US3377290A

US3377290A - Liquid or paste detergent preparations having sulfofatty acid salts as viscosity reducing agents

Info

Publication number: US3377290A
Application number: US380089A
Authority: US
Inventors: Stein Werner; Koch Otto; Weiss Herbert
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1963-07-13
Filing date: 1964-07-02
Publication date: 1968-04-09
Anticipated expiration: 1985-04-09
Also published as: BE650381A; DK119217B; DE1218646B; CH473215A; AT255006B; GB1066764A; NL6406331A; NL145893B

Abstract

Liquid or pasty detergent compositions comprise (a) fatty alcohol sulphates, and (b) mono- and/or di-salts of sulpho-fatty acids containing not more than 50% of fatty acid residues having 16 or more carbon atoms, the amount of (b) being not greater than that of (a); and optionally (c) salts of esters of C8-24 sulpho-fatty acids, in which case the proportion of (a) to the total of (b)+(c) lies in the range 10: 1 to 1: 10. The alcohol residues in (c) may be derived from mono- or poly-hydric alcohols or ether-alcohols, and the cations of (a), (b) and (c) may be one or more of Na, K, Li, NH4 and mono-, di- and tri-ethanolamine. Further optional ingredients include C1-5 monohydric alcohols, C2-5 glycols, di- and tri-ethylene glycol, glycerine, polyglycerines, partial ethers of any of the foregoing polyhydric alcohols with C1-4 monohydric alcohols, Na2SO4, NaCl, NaNO3, alkali metal carbonates, orthophosphates, pyrophosphates, polyphosphates, polymetaphosphates, and silicates, polyacrylates, polymethacrylates, carboxymethylcellulose, cellulose sulphates, and fatty acid amides and alkylolamides.

Description

United States Patent Q 14 Claims. cl. 252-152 The present invention relates to wash-active substance combinations in liquid or paste form, and more particularly to wash-active concentrates having a liquid to pasty consistency, containing a mixture of fatty alcohol sulfate with sulfofatty acid salts and/ or sulfofatty acid ester salts, with the sulfofatty acid salts containing less than about 50% of fatty acid radicals having more than 15 carbon atoms and with the sulfofatty acid ester salts containing fatty acid radicals of 8-24 carbon atoms, whereby the viscosity of the concentrate will be reduced as compared with analogous concentrates omitting the specified sulfofatty acid salts and/or ester salts herein.

Liquid combinations of wash-active substances are used, preferably in more or less concentrated form for the prep aration of baths for treating many different kinds of solid materials, but they are also used for the preparation of liquid washing and cleaning media. These treatment baths can be used in the household, for washing heavy and fine laundry, for example, for washing dishes, for cleansing polished, lacquered or varnished surfaces, for scrubbing tiles, wall coverings, etc. However, industrial plants such as laundries, factories, etc., can use such liquid concentrates for cleansing the surfaces of solid materials or otherwise treating them. In addition to the wash-active substances and the accompanying substances produced by their manufacture, such as sodium sulfate in particular, these liquid concentrates may contain additional conventional components.

In all such cases, it is advantageous for the wash-active substance concentrates to have initially the lowest possible viscosity, because the viscosity is often increased by accompanying substances, and because viscosities that are not excessively high are desirable in the interest of easy handling, such as in the rapid measuring and dilution of the concentrates with water. Concentrates which have a low viscosity and therefore are easy to pump are also desired in the industrial manufacture of solid detergents, especially granulated detergents, particularly when they are to be dried, after the addition of the customary additives, by hot spraying or other methods.

It is an object of the present invention to overcome previous drawbacks and disadvantages with respect to wash-active concentrates and to provide wash-active concentrates having a liquid to pasty consistency of reduced viscosity, containing a mixture of fatty alcohol sulfate with sulfofatty acid salts and/ or sulfofatty acid ester salts of particular chain lengths.

It is another object of the present invention to provide a wash-active concentrate of the foregoing type in which any sulfofatty acid salts present contain less than about 50% of fatty acid radicals having more than 15 carbon atoms and in which the fatty acid radical of any sulfofatty acid ester salts present contain 8-24 carbon atoms.

It is still another object of the present invention to provide wash-active concentrates of the foregoing type which additionally may contain further wash-active ingredients of the conventional type admixed therewith in amounts which in toto do not exceed the amount of fatty alcohol sulfates present.

3,377,290 Patented Apr. 9, 1968 It is still a further object of the present invention to provide a Wash-active concentrate of the foregoing type which permits the inclusion of supplemental washing ingredients without exceeding reasonable levels of viscosity in the workup and use of the resulting wash-active concentrate combinations.

Other and further objects of the present invention will become apparent from a study of the within specification and accompanying examples.

It has now been found in accordance with the present invention that salts of sulfofatty acids which contain not more than 50% of fatty acid radicals with 16 and more carbon atoms, and/or salts of esters of sulfofatty acids containing 8-24, preferably 10-20, and especially 12-18 7 carbon atoms in the fatty acid radical, with monovalent or polyvalent alcohols, are capable of reducing the viscosity of pastes or solutions of fatty alcohol sulfate washactive concentrates, such as aqueous concentrates having a liquid to pasty consistency. The sulfofatty acids in question are monofunctional saturated fatty acids.

For the sake of simplicity, the sulfofatty acid salts, including the monosalts and/ or disalts, will be referred to hereinafter as disalts, the sulfofatty acid ester salts as ester salts and the fatty alcohol sulfates as FAS. The expression total WAS shall mean the total of the components consisting of wash-active substance (WAS),

including the fatty alcohol sulfates, disalts, ester salts, and any other wash-active substances that may be present.

Liquid detergents are described in US. Patent 2,915,473 which may contain, in addition to sulfofatty acid salts with 16-24 carbon atoms (i.e. a-sulfonated fatty acids), alkylbenzene sulfonates or fatty alcohol sulfates (i.e. long chain alkyl sulfates), but nothing is said about the viscosities of these liquid preparations, and from this patent the knowledge cannot be derived that an addition of shorter-chained monosalts, disalts or ester salts could in any way affect the viscosity of the detergents. Heretofore, attempts have often been made to improve liquid detergents by the addition of the known anionic hydrotropic substances, including mainly the sulfonates of benzene, toluene or xylene. These substances, however, in contrast to those used according to the present invention, are not surface-active, and they have proven to have no effect in concentrated aqueous pastes, whereas precisely in the case of such pastes as these the surface-active additives of the present invention have achieved excellent success while advantageously also serving to reduce the viscosity of the fatty alcohol sulfate (i.e. long chain alkyl sulfate).

The total WAS concentration of the pastes or solutions of the present invention may range from 5 to 45%, preferably from 10 to 30%, by weight, with reference to the weight of the total solution or paste, the remainder being water and, if desired, other supplemental conventional ingredients typically usable, for example water soluble organic solvents such as water soluble lower alcohols, etc.

Fatty acids and their mixtures, from which the disalts and ester salts of the present invention are derived, may contain generally 8 to 24, or especially 8 to 20 and preferably 12 to 18 carbon atoms in the fatty :acid radical, not more than 50%, and preferably less than 25%, of fatty acid esters of 16 and more carbon atoms being contained in the fatty acid radical of the esters as is the case with the disalts. Preferred are disalts of fatty acid mixtures in which the percentage having 12 to 14 carbon atoms amounts to at least 50% and preferably 65-85% of the total mixture. The hydrogenated C -C fatty acid fractions of coconut oil or palm kernel oil, for example, are quite suitable. Fatty acid mixtures of different composition are also usable as ester salts, as for example the hydrogenated fatty acids of palm oil and tallow, those obtained from the fats of sea animals, etc. Instead of the disalts or ester salts of natural fatty acids, analogous products made from fatty acids or fatty acid mixtures of synthetic origin can also be used, providing the chainlength percentages meet the above requirements.

The substantially saturated, hydrophobic radicals of sulfofatty acids making up the disalts or ester salts may be straight-chained or branched; the sulfonic acid group is in the alpha position (a-sulfonated fatty acids), in contrast to those sulfonic acid groups produced by the sulfonation of fatty acids or their derivatives which are unsaturated or which contain hydroxyl groups, in which case sulfuric acid semiesters are involved. The fatty acid radicals present in the disalts and ester salts of the present invention, of course, may be all the same or different.

The aliphatic ester groups or alkyl radicals present in the sul-fo ester salts may be derived from rnonovalent alcohols, such as aliphatic alcohols, with, for example, 1 to 12, and preferably 1 to 4 carbon atoms, or from polyvalent alcohols, i.e., polyhydric alcohols, especially from bivalent to tetravalent, i.e., dihydric to tetrahydric, aliphatic alcohols with 2 to 6 carbon atoms, such as glycol or glycerin.

In the case of the ester salts, the alkyl or alcohol radical also has been found to have an effect on the reduction of the viscosity of the concentrates and on the improvement of the solubility of the wash-active substance. If, for example, the desired effect is not achieved by the use of a sulfofatty acid methyl ester, it is recommended to replace the methyl ester with the corresponding ethyl, propyl, isopropyl, butyl or isobutyl ester.

The above-named aliphatic rnonovalent or polyvalent alcohols can be replaced wholly or partially by monovalent, i.e. monohydric, ether alcohols containing as many as 12 carbon atoms and containing the radicals of the above-described rnonovalent or polyvalent alcohols. The ether alcohols themselves may also be rnonovalent or poyvalent. They may be derived, for instance, from monovalent monoalcohols with l to 4 carbon atoms in the molecule and containing no ether groups, or from the ethers of polyalcohols of the same kind, especially from the corresponding polyglycols or polyglycerines, or from ether alcohols developed by the addition of ethylene oxide or propylene oxide onto rnonovalent or polyvalent alcohols. Examples of such ether alcohols are the monomethyl, monoethyl, monopropyl, monoisopropyl, or monobutyl ethers, etc. of ethylene glycol, propylene glycol, butylene glycol and di or triethylene glycol, etc., and the addition products made by the addition of 1 to 7 mols of ethylene oxide or 1 to 5 mols of propylene oxide to glycerine, etc.

Preferably, the ester salts should contain for each sulfonate group present in the molecule not more than 24, and preferably not more than 20 carbon atoms.

The FAS present in the liquid to pasty-wash-active substance combinations of the invention may be derived from fatty alcohols with 10 to 20, and preferably with 12 to 18 carbon atoms, the fatty alcohol radicals being either saturated or unsaturated. Such fatty alcohols are obtained preferably through the reduction of natural fatty acids in the usual way. The preferred chain-length percentages in the disalts and ester salts noted above also apply to those of the fatty alcohols. Accordingly, the FAS can be produced from coconut, palm kernel, palm oil, tallow and marine animal fatty alcohols, these alcohols being fully saturated, or more or less unsaturated in the same manner as the star-ting fatty acids used to form the disalts and ester salts. The sulfates of unsaturated fatty alcohols include also the products which, in the conventional manner, have been sulfated practically only at the hydroxyl group, preserving the doube bond, such as, for example, is the case with oleyl sulfate-1. Instead of those sulfates made from fatty alcohols of natural origin (which are understood to include those obtained from natural fatty acids), sulfates may also be used which have been obtained from synthetically made fatty acids or which have been synthesized in some other manner, as for example by oxosynthesis, Zieglers synthesis, carbon monoxide hydrogenation, etc., some or all of these sulfates being branched if desired.

The hydrophobic radicals present in the FAS, the disalts and the ester salts, of course, may be all the same or different.

In the case of a liquid to pasty wash-active substance combination in accordance with one embodiment of the invention with a total WAS concentration of around 5 to 40, and preferably 10 to 30%, by weight, the range in which a viscosity reduction effectively occurs lies approximately at a quantity ratio of FAS to ester salt and/ or disalt of 1:10 to 10:1; the quantity of the disalts is not to be greater than the quantity of the PAS if no ester salts are present.

The quantity ratio of FAS to ester salt and/or disalt ranges preferably from 8:1 to 1:8, and especially from 4:1 to 1:4, the quantity ratio of ester salt to disalt ranging preferably from 20:1 to 1:10, especially from 15:1 to 1:7, and particularly from 10:1 to 1:4, and the ratio of disalt to FAS being preferably not greater than 8:1, and especially 4: 1, when ester salt is present.

If, in addition to FAS, ester salts and disalts, still other wash-active substances are present, their quantity is to be smaller than that of the FAS, i.e. up to 50% by weight of the FAS content.

The above mentioned further washing active substances which lower the surface tension of the water, include soap and synthetic anionic and/or nonionic products. Suitable substances are the known anionic detergents as alkylated aromatic sulfon-ates, alkylsulfonates, alkyl-glyceryl-ether-sulfonates, fatty acid esters of hydroxysulfonic acids, fatty acid amides of aminosulfonic or aminocarbonic acids, sulfated fatty alcohol polyglycolethers or sulfated alkylphenol polyglycolethers. Suitable nonionic detergents are the polyethylene glycol ethers of fatty alcohols, alkylphenols or polypropylene glycols.

Since the sulfofatty acid salts are very difiicultly soluble, their ability to reduce the viscosities of fatty alcohol sulfate pastes or solutions in accordance with the invention must be considered very surprising. In addition to the ester salts and the disalts, there are indeed other components which, when dissolved in the paste, have an effect on its viscosity. These include particularly inorganic salts, such as the water-soluble washing alkalies, neutral salts, i.e. alkali detergency builder salts, etc., as well as chelate formers, dirt carriers, i.e. soil antiredoposition agents, foam stabilizers, and the like. Nevertheless, the viscosity reduction of the fatty alcohol sulfate pastes or solutions achieved by the addition of ester salts and/or disalts is still retained.

The wash-active substance combinations of the present invention are opaque pastes, or more or less turbid solutions, or even clear solutions, depending upon their concentration and upon the substances dissolved in them. In many cases, turbidity develops only after relatively long storage. This fact is immaterial to the use of the pastes or solutions and does not detract from their usefulness because, for example, when they are used as liquid detergents, they contain either in solution or in suspension still other substances which cause turbidity anyway.

The fatty alcohol sulfates, ester salts and disalts, and any other salt-like wash-activities substances that may be present, may be in the form of sodium salts or in the form of salts of other cations. Such other cations include typically potassium, lithium and ammonium, and also organic bases such as mono, di or triethanolamine. In the manufacture of wash-active substance combinations which contain practically no undissolved components, it may be advantageous to see to it that a plurality of cations are present simultaneously; for example, sodium salts and potassium salts can be used together, or potassium and triethanolamine salts or sodium salts, potassium salts, and triethanolamine salts.

The wash-active substance combinations of the invention may also contain conventional solubilizers. These may be particularly water-soluble oxygen-containing organic solvents, such as monovalent or polyvalent alcohols, ethers of similar or different polyvalent :alcohols, or the partial ethers of polyvalent and monovalent alcohols. These include, for example, the aliphatic monovalent alcohols containing 1 to 5 carbon atoms, glycols with 2 to 5 carbon atoms, dior triethylene glycol, glycerine, polyglycerines and partial ethers of all these polyvalent alcohols wi-th aliphatic monovalent alcohols containing 1 to 4 carbon atoms in the molecule.

On account of their reduced viscosity, the wash-active substance combinations of the invention are especially suitable for the incorporation 'of additional substances such as those used especially in Washing and cleaning. These include the carbonates, orthophosphates, anhydrous phosphates (pyrophosphates, polyphosphates and polymetaphosph-ates) and the silicates of the alkalies, as well as other conventional washing alkalies. Also, the usual organic chelate formers can be incoporated in the preparations of the present invention, as well as foam stabilizers, such as fatty acid amides, fatty alkylol amides, etc., neutral salts, such as sodium sulfate, sodium chloride, sodium nitrate, etc. Moreover, inorganic or organic colloidal substances, water-soluble high-molecular substances, etc., can be added to the concentrates, such as those that serve in the washing process as dirt carriers. In this connection, mention is made of water-soluble salts of polyacrylic acid or polymethacrylic acid, water-soluble derivatives of cellulose or of starch, such as carboxymethylcellulose and ethers of cellulose with oxyalkylsulfonic acids as well as cellulose sulfates.

Liquid wash-active substance combinations with a content of wash-active substances according to the present invention may have approximately the following typical composition:

5-25, preferably 7-20 weight percent of wash-active substance combination.

-45, preferably -30 weight percent anhydrous phosphates or organic chelating agents, preferably pyrophosphates or polyphosphates.

0-6, preferably 2-5 weight percent alkali silicates.

0-5, preferably 0.5-2 weight percent form stabilizers, such as fatty acid amides or fatty acid alkylolamides.

O-lO, preferably 24 weight percent solubilizers.

0-10 weight percent of neutrally reacting, especially inorganic salts, such as Na SO and/or NaCl and/or NaNO Balance: Water (95-55% and preferably 60-80% by weight, less any organic solvent present, such as a Water soluble lower alcoholincluding methanol, ethanol, propanol, or butanol, in an option amount of at most 20% and preferably at most 10% by weight based on the mixture of water and organic solvent).

By varying the formula within the above-stated limits, or by selection of appropriate cations or combinations of cations, liquid washing and cleansing preparations can be made, which contain 'all components in solution or in stable suspension, ie in the form of a wash-active concentrate having a liquid to pasty consistency.

In the specification and claims herein, the numerical data regarding the quantity ratio of FAS to ester salt and/or disalt, when ester salt and disalt are simultaneously present, refer to the total of the amount of ester salt and the amount of disalt present.

Accordingly, the present invention provides a washactive concentrate having a liquid to pasty consistency which comprises a mixture of fatty alcohol sulfate and a member selected from the group consisting of sulfofatty acid salts, sulfofatty acid ester salts, and mixtures thereof, the sulfofatty acid salts containing less than 50% of fatty acid radicals with more than carbon atoms 'and the sulfofatty acid ester salts containing 8 to 24 carbon atoms in the fatty acid radical. Generally, the ratio by weight of the sulfofatty acid salts to the fatty alcohol sulfate is 0.1-1z1, the ratio by weight of the sulfofatty acid ester salts to the fatty alcohol sulfate is 0.ll0:1, and the ratio by Weight of the mixture of the sulfofatty acid salts and ester salts to the fatty alcohol sulfate is 0.1-10z1. Preferably, the mixture of sulfofatty acid ester salts and sulfofatty acid salts is present in the ratio by weight of 0.1-20: l, and the sulfofatty acid salts present contain at least 50% of fatty acid radicals with 12-14 carbon atoms. As for the sulfofatty acid ester salts present, these contain preferably fatty acid radicals with 12-18 carbon atoms and ester radicals in the form of alkyl radicals derived from a member selected from the group consisting of monovalent alcohols with 1-12 carbon atoms in the molecule and polyvalent alcohols with 2-6 carbon atoms in the molecule. The ester radicals are especially useful when in the form of alkyl radicals derived from alcohols which are ether alcohols. Advantageously, the sulfofatty acid ester salts present should contain preferably less than 50% fatty acid radicals with more than 15 carbon atoms, and at most 24 carbon atoms for each sulfonate group present in the molecule.

As for the mixture of sulfofatty acid ester salts and sulfofatty acid salts, the same is present preferably in the ratio by weight of 0.5-2 0'.1 while the ratio by weight of the mixture of sulfofatty acid salts and ester salts to the fatty alcohol sulfate preferably is 0.125-8:l, and the ratio by weight of the sulfofatty acid salts present to the fatty alcohol sulfate is preferably at most 8:1.

As aforesaid, the content of fatty alcohol sulfate is at least as large as the content of any further wash-active substances present in addition to the sulfofatty acid salts and sulfofatty acid ester salts, such further wash-active substances including those conventional substances which lower the surface tension of the water. Also, other components may be present as aforesaid including, inter alia, those substances selected from the group consisting of water-soluable oxygen-containing organic solvents, Washing alkalies, such as alkali carbonates, alkali phosphates, alkali silicates, etc., organic chelate formers, dirt carrier substances, foam stabilizers, neutral alkali salts, and mixtures of the foregoing. The total content of all wash-active substances in the concentrate is preferably between about 5-45% by weight, with the remainder, if desired, being water.

Examples For the manufacture of the liquid or paste wash-active substance concentrates described in the following exampics, the individual components were combined, in the form of their technical raw products, either as aqueous pastes or as dry products, in the percentage composition stated in each case .(all percentages being by weight), adjusted to the desired concentration with water, and completely dissolved by heating. The clear solutions were poured into containers which were sealed and then stored for about three to four weeks. The concentrations thus obtained exhibit structural viscosity; the viscosity of the preparations changes during storage, the change becoming slighter in the course of time, until it becomes negligible after three to four weeks of storage. The change in viscosity is often accompanied by the formation of turbidity, precipitation, loss of homogeneity, etc., which become practically static, too, after three to four weeks. Whenever such turbidity, precipitation or loss of homogeneity had occurred, the solutions were stirred up prior to measuring the viscosity.

The absolute values of the vi-scosities of the wash-active substance concentrates depend more or less greatly on the structure and composition of the starting products used for their manufacture; thus, for example, the salt content of the technical wash-active substances is influential. For this reason, precise comparisons of viscosities are possible only in the case of products which were made from the same starting materials and were treated in the same manner. Such a comparison is possible in the following tables only in the case of products bearing the same eX- Example WAB combmatwn 13 221 y ample number. The variations in the absolute viscosities Substance Weight Percent which can be observed on account of these circumstances are small, however, in comparison with the viscosity re- 2 duction achieved by the invention. To demonstrate this 5 fact, in Examples 6-741 and cl 1a, for instance, the %8 viscosities of concentrates of practically identical compo- 5 sition are given, which were made from different absolute g 17 amounts of fatty alcohol sulfates. 10 4 1 Unless otherwise expressly stated in the following tables, the product identified as PAS was a fatty alcohol 10 sulfate made from a fatty alcohol manufactured by reduction of the C to C fraction of coconut fatty acid; furthermore, all the wash-active substances (WAS) were in the form of sodium salts, and the sulfofatty acid salts were in the form of disalts. The sulfofatty acid salts are identified by the chain length and by an indication of the source of the fatty acids as well as by the addition of the symbol /Di. Accordingly, C /Di signifies the di-salt of a sulfonated C fatty acid, while HPK/Di stands for the disalt of a sulfonated fatty acid made from hydrogenated palm kernel Oil. This method is also applied to the ester salts, in which case the number following the diagonal indicates the chain length of the alcohol. Accordingly, 0 1 signifies the sulfonate of capric acid methyl ester, and C /4 signifies the sulfonate of lauric to NJ to Nab-H H HHv-M- ogogwccnomoommmmmmmomcw mm 5 acid butyl ester, while HPK/ 1 signifies the sulfonate 20 made from hydrogenated palm kernel fatty acid methyl 5;; ester. The hydrogenated palm kernel fatty acid used had 20 77 approximately the following composition: 6 6

5 Laurie acid, approximately 58% Myristic acid, approximately 20% g 16 Palmitic acid, approximately 9% Stearic acid, approximately 13% Z 25 Examples 112 g The viscosities stated in these examples were measured at 20 C. with a Hoeppler viscosimeter. For purposes of comparison, the viscosities of PAS pastes of different concentration are first given:

Viscosities of the aqueous pastes or solutions of FAS which were used for the manufacture of the WAS con- 03 W N N N MN ouuocnouimmso lmmmcimcnsommzow l 0101 WWMMMWMWWWWVW-WWMMWQWWVWWVWWW m centrates: 21. 5

Percent FAS: Viscosity, cp. 5 42 lb HPK2.-- 239 5 1.5 2 HPKiDi The viscosity of a water paste containing 20% PAS 85 and 5% toluene sulfonic acid amounted to 2430 centi poises.

WAS Combination Viscosity Example No. in cp.

Substance Weight Percent 8.8 Examples 13-14 2.5 13,6 1? 5 4 The viscosities of the concentrates described in these 2 examples were not determined with the Hoeppler viscos- 2.5 4.3 7 imeter, but with a rotary viscosimeter according to Drage 2- (Min: Aktiengesellschaft Chemisches Institut, Dr. A; E. 5 i Epprecht, Zurich). The number of the measuring body used is given below in the table. The table also shows 3' 5 4 the viscosities of FAS pastes'without ester salts or di- 20 salts added.

Example WAS Combination Measuring Viscosity No. Body No. in cp.

Substance Wt. Percent Example To manufacture the concentrates described in this example, ester salts or disalts were used, which had been produced from a mixture of one part by weight of hydrogenated stearic acid and two parts by weight of hydrogenated palm kernel fatty acid. The sulfonate of the corresponding methyl ester is designated as HSt-HPK/l, and the salt of the corresponding sulfofatty acid is designated at HSt-HPK/Di. The fatty acid radicals present in these sulfonates were composed 53% of C to C radicals and 47% of C to C radicals. The viscosities of the pastes were measured as described in Examples 13 and 14. For the sake of comparison, the viscosity of the 25% FAS starting paste used to manufacture the blended pastes is stated.

It will be appreciated from the foregoing that the presence of the fatty acid salts and/or sulfofatty acid ester salts of the invention cause a reduction in the viscosity of aqueous preparations containing fatty alcohol sulfate, the reductions being extremely large in most cases, despite variations in the data as between different examples.

Regarding the rotary viscosimeter used in' Examples 13-15, the measuring bodies thereof were mounted on the end of the stirrer shaft such that only a few millimeters clearance was present between the inside wall of the stirring vessel and the periphery of the measuring body. Measuring bodies 1, 20, and 30 were in the shape of a horizontally disposed letter E (anchor stirrer) with the middle vertical arm fastened to the stirrer shaft, the diameters of such bodies being 93, 46, and 23 mm., respectively, and the height of the two outer vertical arms of such bodies being 16, 19, and 19 mm. respectively. On the other hand, measuring body 4 was cruciform in shape with the vertical arm fastened to the stirrer shaft, such vertical arm having a diameter of 5 mm. and a height of 20 mm. while the horizontal arm had a diameter of 3 mm. and a length of 20 mm.

It will be appreciated that the specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention which is to be limited only by the scope of the appended claims.

What is claimed is:

1. Wash-active aqueous concentrate having a liquid to pasty consistency which consists essentially of (a) 5-45% of wash-active substances constituting a mixture of fatty alcohol sulfate having 10-20 carbon atoms and a member selected from the group consisting of tit-sulfofatty acid salts having 8-24 carbon atoms in which less than 50% thereof are a-sulfofatty acid salts having more than 15 carbon atoms, asulfofatty acid aliphatic ester salts having 8-24 carbon atoms in the corresponding a-sulfofatty acid radical and l-12 carbon atoms in the corresponding aliphatic ester radical, and mixtures thereof, in which the ratio by weight of tit-sulfofatty acid salts to the fatty alcohol sulfate is 0.l1:1, the ratio by weight of the a-sulfofatty acid ester salts to the fatty alcohol sulfate is 0.1-1021, and the ratio by weight of the mixture of the tit-sulfofatty acid salts and ester salts to the fatty alcohol sulfate is 0.1-10z1; and i (b) -55% of water. i

2. Concentrate according to claim 1 wherein the mixture of zit-sulfofatty acid ester salts and Ot-SUlfOfatty acid salts is present in the ratio by Weight of 0.1-20: 1.

3. Concentrate according to claim 1 wherein at least 50% of the tic-sulfofatty acid salts are tit-sulfofatty acid salts having 12-14 carbon atoms.

4. Concentrate according to claim 1 wherein the usulfofatty acid ester salts present contain fatty acid radicals with 12-18 carbon atoms and ester radicals selected from the group consisting of alkyl radicals with 1-12 carbon atoms and polyhydric alcohol radicals with 2-6 carbon atoms.

5. Concentrate according to claim 4 wherein the ester radicals are alkyl ether radicals having up to 12 carbon atoms in the alkyl ether moiety.

6. Concentrate according to claim 1 wherein less than 50% of the tat-sulfofatty acid ester salts are a-sulfofatty acid ester salts in the fatty acid radical having more than 15 carbon atoms.

7. Concentrate according to claim 6 wherein the asulfofatty acid ester salts contain at most 25 carbon atoms for each sulfonate group'present in the molecule,

8. Concentrate according to claim 1 wherein the mixture of tit-sulfofatty acid ester salts and a-sulfofatty acid salts is present in the ratio by weight of 0.5-2021, the ratio by weight of the mixture of tit-sulfofatty acid salts and ester salts to the fatty alcohol sulfate is 0.1258:l, and the ratio by weight of the a-sulfofatty acid salts to the fatty alcohol sulfate is at most 8:1,

9. Concentrate according to claim 1 wherein a further substance using in washing and cleaning, and selected from the group consisting of water-soluble oxygen-containing organic solvents, alkali detergcncy builder salts, organic chelate formers, soil antiredisposition agents, foam stabilizers, and mixtures of the foregoing, is also present.

10. Concentrate according to claim 1 wherein all of said salts are salts of cations selected from the group consisting of sodium, potassium, lithium, ammonium, monoethanolamide, diethanolamine, triethanolamine, and mixtures thereof.

11. Concentrate according to claim 10 wherein said onsulfofatty acid salts are monosalts.

12. Concentrate according to claim 10 wherein said u sulfofatty acid salts are disalts.

13. Met-bod of improving the viscosity of a wash-active aqueous concentrate having a liquid to pasty consistency and consisting essentially of fatty alcohol sulfate having 10-20 carbon atoms, which comprises admixing such concentrate with a member selected from the group consisting of tit-sulfofatty acid salts having 8-24 carbon atoms in which less than 50% thereof are int-sulfofatty acid salts having more than 15 carbon atoms, tat-sulfofatty acid aliphatic ester salts having 8-24 carbon atoms in the corresponding a-sulfofatty acid radical and 1-12 carbon atoms in the corresponding aliphatic ester radical, and

mixtures thereof, in a quantity sufficient to provide a resulting wash-active mixture in which the ratio by weight of the a-sulfofatty acid salts to the fatty alcohol sulfate is 0.11:1, the ratio by weight of the a-sulfofatty acid ester salts to the fatty alcohol sulfate is 0.1-10: 1, and the ratio by weight of the mixture of the m-sulfofatty acid salts and ester salts to the fatty alcohol sulfate is 0.1-10z1, and in which theimproved viscosity concentrate consists essentially of 545% of such Wash-active mixture and 95-55% of water, with heating of at least one of the mixture components to dissolve at least some of the resulting mass in the water present.

14. Method according to claim 13 wherein the mixture of a-sulfofatty acid ester salts and u-sulfofatty acid salts is present in the ratio by weight of 0.1-20:1, wherein at least 50% of the u-sulfofatty acid salts are m-sulfofatty acid salts having 12-14 carbon atoms, wherein less than 50% of the a-sulfofatty acid ester salts are u-sulfofatty acid ester salts having more than 15 carbon atoms, wherein the a-sulfofatty acid ester salts contain at most 24 carbon atoms for each sulfonate group present in the molecule, and wherein all of said salts are salts of cations selected from the group consist- References Cited UNITED STATES PATENTS 2,915,473 12/1959 Stirton 252-461 3,101,324 8/1963 Wixon 252-138 10 3,128,294 4/1964 Stirton 252l61 XR FOREIGN PATENTS 1/1962 Canada, 11/1962 Great Britain.

OTHER REFERENCES Surface Active Agents, Schwartz et al., Interscience Publ., New York, 1945, p. 85.

LEON D. ROSDOL, Primary Examiner.

S. D. SCHNEIDER, S. E. DARDEN,

Assistant Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,377,290 April 9, 1968 Werner Stein et a1.

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

Column 6, line 27, "0.S20.l" should read O.S20:l line 40 "soluable" should read soluble Column 8 in the table fourth column, after line 4, insert 4.9 and 3.9 Column 10 lines 38 and 39 cancel "in the fatty acid radical having more than 15 carbon atoms." and insert having more than 15 carbon atoms in the fatty acid radical. line 41, 25" should read 24 Column 12, line 19, "1945" should read 1949 Signed and sealed this 9th day of December 1969 (SEAL) Attest:

Edward M. Fletcher, Jr. I WILLIAM E. SCHUYLER, JR.

Attesting Officer Commissioner of Patents

Claims

1. WASH-ACTIVE AQUEOUS CONCENTRATE HAVING A LIQUID TO PASTY CONSISTENCY WHICH CONSISTS ESSENTIALLY OF (A) 5-45% OF WASH-ACTIVE SUBSTANCES CONSTITUTING A MIXTURE OF FATTY ALCOHOL SULFATE HAVING 10-20 CARBON ATOMS AND A MEMBER SELECTED FROM THE GROUP CONSISTING OF A-SULFOFATTY ACID SALTS AHVING 8-24 CARBON ATOMS IN WHICH LESS THAN 50% THEREOF ARE A-SULOFATTY ACID SALTS HAVING MORE THAN 15 CARBON ATOMS, ASULFOFATTY ACID ALIPHATIC ESTER SALTS HAVING 8-24 CARBON ATOMS IN THE CORRESPONDING A-SULFOFATTY ACID RADICAL AND 1-12 CARBON ATOMS IN THE CORRESPONDING ALIPHATIC ESTER RADICAL, AND MIXTURES THEREOF, IN WHICH THE RATIO BY WEIGHT OF A-SULFOFATTY ACID SALTS TO THE FATTY ALCOHOL SUFATE IS 0.1-1:1, THE RATIO BY WEIGHT OF THE A-SULFOFATTY CID ESTER SALTS TO THE FATTY ALCOHOL SULFATE IS 0.1-10:1, AND THE RATIO BY WEIGHT OF THE MIXTURE OF THE A-SULFOFATTY ACID SALTS AND ESTER SALTS TO THE FATTY ALCOHOL SULFATE IS 0.1-10:1; AND (B) 95-55% OF WATER.