US3029205A - Light duty liquid detergent - Google Patents

Description

United States Patent 3,029,205 LIGHT DUTY LIQUID DETERGENT Lloyd F. Henderson, Fair Lawn, and Francis E. Carroll,

Glen Rock, N.J., assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Filed May 5, 1958, Ser. No. 732,817 7 Claims. (Cl. 252-161) This invention relates to a concentrated liquid detergent solution for dishwashing and light detergent use which remains clear and uniform without separation of solid materials at temperatures as low as 45 F., has good detergency and is high in sudsing power.

Liquid detergents which are solutions of synthetic detergents are available which are useful in washing dishes and slightly soiled fabrics. Such detergents possess special properties attractive to the housewife. There is no need to dissolve the detergent. A washing solution is obtain able simply upon dilution of an easily measured portion of the concentrated liquid with water. However, a liquid detergent should be a clear light-colored liquid, preferably of low viscosity and should not become cloudy or precipitate solids even at low temperatures which may be encountered in storage, to avoid a deterioration in performance due to separation of active ingredients. This circumstance, coupled with the necessity of providing highly concentrated solutions, had made it difiicult to formulate a liquid detergent which would meet the needs of light detergent use and still be competitive from a price standpoint with the dry powdered polyphosphatebuilt anionic detergent product. The dry product of course need not meet special solubility requirements.

It is imperative that the liquid detergent solution be highly concentrated in order to keep at a minimum the volume of solvent in the concentrate and the measured portions used for each wash. The concentration of a liquid detergent for dishwashing should be increased to a point at which four grams of the product when used at 116 F. in six quarts of water of 300 p.p.m. or softer will wash a minimum of thirty plates before suds cease to cover completely the surface of the wash water. This specification is based on plates each soiled with 4.5 grams of a standard soil made up of nine parts of a vegetable shortening and eight parts of flour. This is a rigorous specification. A solution of a 43.5% concentration of sodium phenyl polypropylene sulfonate (the remainder being solvents) will wash less than 30 plates under these conditions.

Light duty liquid detergents are also recommended for fine fabric washing. To be satisfactory for this purpose, four grams of the product in six quarts of water of 300 ppm. or softer at 110 to 125 F. using an artificially soiled fabric should have a rating of at least 27 to 28 D.U.s as measured in the Hunter reflectometer.

Many nonionic detergents are sufficiently soluble in ice Sodium salts of phenyl polypropylene sulfonic acids, for example, are soluble in water only to the extent of 2% at 77 F., increasing to 24% detergent at 77 F., if a solubilizing sulfonate or lower molecular weight, such as hexyl benzene sulfonate, is employed. These solutions are saturated, however, and must be diluted to prevent precipitation of solids if they are to be used or stored at lower temperatures. Also, low molecular weight sulfonate solubilizers appear to affect sudsing adversely.

If a low molecular weight alcohol is used as a solvent, solutions containing as much as 20% sodium phenyl polypropylene sulfonate detergent are obtainable. However, these maximum concentrations are well below that required for a satisfactory liquid detergent. Even a solution containing 43.5% active phenyl polypropylene sulfonate is unsatisfactory, taking into account the specifications mentioned above.

It is evident that no one yet has shown how to incorporate a phenyl polypropylene sulfonate in a liquid detergent which yvill remain clear, homogeneous and pourable at low room temperatures, at least down to 45 F., when highly concentrated, and with balanced sudsing and detergent properties.

In accordance with the instant invention, a light duty liquid detergent solution is provided which contains a phenyl polypropylene sulfonate and which meets the above rewater to permit marketing in liquid solution form in high concentrations. One commercial liquid preparation utilizes an alkyl aryl polyethylene glycol as the detergent and contains 81% active detergent. However, this class of nonionic detergents like most if not all nonionic detergents, is deficient in sudsing and many fewer plates can be washed before disappearance of suds in a dishwashing operation than when anionic detergents are used.

Another commercial liquid detergent utilizes the ammonium salts of fatty alcohol sulfates. These are more soluble than the corresponding sodium and potassium salts, but require bolstering with a monoalkanolamide such as lauric ethanolamide to improve sudsing.

Both of these types of liquid detergents are quite expensive, compared to the readily available alkyl'aryl sulfonates. Alkyl aryl sulfonates have not however been used in liquid detergents in high concentrations.

quirements. This is made possible by a combination of the substantially salt-free phenyl polypropylene sulfonate detergent with a detergent polyethylene oxide thioor oxyether of a hydrophobic hydroxy compound, the total detergent concentration amounting to at least 50% by weight of the solution. Water and a water-miscible aliphatic alcohol of low molecular weight, the latter not exceeding 40% by weight of the solution, are the solvents.

The phenyl polypropylene sulfonate should be substantially salt-free (i.e., not over 0.2% salt as Na SO This is of some importance in a liquid detergent, because the apparent solubility in water of the phenyl polypropylene sulfonate thereby is much improved. However, the solubility is not sufficiently improved solely by the absence of salt to make a phenyl polypropylene sulfonate liquid detergent practical, even with use of an alcohol solvent, as shown by the following data for salt-free sodium phenyl polypropylene sulfonate:

TABLE I Composition (percent) Phenyl poly- Isopro- Condition of Condition of propyl- NazSO H20 pyl al- Composition Composition ens 001101 at 72 F. at 45 F. sulfonote 10 15 67. 5 7. 5 Separates into Preeipitate.

two layers.

8 12 72 8 Clear liquid Do.

6 9 69. 7 15.3 do Separates into three layers, precipitate.

6 9 68 17 Separates into Separates into 1 two layers. three layers. 16 84 Clear liquid Solid. 20 72 8 do Separates into two layers. 40 48 12 Separates into Do.

two layers. 50 25 25 Clear 1iquid Do.

In no case above is it possible to reach the lower limit of 50% active detergent concentration for a practical liquid detergent solution, even at the very high 25% level of alcohol. 7

This objective of the instant invention is however acand a tertiary alkyl carbon at the benzene ring, and have the following general structure:

where M is hydrogen, an alkali metal or an organic amine TABLE II Composition, percent Condition of composition at- No. Na NPG Alcohol- Oronite 1 101 2 H H 72 F 45 F. 22 F.

ratio 1:1

1. 16 84 Clear liquid Solid 2 32 8 60 Cloudy very viscous liquid. Separates Opaque solid into two layers on standing; both very viscous. 3- 20 Clear viscous liquid Cloudy viscous liquid. Separates into two layers; supernatant clear, bottom cloudy. 4 8 do Clear very viscous liquid 5. 16 do Very viscous, slightly cloudy liquid 6 Clear Separates. 7 40 Clear.

1 Phenyl polypropylene sulfonate sodium salt (salt-free).

2 Nonyl phenol condensed with from eight to ten moles of'ethylene oxide.

Composition 2 shows that 1 part alkyl phenol ether detergent to 4 parts phenyl polypropylene sulfonate is too low to show a solubilizing effect. In composition 3, the effect begins to be noticeable, and in composition 4 it is very evident. Composition 5 has 55% active detergent, but is cloudy and viscous at F. None of these compositions would be regarded as suitable. Compositions 6 and 7 illustrate the solubilizing effect of the alkyl phenol ether detergent when an alcohol is used as a solvent.

All of these compositions have a lower proportion of detergent (40% or less) than is desirable, from the standpoint of the specifications mentioned above.

In accordance with the invention, the clarity and viscosity of the liquid detergents are kept up to the requirements at temperatures as low as 45 F. in all cases, and even lower in many instances, by addition of a watermiscible alcohol of low molecular weight in an amount up to about 40% by weight of the liquid detergent. The balanced sudsing and detergency are obtained when from one to twenty parts of the phenyl polypropylene sulfonate are used to each three to one parts of alkyl or aralkyl ether detergent.

Expressed in percents, when the phenyl polypropylene and alkyl or aralkyl ether are the only detergents, the proportion will range from 25 to 95% phenyl polypropylene sulfonate, 40 to 85% being preferred, and from 75 to 5% alkyl or aralkyl ether, 60 to 15% being preferred, based on the total active detergent concentration.

Liquid detergents of the invention containing a phenyl polypropylene sulfonate and alkyl or aralkyl ether detergent in the proportions indicated have a higher sudsing and detergency than either of these detergents alone, in the same amounts, as demonstrated by standardized tests.

The total amount of detergents can be widely varied and from to 80% by weight of the solution would be employed ordinarily. The amount of the detergent is determined by the specifications for light duty liquid detergents set forth heretofore. From 40 to 65% total detergent byweight of the solution is preferred.

The sulfonated phenyl polypropylene alkanes are characterized by the branched chain structure of polypropylene V cation, and R and R are alkyl, of the type formula C H where the whole alkyl chain contains preferably twelve to fifteen carbon atoms and at least one R is a polypropylene group. These are known compounds, whose preparation and properties are set forth in US. Patent No. 2,477,383 to Lewis, issued July 26, 1949; they are available in commerce under the trade names Oronite, Neolene 400 (Sharples Chemical Co.) and Ultrawet.

The anionic phenyl polypropylene sulfonate detergents can be used in the form of the free acid, which can be neutralized in situ in the liquid detergent solution by addition of an organic amine or ammonium hydroxide. They are also readily available as the alkali metal salts, such as sodium, potassium and ammonium, and these would generally be used. However, the ammonium or organic amine salts may be more soluble, and in this event would be preferred, particularly from the standpoint of increasing the detergent concentration to a maximum.

The detergent polyethylene oxide thioand oxyethers of a hydrophobic organic hydroxy compound have the general formula:

where R is a straight or branched chain saturated or unsaturated hydrocarbon group having from eight to eighteen carbon atoms, such as an alkyl group or an aralkyl group having an alkyl group of from eight to twelve carbon atoms and attached to A through the aryl nucleus, A is oxygen or sulfur, and x is a number from eight to twenty.

When R is alkyl it will be evident that the detergent can e regarded as derived from an alcohol or mercaptan of high molecular weight, by condensation with ethylene oxide. Typical of this type of alkyl ether are the condensation products of dodecyl alcohol or mercaptan with from eight to seventeen moles of ethylene oxide. Nonionic 218,? the condensation product of dode'cyl mercaptan with from eight to seventeen moles of ethylene oxide,

R A-[CHrGHnOIr-CHrOHaOH where R is a straight or branched chain hydrocarbon group having at least eight carbon atoms up to approximately eighteen carbon atoms, A is oxygen or sulfur and x is a number from eight to twenty. Typical are the condensation products of octyl and nonyl phenol and thiophenol with from eight to seventeen moles of ethylene oxide.

Typical alkyl groups in the above compounds are, for example, straight or branched octyl, nonyl, decyl, lauryl, oleyl, cetyl, myristyl or stearyl groups.

Commercial products are Triton X-l00, the condensation product of octyl phenol with eight to twelve moles of ethylene oxide (Rohm & Haas), NPG-lOl (Carbon and Carbide Chemical Company), Igepal CO and Antarox A 400, both condensation products of alkyl phenol (alkyl of from eight to sixteen carbon atoms) with eight to twenty moles of ethylene oxide, (General Aniline), Neutronyx 600 (Onyx Oil and Chemical Co.), and NI 8586 and NI 8190 (Oronite Chemical Co.), Nonionic 218 (Sharples Chemical Co.) and Sterox SE (Monsanto Chemical Co.).

These detergents, in conjunction with the phenyl polypropylene sulfonate, are capable of producing a light dutyliquid detergent whose detergency is very satisfactory for dishwashing and like light washing uses.

The lower limit of x is important from the standpoint of detergency. Lower monoalkyl ethers of polyethylene glycol such as ethylene glycol monoether of iso-octyl phenol are not useful, and do not show an enhanced sudsing. The data reproduced below makes this evident.

The superiority of the higher polyethylene glycol ether in number of dishes washed is very marked.

Since the amount of water which the liquid detergent solution will tolerate without clouding or the formation of precipitates is critical, a Water-miscible aliphatic alcohol of low molecular weight can be added to improve stability against clouding and precipitation, and/ or reduce viscosity. Up to approximately 40% alcohol by weight of the solution can be used, the upper limit being controlled by the eifect of the alcohol on the viscosity of the solution.

Usually from 5 to 20% alcohol by weight of the solution is sufficient to meet the solutions particular requirements. Ethyl alcohol is preferred, but the chain length of the alcohol is not critical; methyl, propyl and isopropyl alcohols can be used.

Thus the solvent mixture employed in formulating the liquid detergents of the invention will comprise water and an alcohol and the relative proportions of these two solvents are not critical but will be taken with due consideration to the detergent and other components to produce a detergent solution which does not cloud or form a precipitate at temperatures as low as 45 F. In general, it will be desirable to limit the amount of water to no more than equal that of the alcohol used.

The composition may also contain dyestuffs and perfumes to suit the housewifes desire. It is customary to mask the petroleum odor of phenyl polypropylene sulfonates, and characteristic sulfur odor of thioether nonionic detergents, and those skilled in the art are aware of perfumes which meet this need.

Formulations containing about 41% phenyl polypropylene sulfonates, about 27% ethoxynated alkyl phenol (active basis), 15.5% ethyl alcohol and the remainder water exemplify an application of the principles of selection enumerated above, and display a detergency which is very adequate for dishwashing and light washing use, comparing favorably to dry powdered polyphosphate-built alkyl aryl sulfonate detergents in this respect. The above applies to use of the sodium and potassium salts of the phenyl polypropylene sulfonate. Solubility is at a maximum when ammonium or organic amine salts of the anionic detergent are used.

The above is a preferred embodiment of the liquid detergent of the invention. When prepared using ammonium or amine salts of the detergents, it remains clear at temperatures as low as 0 F. Other exemplifying embodiments follow.

In the examples the dishwashing test data was obtained according to the following standardized test: Six quarts of water of the desired hardness was adjusted to a temperature of 116 F. and the detergent composition to be tested dissolved therein in a concentration of 30 grams. Both soft and hard waters 50 ppm. and p.p.rn. generally are used. The solutions are adjusted to ensure complete solution and then allowed to stand for 45 seconcls at which time dishwashing is begun using plates soiled with a standardized soil composition. Plates are washed until the suds no longer completely cover the surface of the water.

Example 1 A Well balanced formulation of which sixteen ounces is equivalent for light duty use to nineteen or twenty ounces of a dry polyphosphate-built alkyl aryl sulfonate powdered detergent has the following composition:

Dodeoyl mercaptan condensed with eight to seventeen moles of ethylene oxide.

The above liquid detergent solution remains clear at temperatures as low as 45 F. When diluted with Water to a 0.07% washing concentration, the composition sudses well and is capable of Washing a greater number of dishes than formulations containing equivalent quantities of either detergent alone.

Example 2 Sixteen ounces of the following formulation is equivalent to nineteen or twenty ounces of a. polyphosphatebuilt alkyl aryl sulfonate powdered detergent'for light duty use:

, Percent Nonic 218 1 a 24.4 Sodium phenyl polypropylene sulfonate:

Active 41.3

Inert 0.3

Ethyl alcohol 20.0

Water, perfume, et 14.0

LDodeoyl mercaptan condensed with eight to seventeen moles of ethylene oxide.

The above liquid detergent solution remains clear at temperatures as low as 45 F. When diluted with water to a 0.07% Washing concentration, the solution sndses well and washes a greater number of dishes than formulations containing equivalent quantities of either detergent alone.

Example 3 Awell balanced formulation of which sixteen ounces is equivalent for light duty use to nineteen or twenty ounces of a dry polyphosphate-built alkyl aryl sulfonate powdered detergent has the following composition:

Percent Sodium phenyl polypropylene sulfonate (salt-free) 40.9 Triton X-l deodorized 1 27.1 Ethyl alcohol 16.5 Water, perfume, etc 15.5

To illustrate the enhanced effect due to the mixture of 8 ene sulfonate above about the liquid detergent is not clear, containing a precipitate of active detergent. However, dishwashing data was obtained using such detergents as well, to complete the data:

Liquid detergent composition 1 (percent by weight) Example No.

Sodium phenyl Nonyl phenol polypropylene condensed with sulfonate 8 to 17 moles (salt-free) ethylene oxide 63% total active detergent in each case, the remainder 21% ethyl alcohol, 16% water,

DISHWASHING TEST [Number of plates Washed in six quarts of water at 116 F.]

.111. water Example No. p p

A comparison of this data showslExamples 4 to 8 and 13 to 15 to display the enhanced eflect due to the combination of these detergents.

Examples 16 to 23 At a 58% total active concentration, the following data is obtained:

phenyl polypropylene sulfonate and alkyl phenol ether 40 nonionic detergent the following is presented:

Liquid detergegt complositlon l ercen Wei t Liquid detergent composition 1 p y g (percent by Weight) Example No. Y Sodium phenyl Nonyl phenol Example I\o. 45 polypropylene condensed with Sodium phenyl Nonyl phenol sulfonate 8 to 17 moles polypropylene condensed with (salt-free) ethylene oxide sulfonate 8 to 17 moles (salt-free) ethylene oxide 63% total active detergent in each case, the remainder 21% ethyl alcohol, 16% water.

DISH WASH ING 'rns'r [Number of plates Washed in six quarts of water at 116 F.]

At the above concentrations of sodium phenyl polypropylene sulfonate the liquid detergent remains clear at temperatures down to 45 F. without separation of solidv materials. At concentrations of phenyl polypropyl- 58% total active detergent in each case, the remainder 26% ethyl alcohol, 16% water.

DISHWASHING TEST [Number of plates washed in six quarts of Water at 116 F.]

The above solutions remained clear and uniform with-' out separation of solid materials at temperatures down to 45 F. The enhanced effect due to the combination of these detergents is evident in Examples 17 to 21.

9 Examples 24 to 27 [Percent by weight] Each of the above formulations remained clear and uniform without separation of solid materials at temperatures as low as 45 F.

The following table summarizes the dishwashing capacities of these formulations:

Example No. DISHWASHING TEST Ingredients [Number of plates washed in six quarts of water at 116 F.] 24 25 26 27 50 p.p.m. water 180 p.p.m. water Sodium phenyl olypropylene sul- Example No.

fonate (salt-free? 43. 5 Alkyl polyethylene oxide tliioetlicr 25 25 4 3 4 g. 8 E- Polyethylene glycol (in w 300) Al hol 18.8 21.8 18. 8

66. 2 15. 7 12. 7 35 48 38 56 35 55 41 59 37 54 1 32 46 1 The phenyl propylene sulfonate in Examples 24, 25 and 27 was O1()- 35 56 33 43 nite; in Example 26 it was Ultrawet K. 36. 50 34 59 Dodecyl mercaptan condensed with from eight to seventeen moles of ethylene oxide. I

The above solutions remained clear and uniform with- Examples 33 to 37 out separation of solid materials at temperatures down Additio l f l i f h i ti are as f ll to 45 F.

The dishwashing capacity of these formulations is as [Percent by welghtl follows: i

e Example No. Ingredients 50 .m. water 300 .m. water p p p p 33 34 35 36 37 g g g g Ultrawet K 43. 5 43. 5 43. 5 43. 5 43. 5

Antarox A-40O L 25 Example 24- 16 29 15 26 Nonionio 218 3 25 Example 25 s 14 e 13 NPG10 25 i 32 5o 57 Sterox SE 1 25 Triton X-100 25 Ethyl alcohol 18. 75 18. 75 18. 75 18. 75 18. 75 s 7 14 13 Water 12. 75 12. 75 12. 75 12. 75 12. 75 8 14 6 13 Example 26- 12 22 14 21 Example 27, 32 50 35 57 35 1 Sodium phenyl polypropylene sulfouate (salt-free). In as in p 2 Condensation product of alkyl phenol (alkyl of eight to sixteen carbon Examples 25 and 26 are used toatoms) with eight to twenty moles of ethylene oxide. gether 12 14 15 23 3 Dodecyl mcrcaptan condensed with from eight to seventeen moles 01' Increase in plates when poly ethylene OXIdG oxide detergent is used (Example 4 Condensation product of oetyl phenol and polyethylene glycol (eight 1 27) instead of polyethylene glycol to twelve moles of ethylene oxide).

(Example 26) 20 28 21 36 The above solutions remained clear and uniform with- Examples 24, 25 and 26 are not very satisfactory from the sudsing standpoint, as is evident from the number of soiled plates which can be washed. Example 26 is in fact, a little worse than Example 24, showing that the polyethylene glycol has a depressing eflect upon suds.

It is clear that the use of phenyl polypropylene sulfonate and thioether detergents together has an enhanced effect upon sudsing, for the number of plates washed with Example 27 is noticeably in excess of that of any of the other examples.

A comparison of Examples 26 and 27 shows the polyethylene oxide thioether detergent significantly different from polyethylene glycol.

Examples 28 to 32 Additional formulations of the invention are as follows:

[Percent by weight] Example N0. Ingredients Sodium Ororiite 43.5 43.5 43.5 43.5 43.5 Antarox A-40O Z 25 1 Sodium phenyl polypropylene sulfoiiate (salt-free).

2 Condensation product of alkyl phenol (allryl of eight to sixteen carbon atoms) with eight to twenty moles of ethylene oxide.

3 Dodecyl mercaptan condensed with from eight to seventeen moles of ethylene oxide.

4 Condensation product of octyl phenol and polyethylene glycol (eight to twelve moles of ethylene oxide).

out separation of solid materials at temperatures as low as 45' F.

. These dishwashing test results are typical:

1 Included for comparison.

All of the above compositions are satisfactory detergents for dishwashing purposes. The average are from 1 /2 to 2 times that of the Examples 24 and 25.

Examples 38 to 44 A series of compositions were formulated using Sodium Neolene 400 Sulfonate (sodium phenyl polypropylene sulfonate) and Triton X- (octyl phenol condensed with from eight to twelve moles of ethylene oxide). The amounts of each detergentwere as set forth in the table which follows. These were dissolved in a mixture of 26% ethyl alcohol and 16% water.

58% total active detergent in each case, the remainder 26% ethyl alcohol, 16% water.

The compositions tested were tested for uniformity at low temperatures by placing them in a freezing cabinet at --20 C. (4 F.) for seventy hours. This is a very extreme temperature but it will be noted from the following table that all but two of the compositions remained a clear liquid at this temperature. The two compositions which solidified at '20 C. (4 F.) remained liquid at temperatures as low as 45 F.

gen and alkali metal cations, R and R are alkyl groups of the type formula C H and the entire alkyl chain has from twelve to fifteen carbon atoms and at least one R is a polypropylene group, and a nonionic detergent polyethylene oxide ether of a hydrophobic organic compound, said nonionic detergent having the formula:

where R is a hydrocarbon group having from eight to eighteen carbon atoms, A is selected from the group consisting of oxygen and sulfur and x is a number from eight to twenty, representing the average number of ethylene oxide units in the polyethylene oxide chain, in the proportion of from one to twenty parts of the former to from three to one parts of the latter, dissolved in a solvent mixture of water and from 5 to of a water-miscible lower aliphatic alcohol.

2. A concentrated light duty liquid detergent in accordance with claim 1 in which the nonionic detergent is an alkyl phenol ether of a polyethylene glycol.

3. A concentrated light duty liquid detergent in accord- PHYSICAL CHARACTERISTICS OF COMPOSITIONS EXPOSED TO 20 TEMPERATURE FOR SEVENTY HOURS Physical state of liquid detergent formulations-Time of inspection in hours Example 7 Solid Solid Solid Solid Solid Solid Solid. do do do do do -do Do.

Clear liquid Clear liquid Clear liquid Clear liquid Clear liquid... Clear liquid- Clear liquid.

rlo' do do .do do do Do, do do do do Do. do do do "do Do. .(lo do do do Do.

where M is selected from the group consisting of hydroance with claim 1 in which the nonionic detergent is an ether of a polyethylene glycol and an alcohol of high molecular weight.

4. A concentrated light duty liquid detergent in accordance with claim 1 in which the nonionic detergent is an alkyl thiophenol ether of a polyethylene glycol.

5. A concentrated light duty liquid detergent in accordance with claim 1 in which the nonionic detergent is an ether of a polyethylene glycol and a mercaptan of high molecular weight. 7

6. A concentrated light duty liquid detergent in accordance with claim 1 in which the alcohol solvent is ethyl alcohol.

7. A concentrated light duty liquid detergent in accordance with claim 1 in which the alcohol solvent is isopropyl alcohol.

References Cited in the file of this patent UNITED STATES PATENTS 1,970,578 Schoeller Aug. 21, 1934 2,213,477 Steindorfi Sept. 3, 1940 2,469,493 Barker May 10, 1949 2,477,383 Lewis July 26, 1949 2,607,740 Vitale Aug. 19, 1952 2,642,400 Harris June 16, 1953

Claims (1)

1. A CONCCENTRATED LIGHT DUTY LIQUID DETERGENT WHICH REMAINS CLEAR AND UNIFORM WITHOUT SEPARATION OF SOLID MATERIALS AT TEMPERATURE AS LOW AS 45*F. COMPRISING AT LEAST 50% ACTIVE DETERGENT CONSISTING ESSENTIALLY OF A SUBSTANTIALLY SALT-FREE DETERGENT PHENYL POLPROPYLENE SULFONATE HAVING THE GENERAL STRUCTURE: