US2886533A - Promoted detergent compositions - Google Patents

Description

May 12, 1959 Filed. July 17, 1956 L. R..BACON ETAL 2,886,533

FIG

\whmfless Renm 20 Concentration of Hydroxyoihylcolluloso in 0M6 60 O I Hydmxyolhylcellulose Promoter Mixture I Carbon soil Removal Leslie R. Bacon Clifton E. Smith Thomas H Vouqhn INVENTORS.

Attorney 4 Sheets-Sheet 2 May 12, 1959 L. R. BACON ET AL PROMOTED DETERGENT COMPOSITIONS Filed July'l'T. 1956 FIG.

2252 3359i one-3303523 U 020 E $2==83s3 5 2 3 5:22-3:00 8.cm 8 oh 8 b on 3 on 3 2 u u i m 8- m.

4 OQN Own v wmms as mam s wmm Leslie R. Bacon Cli flon E. Smith Thomas H. Van h INMTORs BY g Afloyney v May 12, 1959 R. BACON ETAL 2,886,533

PROMOTED DETERGENT COMPOSITIONS Filed July 17, 1956 4 Sheets-Sheet 3 FIG. 3

Carbon Soil Removal 20 7. 0! Promo": Gelgulaied on Promoter Active Agent Basis o o O o o o 3 a.g 8 9 3 5 w wms w mma wm n i u n s q o Leslie R. Bacon Clifton E. Smith Thomas H. Vaughn INVENTORS.

BYQ My/ Attorney yl 1959 L. R..BACION ETAL 2,886,533

PROMOTED DETERGENT COMPOSITIONS Filed July 17, 1956 4 Sheets-Sheet 4 FIG. 4

i O In E 2 o 3 g E v 5 a ,8 k 3 E 9 i 2 2 E 6 It '8 8 I o o o 0 o o o 0 0 2 2 s s 2 m o v N V 'P P lS 1 96 uouuuag :souomm Leslie R. Bacon Clifton E. Smith Thor-nos H. Vaughn INVENTORS,

BY Isl/4w Attorney United States PROMOTED DETERGENT COMPOMTIONS Leslie R. Bacon, Wyandotte, and Ilifton E. Smith, Dearborn, Mich, and Thomas H. Vaughn, Tenafiy, Ni, .assignors to Wyandotte Chemicals Corporation, Wyandotte, Mich, a corporation of Michigan Application July 17, 1956, Serial No. 598,434

8 Claims. (Cl. 252-133) This application is a continuation-in-part of our copending application, Serial No. 260,448, filed December 7, 1951, now abandoned, which in turn is a continuationin-part of our then copending application, Serial No. 69,252, filed January 5, 1949, which has since issued as US. Patent No. 2,602,781.

The invention hereof relates to promoted detergent compositions and, more particularly, to said compositions wherein the promoter consists essentially of a Water-soluble alkali metal salt of carboxymethylcellulose and a water-soluble hydroxyalkylcellulose.

In recent years synthetic detergents have come into,

widespread use, particularly the anionic detergents, such as the alkylarylsulfonates, the alkyl sulfonates and the alkyl sulfates. These anionic detergents have been compounded with a wide variety of other organic detergents, builders, etc. and their general characteristics are well known to those skilled in the art. In spite of the excellent detersive properties of these anionic detergents, still higher demands are continually being made in order to meet, and to better, the competitive products.

The ability of a detergent composition to remove soil from textiles is measured by a test known as Carbon Soil Remova referred to for the sake of brevity as CSR, and the importance of a high CSR value has long been recognized. However, it more recently has become apparent to those skilled in the art that the cleansing action of any detergent is, in eifect, the difference between the amount of soil removed from the soiled surface and the amount of soil redeposited thereon during the cleaning action.

Consequently, critical examination has been made of detergent compositions in regard to their ability to prevent redeposition of soil, and the test employed .to determine this property is known as the Whiteness Retention Test, referred to for the sake of brevity as WR. Both the CSR and WR tests are hereinafter described in detail.

The sulfur-containing anionic detergents with which the promoters of the present invention are employed have relatively high ability to remove soil (CSR value), but their ability to prevent redeposition of soil (WR value) is only fair and is further decreased by the presence of sodium sulfate, which is normally present in these detergents as they are produced.

It is therefore an object of this invention to improve the property possessed by detergent compositions in general and the aforementioned sulfur-containing anionic detergents in particular of preventing redeposition of soil.

It is also an object of this invention to improve the WR values of such detergents without causing a substantial decrease in their CSR values. I

Patented May 12, 1959 Another object of this invention is to provide a promoter for detergent compositions based on alkylarylsulfonates, alkyl sulfonates or alkyl sulfates, said promoter being capable of effecting a remarkable increase in the detersive properties of said compositions. I

Still another object of this invention is to provide a promoter for detergent compositions which is composed of readily available, inexpensive ingredients.

These and other objects which may appear as this specification proceeds are achieved by this invention which, in summary, arises from our discovery that a promoter consisting of a water-soluble alkali metal salt of carboxymethylcellulose and a water-soluble 'hydroxyalkylcellulose within certain limits greatly enhances the detergent properties of detergent compositions based on the anionic detergents of the group consisting of alkylarylsulfonates, alkyl sulfonates and alkyl sulfates, otherwise referred to herein as sulfur-containing, anionic detergents.

The combination of the water-soluble alkali metal salt of carboxymethylcellulose and a water-soluble hydroxyalkylcellulose together with the detergent produces a synergistic effect insofar as whiteness retention value is concerned, which is clearly not predictable from the Whiteness retention values obtained in connection with the individual components alone and in various combinations,

This is clearly shown in the following Table I, wherein all measurements were made at 140 F. in distilled water at a total detergent composition weight concentration of Keryllsrgnzenesulfonate 2 (40% active agent, 60%

N a; 4 I100 Hydroxyethyleellulose 3 133 Sodium Carboxymethylcellulose 4 211 kerylbenzenesultonate+5% hydroxyet le 44 95% kery1benzenesulfonate+5% sodium carboxyniethylcellulose 164 95% kerylbenzenesulfonate, 1% hydroxyethylcellulose,

4% sodium carboxymethylcellulose- 219 1 Standards A and B are defined hereinafter under the heading Measurement Procedures.

2 A sodium alkylarylsulfonate whose keryl or alkyl group is derived from a petroleum hydrocarbon and contains from 11-1G carbon atoms.

3 A water-soluble type having a degree of substitution of approximately 4 A water-soluble type having a degree of substitution of approximately It will be noted in Table I that the hydroxyethylcell-u- 'lose, although giving a whiteness retention value 33% above the whiteness retention value of the kerylbenzenesulfonate when used alone, actually suppressed the whiteness retention properties of the detergent to a figure less than half of that of the detergent alone. The sodium carboxymethylcellulose kerylbenzenesulfonate combination produced the expected median value. Where a promoter according to the present invention was used, instead of obtaining the expected median between the whiteness retention value of 44% and 164%, a whiteness retention value of 219% was obtained, which is greatly above that of either ingredient used as a promoter by itself. This result is particularly phenomenal in view of the adverse effect of hydroxyethylcellulose upon the whiteness retention properties of kerylbenzenesulfonate-type detergents.

The sulfur-containing anionic detergents with which the sulfonate, whose alkyl group contains an average of 12 carbon atoms and is derived from a petroleum distillate fraction boiling in the range of 150300 C. and whose aryl group is derived from an aromatic hydrocarbon of the benzene series. Such compounds are synthesized according to the processes as disclosed in U.S. Patents Nos. 1,992,160 and 2,220,099. They are commercially available under the product names Kreelon, Nacconol,

Santomerse and Oronite, and include as the aryl group benzene and alkyl-substituted benzenes.

Sodium alkyl sulfate is a sodium salt of sulfated fatty alcohols, such as are derived from coconut oil. This compound may be synthesized according to the process as disclosed in US. Patent No. 1,968,797, and is commercially available under the product names of Duponol ME and Dreft. Sodium lauryl sulfate is a specific example of this class of compounds.

Sodium alkyl sulfonate is derived from predominantly straight chain petroleum hydrocarbons or synthetic hydrocarbons. It can be made by the process disclosed in US. Patent No. 2,197,800. A commercially available form, which was used in compiling the data of Example 1, was sold under the mark MP. 189 and was derived according to the process of claim 1 of said patent. This commercial product is a mixture of sodium alkyl sulfonates with alky ranging from 10 to 16 carbon atoms.

It will be noted that each of the three members of the above identified group of sulfur-containing anionic detergents has a long chain alkyl portion containing from 1018 carbon atoms. Such compounds are commercially available and customarily used in their salt-built form, that is, containing a certain percentage of active agent and the balance usually being sodium sulfate. In the compositions to which our invention relates, such synthetic detergents are present in at least 35% active agent form. Because sodium sulfate has a depressing effect upon the whiteness retention value of detergent compositions, any lesser percentage of active agent may not result in a detergent composition having commercially acceptable WR and CSR values. On the other hand, the synergistic effect of the promoter is present regardless of the percent active agent.

The promoter comprising the present invention has been defined as consisting essentially of an alkali metal carboxymethylcellulose and an hydroxyalkylcellulose. The alkali metal carboxymethylcellulose employed will in most cases be sodium carboxymethylcellulose (CMC) because of its commercial availability. It should be substantially water-soluble, and it has been found necessary that the degree of substitution should be about 0.7 in order to effect the desired water solubility. The alkyl portion of the hydroxyalkylcellulose employed may be ethyl, propyl or a mixture of the two. The theoretical degree of substitution required to obtain the desired solubility of the hydroxyalkylcellulose is between 2.0 and 3.

Other limitations will be developed in conjunction with the drawings wherein:

Fig. 1 is a graph illustrating the effect of varying the composition of the promoter comprising the present invention in a promoter-alkylarylsulfonate mixture,

Fig. 2 is a graph disclosing the effect of varying the composition of the promoter in a promoter-compounded detergent mixture,

Fig. 3 is a graph illustrating the effect of varying the amount of promoter in an alkylarylsulfonate-promoter mixture, and

Fig. 4 is a graph illustrating the efiect of varying the amount of promoter in a promoter-compounded detergent composition mixture.

To illustrate the effect of varying the relative proportions of the alkali metal metal carboxymethylcellulose and hydroxyalklcellulose, reference is made to Fig. 1. As in all data included in the specification, the measurements were made on detergent compositions in distilled water at 140 F. and a total detergent concentration of 0.25%. The detergent composition upon which the data for Fig. l were obtained consisted of 95% by weight kerylbenzenesulfonate (40% active agent +60% Na SO and 5% by weight of the promoter consisting of hydroxyethylcellulose (2.0 degree of substitution) and sodium carboxymethylcellulose (0.7 degree of substitution), which is indicated in both Figs. 1 and 2 by the usual initials CMC." The percentage of hydroxyethylcellulose in the promoter mixture was varied, and the carbon soil removal and whiteness retention values were obtained in accordance with the procedures set forth later on in this specification under the heading Measurement Procedures. The data so obtained are set forth in the following table.

TABLE II Promoter Mixture Percent of Standard B Carboxy- Hydroxymethylethyl- CSR WR cellulose, cellulose, percent percent From a plot of the data of Table II, the characteristic curves of Fig. l were constructed. The dashed line AB indicates the whiteness retention value obtained when the promoter consists solely of sodium carboxymethylcellulose and the dashed line BC marks the upper limit on the weight percentage of hydroxyethylcellulose in the promoter, insofar as an enhanced WR value is concerned. The crosshatched area beneath the whiteness retention curve indicates the area of improvement.

It is apparent from the curves of Fig. 1 that, when the promoter contained greater than about 70% hydroxyethylcellulose, as indicated by the dashed line B-C, the whiteness retention dropped below that obtained with the addition of the sodium carboxymethylcellulose alone (line AB), and carbon soil removal starts to drop off quite sharply. Consequently, the upper useful limit of hydroxyethylcellulose in this particular promoter is approximately 70%. Between 550% hydroxyethylcellulose the whiteness retention values are considerably in excess of those obtained with the addition of the sodium carboxymethylcellulose alone, and the carbon soil removal properties are only slightly less than that obtained with the addition of sodium carboxymethylcellulose alone. The peak of the whiteness retention curve appears at approximately 30% hydroxyethylcellulose, balance sodium carboxymethylcellulose.

The preferred proportions of the hydroxyalkylcellulose and alkali metal carboxymethylcellulose in the promoter will vary with the detergent composition to which the promoter is added; This will become apparent by comparing Fig. 2 with Fig. 1. In conjunction with Fig. l,

the detergent composition was, as already mentioned 95% by weight of kerylbenzene'sulfonate (40% active agent+60% Na SO and 5 by weight of the promoter. In compiling the data for Fig. 2, the following listed detergent composition was used under the same conditions as those noted in regard to Fig. 1, said composition being:

30% kerylbenzenesulfonate (40% active agent+60% Na SO 52%modified soda 5% sodium tripolyphosphate 3% pine oil 10% promoter The data so obtained are set forth in the following table.

TABLE III Promoter Mixture Percent of Stand- Carboxy- Hydroxyand A, R

methylethylcellulose, cellulose, percent percent From a plot of the data in Table III the characteristic curves of Fig. 2 were constructed. The dashed line A-B' indicates the whiteness retention value obtained when the promoter consists solely of sodium carboxymethylcellulose and the dashed line B--C' marks the upper limit on concentration of hydroxyethylcellulose in the promoter, beyond which the synergistic action is no longer of advantage. The crosshatched area beneath the whiteness retention curve again indicates the area of improvement.

The curve in Fig. 2 shows that the addition of inorganic salt builders, pine oil, etc., has not affected the synergistic action of the promoter upon the kerylbenzenesulfonate, but the hump of the curve is much sharper and is shifted toward the lower percentages of hydroxyethylcellulose. The maximum useful amount of hydroxyethylcellulose, as deduced from the curve in Fig. 2, is approximately 50% of the promoter mixture, with the maximum whiteness retention being reached at approximately 25% hydroxyethylcellulose, balance sodium carboxymethylcellulose.

From the above data it may be concluded that, while the preferred proportions of alkali metal carboxymethylcellulose and hydroxyalkylcellulose will vary with the particular detergent composition employed, an effective promoter will be obtained whenever the carboxymethylcellulose predominates and the hydroxyalkylcellulose forms a minor constituent of the promoter. Furthermore, maxi mum promotion appears inthe lower percentages of hydroxyallcylcellulose, preferably between 20-30% of this component,

In order to illustrate the efi'lcacy or" even small amounts of hydroxyethyl cellulose in the promoter mixture, solutions containing 0.2375% lteryl benzene sulfonate (40% active agent plus 60% Na SO and 001.25% of a promoter mixture composed as indicated in the following table, were made up at 140 F. in demineralized water. The following results were obtained:

From the foregoing table, it will be realized that even quite small amounts of hydroxyethylcellulose in combination with carboxymethylcellulose enhances the whiteness retention value of the detergent composition.

The relative proportions of promoter to active agent may be varied within extremely wide limits, as is apparent from Fig. 3, in which the percent of promoter based on promoter active agent is plotted against CSR and WR values.

The data upon which Fig. 3 is based were obtained from measurements made on detergent compositions-in distilled water at 140 F. with a total detergent concentration of 0.25%, and employing the same compounds (keryl benzene sulfonate, sodium carboxymethylcellulose and hydroxyethylcellulose) as were used in connection with Fig. 1. The composition of the promoter was fixed at sodium carboxymethylcellulose and 20% hydroxyethylcellulose, but the amount of promoter in the total active agent-promoter mixture was varied from 095% The data so obtained are set forth in the following table.

TABLE V 80 OMC:20 HEO Percent of Keryl Promoter Mixture Standard B benzene sulfonate (40% Percent Percent Active of Total Based on CSR .WR Agent) Mixture Active Agent Fig. 3 has been drawn with a dashed line D-E to indicate the carbon soil removal value of the detergent without the presence of a promoter. The dashed line E--F indicates the maximum concentration at which the promoter is effective insofar as carbon soil removal value is concerned. The crosshatched area of the carbon soil removal curve indicates the area over which the promoter is effective.

In Fig. 3, it will be observed that the whiteness retention values increased rapidly up to about 10% of promoter and then increased at'a slower but steady rate up to that of a 95% promoter concentration. The carbon soil removal values, on the other hand, leveled ofi at about 30% promoter and dropped below the carbon soil removal value of keryl benzene sulfonate when over 90% promoter was employed. Consequently, up to about 90% promoter may be employed, although from a commercial standpoint up to approximately 30% promoter constitutes a practical range because of cost considerations and because there is no material advantage in adding more than this amount of promoter.

Fig. 4 discloses the effect of varying the amount of promoter (80% sodium carboxymethylcellulose and 20% hydroxyethylcellulose) included in the built detergent composition set forth above in connection with Fig. 2.

7 The curve in this figure was constructed from the data set forth in the following table.

The percent of promoter inthe total promoter-active agent content of the detergent composition is plotted against the percentage whiteness retention value, and a curve quite similar to that shown in Fig. 3 1s obtalned with the exception that the slope of the rise from promoter on up is more gradual than that obtained in Fig. 3 and does not level off until about 40% promoter is reached. Since no significant increase in whiteness retention is obtained when more than 30% promoter is employed, and since the promoter at the present time is much more expensive than the detergent to which it is added, about 30% promoter constitutes a practical upper limit for both the compounded and uncompounded detergent compositions.

In order to reduce the expense and to increase certain detersive properties, it is customary to formulate the synthetic detergents, with which the promoters comprising the present invention are useful, with a number of other ingredients. As shown in Figs. 2 and 4, the present invention is applicable to detergent compositions based upon sulfur-containing anionic detergents, as previously defined herein, that is, compositions wherein these detergent compounds predominate over other detergents present. As used in this specification, the word detergent is not applicable to the inorganic builder salts which do exert some detersive action, but is restricted to organic detergents.

In Figs. 2 and 4, the composition employed contained only 12% keryl benzene sulfonate (active agent), and even lower percentages of the active agent may be used, because it is customary to employ very large percentages of inorganic builder salts, such as the carbonates, bicarbonates, phosphates, sulfates, silicates, etc. These builder salts may comprise from 20-80% of the total detergent composition. In addition, emulsifying agents, such as pine oil may be added along with perfumes, foam suppressors, inert clays, dust layers, etc. These additional ingredients only secondarily affect the synergistic action of the promoter comprising the present invention upon the above defined sulfur-containing anionic detergents, as shown in Figs. 2 and 4 of the drawings and in the following table, in which the detergent composition set forth in connection with Fig. 2 is employed with the promoter indicated.

t Comparing the above data with that in Table I, it will be 'seen that the effect of hydroxyethylcellulose is to depress the whiteness retention of both the compounded and uncompounded keryl benzene sulfonate. Likewise, the carboxymethylcellulose addition increases the whiteness retention value for both compounded and uncompounded detergent, but this increase is not synergistic. When the mixture of hydroxyethylcellulose and sodium carboxymethylcellulose is added to either the compounded or uncompounded keryl benzene sulfonate, an unusual and unexpected increase in the whiteness retention properties of the ultimate composition is obtained.

In view of the foregoing data and curves it may be stated in summary that the present invention resides in a promoter for sulfur-containing, anionic detergent compositions. This promoter consists essentially of a watersoluble hydroxyalkylcellulose and a water-soluble alkali metal salt of a carboxyalkylcellulose. Its concentration in the detergent composition must be at a weight percentage within a range from zero weight percent whereat the carbon soil removal value of the composition is at a minimum to a significant weight percent whereat the carbon soil removal value is again at said minimum, the carbon soil removal value in said range increasing from said minimum to a maximum and then decreasing to said minimum as the concentration of said promoter is increased to said significant weight percent. Said significant weight percent will vary according to the make-up of the detergent composition but in any case the minimum carbon soil removal value is equal to that of the detergent composition without the promoter of this invention.

The concentration of the hydroxyalkylcellulose according to the teachings of this invention is at a weight percentage within a range from zero weight percent whereat the whiteness retention value is at a minimum to a significant weight percent whereat the whiteness retention value is again at said minimum, the whiteness retention value in said range increasing from said minimum to a maximum and then to said minimum as the concentration of the hydroxyalkylcellulose is increased to the latter significant weight percent. This significant weight percent will likewise vary according to the make-up of the detergent composition but in any case the minimum" whiteness retention value is equal to that of the detergent composition containing only the alkali metal salt of carboxyalkylcellulose as the promoter.

Measurement procedures Inasmuch as the data in the numerous examples and tables set forth in this specification were taken over a period of time during which changes were made in the test procedure, the particular test procedure employed has been identified by the Words of Standard A or by of Standard B. These procedures are outlined in detail as follows:

Carbon soil removalStana'ard A:A standard soiled cotton fabric is first prepared as follows: fourteen pieces of a standard muslin (Indian Head muslin 53 x 47, 5.15 oz. per sq. yd. manufactured by Nashua Mfg. Co.) are definished or pre-treated in order to remove the sizing or finish and to shrink the material, by a treatment with caustic soda solution, followed by a wash with sodium stearate, which is then followed by a number of rinses With soft Water. The water used in this operation is softened to below one grain CaCO equivalent to a gallon. Following such pre-treating operation, the muslin is extracted for 5 minutes and tumbled to dryness in a commercial gas-heated laundry dryer. The definished standard muslin, cut in pieces measuring 10 /2" x 36'' are placed in a Monel metal wash wheel containing an emulsion of colloidal carbon black and water-soluble mineral oil. After thorough impregnation of the standard muslin in the carbon black and oil emulsion, it is removed piece by piece and passed once without folding through a c eeses power-driven household type wringer to squeeze out any residual aqueous dispersion, the Wringer pressure being so adjusted as to leave in the cloth an amount of standard soil solution equal to 120%i1% of the dry weight of cloth. The standard soiled muslin or test cloth is then dried and cut into test pieces measuring 2 /2" X 3 /2". Before actual use of the so-prepared standard soiled cloth, it is given a final check by the following described carbon soil removal test in a standard detergent solution, and over a range of several solution concentrations.

To evaluate the soil removal characteristics of synthetic detergent compositions, 0.25% by weight solutions of the composition to be tested are prepared in distilled Water and 100 ml. portions of such solution are added to each of one-pint jars of a Launder-Ometer (type 12Q-EF-SPA, manufactured by Atlas Electric Devices Company) standard laundry test machine.

Fifteen 4 diameter stainless steel balls are placed in each jar, after which two pieces of the previously prepared standard soiled cloth are added to each of nine jars. In the tenth jar are placed two pieces of unsoiled but pretreated cloth and this latter jar serves as a blank for determining the turbidity of the detergent solution. The so-prepared jars, heated to a temperature of 140:L2" F. in a constant temperature bath are then placed in the Launder-Ometer" and run for 10 minutes at a speed of 42:1 r.p.m. The jars are then removed from the test machine and replaced in the constant temperature bath. The contents of each jar to which the standard soiled cloth has been added are poured through a coarse screen to separate the steel balls and the standard soiled cloth from the soil suspension which is collected in a large beaker. The composite suspension thus attained is mixed thoroughly and a sample placed in a 10 mm. light absorption cell. The light absorption of this composite solution, as well as the light absorption of the solution in the tenth or blank jar containing the unsoiled cloth test pieces is then measured (by a Fisher Electrophotometer). By means of a calibration curve for the Fisher Electrophotometer, such curve being constructed by obtaining light absorption values of known quantities of carbon black dispersion added to distilled water, the carbon soil removal value sought (in mg. of carbon per liter of solution) is obtained by taking the difference between the converted values of the light absorption of the composite solution or suspension from the nine jars and of the light absorption of the suspension in the blank jar.

The carbon soil removal values are then reported as a percentage of that of a standard detergent solution used as a reference or control material viz. by dividing the mg. of carbon removal value of the test material composition by the mg. of carbon removal value for the standard or control detergent solution which is determined concurrently in the same test run and on the same standard soiled test cloth, and multiplying by 100.

The standard detergent solution used throughout the tests reported herein was a 0.25% solution of sodium keryl benzene sulfonate in distilled water.. The sodium keryl benzene sulfonate was prepared by efiecting a Friedel-Cra fts condensation of a chlorinated petroleum hydrocarbon distillate (derived from a hydrocarbon distillate having 9-16 carbon atoms and boiling in the range of ISO-300 C.) with benzene and thereafter sulfonating the keryl benzene compound to form the keryl benzene sulfonic acid, which was subsequently neutralized with caustic soda to form the water-soluble sodium keryl benzene sulfonate. After the neutralization of the sulfonic acid, sufficient sodium sulfate was added so that the final product contained approximately sodium keiyl benzene su'l-fonate and approximately sodium sulfate. Actual analysis of the product showed 0.6% moisture, 1.0% unsulfonated oils, 60% sodium sulfate and 38.4% sodium keryl benzene sulfonate.

Carbon soil removal-Standard B.This procedure is identical withStandard A except for the following:

(a) The pretreatment of the swatches was eliminated.

(b) A continuous 10 strip of muslin was used in place of the 10 /2 x 36" pieces employed in Standard A. The soiling was accomplished ina bath of the same composition as employed in Standard A. A continuous procedure, however, was-used by which the fabric was drawn lengthwise through the soil dispersion, passed through squeeze rolls and a brush and heater arrangement, with subsequent drying.

(c) In place of the Fisher Electrophotometer used in Standard A, a Lumetron Colorimeter was employed.

(d) The standard detergent, which is a commercial product, had the following analysis: moisture 0.54%, unsulfonated oil 1.46%, sodium sulfate 56.5% and sodium keryl benzene sulfonate 41.5%.

Whiteness retention-Standard A.-B-leac'hed, unfinished, clean Indian Head muslin, count 58 x 47, weight 4.7 oz./sq. yd. (Nashua Manufacturing Company) is cut into swatches measuring 2 /2" x 3 /2". The light reflectance of each side of every swatch is measured by means of a Hunter Multipurpose Reflectometer equipped with a green filter, using a standard white backing with a reflectance of 68.8% behind the cloth swatch. The average of such values of each side of each test piece is calculated and recorded. A standard soil suspension is prepared by diluting 28.55 grams of an aqueous carbon dispersion containing 35% carbon Aqua Blak B, Binney and Smith Co.) to 1 liter in a volumetric flask of distilled water.

A 0.25% distilled water solution of the detergent compound to be tested is then made up by adding 2.5 grams of the compound to a small amount of distilled water in a 1 liter volumetric flask. The previously prepared soil suspension is shaken vigorously and 50 ml. then pipetted into the flask containing the detergent. Suflicient distilled water is then added to this flask to make up to the oneliter mark.

The resultant mixture of detergent and carbon soil suspension is pipetted in ml. portions into each of 5 Launder-Ometer jans, each jar containing fifteen /1." stainless steel balls. The jars and contents are brought to a temperature of i2 F. in a constant water bath, then placed in the Launder-Ometer and rotated for 5 minutes at 42:2 rpm. The Launder- Ometer is thereafter stopped and Without removing the jars from the machine, the lids are opened and two standard cloth swatches, prepared as previously described, are placed in each jar after soaking for exactly 1 minute in distilled water without subsequent draining. The lids are replaced on the jars and the latter are rotated for an additional 30 minutes in the Launder-Ometer. The swatches are then removed and immediately rinsed by flowing 3 liters of distilled water continuously through a rinsing flask while shaking, and for a period of 5 minutes. Immediately after rinsing, the swatches are removed from the rinsing flask and placed on flat clean paper towels. The swatches are pressed dry on a laundry press set at a temperature of 328-338 F. After pressing, the reflectance of both sides of each swatch is again measured by the Hunter Reflectometer and the average reflectance of all swatches calculated and recorded. The whiteness retention value is then calculated as follows:

The whiteness retention values are reported herein as a percentage of that determined in the standard detergent solution described under the Carbon Soil Removal-- Standard A viz. by dividing the percent whiteness retention determined in the test material by the percent white-- ness retention determined in the standard control detergent solution which is determined concurrently'in the same test run and on the same standard test cloth, and multiplying by 100.

Whiteness retentinStandard B.-This procedure was the same as Standard A with the following exceptions:

(a) A different lot of muslin was employed.

(b) Reflectance readings were taken on a -swatch thickness instead of one.

(0) The 5-minute period of rotation in the constant temperature water bath was eliminated.

(d) Oven drying on steel plates was substituted for pressing of the swatches before reading final reflectance.

(e) the standard reference detergent employed was that described under Carbon Soil Removal-Standard B.

To further illustrate the features of this invention and to assist those skilled in the art to a further understanding of the invention the following examples are set forth.

Example 1 A series of detergent compositions was made up containing 5% promoter consisting in turn of hydroxyethylcellulose and 80% sodium carboxymethylcellulose, and the remaining 95% consisting of a sulfur-containing anionic detergent. These compositions were dissolved in distilled water at 140 F. at a total concentration of 0.25 In a second series of tests the sulfur-containing anionic detergents, without any promoter, were dissolved in distilled water at 140 F. at a total concentration of 0.25%. Each of these solutions was measured for carbon soil removal and the whiteness retention values, using procedure B in each case, and the data are recorded in the following table:

Thus, it is to be observed that the promoter of. this invention exerts a synergistic effect on sulfur-containing anionic detergents.

Example 2 In order to show the efficacy of various hydroxyalkylcelluloses in the promoter mixture, a detergent composition comprising 95 keryl benzene sulfonate active agent) and 5% promoter mixture containing 80% sodium carboxymethylcellulose and 20% of a series of hydroxyalkylcelluloses was dissolved in distilled water at 140 F. at a total concentration of 0.25%. The carbon soil removal and whiteness retention values of these solutions were determined, using procedure B in each case, and the results are set forth in the following table:

TABLE IX Hydroxyalkyleellulose CBR, WR,

Percent Percent Hydroxypropylcellulose 168 193 Hydroxyethylpropylcellulose... 162 219 Hydroxyethylcellulose 156 219 12 It will be observed that each of the water-soluble hydroxyalkylcelluloses employed functioned synergistically with the sodium carboxymethylcellulose to enhance the whiteness retention value of the detergent composition .used.

What is claimed is: 1. A promoted detergent composition consisting essentially of (1) about 10 to 95 weight percent of a sulfurcontaining anionic built detergent wherein the anionic sulfur-containing compound is present in at least about 35 weight percent active agent form and (2) about 5 to weight percent of a promoter, said promoter consisting of about 50 to 99 weight percent of a water-soluble alkali metal salt of carboxymethylcellulose and about 1 to 50 weight percent of a water-soluble hydroxyalkylcellulose selected from the group consisting of hydroxyethylcellulose, hydroxypropylcellulose and hydroxyethylpropylcellulose.

2. A promoted detergent composition in accordance with claim 1 wherein said sulfur-containing compound is selected from the group consisting of the alkali metal salts of alkylarylsulfonates, alkylsulfonates and alkylsulfates, said alkyl radical in each instance having between about 10 to 18 carbon atoms.

3. A composition in accordance with claim 1 wherein said sulfur-containing anionic compound is sodium kerylbenzenesulfonate and consists of at least about 40 weight percent of said built detergent.

4. A composition in accordance with claim 1 wherein the concentration of said promoter is in the range of about 1 to 30 weight percent.

5. A composition in accordance with claim 1 wherein the hydroxyalkylcellulose is hydroxyethylcellulose.

6. A composition in accordance with claim 1 wherein the promoter consists of about 20 to 30 weight percent of hydroxyethylcellulose and the balance being sodium carboxymethylcellulose.

7. A promoted detergent composition consisting essentially of about 30 weight percent of sodium kerylbenzenesulfonate (40% active agent plus 60% sodium sulfate), about 52 weight percent modified soda, about 5 weight percent of sodium tripolyphosphate, about 3 Weight percent of pine oil and about 10 weight percent of a promoter, said promoter consisting of about 1 to 50 weight percent of water-soluble hydroxyethylcellulose and the balance being water-soluble sodium carboxymethylcellulose.

8. A promoted detergent composition consisting essentially of (1) about weight percent of an anionic built detergent wherein sodium kerylbenzenesulfonate comprises at least about 40 weight percent of said built dctergent and (2) about 5 weight percent of a promoter, said promoter consisting of about 1 to 50 weight percent of water-soluble hydroxyethylcellulose and the balance being water-soluble sodium carboxymethylcellulose.

References Cited in the file of this patent UNITED STATES PATENTS 2,335,194 Nusslein Nov. 23, 1943 2,566,501v Smith Sept. 4, 1951 2,579,381 Funderburk Dec. 18, 1951 2,602,781 Bacon July 8, 1952 FOREIGN PATENTS 805,718 France Aug. 31, 1936

Claims (1)

1. A PROMOTED DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF (1) ABOUT 10 TO 95 WEIGHT PERCENT OF A SULFURCONTAINING ANIONIC BUILT DETERGENT WHEREIN THE ANIONIC SULFUR-CONTAINING COMPOUND IS PRESENT IN AT LEAST ABOUT 35 WEIGHT PERCENT ACTIVE AGENT FORM AND (2) ABOUT 5 TO 90 WEIGHT PERCENT OF A PROMOTER, SAID PROMOTER CONSISTING OF ABOUT 50 TO 99 WEIGHT PERCENT OF A WATER-SOLUBLE ALKALI METAL SALT OF CARBOXYMETHYLCELLULOSE AND ABOUT 1 TO 50 WEIGHT PERCENT OF A WATER-SOLUBLE HYDROXYALKYLCELLULOSE SELECTED FROM THE GROUP CONSISTING OF HYDROXYETHYLCELLULOSE, HYDROXYPROPYLCELLULOSE AND HYDROXYETHYLPROPYLCELLULOSE.

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