US2949425A - Mixed detergent composition - Google Patents

Description

Aug. 16, 1960 P. T. VITALE ET AL 2,949,425

MIXED DETERGENT COMPOSITION Filed May 28, 1956 Patented Aug'. 16, 1960 Mixup DETERGENT COMPOSITION Peter T. Vitale, Fresh Meadows, and Robert Louis Bruns, Staten Island, N.Y., and Ralph Spencer Leonard, Berkeley Heights, NJ., assignors to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware Filed May 28, 1956, Ser. No. 587 ,513

Claims. (Cl. 252-138) The present invention relates to a detergent composition characterized by controlled foaming power regulated according to natural variations in water hardnesses and designed for optimum relationship between foam and detergency which comprises a blend of water-soluble propylene tetramer benzene sulfonate and propylene pentamer benzene sulfonate detergents, and a water-soluble inorganic polyphosphate forming water-soluble cornplexes with hard water salts, as hereinafter described and claimed.

In many household detergency operations, a high level of foaming power has considerable consumer appeal. Furthermore, many housewives consider or use a particular suds level or height as the sole or major criterion for adequate concentration of the detergent composition in the Washing bath, regardless of the water hardness. For comparable detersive eficiency, the use of hard water as the washing medium generally requires more detergent product than does the use of soft water. There is a natural variation moreover in the hardness depending upon geographical location and type of water treatment. Under such conditions, the foaming power in Water of varying hardnesses is an important consideration in the formulation of a successful and commercially acceptable detergent composition. It would be advantageous to devise, if possible, a detergent `composition with a modied foam behavior that would be responsive and proportional to the water. hardness. Such a foam pattern would not falsely indicate the presence of an adequate washing concentration. In contrast, the housewife would be confronted with a vivid and realistic graphic representation of the need for addition of more or less product to her wash depending mainly upon the` water hardness.

Among the well known detergent materials are the various alkyl aryl sulfonates. A particular commercial alkyl aryl sulfonate material is the propylene tetramer benzene sulfonate detergent. This material possesses a fair amount of foaming power in soft water but does not exhibit optimum performance unless relatively large quantities are added tO the washing bath. The sudsing power of this tetrarner material is comparatively high in hard Water. ene tetramer benzene sulfonate base as the sole organic detergent may be considered as having a foam deficiency in soft water and do not exhibit :the desired foam pattern outlined above.

It has now been Ifound that a detergent composition characterized by such controlled foaming power dependent in part upon water hardness and exhibiting other 'benecial properties can be formulated by a careful choice of ingredients and their proportions.

In accordance with the present invention, such detergent composition comprises a ternary combination of Water-soluble propylene tetramer benzene sulfonate detergent, water-soluble propylene pentamer benzene sul- Detergent `compositions having a propyl-V fonate detergent and water-soluble inorganic polyphosphate salt forming water-soluble complexes with hard water salts, the ratio of the pentamer sulfonate detergent to tetramer sulfonate detergent being from about 90:10 to 70:30 Iby Weight, and theamount of said polyphosphate `salt being sucient to sequester said hard water salts. Other significant features and preferred embodiments will be apparent in the following description.

This novel detergent composition is characterized by many desirable properties. The particular blend of ingredients results in an all-purpose synthetic detergent composition which exhibits superior performance in all water hardnesses. There is exhibited a synergism in foaming power, particularly in soft Water at low concentrations in the washing machine. In addition, the markedly increased foaming characteristics are properly balanced for Washing -baths of varying water hardnesses, i.e., the suds are more profuse in soft Water than in hard Water for a given concentration so that less detergent will be used where less is actually needed. There is obtained a high level of washing power, particularly in dishwashing performance andthe laundering of soiled textiles and the like. The pentamer sulfonate material when employed individually is particularly deficient inV foaming in hard water but, in combination with the tetiarner sulfonate and said polyphosphate, there is achieved improved solubility, emulsication and foaming propylene is polymerized to form a polypropylene product which is essentially the tetramer and has an averageA molecular weight equivalent to a dodecyl group and a characteristic .branched-chained structure due to the polymerization. The propylene pentamer is formed `similarly by controlled polymerization of propylene. Benzene is alkylated with each of these propylene products in the presence of a Friedel-Crafts type catalyst, usually aluminurn chloride, hydrogen fluoride or sulfuric acid, to `form the corresponding propylene tetramer benzene and propylene pentamer benzene materials. The pro ducts are sulfonated in known manner with a sulfonating agent, such as 20% oleum at 90 F., and neutralized with alkali to form the corresponding water-soluble higher alkyl benzene sulfonate detergent salts. lt' is preferred to use the alkali metal salts such as the sodium, potassium yand lithium salts although other highly soluble salts such as the ammonium, and lower alkylolarnine, e.g. monoand triethanolamine, salts may be employed also. l'In addition, the product contains varying `amounts of Water-soluble inorganic sulfate `salts resulting from the neutralization of the excess sulfuric acid employed in the sulfonation reaction.

The propylene tetrarner lbenzene material in the form of the corresponding sul-fonate has been employed in Icommercial detergent compositions. In general, the propylene tetramer benzene fraction 'nas an average molecular Weight of about 242450, as determined lby titration of the benzidine :salt of the sulfonate material. It has an approximate distillation range as follows: Initial BP. 500 F. minimum, BP. at 10% recovery S25-550 F., B.P. at 50% recovery S45-560 F., BP. at 95% recovery 590-600 F., and an endpoint of 635 F. maximum. A material having the following analysis: Average M.W.-245, initial Bl". 526 F., BP. at 10% recovery 543 F., B.P. at 50% recovery 558 F., B.P. at recovery 581 F., etc., is illustrative of a typical propylene tet-rainer material. Where references are made The propylene pentamer benzene material has been found to vary according to the manufacturer such that it may affect the performance of the corresponding sulfonate product. It has been found that the molecular weight and distillation characteristics `of the propylene pentamer benzene material provide a criterion for the determination and selection of those materials which result in superior performance Aof the ultimate mixed detergent composition. In correlating the distillation ranges with the perfomance of the corresponding prppylene pentamer sulfonate, the extent of the boiling point ranges is an important consideration.. In general, the propylene pentamer benzene should have an average molecular weight of about 260-310, preferably 27.0-300, a distillation forerun of less than about 50 F., prefer.- ably less than 30 F., kand a distillation center Ycut or middle range of less than 75 F., preferably less 'than 50 F. The forerun is .the diterence in temperature between the initial boiling point, usually at least about 550 F., andthe boiling point at of the material distilled. The middle range is the difference in temperature between the boiling points at 1.0% and 90% distilled. The

alkylated benzene may have such characteristics as manu-V factured in a controlled manner or it maybe fractionated in any suitable manner. Examples of suitable propylene pentamer benzene materials have the following approximate distillation ranges in degrees F.:

The Water-soluble inorganic polyphosphate salts which form water-soluble complexes in hard Water are the alkali metal (including ammonium) tripolyphosphates and hexametaphosphates. Examples are sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate (Cal-gon) andthe like. These materials are essential to perform a variety of functions related to the foaming power and detergency of the present compositions. Since the propylene pentamer benzene sulfonate detergent forms insoluble salts with hard water salts, the said polyphosphate should be used in sutiicient quantities to aord ample protection for the pentamerbenzene sulfonate detergents against the calcium and magnesiurn ions present in hard water. For example, it has been found that at least about 0.05% of sodium tripolyphosphate is required in Water of 100 p.p.m. hardness (calculated as calcium carbonate) and in the presence of 0.1% sodium propylene pentamer benzene sulfonate detergent. In the presence of hard water of 300 ppm., about 0.15% sodium tripolyphosphate is required to neutralize the hardness, e.g. calcium ions, and permit said sulfonate detergent to exert maximum foaming and washing power. These particular phosphate salts kresult also in optimum detergency and do not form insoluble salts with calci-um or Kmagnesium ions which tend to deposit upon the ltextiles during the Washing and rinsing operation, as contrasted With other phosphate materials such as sodium pyrophosphate which forms relatively insoluble salts with water hardness.

The specified phosphates exert unique foaming eifects in combination with the pentamer benzene sulfonate detergent. The presence of said phosphates exerts a marked activating eifect on the foam due to their peculiar salt effect upon the pentamer benzene sulfonate detergent. For example, the sodium tripolyphosphate and hexarnetaphosphate improve the foam of the pentamer .sulfonate markedly in distilled water and to a degree much greater than other salts, such as sodium sulfate, trisodium phosphate or sodium pyrophosphate Whereas the elfect of all of these builder salts upon the propylene tetramer benzene sulfonate is approximately the same.

As indicated, the ratio of the propylene pentamer to tetramer benzene sulfonate detergents is an important consideration. It has been found that, where the ratio is from about 70:30 to 90:10 by weight and preferably about :20, there is obtained a synergistic increase in the foaming power in soft Water in the presence of the polyphosphate, as compared to the effects obtained when using these sulfonate detergents individually. The mixed detergent composition Within these proportions exhibits more sudsing power in soft water than in hard Water under comparable conditions, and possesses the desired foam behavior pattern therefore.

In such Vbuilt compositions designed for laundering of soiled textiles and cleansing of household utensils and the like, the composition will have the blend of the sulfonate detergents in said proportions, with the balance being primarily Water-soluble inorganic builder salts having about 10 to 60% of said polyphosphate salt by Weight of the total solids. In general, the total amount of the propylene tetramer and pentamer sulfonatedetergents will be usually from about 5 to 50% by weight, preferably l0 to 40%, and said polyphosphate salts will be about 10 to 60%, preferably about 20 to 60% by Weight on a dry basis, the balance of total solids being primarily water-soluble norganc neutral salts such asV sodium sulfate and the like.

These ingredients may be mixed in any suitable manner. The detergent composition is prepared preferably in particulate form by heat-drying in known manner an aqueous slurry of `the ingredients, such as by spray-drying or drum-drying .the mixture at a temperature above 212 F. In such laundering mixtures in particulate form, the detergent composition may include various other substances employed in the lart generally `in such detergent composition provided that the use `of any such materials does not substantially adversely aifect the desired effects of the indicated combination of ingredients. These optional materials may be inorganic or organic in structure and may be added to the composition in any suitable manner, such as by addition to the crutcher mixture prior to heat-drying. Examples of suitable materials are alkali metal silicates and carbonates, alkali metal phosphates, alkali metal carboxymethylcellulose, lauric monoethanol amide, lauric diethanolamide, optical brightener or fluorescent dye, fatty alcohols, perfume, color and the like.

The accompanying figures and data are illustrative of the nature of the present invention but it is to be understood that the invention is not limited thereto. These ligures represent the results obtained by testing specied detergent compositions under practical use conditions. 'Ihe various curves shown `therein. are believed to have indicated critical curvatures based upon the test data. Theoretically, the specific shape of the curves will be influenced in degree by modifications of compositions and conditions.

Figure 1 sets forth a series of curves obtained by plotting as the ordinate the foam height in inches which 1s generated or remains at the end of a ten minute washing period during the washing at F. of a six `pound load of soiled textile items in an electric washing machine using compositions A and B separately in soft Water and in hard Water, versus the total concentration of the detergent composition which is added to the washing baths as the abscissa. Composition A comprises essentially 35% mixed sodium alkyl benzene sulfonate detergent (4:1 of propylene pentamer to tetramer), 40% sodium tripolyphosphate, 20% sodium sulfate with the balance being minor amounts of sodium silicate, sodium carboxymethylcellulose, moisture, fluorescent dye, perfume and the like. Composition B is essentially the same kexcept that it contains 35% sodium propylene tetramer benzene sulfonate detergent as the sole organic detergent. The propylene tetramer benzene material before sulfonation had the indicated typical analysis and the propylene pentamer benzene material before sulfonation had characteristics similar to that of material C previously set forth.

Certain facts will be noted from the curves obtained by use of composition A characterizing the present invention and composition B corresponding to a commercial detergent composition:

(l) Composition B exhibits more foam in hard water than in soft water at the lower concentrations, e.g. 0.l-0.3%, and essentially equal foam at higher concentrations.

(2) Composition A comprising the mixed detergents exhibits a diverse foam behavior pattern whereby much greater foam is generated in soft water than in hard water, particularly at the lower concentrations. This foam pattern permits use of the accepted practice of the` housewife which employs sudsing power as a general guide or indicator of the detergent concentration to beemployed in the washing machine. For purposes of illustration, it will be noted that a greater detergent concentration is required in hard water to achieve a particular suds level than in soft Water.

(3) In general composition A gave a higher level of foam than composition B under most conditions.

The foam data are representative of the marked foam improvement over a wide range of concentrations in the Washing machine which is obtained by use of the specified blend of detergents in accordance with the presenr invention. Similar foam improvement in washing machine tests are observable in the ilash or initial suds volume, after addition of the soiled load to the washing -machine, and during the course or the entire washing operation.

Figure 2 represents a series of curves obtained as a result of dishwashing performance of representative detergent compositions in practical dishpan tests wherein a small amount of the detergent composition is added to a dishpan of water and greased dishes are washed by hand. The number of greased plates which can be washed before the foam end-point or collapse of the foam furnishes an additional basis of comparison. In Figure 2 the number of greased plates washed until the foam end point is plotted similarly against the concentration of the detergent composition in soft water in the dishpan. In these tests a composition comprising 35% sodium sulfonate detergent, 40% sodium tripolyphosphate, 3% sodium carbonate and the balance sodium sulfate was employed for all of the test compositions which differed from one another only in the character of the sulfonate detergent. Composition C contained said 4:1 mixture of the propylene pentamer to propylene tetramer benzene sulfonate detergents, composition D had the propylene pentamer benzene sulfonate detergent solely, and composition E contained the propylene tetramer benzene sulfonate as the sole organic detergent.

ItY will be apparent from Figure 2 that:

(1) Composition C of the present invention shows a synergistic increase in the number of plates Washed until the foam end-point is observed upon increasing concentrations from above 0.1% to 0.4% by weight.

(2) Such effects are not predictable from the performance curves of compositions D and E containing the propylene pentamer and tetramer benzene sulfonate detergents respectively.

In such dishwashing operations, there are a number of other signicant advantages which are obtained with use of the detergent mixture. There is obtained a high degree of clarity of the washing solution and superior emulsication of the grease for longer periods of time using the mixed detergents in comparison to the use of the same detergents individually.

The following examples are additional illustrations of compositions of the present invention. The proportions indicated are the approximate amounts by weight on a dry basis in the tinal detergent composition.

Compositions Ingredients I II III IV Polypropylene benzene sulfonate detergents. 35 30 25 25 Sodium tripolyphosphate 40 40 40 50 Sodium silicate 7 7 7 7 Sodium sulfate 10 15 20 10 The balance being small amounts of sodium carboxymethylcellulose, optical brightener, etc. The polypropylene benzene sulfonate detergent content is a 4:1 blend of the sodium propylene pentamer and tetramer benzene sulfonates.

The above ingredients for each composition are mixed at about 140 F. in a soap crutcher to form an aqueous slurry of about 60% solids. This slurry is submitted to spray-drying with heated air at a temperature of about 350 F. with a resultant moisture loss of almost 40%. The resulting compositions are recovered in the form of beads and possess a high degree of detersive and foaming properties in both hard and soft water. The foam behavior of these compositions is responsive to the water hardness as previously described.

Although the present invention has been described and illustrated with a reference to specic examples, it is understood that modications and Variations `of composition and procedure are contemplated within the scope of the appended claims.

Having thus described the invention, what is claimed 1s:

l. A detergent composition characterized by controlled foaming power regulated according to variations in water hardnesses and consisting essentially of a ternary combination of Water-soluble propylene tetramer benzene sulfonate detergent, water-soluble propylene pentamer benzene sulfonate detergent and water-soluble inorganic polyphosphate salt forming water-soluble complexes with hard water salts, the propylene tetramer benzene material of said sulfonate having an average molecular weight of about 242-250, the propylene pentamer lbenzene material of said sulfonate having an average molecular weight of about 260-310 and distillation ranges of less than about 50 F. from the initial boiling point to 10% recovery and less than 75 F. between the :boiling points at 10% and 90% recovery, the ratio of the pentamer sul'fonate detergent to tetramer sulfonate detergent being from 90:10 to 70:30 by weight, and the amount of said polyphosphate salt being from about 10 to `60% by weight of the composition.

2. A detergent composition characterized by controlled foaming power regulated according to variations in water hardnesses and consisting essentially of a ternary combination of water-soluble `propylene tetramer benzene sulfonate detergent, Water-soluble propylene pentamer benzene sulfonate detergent and water-soluble inorganic tripolyphosphate salt, the propylene tetramer benzene material of said sulfonate having an average molecular weight of about 242-250, the propylene pentamer benzene material of said sulfonate having an average molecular weight of about 260-310 and ydistillation ranges oft less than about 50 F. from the initial boiling point to 10% recovery and less than 75 F. between boiling points at 10% and 90% recovery, the ratio of the pentamer sulfonate detergent to tetramer sulfonate detergent being from :10 to 70:30 by weight, and the amount of said tripolyphosphate salt being from about 10 to 60% by Weight of the composition.

3. A detergent composition characterized by controlled foaming power regulated according .to variations in water hardnesses and consisting essentially of a ternary combination of sodium .propylene tetramer benzene sulfonate detergent, sodium propylene pentamer benzene sulfonate vdetergent and sodium tripolyphosphate, lthe propylene tetramer benzene material of said sulfonate having an average molecular weight of about 242-250, the propylene pentamer benzene ymaterial of said sulfonate having an average molecular Weight of about 260-310 and distillation ranges of less than about 50 F. from the initial boiling point to 10% recovery and less than 75 F. between the boiling points at 10% and 90% recovery, the ratio of the pentamer sulfonate detergent -to tetramer sulfonate detergent being from 90: 10 to 70:30 by weight, and the amount of said sodium tripolyphosphate salt being from about 10 to 60% by weight of the composition.

4. A detergen-t composition characterized by controlled foaming power regllated according to variations in Water hardnesses and consisting essentially of about to 50% by weight of a mixture of sodium propylene tetratner benzene sulfonate detergent and .sodium propylene pentamer sulfonate detergent, the propylene tetramer benzene material of said sulfo'nate having an average molecular weight of about 242250, .the propylene pentamer benzene material of said sulfonate having an average molecular weight of about 260-310 and distillation ranges of less than about 50 F. from the initial boiling point to recovery and less than 75 F. between the boiling .points at 10% and 90% recovery, the ratio of the pentamer sulfonate detergent to tetrarner sulfonate detergent being from 90:10 to 70:30 by weight, and the balance of the composition being primarily water-soluble inorganic builder salts having about 10 to 60% of sodium tripolyphosphate by weight of the total solids.

5. A detergent composition characterized by controlled foaming power regulated according to variations in Water hardnesses and consisting essentially lof a ternary combination of sodium propylene tetramer benzene sulfonate detergent, sodium propylene pentamer benzene sulfonate detergent and sodium tripolyphosphate, the propylene tetramer benzene material of said sulfonate having an average molecular weight of about 242-250 and a distillation range having an initial boiling point of 500 F, minimum, a boiling point at 10% recovery of 525-550 F., a boiling point at recovery of S45-560 IF., a boiling point at 95% recovery of 590-600 F. and an end point of 635 F. maximum, the propylene pentamer benzene material of said sulfonate having an average molecular weight of about 260-310 and a distillation range having an initial boiling point of 550 F., less than about 50 F. from the initial boil-ing .point to 10% recovery and less than F. between the boiling points at 10% and 90% recovery, the ratio of the said pentamer sulfona-te detergent lto tetramer sulfonate detergent being from about :10 to 70:30 by weight, and the amount of said sodium tripolyphosphate salt being yfrom about 10 to 60% by Weight of the composition.

References Cited in the flle of this patent UNITED STATES PATENTS

Claims (1)

1. A DETERGENT COMPOSITION CHARACTERIZED BY CONTROLLED FOAMING POWER REGULATED ACCORDING TO VARIATIONS IN WATER HARDNESSES AND CONSISTING ESSENTIALLY OF A TERNARY COMBINATION OF WATER-SOLUBLE PROPYLENE TETRAMER BENZENE SULFONATE DETERGENT, WATER-SOLUBLE PROPYLENE PENTAMER BENZENE SULFONATE DETERGENT AND WATER-SOLUBLE COMORGANIC POLYPHOSPHATE SALT FORMING WATER-SOLUBLE COMPLEXES WITH HARD WATER SALTS, THE PROPYLENE TETRAMER BENZENE MATERIAL OF SAID SULFONATE HAVING AN AVERAGE MOLECULAR WEIGHT OF ABOUT 242-250, THE PROPYLENE PENTAMER BENZENE MATERIAL OF SAID SULFONATE HAVING AN AVERAGE MOLECULAR WEIGHT OF ABOUT 260-310 AND DISTILLATION RANGES OF LESS THAN ABOUT 50*F. FROM THE INITIAL BOILING POINT TO 10% RECOVERY AND LESS THAN 75* F. BETWEEN THE BOILING POINTS AT 10% AND 90% RECOVERY, THE RATIO OF THE PENTAMER SULFONATE DETERGENT TO TETRAMER SULFONATE DETERGENT BEING FROM 90: 10 TO 70:30 BY WEIGHT, AND THE AMOUNT OF SAID POLYPHOSPHATE SALT BEING FROM ABOUT 10 TO 60% BY WEIGHT OF THE COMPOSITION.

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