patent 3,308,067, issued Mar. 7, 1967.

The polycarboxylate materials described by N. B. Tucker, US. Patent 2,264,103, issued Nov. 25, 1941, are also suitably employed herein. For example, aconitic acid, mellitic acid and the pentaand 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 of Burton H. Gedge, e.g., ternary mixtures of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane-l-hydroxy-l,l-diphosphonate. The above described builders can also be utilized singly in this invention.

Various polyelectrolytes such as carboxymethylcellulose, 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 stilbene's, furans, thiophenes and the like, are all useful with the laundering aids and can be incorporated therein.

The following are examples of typical detergent formulations and presoak compositions suitable for use in combination with the trapper materials employed in the present invention to provide laundering aids. The formulations noted 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 DETERGENT COMPOSITION B Weight percent Sodium soap of 20:80 coconut:tallow fatty acids 90 Sodium silicate Tetrasodium pyrophosphate 3 Sodium chloride 1.5 Additives 1 (optional) 0.05 Moisture Bal.

1 Including perfumes and optical brlghteners.

DETERGENT COMPOSITION C Weight percent Sodium linear dodecylbenzenesulfonate 17.5

Sodium tripolyphosphate 50 Sodium sulfate 14 Sodium carboxymethylcellulose 0.5 Sodium silicate 7 Additives (optional) 0.10 Moisture Bal.

1 Including perfumes and optical brlghteners.

DETERGENT COMPOSITION D Weight percent Dimethyldodecylphosphine oxide 5 Condensation product of 11 moles of ethylene oxide with 1 mole of coconut fatty alcohol Tetrasodium methylenediphosphonate 10 Sodium tripolyphosphate 60 Sodium carboxymethylcellulose 0.5 Sodium silicate 10 Moisture Bal.

DETERGENT COMPOSITION E Weight percent Sodium tallowalkylsulfate 7 Sodium linear dodecylbenzenesulfonate 7 Sodium tripolyphosphate 50 Sodium carbonate 10 Sodium sulfate 10 Potassium dichlorocyanurate (bleach) Perfume 0.05 Moisture Bal.

DETERGENT COMPOSITION F (LIQUID) Weight percent Sodium-3-dodecylaminopropionate 6 Sodium linear dodecylbenzenesulfonate 6 Potassium pyrophosphate Potassium toluenesulfonate 8 Sodium silicate 3.8

Carboxymethylhydroxyethylcellulose 0.3 Additives 1 (optional) 0.05 Water Bal.

1 Including perfumes and optical brighteners.

DETERGENT COMPOSITION G (LIQUID) Weight percent Sodium linear dodecylbenzenesulfonate 6 Dimethyldodecylamine oxide 4 Trisodium ethanel-hydroxy- 1 l-diphosphonate 10 Tripotassium nitrilotriacetate 10 Potassium toluenesulfonate 8 Sodium silicate (ratio SiO :Na O of 2:1) 3.8 Potassium dichlorocyanurate (bleach) 5 Sodium carboxymethylcellulose 0.3 3 morpholino 2,5 diphenylfuran (optical brightener) 0.20 Perfume 0.10

Water Bal.

8 DETERGENT COMPOSITION H Weight percent Sodium salt of SO -sulfonated tetradecene 40 Dimethyl coconutalkylammonio acetate 10 Trisodium ethane-hydroxy triphosphonate 30 Sodium carbonate 10 Moisture Bal.

DETERGENT COMPOSITION I Weight percent Tetradecyl-p-methoxysulfonate 7.5 Sodium tallowalkylsulfate 2 Hydrogenated marine oil fatty acid suds depressant 2.2 Sodium tripolyphosphate 40 Trisodium nitrilotriacetate 20 Sodium silicate (2:1 ratio siO zNa O) 10 Sodium sulfate 13 Perfume 0.20

Water Bal.

DETERGENT COMPOSITION J Weight percent Weight percent Sodium tallowalkylsulfate 5 3(N,N dimethyl-N-dodecylammonio)-2-hydroxypropane-l-sulfonate 12 Sodium salt of SO -sulfonated a-tridecene 5 Sodium tripolyphosphate 30 Trisodium nitrilotriacetate 20 Sodium silicate (SiO :Na O=1.6:1) 10 Sodium sulfate 10 Sodium carboxymethylhydroxyethylcellulose 0.3 3-deca(oxyethylene)-2,5-diphenylfuran 0.1 Perfume 0.05 Moisture Bal.

DETERGENT COMPOSITION L (FOR COOL WATER USE) Weight percent Sodium tallow alkyl sulfate 5 3(N,N dimethyl-N-hexadecylammonio)propane-1- sulfonate 5 Dimethyldodecylphosphine oxide 10 Trisodium ethane-l-hydroxy-l,l-diphosphonate 5 Trisodium nitrilotriacetate 10 Sodium tripolyphosphate 40 Sodium silicate (Na O:SiO =1:2.5) 10 Sodium carboxymethylcellulose 0.3 Sodium sulfate 10 Moisture Bal.

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% to about 2%, 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 laundering aids of this invention comprise amine-coated cellulosic dirt and anionic dye trapper materials in combination with any of the above exemplary detergent compositions, with or without 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 F. to about 212 F., preferably from about 75 F. to about 160 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 efficiently 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 copending application of Edwards, cited above, incorporated herein by reference, discloses a variety of water-insoluble cellulosic substrates, especially cotton, which have first been treated in various ways to establish anionic functional groups on the surface of said insoluble substrates and have been subsequently treated with various polyamines of the type hereinbefore detailed so as to chemically affix said polyamines on the surface of said anionic substrate materials. In this manner, waterinsoluble cellulosic substrates, especially cotton, having anionic phosphorylated, sulfoethylated, sulfatoethylated, phosphatoethylated, carboxymethylated, and succinated surfaces are coated with from about 0.1% to about 100%, by weight of substrate, of poly-amines such as stearoylated polyethylenimine and a variety of other alkylated and alkanoylated poly-amines which are not removed on contact with water. Any of the water-insoluble, surface-modified substrates of Edwards can be employed herein in combination with detergents and soaps to provide laundering aids. The following examples demonstrate the laundering aids of this invention comprising a variety of trapper materials prepared in the manner of Edwards and a variety of detergent compositions much like those available commercially. The examples are intended to illustrate the present invention but are not intended to be limiting thereof. The terms 100% SPEI, 50% SPEI, etc., relate to the percent of the nitrogen atoms in polyethylenimine which are alkylated or alkanoylated. Similar terminology is used with the other alkylated and alkanoylated poly-amines employed herein.

EXAMPLE -I Phosphorylated cotton terry fabric is prepared by rinsing said fabric with a solution of 300 g. of urea and 279 ml. of phosphoric acid in 721 ml. H and heating said fabric at 300 F. for 30 minutes, all in the manner of Edwards, above, and contains about 5.3% phosphorus (about 100% phosphorylated). The fabric is cut into cloths (about 8 in. square) weighing about 40 g. and coated with about 12 g. of 20% SPEI (avg. mol. wt. 55,000). The cloths are folded into bag-like articles, filled with about 2 oz. of detergent composition A, above, and sewn shut, 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 the laundry bath.

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, and equivalent laundering aids are obtained.

In a modification of the above process a commercially available cellulose sponge (40 g.) is soaked in a water solution of 20% urea and 60% phosphoric acid, and dried at 300 F. for one hour. The phosphorylated sponge (about phosphorylated) is coated with 10 g. of 20% SPEI (avg. mol. wt. 100,000) and rinsed to remove any excess 20% SPEI. The sponge is then soaked in detergent composition F and detergent composition G, respectively, and provides a laundering aid comprising a trapper sponge impregnated with a detergent composition. Alternatively, the sponge is soaked in an aqueous solution of detergent composition A, B, C, D, E, H, I, J, K, and L, respectively, 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.

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 a 1% 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.

A laundering aid comprising a trapper material in a detergent tablet is prepared as follows: a trapper cloth (about 6 in. x 6 in. weighing about 30 g.) comprising phosphorylated cotton terry cloth containing about 5.3% phosphorus on which is adsorbed from about 0.1 g. to 7 g. of 20% SPEI is prepared in the manner of the copending application of Edwards, above, and is compacted by folding into a cloth object having the dimensions approximately 0.5 in. x 1 in. x 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 aqueouslaundry bath at a temperature of about F. and said detergent composition dissolves and releases said trapper cloth. In a modification of this laundering aid, detergent compositions B, C, D, E, H, I, I, K, and L, above, respectively, are used to form said tableted detergent object containing a trapper cloth.

The above laundering aids comprising detergent compositions and trapper cloths and sponges are prepared using the following trapper materials: (.1) cotton terry cloth (30 g.) containing about 1.1% phosphorus (about 20% phosphorylated) on which is coated about 2 g. of 5% SPEI, 20% SPEI, 50% SPEI, and 100% SPEI, respectively, per gram of cloth (avg. mol. wt. of the various SPEI materials is 20,000); (2) cotton terry (3.0 g.) containing about 3.2% phosphorus (about 60% phosphorylated) on which is adsorbed about 10 g. of 5% SPEI, 20% SPEI, 50% SPEI and 100% SPEI, respectively, per gram of cloth (avg. mol. wt. of the various SPEI materials is 5,000); and (3) cotton terry (30 g.) containing about 5.3 phosphorus (about 100% phosphorylated) on which is adsorbed about 0.5 g. of 5% SPEI, 20% SPEI and 50% SPEI, respectively, per gram of cloth (avg. mol. wt. of the various SP-EI materials is 300,000). Laundering aids fashioned from any of these trapper materials and detergent formulations A through L, above, satisfactorily release said detergents into aqueous laundry baths and release said trapper materials to perform their dirt and anionic dye trapping functions therein.

EXAMPLE II Cotton terry fabric is partially carboxymethylated by wetting with 40% aqueous monochloroacetic acid and dried; following this treatment the carboxymethylated cotton terry is coated by rinsing with an alcoholic solution of 20% SPEI (avg. mol. wt. ca. 1 million) in the manner of Edwards, above. The resulting trapper cloth containing about 2%-l5% of the SPEI, by weight, is formed into a bag-like object, about 2 oz. of detergent composition A is enclosed therein and the bag is sealed, thereby providing a laundering aid.

In the above laundering aid the carboxymethylated cotton terry bag coated with 20% SPEI is replaced, respectively, by the following trapper cloth bags prepared in the manner of the copending application of Edwards: (1) succinated clothcotton terry heated with a solution of succinic anhydride in dry pyridine for 26 hours, washed, and coated with 30%, by weight, of SPEI (avg. mol. wt. 200,000); (2) sulfatoethylated cloth-cotton terry treated with a solution comprising sodium hydroxide, 10% 2-chloroethylsulfuric acid and 65% water and heated 45 minutes at 100 C. then coated with 20%, by weight, of 80% SPEI (avg. mol. wt. 500,000); (3) sulfoethylated clothcotton terry treated with a solution comprising 25% sodium hydroxide, 10% 2-chloroethylsulfonic acid and 65% water heated for 45 minutes at 100 C. then coated with 1%, by weight, of 50% SPEI (avg. mol. wt. 10,000); (4) phosphatoethylated clothcotton terry treated with a solution comprising 10% sodium hydroxide, 20% chloromethylphosphoric acid and 70% water and heated minutes at 100 C., then coated with 60%, by weight, of 20% SPEI (avg. mol. wt. 1,000); equivalent results are obtained in that the respective laundering aids release the detergent composition in the laundry bath and trap dirt and anionic dyes.

The respective trapper cloth bags are filled with about 2 oz. of detergent compositions B, C, D, E, H, I, J, K, and L, above, respectively, and equivalent laundering aids are obtained.

In a modification of the above articles, a commercially available cellulose sponge is rinsed in a solution comprising 10% sodium hydroxide, 20% chloroethylphosphoric acid, and 70% water, at 100 C. for about 30 minutes and dried. The resulting phosphatoethylated sponge is coated with 2 g. of 20% SPE'I (avg. mol. wt. 50,000) and rinsed to remove any excess SPEI. The sponge is then soaked in detergent composition F and detergent composition G, respectively, and provides a laundering aid. Alternatively, the phosphatoethylated sponge is soaked in an aqueous solution of detergent compositions A, B, C, D, E, H, I, J, K, and L, respectively, and laundering aids releasably containing these detergent compositions are secured.

A laundering aid comprising a trapper material in a detergent tablet is prepared as follows: a trapper cloth (about 6 in. x 6 in. weighing about 30 g.) comprising carboxymethylated cotton terry on which is adsorbed about 6 g. of 20% SPEI (mol. wt. in range 1,000-100,- 000) is compacted by folding into a cloth object having the dimensions approximately 0.5 in. x 1 in. x 2 in. About 2.5 oz. of detergent formulation A, above, is molded around the folded trapper cloth and compacted in a press to form a tablet, said tablet containing in its interior said trapper cloth. The laundering aid in the form of a detergent tablet containing the trapper cloth is added to an aqueous laundry bath at a temperature of about 120 F. and said detergent composition dissolves and releases said trapper cloth.

In a modification of this article of manufacture, sodium tallow fatty acid, Cm-C sodium linear alkyl sulfonate, and detergent compositions B, C, D, E, H, I, J, K, and L, above, respectively, are used to form the laundering aid comprising said tableted detergent object containing a trapper cloth.

EXAMPLE III Cotton muslin is phosphorylated by rinsing in an aqueous solution comprising 20% urea and 60% phosphoric acid and drying at 300 F. for about one hour. The cloth is then rinsed in a 10% solution of 50% stearoylated polyethylenimine (avg. mol. wt. 25,000) (50% SPEI) and provides a trapper cloth coated with about 10%, by

12 weight, of said 50% SPEI. The trapper cloth is formed into a bag and filled with about 6 oz. of detergent composition A, above. The bag is added to a laundry bath (water at pH 10) with soiled fabrics and releases said detergent therein. The fabrics are agitated and the trapper cloth bag adsorbs dirt and anionic dyes on its surface.

The cotton muslin is replaced by cellulose sponge, cotton batting (compacted into a non-woven mat), compressed kapok and dewaxed cellulose fibers and equivalent results are secured in that laundering aids made from these materials release detergents to aqueous laundry baths and scavenge dirt and anionic dyes.

The phosphorylated cotton muslin is replaced by phosphoroethylated cellulose, succinated kapok, sulfoethylated cellulose sponge and sulfatoethylated dewaxed cotton fibers and equivalent articles comprising a detergent composition and trapper bag are secured.

In the above article, detergent composition A is replaced by sodium dodecylbenzenesulfonate, and by detergent compositions B, C, D, E, F, G, H, I, J, K and L, respectively, and equivalent articles are secured.

In the above laundering aid, detergent composition A is replaced by an equivalent amount of the sodium, potassium, lithium, rubidium, cesium, ammonium and diethanolammonium salts of a C -C fatty acid saponification fraction, respectively, and equivalent articles are secured.

In the above article the 50% stearoylated polyethylenimine trapper cloth coating is replaced by 50% stearoylated di-ethylenimine, 70% stearoylated tri-ethylenimine, 10% stearoylated di-propylenimine, 50% docosylated dibutylenimine, 15% stearoylated polypropylenimine (avg. mol. wt. 20,000), 20% stearoylated polymethylenimine (avg. mol. wt. 100,000), 10% stearoylated polybutylenimine (avg. mol. wt. 300,000), 15% hexanoylated polymethylenimine (avg. mol. wt. 25,000), 50% dodosanoylated-50% ethylated polybutylenimine (avg. mol. wt. 50,000), 5% octanoylated-5% methanoylated polymethylenimine (avg. mol. wt. 10,000), 20% hexylated polyethylenimine (avg. mol. wt. 3,000), 5% docosylated polyethylenimine (avg. mol. wt. 1,000), docosylated polybutylenimine (avg. mol. wt. 100,000), and 50% methylated-50% docosylated polyethylenimine (avg. mol. wt. 1 million) respectively, and equivalent articles are secured.

It is to be understood that the lanudering aids of the present invention are suitable for use in all manner of aqueous laundering processes. It is well-known that such laundering processes may involve additional steps such as bleaching with hypohalite solutions and fabric softenmg and antistatic treatment involving quaternary ammonlum salts. Such laundering, bleaching and treating processes are commonly carried out at temperatures from about 70 F. to about 212 F. over a pH range of about 3 to 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 these common laundry additives.

I"? N-(CH L J.

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 groups containing from about 1 to about 22 carbon atoms, from about 5% to about 100% of the nitrogen atoms in said polymeric amine being substituted with said alkyl or alkanoyl groups containing 6 to 22 carbon atoms; and (2) a member selected from the group consisting of watersoluble anionic, nonionic, ampholytic and zwitterionic organic detergent compounds in releasable combination with said substrate in an amount to provide good fabric cleansing.

2. A laundering aid according to claim 1 wherein the water-insoluble anionic cellulosic substrate is phosphorylated cotton.

3. A laundering aid according to claim 1 wherein the water-insoluble anionic cellulosic substrate is sulfatoethylated cotton.

4. A laundering aid according to claim 1 wherein the water-insoluble anionic cellulosic substrate is sulfoethylated cotton.

5. A laundering aid according to claim 1 wherein the water-insoluble anionic cellulosic substrate is carboxymethylated cotton.

6. A laundering aid according to claim 1 wherein the water-insoluble anionic cellulosic substrate is phosphatoethylated cotton.

7. A laundering aid according to claim 1 wherein the water-insoluble anionic cellulosic substrate is succinated cotton.

8. A laundering aid according to claim 1 wherein the polymeric amine coating is stearolyated polyethylenimine wherein from about 10% to about 50% of the nitrogen atoms are stearoylated.

9. A laundering aid according to claim 1 wherein the 14 cellulosic substrate material is cotton the surface of which is from about 20% to about 100% phosphorylated and wherein the nitrogen compound chemically aflixed to the surface is polyethylenimine having about 20% of the nitrogen atoms stearoylated.

10. A laundering aid according to claim 1 wherein the water-soluble organic detergent is a sodium, potassium, ammonium or alkanolammonium salt of a fatty acid having from 10 to 22 carbon atoms.

11. A laundering aid according to claim 1 wherein the water-soluble organic detergent comprises a watersoluble salt of an organic sulfuric acid reaction product having in the molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.

References Cited UNITED STATES PATENTS 2,467,523 4/ 1949 Dudley 252-480 2,743,232 4/ 1956 Chance et al 252-179 3,233,962 2/1966 Nelson 8116.2 3,393,968 7/1968 Segal 8116.2 3,424,545 1/ 1969 Bauman 252-89 LEON D. ROSDOL, Primary Examiner W. E. SCHULZ, Assistant Examiner US. Cl. X.R.

8-116.2; 2S2544, Digest 11, Digest 15