US3523088A - Novel antiredeposition agent and built detergent compositions containing said antiredeposition agent - Google Patents

Description

Aug. 4, 1970 w. L. 3, NOVEL .NTIREDEPOSITION AGENT Km) BUILT DETERGENT COMPOSITIONS Filed Dec. 13, 1966 ET AL 523,688

CONTAINING SAID ANTIREDEPOSITION AGENT 5 Sheets-Sheet 1 I I l I I I l o 2 2 2 9 N v w w 2 z I I I I 8 E INVENTORS & 3 Walter L. Dean 8 George N. Ferguson ATTORNEY 3,523,088 gOMPOSITIONS xv. L. DEAN ET AL Aug. 4, 1970 CONTAINING Filed Dec. 13, 1966 5 Sheets-Sheet 2 Q0 Q0 mo Q6 Q0 we Q0 Mo 6 o l o l I TI Qz Nina. 39E 20E 28 7 w E: 520 36528 $53 205813??? m N wE Q q I III llll h Q l vz0mo o o o \O L w s m Y m w n g I R N m 00 W 4w mL .A r e n m m w I 0 ma n w 8 PS hr ZO mOn mOum .Z

Aug. 4, 1970 w. L. DEAN F 3,0

NOVEL ANTIREDEPOSITION AGENT AND BUILT DETERGENT COMPOSITIONS CONTAINING SAID ANTIREDEPOSITION AGENT Filed Dec 13, 1966 5 Sheets-Sheet 5 226828 EHEMEQ 6 5:053 20 EQQZQZZEEOQ 81-020 To Emma s m Y Q0 Q0 we Q0 Q0 To To No 6 o m n m. w m w Ar. 1% E D. f n T or w L N AT n m n I I O T m w mu ,m 8N Qz o- $8; 205 29 w. 0 0% \..@N Q2 25 36.528 5G3 zoEwonmfimii l Y I NI 0 l N v x l\ 1 w I I I m zotbu 27E 9 w3 zoEmonmawmifi Q I bl! Ill I all ll III -II I \\\O zo z 2 mv m- United States Patent 3,523,088 NOVEL ANTIREDEPOSITION AGENT AND BUILT DETERGENT COMPOSI- TIONS CONTAINING SAID ANTIRE- DEPOSITION AGENT Walter L. Dean and George N. Ferguson, Memphis, Tenn., assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio Filed Dec. 13, 1966, Ser. No. 601,441 Int. Cl. C11d 3/065, 3/08 US. Cl. 252138 2 Claims ABSTRACT OF THE DISCLOSURE An antiredeposition agent having special utility in the washing of synthetic fabrics, synthetic-cotton blends, cotton fabrics, and mixtures thereof, which consist essentially of (a) from about 40% to about 95% alkali metal carboxymethylcellulose having a DS within the range of from about 0.4 to about 1.5 and a DP within the range of from about 200 to about 4000; and (b) from about 5% to about 60% hydroxypropylcellulose having an MS within the range of from about 2 to about 5 and a DP within the range of from about 100 to about 1200.

This invention relates to a novel antiredeposition agent for use in built detergent compositions. More specifically, the invention involves an antiredeposition agent which exhibits about the same level of efficacy as the best currently known antiredeposition agents in regard to conventional cotton fabrics and exhibits a high level of efficacy in regard to modern synthetic fabrics. In essence, the novel antiredeposition agent of this invention consists of a certain combination of a specific alkali metal carboxymethylcellulose and a specific hydro-xypropylcellulose. Hereinafter, alkali metal carboxymethylcellulose and hydroxypropylcellulose are referred when appropriate as CMC and HPC, respectively.

Combinations comprising CMC and a hydroxyalkylcellulose, e.g., HPC, have been disclosed as antiredeposition agents in US. Pat. 2,886,533, granted May 12, 1959 to L. R. Bacon et al. A primary characterizing feature of the present invention resides in the use of a highly specific HPC in the CMC-HPC combination.

Conventional built detergent compositions perform well their function of removing soil and other unwanted matter from fabrics. However, during the washing cycle, some of the removed soil tends to redeposit on the fabric. Thus,

it is common to incorporate an antiredeposition agent in built detergent compositions. An antiredeposition agent retards the removed soil from redepositing on the washed fabric.

CMC is currently the most popular and widely used antiredeposition agent. A large number of commercially available built detergent compositions, either for house hold or industrial use, contain CMC, and the antiredeposition efficacy of CMC is well known. However, it is also well known to those skilled in the art that such efficacy is achieved only with cotton fabrics and that CMC has essentially no antiredeposition effect when the material to be washed is a synthetic fabric or a synthetic-cotton blend.

It is highly desirable to discover an antiredeposition agent which is effective with synthetic fabrics or syntheticcotton blends, e.g., polyamides such as nylon; polyesters such as Dacron and Kodel; polyvinyl derivatives such as Orlon, Creslan or Dynel; and cellulose ester fibers such as Arnel, because of the current widespread use of such materials. The problem is not a simple one, however, because of the fact that antiredeposition agents which 3,523,088 Patented Aug. 4, 1970 have efiicacy with synthetic fabrics or synthetic-cotton blends have, in general, an adverse antiredeposition effect on cotton. Moreover, as a practical matter, the ordinary load of clothes to be washed consists of a mixture of cotton fabrics, synthetic fabrics and synthetic-cotton blends. Therefore, an antiredeposition agent effective with both cotton and synthetic fabrics is in great need but is difficult to achieve.

Accordingly, it is an object of this invention to provide a novel antiredeposition agent for use in built detergent compositions.

It is a further object of this invention to provide a novel antiredeposition agent for use in built detergent compositions, said agent being effective with synthetic fabrics, synthetic-cotton blends and cotton fabrics.

It is a more specific object of this invention to provide built detergent compositions which contain a novel antiredeposition agent and wihch have special utility in the washing of synthetic fabrics, synthetic-cotton blends, cotton fabrics and mixtures thereof.

The above and other objects can be achieved by a novel antiredeposition agent, which consists essentially of:

(a) From about 40% to about alkali metal carboxymethylcellulose having a DS within the range of from about 0.4 to about 1.5 and a DP within the range of from about 200 to about 4000; and

(b) From about 5% to about 60% hydroxypropylcellulose having an MS within the range of from about 2 to about 5 and a DP within the range of from about to about 1200. (DS, DP and MS are defined more fully hereinafter.)

Alkali metal in the above expression is selected from the group conissting of sodium, potassium, lithium and ammonium, of this group, sodium (Na) is highly preferred.

A preferred antiredeposition agent of this invention consists essentially of:

(a) From about 65% to about 80% sodium carboxymethylcellulose having a DS within the range of from about 0.4 to about 0.9 and a DP within the range of from about 500 to about 2000; and

(b) From about 20% to about 35% hydroxypropylcellulose having an MS within the range of from about 2 to about 3.5 and a DP within the range of from about 600 to about 1100.

A specific highly preferred antiredeposition agent of this invention consists essentially of:

(a) About 71% sodium carboxymethylcellulose having a D8 of about 0.7 and a DP of about 1500; and

(b) About 29% hydroxypropylcellulose having an MS of about 2.8 and a DP of about 900.

Another specific highly preferred antiredeposition agent of this invention consists essentially of:

(a) About 71% carboxymethylcellulose having a D3 of about 0.7 and a DP of about 1500; and

(b) About 2 9% hydroxypropylcellulose having an MS of about 2.4 and a DP of about 1050.

The above percentages and all others specified herein are by weight. FIGS. I and II are plots illustrating the antiredeposition effect of CMC and HPC used individually. FIG. III illustrates the antiredeposition effect of a preferred CMC-HPC combination of the invention used at a varying total concentration. FIG. IV illustrates the relationship between antiredeposition effect and the ratio of HPC to CMC. FIG. V shows the relationship between antiredeposition effect and the MS and DP of the HPC. The DP of the HPC is one of the most critical elements of the present invention. These figures are discussed in detail hereinafter.

The meaning of the terms degree of substitution (DS), MS and degree of polymerization (DP) is given in the following discussion: There are three bydroxyl groups in each anhydroglucose unit in the cellulose molecule. DS is the average number of hydroxyl groups substituted in the cellulose per anhydroglucose unit. MS is the average number of moles of reactant combined with the cellulose per mole of anhydroglucose unit. For CMC (or other carboxyalkyl, alkyl or acyl derivatives of cellulose) the DS and MS are the same. For the hydroxyalkyl derivatives of cellulose, e.g., HPC, degree of substitution is generally expressed in terms of MS rather than DS. The reason for this is that each time a hydroxyalkyl group is introduced into the cellulose molecule one hydroxyl group disappears and a new one is formed which itself is capable of hydroxyalkylation. As a result of this, side chains of considerable length may form on the cellulose molecule. Thus, from the foregoing it will be seen that the D5 of a cellulose derivative can be no higher than three, whereas the MS may be considerably higher than three depending on the extent to which said chains are formed.

DS values, as expressed herein, are based on calculations according to the Wilson method as disclosed in Svensk Papperstidning 59, 218 (1956). 'MS values, as expressed herein, are based on calculations according to the Ziesel-Morgan HI ether-cleavage method as disclosed in Industrial Engineering Chemistry 18, 500 (1946).

A second important physical property of cellulose or a cellulose derivative is molecular weight, which is more commonly expressed in terms of degree of polymerization (DP). This in turn is often stated as the degree of polymerization of the cellulose pulp from which the derivative in question is prepared. Therefore, as used herein, DP refers to the viscosity average degree of polymerization of cellulose pulp as determined from the viscosity (V) of 0.5% solutions of cellulose in cupriethylenediamine (1.0 molar in copper, 2.0 molar in ethylenediamine) according to Method T 230 sin-50 of the Technical Association of the Pulp and Paper Industry. The DP is calculated from the formula:

DP=1,439 log (V)387 1 The CMC useful in the novel antiredeposition agent of this invention can be prepared by any of the methods known in the art so long as the specified limitations on DS and DP are observed. For example, the CMC can be prepared by the methods disclosed in the copending US. patent application of Russell Nelson, Ser. No. 387,378, filed Aug. 4, 1964, and now US. Pat. 3,347,855, and in U.S. Pat. 2,553,725.

The hydroxypropylcellulose can also be prepared by methods known in the cellulose art so long as the proper requirements for MS and DP are observed. For example, the HPC can be prepared according to the disclosure in Belgium Pats. 643,558 and 643,559.

It is to be noted that commercially available CMC or HPC often does not comprise 100% of the subject cellulose derivative'For example, a common commercial grade of CMC contains about 61% CMC, the balance being comprised of inert materials consisting essentially of sodium chloride. However, use of this type of material is satisfactory herein so long as the actual amount of CMC or HPC is within the specified range. That is, reference herein to amounts of CMC or HPC is on an active basis.

One of the advantageous features of this invention is the fact that the novel antiredeposition agent is highly effective when used at very low levels in built detergent compositions. More specifically, the built detergent compositions of this invention contain the novel antiredeposition agent in an amount of from about 0.1 to about 1.2%, preferably from about 0.3% to about 0.6%, based on the weight of built detergent composition. The lower limit DP determined in the way described above is equivalent to DP determined by Method T-23S 5511-63 of the Technical Association of the Pulp and Paper Industry. According to this method, the DP is calculated from the intrinsic viscosity 5111] ($5 [:el]lulose nitrate in ethyl acetate by the formula:

.4 (0.1%) is the minimum amount of agent required to render clear and desirable antiredeposition results. Significant additional antiredeposition results are not achieved with amounts of agent in excess of the upper limit (1.2% It is significant and advantageous that this upper limit can be so relatively low because the use of high levels of cellulose materials in detergent compositions, e.g., greater than about 5%, tends to impart undesirable starch-type (stiffening) eifects to the fabrics being washed.

As stated above, the built detergent compositions of this invention contain from about 0.1 to about 1.2% of the novel antiredeposition agent. The other essential components are a detergent and a builder salt. These composi tions can be prepared in solid or liquid form. The solid, e.g., granular or flake, compositions generally contain from about 5% to about 50% of a detergent component and from about 95% to about 50% of a builder component selected from water-soluble inorganic alkaline builder salts, organic sequestrant builder salts, or mixtures thereof. The liquid compositions generally contain from about 5% to about 40% detergent and from about 95% to about 60% of a water-soluble inorganic alkaline builder salt or organic sequestrant builder salt or mixtures thereof, in a suitable liquid vehicle, e.g., water, alcohol or mixtures thereof. The liquid compositions preferably have a pH ranging from about 9 to about 12, as do the solid compositions when dissolved in aqueous media.

Preferably, the detergent is selected from the group consisting of anionic, nonionic, ampholytic, zwitterionic detergents and mixtures thereof.

A preferred built detergent composition contains from about 5% to about 25% detergent selected from the group consisting of anionic, nonionic, ampholytic, zwitterionic detergents and mixtures thereof, and from about 50% to about of builder component selected from the group consisting of water-soluble inorganic alkaline builder salts and organic sequestrant builder salts and mixtures thereof, and from about 0.1% to about 1.2% of an antiredeposition agent as described herein.

The following are specific examples of detergents that can be used in the compositions of the present invention:

(A) ANIONIC SOAP AND NON-SOAP SYNTHETIC DETERGENTS This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium 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, from 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 -C carbon atoms) pro duced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about carbon atoms, in straight chain or branched chain configuration, especially those of the type described in United States Letters Pats. Nos. 2,220,099 and 2,477,383; 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.

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 amide 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 United States Letters Pats. 2,486,921; 2,486,922; and 2,396,278.

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-octadecyl-sulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl ester of sodium sulfosuccinic acid.

Anionic phosphate detergents 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 phosphorous. The more common solubilizing groups, of course, are AO H, SO H and CO H. Alkyl phosphate esters such as (R-O) PO H and ROPO H in which R represents an alkyl chain containing from about 8 to about 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 -M 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 soluble cation such as hydrogen, sodium, potassium, ammonium or substituted ammonium; and in which n is an integer from 1 to about 40.

A specific anionic detergent which can be used in the present invention is described more fully in the U.S. patent application of Phillip F. Pflaumer and Adri-aan Kessler, Ser. No. 561,397 filed June 29, 1966 and now U.S. Pat. 3,332,880. This detergent comprises by weight from about to about 70% of Component A, from about 20% to about 70% of Component B, and from about 2% to about 15% of Component C, wherein:

(a) Said Component A is a mixture of double-bond positional isomers of water soluble salts of alkene-lsulfonic acids containing from about 10 to about 24 carbon atoms, said mixture of positional isomers including by weight about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about of a betagamma unsaturated isomer, about 5% to about 25 of a gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;

(b) Said Component B is a mixture of water soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 10 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom; and

(c) Said Component C is a mixture comprising from 30-95% water-soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 10 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

(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 mole cule 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% 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) Those 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% to about 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 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from to 14 carbon atoms.

(4) Nonionic detergents include nonyl phenol condensed with either about 10 or about 30 moles of ethylene oxide per mole of phenol and the condensation products of coconut alcohol With an average of either about 5.5 or about 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 mercaptin condensed with 10 moles of ethylene oxide per mole of mercaptan; bis- (N-Z-hydroxyethyl) lauramide; nonyl phenol condensed with 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 'R R N O (amine oxide detergent) wherein R is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R which is an alkyl group containing from about 10 to about 18 carbon atoms and 0 ether linkages, and each R and R are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms;

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-(Z-hydroxyethyl) dodecylamine oxide bis- Z-hydroxyethyl) -3-dodecoxyl-hydroxypropyl amine oxide (Z-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 R R P O (phosphine oxide detergent) wherein R is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R which is an alkyl group containing from about 10 to about 18 carbon atoms and 0 ether linkages, and each of R and R 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:

and the corresponding dccyl, hexadecyl, and octadecyl homologs of the above compounds.

(7) A detergent having the formula (sulfoxide detergent) wherein R 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 being an alkyl radical containing 0 ether linkages and containing from about 10 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.

octadecylmethyl sulfoxide dodecylmethylsulfoxide tetradecyl methyl sulfoxide 3-hydroxytridecyl methyl sulfoxide B-methoxytridecyl methyl sulfoxide 3-hydroxy-4-dodecoxybutyl methyl sulfoxide octadecyl Z-hydroxyethyl sulfoxide dodecyl'ethyl sulfoxide (C) AMPHOLYTIC SYNTHETIC DETERGENTS Ampholytic synthetic detergents can be broadly described as 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, sulfo, sulfato, phosphate, or phosphono. Examples of compounds falling Within this definition are sodium 3-(dodecylanuno)-propionate H C 2Hnl iC H2 C 112% O Na sodium 3 -(dodecylamino)propane-1-sulfonate C rzHzall CH2 C 112C 1128 0 3N3 sodium 2- (dodecylamino)ethyl sulfate H o HHm IOHZGHZO s O Na.

sodium 2- (dimethylamino) octadecanoate CXfiHQQCHCHZ O Na H3C-NC H3 disodium 3 (N-carboxymethyldodecylamino propane-1- sulfonate C HaCHrCHzS O 3N8.

C lzHzsN 0 ll CHzCONa 9 disodium 2-(oleylamino)ethyl phosphate H 013E145 CHzCHzO l (0N8):

disodium 3 (N-methylhexadecylamino)propyl 1 phosphonate CH; 0 01,1135 CHZCH2CH2;(ONB)I disodium octadecyl-irninodiacetate C1aH 1N( CHM?! O Na): sodium 1-carboxymethyl-Z-undecylimidazole, and

i N-OHzc 0 Na CuH23 disodium 2-[N (2 hydroxyethyl) octadecylamino] ethyl phosphate 0 CHQCHiO (ON3)2 C1a a1 C H2 C H2 0 H (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 8 to 18 carbon atoms, and at least one aliphatic substituent contains an anionic watcrsolubilizing group, e.g., car-boxy, sulfo, sulfato, phosphato or phosphono. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecyl-ammonio) -2- hydroxypropane-l-sulfonate CH3 OH c n b cmcnomso 3 (N,N dimethyl-N-hexadecylammonio)propane-l-sulfonate 2- (trimethylammonio) ethyl dodecylphosphonate 10 ethyl 3- (N,N-dimethyl-N-dodecylammonio) propylphosphonate 3 P,P-dimethyl-P-dodecylpho sphonio) propane-1- sulfonate CH C12HuI -CHZCH2CHZSO3 G3 CH 2-(S-methyl-S-tert-hexadecyl-sulfonio)ethane-lsulfonate C H: R-gg-C HzCHzS 0 R=t etraisobut ylene 3 (S-methyl-S-dodecylsulfonio) propionate 0 l wmecmomb-o sodium 2- (N,N-dimethyl-N-dodecylammonio)ethyl phosphonate 0 0N8 l C 12H25NCH2CH2 4-(S-methyl-S-tetradecylsulfonio)butyrate 1- (Z-hydroxyethyl) -2-undecylimidazoliuml-acetate N-CHzCHzOH OuHzs o e oath-m 9 Z-(trimethylammom'o) octadecanoate u C1aH CHCO 9 N 0 a): ea

and 3-(N,N-bis (2-hydroxyethyl) -N-octadecylammonio)-2hydroxy-propane-l-sulfonate.

CHzCHzOH Some of these detergents are described in the following US. patents: 2,129,264; 2,178,353; 2,774,786; 2,813,898; and 2,828,332.

The anionic, nonionic, ampholytic and zwitterionic deter-gents mentioned above can be used singly or in combination in the practice of the present invention. However, the anionic detergent surfactants are highly preferred.

Examples of water-soluble inorganic alkaline detergency builder ingredients are salts such as alkali metal 1 1 carbonates, phosphates, polyphosphates and silicates. Specific examples of such salts are sodium and potassium tripolyphosphates, carbonates, pyrophosphates, phosphates and hexametaphosphates.

Examples of organic alkaline sequestrant builder ingredients that are preferred are (1) alkali metal amino polycarboxylates [e.g., sodium and potassium ethylene diaminetetraacetates, N (2 hydroxyethyl) ethylene diaminetriacetates, nitrilotriacetates, and N (2 hydroxyethyl)-nitrilo diacetates]; (2) alkali metal salts of phytic acid [e.g., sodium and potassium phytates-see US. Pat. 2,739,943]; (3) water-soluble ethane 1-hydroxy-1,1-diphosphonates [e.g., preferably the trisodium and tripotassium saltssee US. Pat. 3,159,581]; (4) water-soluble salts of methylene diphosphonic acid [e.g., trisodium and tripotassium methylene diphosphonate and other salts described in US. Pat. 3,213,030]; (5) water-soluble salts of substituted methylene diphosphonic acids [e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene and halomethylidene .diphosphonates and the other substituted methylene diphosphonates disclosed in the copendin-g application of Clarence H. Roy, Ser. No. 266,055, filed Mar. 18, 1963 and now US. Pat. 3,422,021]; (6) water-soluble salts of polycarboxylic acid polymers and copolymers as described in the copending application of Francis L. 'Diehl, Ser. No. 269,359, filed Apr. 1, 1963 and now US. Pat. 3,308,067 [e.g., polymers of itaconic acid, aconitic acid; maleic acid; mesaconic acid; fumaric acid; methylene malonic acid; and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene]; and (7) mixtures thereof.

Mixtures of any and all of the organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964 and now US. Pat. 3,392,121, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitn'lotriacetate and sodium ethane-1- hydroxy-l,l-diphosphonate. These ternary mixtures can fall within the ternary diagram ABCDEF in the drawing of the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964, which drawing is incorporated by reference herein. Binary mixtures of these same three builders, e.g., a mixture containing 10% to 85% of sodium tripolyphosphate and 90% to sodium nitrilotriacetate or a mixture containing 30% to 90% of sodium nitrilotriacetate and 70% to 10% of sodium ethane 1 hydroxy 1,1-di-phosphonate, are also preferred as well as a mixture of 30% to 80% of sodium u'ipolyphosphate with 70% to of sodium ethane-1- hydroxy-1,1-diphosphonate.

The detergent compositions of this invention can contain, if desired, up to about 5% of any of the usual adjuvants, diluents and additives, e.g., moisture, perfumes, other organic detergent surfactants, anti-tarnishing agents, bacteriostatic agents, dyes, fiuorescers, and the like, without detracting from the advantageous properties of the compositions.

The detergent compositions of this invention often tend to be corrosive toward aluminum; thus, if the detergent solution is to contact this metal repeatedly or for prolonged periods of time, especially at elevated temperatures, a corrosion inhibitor should be desirably included. Soluble silicates are highly effective inhibitors when added to the compositions of this invention, preferably at levels of from about 3.5% to about 10%. Potassium, or preferably sodium silicates having a weight ratio of SiO /M O of from about 1.0 to about 2.6 and preferably from 1.6 to about 2.6 can be used. M in this ratio refers to sodium or potassium.

In the embodiment of this invention which provides for a built liquid detergent, a hydrotropic agent may at times BUILT LIQUID DETERGENT COMPOSITION Percent Sodium dodecylbenzenesulfonate (the dodecyl radical being derived from polypropylene, predominantly tetrapropylene averaging 12 carbon atoms) 6.0 Dimethyldodecylamine oxide 6.0 Trisodium ethane-l-hydroxy-l,l-diphosphonate 20.0 Potassium toluenesulfonate 8.0 Sodium silicate (ratio SiO :Na O of 2.45:1) 3.8 Antiredeposition agent consisting essentially of Sodium CMC having a D5 of 0.6 and a DP of 1600, and 35% HPC having an MS of 2.0 and a 'DP of 265 0.1

Water balance.

B'UILT GRANULAR DETERGENT COMPOSITION Percent Sodium dodecylbenzenesulfonate (dodecyl group derived from tetrapropylene) 17.5 Sodium tallow alkyl sulfate 3.5 Sodium tripolyphosphate 47.0 Sodium silicate (ratio siO zNa O of 2:1) 6.0 Sodium sulfate 20.8 Cocount fatty acid ethanolamide 2.? Perfume and optical brightener 1.0

Antiredeposition agent consisting essentially of 80% Potassium CMC having a D8 of 0.8 and a DP of 1000, and 20% HPC having an MS of 2.0 and a DP of 900 Moisture balance.

BUILT GRANULAR DETERGENT COMPOSITION Percent Sodium linear dodecylbemenesulfonate 7.5

Nonionic detergent (a mixture of 1.5% Ucon and .5 Pluronic L-64) 1 2.0 Hydrogenated marine oil fatty acid 2.2 Trisodium ethane-l-hydroxy-l,l-diphosphonate 59.6 Sodium silicate (ratio SiO :Na O of 2:1) 9.7 Sodium sulfate 13.5

Perfume and optical brightener 1.0 Antiredeposition agent consisting essentially of Ammonium CMC having a D5 of 0.5 and a DP of 700, and 25% HPC having an MS of 3.0 and a DP of 1100 0.5

Water balance.

BUILT GRANULAR DETERGENT COMPOSITION Percent Sodium linear dodecylbenzenesulfonate 20.0 Potassium toluenesulfonate 2.0 Trichlorocarbanilide (as a bacteriostat) 0.5 Sodium tripolyphosphate 30.0 Sodium silicate (ratio SiO :Na O of 2:1) 6.0 Sodium sulfate 32.3 Fatty acid ethanolamide 1.6

Antiredeposition agent consisting essentially of Sodium CMC having a D8 of 0.7 and a DP of 1600, and 20% HPC having an MS of 2.5 and a DP of 900' Water 13 BUILT LIQUID DETERGENT COMPOSITION Percent 3 (N,N diemethyl N hexadecylammonio) 2-hydroxypropane-l-sulfonate 12.0 Trisodium ethane-l-hydroxy-1,1-diphosphonate 20.0 Sodium silicate (SiO :Na O:1.6:1) 3.8 Potassium toluenesulfonate 8.5 Fluorescent dye .12 Perfume .15 Benzotriazole .02

Antiredeposition agent consisting essentially of 70% Sodium CMC having a DS of 0.9 and a DP of 1800, and 30% HPC having an MS of 2.4 and a DP of 1060 .6

Water 54.4

Ucon and L-64 are condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol and having molecu- IZU. weights of approximately 3000 and 8000 respectively.

BUILT GRANULAR DETERGENT COMPOSITION Percent 3 (N,N-dimethyl-N-hexadecylammonio) propanel-sulfonate 17.0 Of a 1:1:1 mixture of trisodium ethane-l-hydroxy- 1,1-diphosphonate, sodium tripolyphosphate and sodium nitrilotriacetate 45.0 Sodium-silicate (Na O:SiO =1:2.5) 6.0 Sodium sulfate 28.0 Antiredeposition agent consisting essentially of 78% Sodium CMC having a D8 of 0.7 and a DP of 1400, and 22% HPC having an MS of 2.5 and a DP of 650 0.4

Water 3.5

Miscellaneous balance.

Excellent cleaning performance and whiteness maintenance (antiredeposition) results are obtained by laundering with all of the above compositions.

The following antiredeposition experiments were performed in order to illustrate the efiicacy of the novel antiredeposition agent of this invention on cotton, synthetics and synthetic-cotton blends. The experiments were conducted as specified below:

SOIL COMPOSITION 0.02 g./l. carbon black (Interchernical Lampblack #10) 0.40 g./l. simulated natural soil having the composition: Percent by weight Saturated fatty acids (total) 26.72

Lauric acid (C 1.75 Myristic acid (C 5.57

Palmitic acid (C 11.15

The ingredients of the simulated natural soil were combined by heating and mechanically stirring.

1 4 DETERGENT COMPOSITION 2.5 g./l. conventional built granular detergent having the composition:

Percent by weight Sodium dedecylbenzenesulfonate, dodecyl derived from tetrapropylene (ABS) 20.0 Sodium tripolyphosphate (STP) 50.0 Sodium sulfate (Na SO 24.0

Sodium silicate 6.0

Antiredeposition agent as specified.

HARDNESS 7 grains per US. gallon 120 p.p.m. CaCl CLOTH LOAD 3%" x 3 /2 swatches weighing a total of 14.3 g.i0.3 g. and comprising: five cottom muslin swatches, four nylon swatches, and four Dacron swatches EQUIPMENT Waring blender (5 cup size) Tergotometer having four l-liter beakers (U.S. Testing Co.) Hunterlab color-difference meter Circulating air oven Clothes wringer PROCEDURE (1) The amounts of ingredients required for four liters of washing solution (four beakers) were calculated.

(2) The ingredients were weighed in the following order and transferred to the Warning Blendor.

(a) STP (b) Na SO (c) CaCl ((1) Carbon black (e) Soil (f) Sodium silicate (g) ml. aqueous ABS solution containing the required amount of ABS (3) The volume in the blender was inucreased with demineralized water to 1%. cups and the contents were agitated for thirty minutes.

(4) The concentrated mix was then transferred to a 1 liter graduate using demineralized water to aid in a quantitative transfer. The volume in the graduate was diluted to one liter with demineralized water and the contents of the graduate were transferred to a 3-liter beaker and then diluted to two liters with two 500-ml. portions of demineralized water. The mixture was kept agitated and divided into four equal portions in l-liter graduates. The mixtures were then diluted to one liter and transferred to the Tergotometer beakers.

(5) The pH of each solution was adjusted to 10.0.

(6) The beakers were placed in the Tergotometer bath which was preheated at 142 F., and the agitators started.

(7) The antiredeposition agents to be tested were transferred from a weighing bottle to the wash solution in the Tergotometer beakers, and given time to dissolve.

(8) After the wash solution had reached the desired temperature (140 F.), agitation was stopped, the fabrics were added as rapidly as possible (one swatch at a time), and agitation was resumed and continued for one hour at cycles/minute.

(9) The fabrics were removed and passed through a wringer. The fabrics were put in clean (7 grain hardness) water at room temperature and rinsed for two minutes at 110 cycles/min. The temperature rose slightly during the rinse since the beakers were in the heated Tergotometer bath.

(10) The fabrics were removed, squeezed by hand, spread out on a blotter and dried for one hour at 65 C.

(11) The cloth swatches were ironed with a medium temperature iron (rayon setting) and read on the Hunter- It can be seen antiredeposition K Cotton 16 FIG. II is a plot of the data from tests 4, 8, l2 and 16. More specifically, FIG. II illustrates the antiredeposition value (W- W) of HPC used alone. It can be seen from FIG. II that HPC exhibits a high level of antiredeposition eflicacy with regard to nylon and Dacron (Columns I and I of Table I), but exhibits an adverse antiredeposition effect with cotton (Column K of Table I).

FIG. III is a plot of the data from tests 20, 21 and 22. More specifically, FIG. III illustrates the antiredeposition invention comprising 71% NaCMC and 29% HPC. It can be clearly seen from FIG. III that this NaCMC HPC combination exhibits a high level of antiredeposition efiicacy with regard to both cotton and synthetic fabrics. FIG. IV is plot of the data from all tests 1 through 22, excluding tests 16 and 20. More specifically, FIG. IV illustrates the antiredeposition value (WW) of various NaCMCHPC combinations used in amounts 0 within the range of from 0.20% to 1.2%.

from FIG. IV that for a high level of efficacy to be achieved with both cotton and synthetic fabrics, the antiredeposition agent must contain about 4095% NaCMC and about 560% HPC. Below about 5% HPC, a significant antiredeposition effect on synthetic fabrics is not realized. Above about 60 HPC, a significant antiredeposition effect on cotton is not realized. FIGURE IV also illustrates the overall preferred results obtained with a NaCMC-HPC combination containing 60-80% NaCMC and about 20-35% HPC. FIG. III further illustrates the highly preferred results obtained with an NaCMC-HPC combination containing about 71% NaCMC and about 29% HPC. In this example, substantially equivalent results are obtained when the NaCMC is replaced by another alkali ON ANTIREDEPOSITION Antiredeposition Agent yweight in antiredeposi- Antircdepositlon valu tion agent N.ZB.S. whiteness units (W) W-W 0 D E F G H I NaCMC HPC Total NaCMC HPC Nylon Dacron Cotton Nylon Dacron 15 lab Color Difference meter; the whiteness values were calculated in whiteness units (W) using the equation:

Example I A series of 22 tests were performed to illustrate the eifects of (1) varying the proportions of NaCMC and HPC in the antiredeposition agent and (2) varying the Percent by weight based Percent b on amount of detergent composition where L is the grayness (or lightness) value, a is the redness value and b is the yellowness value (a and b are greenness and blueness respectively).

(12) Based on a statistical study of seventeen prior tests, it was calculated that a significant and real difference in antiredeposition effect existed in the following incre- 10 effect of a Preferred antlredeposltion agent of the Presfint In Table I, W is the average number of whiteness units obtained when no antiredeposition agent was used.

TABLE I.EFFECT 0F CONCENTRATION OF HPC, NACMC AND HPC-CMC COMBINATIONS ments:

Nylon0.66 whiteness units Dacron0.67 whiteness units Cotton-1.30 whiteness units total concentration of antiredeposition agent. The NaCMC was a highly preferred species having a D8 of 0.7 and a DP of 1500. The HPC was also a highly preferred species having an MS of 2.4 and a DP of 1050. The data are tabulated in Table I and plotted graphically in FIGS. I through IV.

For nylon, the value of W was obtained by calculating the average of tests 1 (75.9), 3 (76.3), 11 (73.3), 15 (73.4), and 19 (73.1) which equals 74.6. For Dacron, W was 72.3 and for cotton it was 85.2. The values of Columns 1, J, and KWere obtained by subtracting the W (average whiteness obtained for each material without an antiredeposition agent) from W, the actual measured whiteness value obtained with an antiredeposition agent.

Test:

To "236 .025 .493 196 N 2 n u u h n "7 "94 3 687 W391 306 805 .m .m n n w .m m mm w 1..

u n n n 8198793727232072535537 5 0 om &em3 7 5 9 3 0 5 0 om2 1 2 2 88$ 98879887998899mm999 1 81 w maw oaa muh uni ni L 0 0 0 0 00 0 0 0 0 0 0 0 0 0 2 2 4 82 w m w h n w m t i ooi L 0 0 0 0 0 0 0 0 0 00 09 mm am ma aw mzz 0 0 0 0 0 0 0 0 00 0 Average W (No antiredeposition agent) Nylon 74.6, Dacron 72.3, Cotton 85.2.

FIG. 1 is a plot of the data from tests 5, 9, 13 and metal CMC wherein the alkali metal is selected from 17. More specifically, FIG. I illustrates the antrredepOSlthe group consisting of potassium, lithium and ammonium.

Example II A series of 13 tests were performed to illustrate the eifect of varying the MS and DP of HPC. The varying HPC compositions were tested in a preferred antire- Th NaCMC was comprised of 61% pure NaCMC; the deposition agent comprising 71% HPC and 29% balance consistededesseltlltifilylof s odiu r ciloride. Coneentpa- NaCMC. The antiredeposition agent was used in a preg%f%g m a e an m e gums on an acme ferred amount of 0.4% by weight based on the amount of tion value (WW) of NaCMC used alone. It can be seen from FIG. I that NaCMC exhibits a high level of antiredeposition efficacy with regard to cotton (Column K of Table I), but exhibits essentially no antiredeposition 7() effect with nylon and Dacron (Columns I and I of Table I).

TABLE II.EFFECT OF HPC, MS AND DP IN A PRE ANTIREDEPOSIIION AGENT 1.2% based on the amount of detergent composition, of an antiredeposition agent consisting essentially of:

FERRED NaCMC-HPC Antirodeposition Value HPC whiteness units (W) W-W composition (1v P) Nylon Dacron Cotton Nylon Dacron Cotton Average W (N o anti-redeposition agent) nylon 73.4, Dacron 72.7, Cotton 85.3.

FIG. V is a plot of the data from tests 23 through 35 FIG. V is scaled so that a vertical distance as indicated in the lower left hand corner of FIG. V corresponds to an antiredeposition value (WW) of whiteness units.

It can be seen from FIG. V that an unexpectedly high level of antiredeposition efficacy is achieved with cotton and synthetic fabrics when the HPC contained in the NaCMCHPC combination has an MS greater than about 2.0 and a DP within the range of from 100 to about 1200. FIG. V further illustrates the highly preferred results obtained when the HPC contained in the NaCMC-HPC combination has an MS within the range of from about 2.0 to about 3.5 and a DP within the range of from about 600 to about 1100.

Example III (a) about 71% sodium carboxymethylcellulose having a degree of substitution of about 0.7 and a degree of polymerization of about 1500; and

(b) about 29% hydroxypropylcellulose having an MS of about 2.8 and a degree of polymerization of about 900.

2. A composition consisting of a built detergent composition containing 20% sodium dodecylbenzenesulfonate, sodium tripolyphosphate, 24% sodium sulfate and 6% sodium silicate, and from about 0.1% to about 1.2% based on the amount of detergent composition, of an antiredeposition agent consisting essentially of:

(a) about 71% sodium carboxymethylcellulose having a degree of substitution of about 0.7 and a degree of polymerization of about 1500; and

(b) about 29% hydroxypropylcellulose having an MS of about 2.4 and a degree of polymerization of about 1050.

CMO COMBINATION PRISED OF SYNTHETIC-COTTON BLEND ON ANTIREDEPOSITION WITH FABRIC COM- Antiredeposition Agent Percent by weight based Percent by weight on amount of detergent in antiredeposition White Anti recomposition agent ness deposition units value, NaCMC HPC Total NaCMC HPC WW It can be observed from Table HI that a NaCMC-HPC References Cited combination of the invention (test 39) is superior in anti- UNITED STATES PATENTS redepositron efficacy with a synthetic-cotton fabric as 2 886 533 5/1959 Bacon et al 252 138 d th M t 8 t 7 fggi fi fi e1 er Nac C (est 3 or HPC (est 3 3,342,805 9/1967 Callehan 260 232, What is claimed is: 3,374,224 3/ 1968 Sommers 260-231 '1 A composition consisting of a built detergent com- HERBERT B. GUYNN, Primary Examingr position containing 20% sodium dodecylbenzenesulfonate, 50% sodium tripolyphosphate, 24% sodium sulfate and US. Cl. X.R,

6% sodium silicate, and from about 0.1% to about UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N0. Dated August 4, Inventor) Walter L. Dean and George N. Fe

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

[- Column 5, line 40 "phosphorous" should be phosphorus 1 Column 5, line 53, after first formula the word or was omitted.

Column 11, line 12, "U.S Patent 2,739,943" should be U.S. Patent 2,739,942

Column 14, line 5, "dedecylbenzenesulfonate" should be dodecylbenzenesulfonate Column 14, line 32, "Waring Blendor" should be Waring Blender Column 15, Table I, in the title NACMC" should be NaCMC Column 15, Table I, Test 13, Column K Cotton, "0.8"

should be 8.0

Column 15, Table I, Test 20, Column E HPC, "19" should bidlu' LU LA D SELLED 3.2113 1 JAN. 5,1971

S Atwat:

mama m. mach. in mm 1:. m. Atwating Officer communal of Patents

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