US3485762A - Laundry detergents containing ammonium salt of styrenemaleic anhydride copolymer and non-ionic,hydroxyl-containing surfactant - Google Patents

Description

3,485,762 LAUNDRY DETERGENTS ONTATNTNG AMMO- NTUM SALT OF STYRENEMALETC ANHYDRTDE COPOLYMER AND NON-TONIC, HYDROXYL- CONTAINING SURFACTANT Bob G. Gower, Park Forest, Henry V. Isaacson Oak Forest, and David W. Young, Homewood, TIL, assignors to Sinclair Research, Inc New York, N.Y., a corporation of Delaware No Drawing. Filed May 24, 1966, Ser. No. 552,412 Tut. (ll. Clld 1/83 US. Cl. 252-452 9 Claims ABSTRAiIT OF THE DISCLOSURE A detergent composition is disclosed containing about 40 to 90% of an alkaline builder, a minor amount of an ammonium salt of a styrene maleic anhydride resin of about 1 to 4 moles of styrene per mole of maleic anhyhydride, and about 10 to 50% of a non-ionic, hydroxylcontaining surfactant condensation product of an alkylene oxide of about '2 to 6 carbon atoms. Additionally the styrenemaleic anhydride resin may be partia ly esterified with the non-ionic surfactant.

This invention relates to improved detergent compositions for the laundering of textiles. More particularly, it concerns the use of styrene-maleic anhydride resins in laundry detergents to form compositions which possess excellent emulsifying, dispersing and suspending properties and, th refore, show exceptional cleaning power.

A large number of detergent c mpositions are known in the art and they generally include the many well-known detergents used in the household, as well as the heavy duty detergents which are used in industrial operations for cleaning highly soiled textiles. New synthetic fabrics, for example, Dacron and Dacron-cotton containing materials, present many cleaning problems for present day detergents. One of the difficulties enc untered in laundering synthetic fabrics using these detergents concerns the ability to remove heavy soils and at the same time retain fabric whiteness. These detergent compositions must generally use laundering temperatures of about 190195 F. for industrial laundering and about l-l50 F. for household laundering to obtain satisfactory soil r moval. Although these temperatures afford satisfactory cleaning, it has been found that during the first several washings, the colored fabrics may bleed excessively and the color may be picked up by the lighter colored fabrics in the wash. Conventional detergents also suffer from many other deficiencies such as poor emulsifying and inadequate dispersing properties; and after the removal of the soil from the fabric, an inadequacy towards preventing the redeposition of the soil and dye on the fabric before the laundering cycle is completed.

According to the present invention, improved detergent compositions have been produced which are very effective for cleaning highly soiled textiles such as synthetic fabrics, for example, Dacron and Dacron-cotton containing fabrics, and at the same time will retain fabric whiteness. These improved detergents prevent deposition of soil and dye on the textile by their suspending action, and therefore will provide greatly improved whiteness retention during laundering. The laundry detergents of the present invention also possess effective emulsifying, wetting and dispersing properties, excellent stability, and outstanding cleaning power for rem ving oil, grease, carbon black and other types of dirt from textiles.

In accordance with the present invention, it has been discovered that detergent compositions containing styrenenited States Patent 0 "ice maleic anhydride resins in combination with hydroxylcontaining nonionic surfactants afford the improvements and advantages discussed above. In the detergent compositions of the present invention, the styrene-maleic anhydride resins have several functions Because of their surface-active properties, these resins can act as stabilizers for liquid detergents, preventing their breakdown into a two-phase system. They also may act as part of the organic active component aiding in the wetting of the fabric and soil, and further as dispersing agents by dispersing the dirt out of the fabric into the washing medium. Most important, the styrene-maleic anyhdride resins can function as suspending agents by suspending dirt and dye in the washing medium, thus preventing redeposition of the dirt or dye on the fabric. The styrene-maleic anhydride resin component of these detergents may be utilized either as such or as a partial ester there f or, more advantageously, as a partial ester with a hydroxylcontaining nonionic surfactant, such as, for example, the reaction products of alkyl phenols with alkylene oxides.

The styrene-maleic anhydride resins used in the detergent composition of the present invention are the ammonium salts of these resins, including their partial ester derivatives, having about 1 to 4 moles, preferably about 1 to 3 moles of styrene per mole of maleic anhydride. If desired, maleic acid can be used instead of maleic anhydride in formation of the resins with styrene. These resinous polymers contain repeating styrene-maleic anhydride units and preferably have an average molecular weight of at least about 500 to about 50,000. The preferred average molecular weight of the resins is about 700 to 3000. The melting points of these lower molecular Weight polymers will often range from about 100 to 200 C. as determined by the Fisher-Johns melting point apparatus. The determination of average molecular Weight as used herein is made by the thermoelectric differential vapor pressure lowering method on a microlab osmometer. The polymers of styrene and maleic anhydride can be prepared by known methods. A preferred method is by solution polymerization where the monomers are polymerized in a suitable solvent employing as a polymerization catalyst a free-radical peroxide catalyst, preferably benzoyl peroxide or dicumyl peroxide, at a temperature of about to 300 C. or more. Suitable solvents include the aromatic hydrocarbon solvents, such as cumene, p-cymene, xylene, toluene, etc. The aromatic solvents may serve as chain-terminating solvents and give lower molecular weight products. Other suitable solvents are the ketones, such as methylethyl ketone, which may also be chain-terminating solvents. The preferred manner of carrying out the polymerization is by what is known in the art as incremental feed addition. By this method the monomers and catalyst are first dissolved in a portion of the solvent in which the polymerization is to be conducted and the resulting solution fed in increments into a reactor containing solvent heated to reaction temperature, usually the reflux temperature of the mixture. When an aromatic solvent is employed as the solvent for the polymerization, the formation of the polymers causes a heterogeneous system, the polymer layer being the heavier layer and recoverable by merely decanting the upper aromatic solvent layer and drying. On the other hand, when a ketone is the solvent, the formed polymer is usually soluble in the solvent media so that recovery of the products neces sitates a solvent-stripping operation. The styrene-maleic anhydride resins can be used in minor amounts, e.g., of about 01-20 percent by weight of the total solids of the detergent composition, preferably about 1-10 percent. By total solids of the detergent composition is meant the components other than water and hydrocarbon solvent, if any be present.

The hydroxyl-containing nonionic surfactants or organic active components of the present invention are the condensation products of an alkylene oxide of say 2 to 6 carbon atoms such as, for example, ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, etc., preferably ethylene oxide, with an organic compound containing at least 6 carbon atoms and often up to about 30 carbon atoms or more, and a reactive hydrogen atom. Such compounds containing reactive hydrogen atoms include aromatic, monoand poly-hydroxy compounds such as phenols, naphthols, benzene and naphthalene diols, triols, tetrols, and the like. In this group, alkyl phenols containing from 1 to 3 alkyl substituents of from 4 to 20 carbon atoms each are preferred. Some examples of such compounds are the normal and isomeric mono-, diand tri-butyl, nonly, and octadecyl-phenols and cresols; and phenols and cresols which may be substituted with a plurality of different such alkyl groups. Another preferred group of compounds containing reactive hydrogen groups include aliphatic monoand poly-hydroxy compounds such as fatty alcohols. Such compounds often have up to about 25 carbon atoms, e.g. trimethylene glycol, glycerol, allyl alcohol, sec-butyl alcohol, butanediol 1,3, isopropylvinyl carbinol, octanediol 1,2, lauryl alcohol, pentadecanol, cetyl alcohol, octadecanol, docosanol, pentaeicosanol, etc.

The amount of alkylene oxide condensed with the reactive hydrogen-containing compounds, i.e., the length of the oxyalkylene chain, may depend upon the particular compound with which it is condensed and also the particular styrene-maleic anhydride resin used. Generally, an amount of alkylene oxide should be employed which will result in a condensation product containing from about 20 to 85 percent by Weight of combined alkylene oxide. However, the effective amount of alkylene oxide for obtaining the desired balance, may be readily determined in any particular case by preliminary tests and routine experimentation. For example, the number of ethylene oxide units may often be from about 4 to 15 depending upon the particular styrene-maleic anhydride resin used. The nonionic surfactants can be present in the detergent composition in amounts, e.g. of about to 50% by weight, advantageously about 20 to 50%, based on the solids of this composition.

When the nonionic surfactants and the styrene-maleic anhydride resins are combined in the detergent composition, they may be present as a physical mixture or as a partial ester of the nonionic hydroxyl-containing surfactant with styrene-maleic anhydride resin. The partial esters can be readily prepared by bulk reaction of molten styrene-maleic anhydride resins with the hydroxyl-containing surfactants or may be prepared by reaction in solution. Physical mixtures are prepared by solution of the nonionic surfactants and styrene-maleic anhydride resins in dilute aqueous alkali. Such mixtures may have present some partial esters of the surfactant and resin.

Although styrene-maleic anhydride resins will combine with the nonionic surfactants mentioned above to achieve the combination necessary to produce the improved detergents of the present invention, it has been found that a detergent with particular effectiveness can be obtained by balancing the hydrophobic-hydrophylic characteristics of the styrene-maleic anhydride resin and the nonionic surfactants with the wash temperatures. For example, the styrene-maleic anhydride resins afford maximum effective properties to the detergent composition when combined with nonionic surfactants containing about 4 to 12 ethylene oxide units, often about 9 to 12 ethylene oxide units when using a wash temperature of about 120-170" F. When the desired wash temperature is about 170-190" F., maximum properties are obtained when the styrene-maleic anhydride resins are combined with nonionic surfactants containing about 12-15 ethylene oxide units.

A typical heavy duty detergent composition incorporating the styrene-maleic anhydride resins and the nonionic surfactants of the present invention is shown in Table I.

TABLE I Component: Parts by wt. Tergitol 15-S12 60.0

(nonionic surface active agent) Styrene-maleic anhydride resin A 5 .0 Sodium silicate 58.0 Sodium hydroxide 12.0 Potassium pyrophosphate 30.0 CMC-T (suspending aid) (optional) 1.0

1 Condensation product of a secondary alcohol of about 15 iarbgn atoms with ethylene oxide in a mole ratio of about i inmonium salt of a styrene-maleic anhydride resin, hav ilngooa styrene to maleic anhydride ratio of 2:1, mol. wt.-

3 Sodium carboxymethylcellulose, technical grade.

As can be observed from Table I, the detergent compositions of the present invention may also include other conventional detergent constituents such as, for example, alkaline builders and may, if desired, include fabric whiteners, other soil suspending agents, etc. Alkaline builders function as Water softeners and also aid in the removal and suspension of dirt and often represent about 40 to percent of the detergent compositions based on total solids, preferably about 50 to 70%. Typical alkaline builders which can be used in heavy duty detergent com positions include alkali metal carbonates, borates, phosphates, bicarbonates, silicates, sulfates, ammonia, organic amides, and the like. Although the styrene maleic anhydride resins function as soil suspending agents, additional suspending aids may be used. These soil suspending aids act with the styrene maleic anhydride resins in the detergent composition to suspend the soil in the washing medium and prevent redeposition of the soil on the fabric. The soil suspending agents which can be used in detergent compositions are generally water-soluble polymeric materials such as cellulose glycollic acid, cellulose ethane sulfonic acid, hydroxy-ethyl methyl cellulose. starch, hydroxyethy starch, starch glycollic acid, polyalkylene glycols, etc. The soil suspending aids when used in the detergent composition of the present invention may be present in amounts up to about 1% or more by weight of the total solids. The fabric whiteners which may be used are dependent primarily on the particular fabric to be cleaned, and any type normally utilized in such detergents for whitening and brightening effects may be employed. As examples of such agents there may be mentioned stilbenes, diamino stilbenes, acylated, cyanuric and triazolyl derivatives of such stilbenes, diphenyl derivatives, dibenzothiophene derivatives, aminocoumarone salts, derivatives of diazotized amino-containing benzoxazole, benzthiazole and benzimidazole compounds, and the like. The fabric whiteners when used in the aqueous detergent composition of the present invention may be present in amounts of 0.05 to about 0.25% by weight. It may also be desired to include a hydrocarbon solvent in the detergent composition of the present invention. In such a case the solvent may be present for example in amounts of 0.5 to about 2% of the aqueous composition.

The total amount of detergent of the present invention which can be used in a wash solution can vary depending for example upon the textiles to be washed, the amount of soil contained in the textiles, laundering temperature, etc. However, a total detergent amount of 0.05 to about 2% by weight has been found to be effective for washing solutions.

The advantages of using the maleic anhydride resins and the nonionic surfactants in heavy duty detergent composition over detergents not containing these additives will be apparent by referring to the following exam les.

5 EXAMPLE I A series of different detergent compositions was prepared using nonionic surfactants, styrene-maleic anhytion were measured. Table II gives the concentrations of the various components as they were present in the wash solution and the results of these tests.

TABLE II Surfactant Resin Builders Washing Nonionic Amount StyreneMaleic Amount Amount Temp., Surfactant (Percent) Anhydride Resin (Percent) Inorganic Builders (Percent) F. Results Sodium Inetasilicate 0.1 Good cleaning severe o Tergltol S 3 v {Potassium pyrophosphate 0. 4 i redeposition of soil. D 01 0 3 jStryene-maleic {Sodium metasilicate 0.1 h {Good cleaning, no

Lanhydride resin A. [Potassium pyrophosphate.-- 0.4 apparent redeposition. Makmkm 3 0 3 J Sodium Inetasilicate. 0. 1 {Good cleaning, severe {Potassium pyrophosphate... 0. 4 redeposition. D03 0 3 {Styrene-maleic O5 Sodium metasilicate -i 0.1 1 {Good cleaning, no

anhydride resin A. Potassium pyrophosphate 0. 4 J apparent redeposition. D03 0 3 .{Sodium Inetasilicate 0. 1 Good cleaning, moderate Potassium pyrophosphate 0. 4 redeposition of soil. D03 0 3 Styrene-rnale1c l 0 05 {Sodium metasilicate 0. 1 1 Good cleaning, no

anhydnde resin A. J gogassium pyrophosphateui 4 J P apparent redeposltion. 4 o ium me asi icate .1 our 0 caning, severe sm'fomc LR 120 3 {Potassium pyrophosphate 0. 4 redeposition.

D04 0 3 IStyrene-rnaleio 05 Sodium metasilicate O. 1 Good cleaning, no

"""""""" [anhydride resin A. Potassium pyrophosphat 0. 4 apparent redeposition.

1 2 See footnotes 1 and 2, Table I.

3 Condensation product of an alkylphenol with ethylene oxide in a mole ratio of about 1:10. 4 Condensation of an alcohol of about 12-18 carbons with ethylene oxide in a mole ratio of about 1:12.

EXAMPLE II The detergent compositions of Example I were treated with Tintex 25 Navy Blue dye so that the dye was present in an amount of 0.025% in the washing media. White Dacron-cotton fabrics containing Dacron and 35% cotton were washed for 15 minutes in these dilute dye solutions and the deposition of dye on the fabric measured. The fabrics were not rinsed. These experiments gave more controllable dye concentrations than does the actual fading of colored fabrics. Results of these tests are given in Table III.

TAB LE III Surfactant Resin Builders Washing Nonionic Amount Styrene-Maleic Amount Amount Temp., Surfactant (Percent) Anhydride Resin (Percent) Inorganic Builders (Percent) F. Results Sodium metasilicate... 0. 1 Severe deposition of Tergltol 3 "{Potassium pyrophosph 0. 4 dye, fabric dark blue.

. li ht deposition Styrene-maleic Sodium rnetasilicate 0. 1 ery S D01 3 {anhydride resin A 05 {Potassium pyrophosphate..- 0. fi gzg fig Very Sodium metasilicate 0. 1 Severe deposition of Makoudo a 3 "{Potassium pyrophosphate... 0. 4 i ye.

Styrene-maleic Sodium metasilicate 0. 1 Very slight D03 3 {anhydride resin A. 05 {Potassium pyrophosphate. 0. 4 L deposition of dye.

1 Sodium metasilicate 0. 1 Severe deposition of D03 3 [Potassium pyrophosphate.-- 0. 4 dye.

Styreneqnaleic Sodium metasilicate 0. 1 Very slight D03 3 {anhydride resin A. 05 {Potassium pyrophosphate 0. 4 i140 deposition of dye.

Sodium metasilicate 0. 1 Severe deposition of Surfomc LR-IZO 3 "{Potassium pyrophosphate..- 0. 4 dye.

Styrene-malelc Sodium metasilicatem" 0. 1 ery slight D03 3 {anhydi-ide resin A. 00 {Potassium pyrophosphat 0.4 deposition of dye.

1 2 See footnotes 1 and 2, Table I. 3 Condensation product of an alkylphenol with ethylene oxide in a mole ratio of about 1:10. 4 Condensation of an alcohol of about 1218 carbons with ethylene oxide in a mole ratio of about 1:12.

7 EXAMPLE In A series of detergent compositions was prepared using nomonic surfactants, styrene-maleic anhydride resins, in-

they were present in the wash solutions and the results of these tests.

TABLE IV 70-90 Kauri Surl'ac- Butanol tant Resin Builders Hydrocar- Washing Nonionic Suriac- Amount Styrene-Maleic Amount Amount bon Solvent Temp., tant (percent) Anhyride Resin (percent) Inorganic Builders (percent) (percent) F. Results Potassium 51 Moderate to severe Surfonic LR120 0 3 Pyrophosphate 0 1.0 175 soil redeposition,

Potassium carbonate.-. adequate cleaning.

- Potassium pyrophos- Slight soil redeposi- DO 1 0.3 g gg g g gg mz} 0. phate 1. 0 115 tion, adequate y Potassium carbonate-.. cleaning.

- Moderate to severe Potassium pyrophos- Surfonie LR74 0 3 phate 2g} 1. 0 175 ig ggggggg Potassium carbonate emailing Potassium pyrophos- Slight soil redeposi- Do 0. a f gffi g f fi'} 0. 05 ph e 52} 1. 0 175 tion, adequate y e Potassium carbonate. cleaning.

Potassium pyrophos- O 5 M oderate to severe 0 3 ggg g j: 0. 0 175 soil redeposition.

Styrene-maleic an- D0 0 3 hydride resin 01 gg f PX ff ff 0. 5 1 O 175 Slight to moderate gggsgteepa l 00-- Potassium carbonateflu 0.25 redeposltlon.

1 Condensation of an alcohol of about 12-18 carbons with ethylene oxide in a mole ratio of about 1:12. 2 Condensation product of a fatty alcohol of about 1248 carbons with ethylene oxide in a mole ratio of about 1:7.4. 3 Ammonium salt of a styrene-maleic anhydride resin, having a styrene to maleic anhydride ratio of 2:1, Mol. Wt.=l700.

4 Ammonium salt of Resin BIgepal CO-630 ester. Partial ester (=40% halt ester) of Resin B with Igepal 00-630 which is a condensation product of nonylphenol with ethylene oxide in a mole ratio of about 1:0.5 Resin B is the acid form of Resin A.

EXAMPLE IV 35 organ: and 70-90 Kaun Enamel i l A series of detergent compositions was prepared using Solvent Whlte Dacron-cotton fabncs Comalnmg nonionic surfactants, styrene-maleic anhydride resins, in- Dacron and 35% cotton were partially soiled with N0. organic builders and 90 Kauri Butanol hydrocarbon 6 fuel oil so that each fabric consisted of a soiled and an 40 Solvent Tillie? 25 y y t added that unsoiled portion. The soiled fabrics were allowed to age was present the washmg medla. an f OI f 18 h Th f b th wa h d E m 1 I 0.025%. White Dacron-cotton fabrics containing 65% or a ncs r an e as m Xa p e Dacron and 35% cotton were washed in these dilute dye and both cleamng and soil redeposition measured. Table solutions as in Example 11 and the deposition f dye Onto IV gives the concentrations of the various components as the fabrics measured. The fabrics were not rinsed. The

45 results of these tests are given in Table V.

TABLE V 70-90 Kauri Surfae- Butanol tant Resin Builders Hydrocar- Washing Nonionie Surfac- Amount Styrene-Maleic Amount Amount bon Solvent Temp., tant (percent) Anhyride Resin (percent) Inorganic Builders (percent) (percent) F. Results gogium siligate d 0. 29 s d t I o ium hy roxi e 0.06 evere eposi iono Terg1tol15-S 12-... 0.25 Potassium pyrophos 1.0 190 phate 0.15

2 3 ii d d v r m d 0 mm Y IOXl eerysig BPOSI- Do ResmA 0'O05 Potassium pyrophos- 190 tion of dye.

phate 0.15

- v Sodium silicate. 0.29 ery slight deposi- Resm B-Terg1tol Sodium h v v ydrox1de- 0.06 tion of dye. 0 5{ 1s 3 1 1 m 0-001 {Potassium PYPOPhOS, L0 190 phate 0.15

gogium slilicciate d. 0.29 V h d i o ium y roxi e 0.06 ery slig t eposi- DO 25 Resm C 2 005 Potassium pyrophos- 0 190 tion of dye.

phate 0.15

Sodium metasilicate 0.1 Surfonic LR- 0. 25 Potassium pyropllos- 1.0 ggff depmmon phate 0.4

Sodium metasilicate 0. 1 i Very slight deposi- ResmA SQ{ Z P I 2PPR tion oidye.

l Ammonium salt of Resin B-Tergitol 15-8-12 partial ester. About 5% half ester of styrene-maleic anhydride resin B with Tergitol 15-8-12 (identified earlier) and 65% half ester with n-propyl alcohol.

2 Resin CAmmonium salt of 50% half-ester of styrene-maleic anhydride resin D with butylcellosolve.

Resin 13-1 :1 styrene to maleic anhydride mole ratio, mol. wt.=l600.

As can be seen in Table VI, experiments 1 to 4 show the ammonium salt of the styrene-maleic anyhdride resins to be superior to the sodium salt of these resins as a dye suspending agent. Experiments 5 to 8 also show the ammonium salt of these resins to be superior to the so dium form as a soil suspending agent.

Experiments 9 to 11 in Table VII show that it is advantageous to use the higher ratios of styrene to maleic anhydride in the detergent compositions of the present invention.

TABLE VIL-MEASUREMENT OF soIL SUSPENSION [1:1, 2:1, 3:1 styrene:maleic anhydride] All concentrations same as previous soil suspending case (experiments 5 8) except for suspending agent. Detergent concentration in wash solution:

Surfonic Lit-120 O. 3

Potassium pyrophosphate Potassium carbonate Hydrocarbon solvent 1.

Suspending Agent Experi- Amount ment suspending Agent (Percent) Results 1 9 Styrene-maleic anhydride (1:1) polymer, mol. wt.-1600).

Styrene-maleic anhydride (2:1 polymer, mol. wt.-1700).

0. 00 Very poor soil susspension.

0. Good soil suspension.

Slight deposition on fabric.

1 The cleaning power was equivalent in all examples.

It is claimed:

1. A laundry detergent composition consisting essentially of about 40 to 90 weight percent of alkaline builder, about 0.1 to 20 weight percent of the ammonium salt of resinous polymer consisting essentially of styrene and maleic anhydride having a mole ratio of about 1 to 4 moles of styrene per mole of maleic anhydride and a molecular weight of about 500 to 50,000, and about 10 to 50 weight percent non-ionic, hydroxyl-containing surfactant condensation product of alkylene oxide of about 2 to 6 carbon atoms and hydroxyl-containing organic compound containing about 6 to 30 carbon atoms, said amounts being based on total solids, said condensation product having about to 85 weight percent of said alkylene oxide.

2. The composition of claim 10 wherein said styrenemaleic anhydride polymer and said condensation product are present in the detergent composition as a physical mixture.

3. The composition of claim 10 wherein the styrenemaleic anhydride polymer is present in the detergent composition as a partial ester of said polymer with said nonionic, hydroxyl-containing surfactant.

4. The composition of claim 10 wherein said alkylene oxide is ethylene oxide and the styrene-maleic anhydride polymer has a molecular weight of about 700 to 3000.

5. The composition of claim 13 wherein said alkaline builder is present in an amount of about 50 to weight percent, the ammonium salt of the styrene-maleic anhydride polymer is present in an amount of about 1 to 10 weight percent, and the non-ionic hydroxyl-containing surfactant is present in an amount of about 20 to 50 weight percent.

6. The composition of claim 10 wherein the non-ionic hydroxyl-containing surfactant has about 4 to 15 ethylene oxide units.

7. A laundry detergent composition consisting essentially of about 40 to weight percent of alkaline builder. about 0.1 to 20 weight percent of the ammonium salt of a resinous polymer consisting essentially of styrene and maleic anhydride having a mole ratio of about 1 to 3 moles of styrene per mole of maleic anhydride and a molecular weight of about 700 to 3000, and about 10 to 50% of nonionic, hydroxyl-containing surfactant consisting essentially of the condensation product of ethylene oxide and a compound selected from the group consisting of alkyl phenols of from about 1 to 3 alkyl substituents of from about 4 to 20 carbon atoms each, and fatty alcohols of up to about 25 carbon atoms, said condensation product having about 9 to 15 ethylene oxide units, said amounts be ing based on total solids of the composition.

8. The composition of claim 5 wherein the alkaline builder is present in an amount of about 50 to 70 weight percent, the ammonium salt of the styrene-maleic anhydride polymer is present in an amount of about 1 to 10 weight percent, and the non-ionic, hydroxyl-containing surfactant is present in an amount of about 20 to 50 weight percent.

9. The composition of claim 7 wherein the condensation product is of ethylene oxide and nonyl phenol.

References Cited UNITED STATES PATENTS 2,621,169 12/1952 Robinette et a1 260-785 FOREIGN PATENTS 227,960 6/ 8 Australia.

LEON D. ROSDOLL, Primary Examiner M. HALPERN, Assistant Examiner US. Cl. X.R. 252-137, 135, 156

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 1 1- Dat d December 23, 1969 Robert G. Gower, Henry V. Isaacson & David W. Young It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Table VI, between the column headed "Hydrocarbon Solvent" and the column headed "Dye Amount" insert an additional column headed Dye-.

In Table VI, in said additional column headed "Dye", and opposite each of Experiments 1, 2, 3, and 4, insert --'Iintex 25 Navy Blue--.

In Table VI, above "No. 6 fuel oil" in Experiment 5, insert a column heading entitled --Soil--.

In Table VII, Experiment 9, delete "0.00" and insert therefor O .05-

In claims 2, 3,4 and 6, line 1 of each, delete "l" and insert therefor --l-.

In claim 5, line 1 thereof, delete "l3" and insert therefor 4 In claim 8, line 1 thereof, delete "5" and insert therefor Signed and sealed this th day of March 1 971 (SEAL) Attest: m ass ssme- FORM PO-105O (10-69) 5 a u.s. oovzmmem nmmuo orncz; nu 0-3564)