US3413221A

US3413221A - Wash agents

Info

Publication number: US3413221A
Application number: US568677A
Authority: US
Inventors: Gotte Ernst; Stein Werner; Weiss Herbert
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1961-03-01
Filing date: 1966-07-28
Publication date: 1968-11-26
Anticipated expiration: 1985-11-26
Also published as: DE1170573B; DE1170573C2; GB980543A; DE1155556B; GB1022663A; NL292581A; BE632155A; NL275383A; CH455113A; NL136748C; BE614508A; CH417827A

Description

United States Patent 3,413,221 7 WASH AGENTS Ernst Gotte, Dusseldorf-berkassel, Werner Stein, Dusseldorf-Holthausen, and Herbert Weiss, Cologne-Deutz, Germany, assignors to Henkel & Cie, G.m.b.H., Dusseldorf-Holthausen, Germany, a corporation of Germany No Drawing. Continuation of application Ser. No. 171,283, Feb. 5, 1962. This application July 28,

1966, Ser. No. 568,677 Claims priority, appligtlltion Germany, Mar. 1, 1961,

14 Claims. (ci. 252-138) ABSTRACT OF THE DISCLOSURE foam improvement agents, wash alkalis, anhydrous phosphates, perborate, stabilizer therefor, weak acid reacting compounds, and/ or soil removing agents.

This application is a continuation of application Ser. No. 171,283, filed Feb. 5, 1962, now abandoned.

This invention relates to improved wash agent compositions, and more particularly it relates to improved wash agent compositions comprising synergistic mixtures of sulfonated salts of saturated fatty acid esters, sulfated fatty alcohols and/or alkyl benzene sulfonates.

Dialkyl salts of sulfonated fatty acids alone and 1n combination with alkali alkylbenzene sulfonates and/or alkali salts of sulfated fatty alcohols have already been evaluated with respect to their effectiveness as wash agents. The salts of sulfonated fatty acids alone, the salts of alkyl benzene sulfonates, and the salts of the fatty acids alone have been found not to be entirely satisfactory due to their limited solubility at operating temperatures, the ultimate expense to the consumer, their effectiveness as dirt removal agents, etc. In certain instances as, for example, in the case of the combination of long chain alkyl sulfates and alkali salts of sulfonated fatty acids, the mixture has been found to be characterized by synergism.

One of the objects of the invention is the provision of a novel washing agent composition of the type indicated possessing superior properties, making it especially advantageous for use in various laundry applications.

Another object of the invention is the provision of wash-agent compositions which are adapted for use either as fine or boiling wash-agents and which are superior to the wash-agents of the same general type now available.

Another object of the invention is to provide improved wash-agent compositions based on mixtures of sulfonated salts of saturated fatty acid esters, sulfated fatty alcohol and/ or alkyl benzene sulfonates.

Other objects will appear hereinafter.

In accordance with the invention, it has been found that wash-agents having superior properties are obtained by combining a sulfonated salt of a saturated fatty acid ester with a sulfated fatty alcohol and/or an alkyl benzene sulfonate.

The alkyl benzene sulfonates in accordance with the invention are preferably selected so that the alkyl radical contains chain branchings, as a result of which the same are much more slowly decomposed by bacteria in the Birth-Lite;

b.- er.

Patented Nov. 26, 1968 liquid washing medium than are alkyl benzene sulfonates characterized by straight alkyl chains. The alkyl benzene sulfonates, in accordance with the invention, are generally produced by polymerizing propylene, condensing a polypropylene with benzene to obtain the alkyl benzene, and thereafter sulfonating the alkyl benzene. The polypropylene benzene sulfonates having 9-15 carbon atoms in the alkyl radical and in particular having 12 carbon atoms in the alkyl radical have proved especially effective. Generally, at least of the alkyl benzene molecules present in an isomeric mixture possess 12 carbon atoms in'the alkyl radical, and these alkyl benzene sulfonates have come to be called by the term tetrapropylene benzene sulfonate. However, in accordance with the invention, it has been established that, in addition to tetra-propylene benzene sulfonate, alkyl benzene sulfonates, the alkyl component of which exhibits other branchings or alkyl benzene sulfonates the alkyl component of which is of an unbranched nature-i.e., straight chainmay also be satisfactorily used in the compositions of the invention.

The sulfated fatty alcohols used in the present invention are obtainable from saturated or unsaturated, and preferably straight chain fatty alcohols, having l020 and preferably 12-18 carbon atoms in their molecule.

The sulfonated fatty acid ester salts for use in the compositions of the invention are obtained in the known manner, either by the introduction of the sulfonic acid group into the fatty acid radical, followed by esterification of the carboxylic group by means of a monovalent alcohol, or, alternatively, by introducing the sulfonic acid radical into an ester obtained by esterifying a fatty acid by means of a monovalent alcohol. Both of these alternative processes produce esters of sulfonic fatty acids The fatty acids which may be.used are preferably saturated straight chain fatty acids having l0-20, and preferably 12-18, carbon atoms, and the alcohol radical is preferably derived from a monovalent straight chain saturated aliphatic alcohol having 1-10 carbon atoms in its molecule. The starting fatty acid and alcohol are selected with a view that the ester product produced contains at least 11 and, at most, 22 carbon atoms, preferably 13-20 carbon atoms.

The various esters falling within the aforesaid definition are all water-soluble but to different degrees; their solubility decreasing with an increase in the number of carbon atoms present in the molecule. In addition, the washing and the foaming properties of the sulfonated ester salt are dependent on the molecular size. Generally, the general statement may be made that the more readily soluble compounds, i.e., those having a smaller number of carbon atoms, are characterized by a better foaming capacity, while the other ester salts having the larger number of carbon atoms are capable of effecting a better washing. However, the washing and foaming capabilities of the sulfonated ester salts in addition are dependent on the structure of the compound, and specifically the combination of fatty acid and fatty alcohol employed in the esterification, the other materials which are present in the washing medium and, for example, those contributing to the hardness or softness of the water as well as on the temperature of the washing medium. While the more readily soluble sulfonated ester salts are equally suitable for use at room temperature or at slightly increased temperatures as, for example, up to about 50 C., the less readily soluble sulfonated ester salts are advantageously used only at higher temperatures of about S0-l00 C. It is, therefore, advisable in selecting a sulfonated ester salt salt for the combination to suit the compound selected for its intended use.

The sulfonated ester salts of fatty acids having 12-14 carbon atoms and alcohols having 1-4 carbon atoms have been found to be particularly good foam-producing agents while'the sulfonated ester salts of fatty acids having 16- 18 carbon atoms and alcohols having 1-4 carbon atoms, the total number of carbon atoms present in the ester molecule not exceeding 20, demonstrate especially good washing properties. Between the two groups of sulfonated ester salts as above set out are to be found the compounds having foaming and washing properties intermediate those of the two groups and in certain instances as, for example, the sulfonated ester salts of palmitic acid esters of alcohols having 2-4 carbon atoms in the molecule which constitute good foaming as well as good washing agents.

In the preparation of the sulfonated ester salts in accordance with the invention, the fatty acids are generally of natural origin and, in the production of the sulfonated ester salt, the starting fat material is selected on the basis that its fatty acid composition will come closest to that which is required for producing the desired properties in the final sulfonated salt ester.

In preparing sulfonated ester salts characterized by good foaming properties, the fat starting materials which are selected are those whose fatty acid components in the main consist of fatty acids having 12-14 carbon atoms. This fat starting material includes the so-called lauric acid fats" by which is intended the group of fats so termed and further defined in A. E. Bailey: Industrial Oil and Fat Products, New York, 1951, page 121. The most important fats and those of greatest practical significance coming within this definition are enumerated by Bailey at pages 133-138 of the aforesaid publication. In the production of sulfonated ester salts having good washing properties, there may be employed the other natural fats and/or their hydrogenation products, which preferably contain 16-18 carbon atoms. It has been found that the esters of hydrogenated tallow fatty acids are particularly favorable starting materials in this connection.

According to the invention, the combinations are optimally effective when the sulfonated ester component is present in an amount of from 20-90 weight percent of the total synthetic wash-active material, the alkyl benzene sulfonate and/or sulfated fatty alcohol constituting the remainder. The alkyl benzene sulfonate and sulfated fatty alcohol may be present in any desired mixing ratio. Preferably, the sulfonated ester salt is present in an amount of from 35-70 weight percent referred to the combination washing agent.

In many instances, the composition producing optimal effect as regards washing capacity for a specific combination of wash-active substances is also capable of producing the optimal foaming capacity. Such combinations are then advantageously employed in the production of a foaming wash-agent. The foaming quality of such agents may be further improved through the addition of any of the known foaming stabilizers to the composition.

In other combinations, the optimal ranges for superior washing and foaming qualities do not coincide and in such instances as, for example, in the cases of agents characterized by good washing and mediocre to poor foaming properties, the combinations are suitable for the production of low foaming preparations and are particularly advantageously used in washing machines.

A particular advantage and desirable characteristic of the wash-active combinations, in accordance with the invention, are to be found in the fact that the sulfonated ester salts and the sulfated fatty alcohols so far as they are derived from straight-chain fatty alcohols, are excel lently biologically exhausted-i.e., destroyed-in water. As a result, the danger of froth or foam formation on the waste water is substantially eliminated even in con= nection with the use of the combinations of the invention,

which additionally contain the alkyl benzene sulfonates or tetrapropylene benzene sulfonates, both of which are not readily decomposed. The foaming property of the waste water remaining after the washing treatment is therefore not only diminished in that the concentration of the total wash-active substances becomes less with the exhaustion of the sulfonated ester salt but also in that the combination is taken out of the range of optimal composition for improved foaming capacity by the destruction of the sulfonated ester salt which has taken place.

The wash-agent combinations in accordance with the invention are suitable for use per se or in admixture with the conventional products employed in the formulation of wash-agents for use in the washing and bleaching treatment of textiles, and which impart to the preparation. as determined by its intended use, a pH value within the range of 6-12. The pH value is determined using as the test sample a 1% solution of a wash-agent. The pH range extending from 6-12 includes the agents intended as fine wash-agents and which are required to be regulated so as to have a slightly acid to alkaline pHi.e., approximately within the range of 68.5, and preferably within the range of 7-8, as well as the agents intended for use as boiling wash-agents and having a pH value approximately within the range of 9-12 and preferably of from 9.5-1L5.

The wash-agents in accordance with the invention may be employed in conjunction with neutral or alkaline reacting salts, slightly acid reacting compounds, as well as the customary agents used to improve foaming, soil removal, and such additives as bleaching agents, corrosion protection agents, etc.

A neutral reacting salt which is most advantageously used is sodium sulfate, the same additionally acting to improve the effectiveness of the combination in accordance with the invention.

The wash-alkalies which are suitable for use in connection with the invention include the alkali carbonates, alkali-bicarbonates, water-soluble alkali silicates, alkaliorthophosphates, etc.

The combination wash-agent in accordance with the invention may be used to particular advantage in conjunction with the anhydrous phosphates. The anhydrous phosphates employed may be any polyphosphate, such as, a pyrophosphate or metaphosphate, the tripolyphosphates and tetrapolyphosphates having been found to possess particular practical significance. The pyroand polyphosphates are alkaline in reaction and are therefore able, when used alone in boiling wash-agents, to impart to the same the necessary alkalinity. However, the metaphosphates produce a slightly acid reaction and are therefore advantageously utilized in the production of fine wash-agents serving to decrease the pH value of the resulting combination. Examples of other phosphates suitable for the same purpose include the acid orthophosphates and the acid pyrophosphates. Weak inorganic or organic acids or acid salts of strong inorganic acids, such as, for example, boric acid, citric acid, oxalic acid, lactic acid, glycolic acid, tartaric acid, and amido-sulfonic acid, are instances of other materials suitable for use in regulating the pH value of the washing agent.

Still further, the preparation in accordance with the invention may be used in combination with the other ordinary substances as are used in wash-agents. These substances include inorganic or organic active oxygen carriers, as, for example, the percompounds and, in particular, sodium perborate. Products functioning to improve the soil removal property and foaming qualities of the combination wash-agent are additionally included in the preparation of the wash-agent. Instances of substances serving to improve the soil removal capacity of the wash-agent include water-soluble colloids, and preferably those of an organic nature, as, for example, the water-soluble salts of polymeric carbon acids, sizes, gelatin, salts of ether carbon acids or ether sulfonic acids of starch or cellulose, or salts of acid sulfuric acid esters of cellulose or starch. Additives for improving the foaming capacity of the wash-agent combination of the invention include fatty acid amides which may be substituted at the nitrogen atom with alkylor alkylol-radicals having at most 6 carbon atoms per radical, as well as the addition products of ethylene oxide to these unsubstituted or substituted fatty acid amides.

The salts which may be added to the wash-agents in accordance with the invention may be derived from inorganic or organic alkalies as, for example, from sodium, potassium or fiom the easily soluble organic amines. Such salts include alkylol amines, for example, mono, di, or triethanolamine. The easily soluble salts which may be used in conjunction with the wash-agent combination of the invention include wash-active organic sulfates or sulfonates, such additions being particularly valuable in the production of the wash-agents to be used in paste or liquid form.

It can be appreciated that it is generally desirable in compounding wash-agent preparations so that, in s;ite of the high concentration of active material, they do not form precipitates readily. To this end it is advisable to use, in connection with the additions, anions which are already present in the wash-agent, although similar thought has to be given to the anionic wash-active additives as they are advantageously added in the form of their readily soluble salts with inorganic or organic cations. It is, therefore, advisable to provide, in many instances, for the presence of various cations in the washing combination, paving the way for satisfactory further additions.

It has been found advantageous to include in the final preparations certain solving agents as exemplified by the hydrotropic materials of the type of toluene or' xylene sulfonates and, in addition, water-soluble organic solvents. The water-soluble organic solvents which are particularly suitable are those having boiling points above 100 C., such as, for example, the ethers or polyethers of polyvalent alcohols and the partial ethers of polyvalent and monovalent alcohols. Instances of suitable solvents include tri-, tetraor polyethyleneglycol, polyglycerins, the partial ethers of ethyleneglycol, propyleneglycol, glycerin, and aliphatic monovalent alcohols having 1-4 carbon atoms.

The wash-agents, in accordance with the invention, as has already been noted, are suitable for use alone or in combination with various additives, instances of which have been set forth. Additionally, the agents or the compositions containing the same as active ingredients, can be employed in the solid form (powder or lumps), as pastes or creams or in the form of their solutions.

In order to enable those skilled in the art to even more fully appreciate the nature of the invention, the following examples are given as illustrative of specific embodiments of the invention. It will be understood that they are given by way of example only, in order that those skilled in the art will have a clearer picture of how the invention may be successfully practiced, and are not to. be construed as limiting the invention in any way. Thus, for example, the proportions of the components, the temperature of the washing medium, the additions, etc., and other conditions, may be varied without departing from the scope of the invention as defined in the appended claims.

The results described in the examples were obtained in laboratory tests in which the wash-active combinations, in accordance with the invention-the components being present as sodium salts-were studied using two different kinds of laundry as test matteri.e., that conventionally designated fine laundry and a more heavily soiled cotton laundry conventionally designated boiling laundry. These two types of laundry present different soil removal problems and wash-active agents effective with one are not necessarily effective with the other. In the fine laundry tests, wool soiled with a skin secretion was washed employing therefor a bath ratio of 1:40.

Further conditions employed in the laundering tests are set forth as required in the examples. In connection with such conditions, there are noted, for the same, in the examples, those combinations of the wash-active substances which under such established conditions are possessed of good washing activity (cleaning properties) and/or good foamingproperties-that is, in which the eflect reported was at least as great but preferably greater, i.e., over that of the effect alone of the most important component of the wash-active combination and the optimal range within which a clearly synergistic effect could be recognized and, specifically, in which the effect of the combination considerably exceeded the sum of the individual components effects. In considering the ranges of a good or optimal effect, as indicated in the examples, it must be taken into account that the same are to a degree dependent on the conditions of use of the wash-agents as, for example, on the concentration, degree of water hardness, further constituents of the wash-agent, etc.

The tests were carried out using as wash-agents, agents in which the wash-active substance was only present in combination with sodium sulfate, in order that the effect of the wash-active substance as far as possible be unaffected by the effect of any of the other possible washagent additions.

By the term wash-agent there is intended the technical more or less pure wash-active substance combinations which, as a result of their manufacture, still contain slight amounts of sodium sulfate as well as the products which have been processed to completion, as, for example, by addition thereto of the conventional wash-agent additions and which qualify as fine or boiling wash-agents. In the case of the fine wash agents, sodium sulfate may be present in large quantities since the same consists in the effect of the wash-active substance or substances. In certain instances the washing effect of the fine wash-agent can be increased by replacing the sodium sulfate by magnesium sulfate and particularly if the magnesium sulfate which is added is not brought into precipitation by the other wash-agent components.

The wash-agents in accordance with the invention have approximately the following composition:

5-75 weight percent and preferably 10-35 weight percent of a wash-active combination in accordance with the invention;

0-20 weight percent and preferably 1-5 weight percent of a foam stabilizer; the same must not however amount to more than 50 weight percent referred to the total amount of synthetic anionic wash-active substances of the sulfate or sulfonate-type present;

0-70 weight percent and preferably 10-50 weight percent of wash alkalis;

0-70 weight percent and preferably 5-40 weight percent of anhydrous phosphates;

0-3.5 weight percent and preferably 0-3 weight percent of an active oxygen material present as any of the conventional active oxygen carriers as, for example, a percompound;

0-15 weight percent and prefarbly 3-10 weight percent of a sabilizer for the active oxygen compound;

0-20 weight percent and preferably 0-10 weight percent of a slightly acid reacting compound;

0-2 weight percent and preferably 0.2-1.5 weight percent of an additive or additives serving as soil removal agents.

It is, of course, to be understood that the wash-active combinations of the invention may be used in other concentrations and proportions than are indicated in the examples and that it is not intended to limit the invention to those values as set out in the examples. Preferably, the

7 range of concentration of the wash-active combination lies beween 0.3- g./l. and most preferably within the range of 0.5-2 g./l.

Example 1 Wash-agent composition:

33 weight percent of a mixture of tetrapropylene benzene sulfonate and a sulfonated palmitic acid ethyl ester salt;

67 weight percent Na SO Conditions of use:

1 g./l. agent in water of German hardness and having a temperature of 40 C.

Good or optimal foaming capacity at:

30-70 (40-60) weight percent sulfonated fatty acid acid ester salt.

Example 2 A wash-agent of the type as set out in Example 1 and under the working conditions therein indicated is utilized with good or optimal washing capacity it the sulfonated palmitic acid ethyl ester salt is replaced by the following sulfonated ester salts:

-90 (20-50) weight percent of the sulfonated ester salt of palmitic acid methyl ester; 20-90 (-90) weight percent of the sulfonated ester salt of palmitic acid isopropyl ester; 40-90 weight percent of the sulfonated ester salt of palmltic acid butyl ester;

20-95 (30-90) weight percent of the sulfonated ester salt of stearic acid ethyl ester;

-95 (-90) weight percent of the sulfonated ester salt of stearic acid isopropyl ester.

Example 3 Wash-agent composition:

30 weight percent of a mixture of a sulfated C -C fatty alcohol and a sulfonated palmitic acid butyl ester salt;

70 weight percent Na SO Conditions of use:

1 g./l. of wash-agent in water having 20 German hardness and a temperature of 40 C. Good or optimal washing capacity:

20-90 (30-80) weight percent of sulfonated ester salt.

Example 4 Wash-agent composition:

24 weight percent of a mixture of tetrapropylene benzene sulfonate, a sulfated C -C fatty alcohol, and the sulfonated ester salt of a hydrogenated palm kernel fatty acid isopropyl ester;

42.6 weight percent Na P O 6.7 weight percent Na O.3.3SiO

26.7 weight percent Na SO Conditions of use:

1 g./l. wash-agent in permuted water having a temperature of 40 C.

Optimal foaming properties using as source of soiling of the cloth a skin secretion:

10-30 (15-25) weight percent of sulfonated ester salt;

65-45 (60-50) weight percent of fatty alcohol sulfate:

15-45 (25-35) weight percent of tetrapropylene benzene sulfonate.

Example 6 Wash-agent composition:

20 weight percent of a mixture of a sulfated C -C fatty alcohol and the sulfonated ester salts of the methyl esters of a hydrogenated tallow-fatty acid and a hydrogenated palm kernel fatty acid;

weight percent Na SO Conditions of use:

1.5 g./l. of wash-agent in water having a 10 German hardness and a temperature of 40 C. Good or optimal washing capacity:

8-43 (18-27) weight percent of fatty alcohol sulfate;

57-92 (73-82) weight percent of the sulfonated ester salt of hydrogenated tallow fatty acid methyl ester;

0-16 (0-2 weight percent of the sulfonated ester salt of hydrogenated palm kernel fatty acid methyl ester.

Good or optimal foaming capacity:

13-l9 (17) weight percent of fatty alcohol sulfate; 20-57 (31-33) weight percent of sulfonated ester salt of hydrogenated tallow fatty acid methylester; 38-67 (49-51) weight percent of sulfonated ester salt of hydrogenated palm kernel fatty acid methylester.

As the ranges in which good or optimal foaming capacity are obtained do not overlap in this example of wash-active combination, it is advantageously applied in the production of wash-agents characterized by low foaming capacity.

Example 7 Wash-agent composition:

20 weight percent of a mixture of a sulfated C -C fatty alcohol and the sulfonated ester salts of the hydrogenated ethylesters of a tallow fatty acid and a palm kernel fatty acid;

80 weight percent Na SO Conditions of use:

5-51 (5-48) weight percent fatty alcohol sulfate;

45-88 (52-85) weight percent of the sulfonated ester salt of hydrogenated tallow fatty acid ethylester;

0-45 (0-25) weight percent of the sulfonated ester salt of hydrogenated palm kernel fatty acid ethylester.

Within the range which has been indicated for optimal washing capacity, the optimal foaming capacity is to be found in the following compositions:

15-25 weight percent fatty alcohol sulfate; 55-65 weight percent sulfonated ester salt of hydrogenated tallow fatty acid ethylester; 15-25 weight percent sulfonated ester salt of hydrogenated palm kernel fatty acid ethylester.

Example 8 Wash-agent composition:

30 weight percent of a mixture of tetrapropylene benzene sulfonate, a sulfated G -C fatty alcohol and equal parts by weight of q-sulfonic acid salts of hydrogenated tallow fatty acid ethylester and of hydrogenated palm kernel fatty acid ethylester;

70 weight percent Na SO Conditions of use:

1.5 g./l. of wash-agent in water having a 10 German hardness and a temperature of 40 C. Good or optimal. washing and foaming capacity:

9 37-80 (43-62) weight percent tetrapropylene benzene sulfonate; -38 (0-27) weight percent fatty alcohol sulfate; 15-54 (28-40) weight percent sulfonated ester salt.

Example 9 The foaming properties of two wash-agents having the following general composition were determined according to the procedure hereinafter set out:

The remainder consisting of sodium sulfate and water.

Normally soiled household laundry was washed for 15 minutes in a rotating vane-type of laundry machine employing, as washing medium, a bath having a concentration of 4 g./l. of wash-agent in water having 16 German hardness and which had been heated to a temperature of 90 C. In each run 4 liters of the washing medium which had been used in the run were removed following completion of the washing. The used washing medium withdrawn at a temperature of 80, 60, 40, and 25 C., respectively, was permitted to flow from a vessel having an outlet of 3.25 mm. clear width within 4 minutes from a height of 80 cm. into a cylindrical vessel having a diameter of 21.5 cm. The quantity of foam which was formed as a result in the collecting vessel was measured immediately, and at subsequent intervals of 1, 3, 4, 5, and 10 minutes and the heights of the foam recorded in each instance added together. The sum thereby obtained constitutes a good gauge for the foaming properties of the solution being measured under conditions closely paralleling those in actual practice. It takes into consideration the initial foaming capacity as well as the foam stability. The two washing agents which were tested both contained 20 weight percent of wash-active substance, in one instance, the wash-agent consisted of 16 weight percent .tetrapropylene benzene sulfonate and 4 weight percent of a sulfated C t-C fatty alcohol, while, in the other instance, the tetrapropylene benzene sulfonate had been replaced by one-half by a sulfonated hydrogenated palm kernel fatty acid methylester. The latter washing agent was superior in the foaming properties observed to the agent which contained only the tetrapropylene benzene sulfate.

Example 10 Wash-agent composition:

30 weight percent of a mixture of a sulfated C -C fatty alcohol and the sulfonated ester salt of the ethylester of a hydrogenated palm kernel fatty acid; 50 weight percent Na SO 20 weight percent Na P- .O-,. Conditions of use:

1.5 g./l. of wash-agent in water having a 10 German hardness and a temperature of 40 C. Good optimal washing capacity:

23-90 (40-80) weight percent of sulfonated ester 1.. As the sulfonated ester salt used herein displays an excellent foaming behavior, a good or optimal foaming capacity is limited to the comparatively narrow range of 2 390 (60-70) weight percent of sulfonated ester Example 11 Wash-agent composition:

30 weight percent of a mixture of a sulfated C -C fatty alcohol and the sulfonated ester salt of the ethyl ester of a hydrogenated tallow fatty acid; 50 weight percent Na,so,-,

20 weight percent Na P O Conditions of use:

1.5 g./l. wash-agent in water having a 10 German hardness and a temperature of 40 C. Good or optimal washing and foaming capacity:

30-90 (40-60) weight percent of sulfonated ester salt.

Example 12 Wash-agent composition:

30 weight percent of a mixture of a sulfonated ester salt of a hydrogenated palm kernel fatty acid ethyl ester with an alkyl benzene sulfonate, the alkyl COmPOl'lCjli of which is substantially unbranched and which may be, for example, derived by carbonmonoxide hydrogenation of a C -C hydrocarbon fraction, followed by chlorination, condensation with benzene, and sulfonation of the alkyl benzene, or, alternatively, by condensing a corresponding fraction of an essentially straight-chain olefin, obtained from a natural source, condensing the same with benzene, and sulfonating the alkyl benzene condensation product. Alkyl benzene sulfonates thus produced are characterized by a content of compounds having 12 and 13 carbon atoms in the alkyl radical of more than 50%. 70 weight percent sodium sulfate.

Conditions of use:

1.5 g./l. wash-agent in water of 10 German hardness and having a temperature of 40 C.

Good or optimal washing capacity:

10-60 (25-35) weight percent sulfonated fatty acid ester salt;

Good or optimal foaming capacity:

20-90 (45-55) weight percent sulfonated fatty acid ester salt.

Example 13 Wash-agent composition:

30 weight percent of a mixture of the sulfonated ester salt of a hydrogenated tallow fatty acid ethyl ester with an alkyl benzene sulfonate as described iri Example 12.

70 weight percent of sodium sulfate.

Conditions of use:

Good or optimal washing capacity:

20-90 (45-55) weight percent ester salt;

Good or optimal foaming capacity:

5-25 (10) weight percent sulfonated fatty acid ester salt.

What is claimed is:

1. A washzagent consisting essentially of:

(1) as first component, about 20-90 weight percent of a sulfonated fatty acid ester salt constituting the salt of an'ester of a saturated fatty acid having from 10-20 carbon atoms and a saturated monovalent aliphatic alcohol having 1-10 carbon atoms, c0ntain ing the sulfonic acid group in the fatty acid radical and having the formula SOs wherein R-CH-COO designates the fatty radical and R the monovalent aliphatic alcohol radical, and

(2) as second component, about -10 weight percent of at least one member selected from the group consisting of sulfated fatty alcohols having 10-20 carbon atoms in the alkyl radical and alkyl benzene sulfonates having 9-15 carbon atoms.

2. A wash agent according to claim 1 additionally containing sodium sulfate up to 80 percent of the total mixture.

3. A wash agent according to claim 1, wherein said sulfonated fatty acid sulfonated ester salt is present in an amount of between about 35 and 70 weight percent based on the weight of the sulfonated ester salt together with said second component.

4. A wash agent according to claim 1, the 1 percent aqueous solution of which has a pH of 6-12.

5. A wash agent according to claim 1, wherein the total number of carbon atoms in said sulfonated ester salt does not exceed 20.

6. A wash agent according to claim 1, wherein said sulfonated ester salt has 13-20 carbon atoms.

7. A .wash agent according to claim 1, wherein said alkyl benzene sulfonate is tetrapropylene benzene sulfonate and said sulfated fatty alcohol has 12-18 carbon atoms.

8. A wash agent according to claim 1, wherein said sulfonated ester salt constitutes the esterification product of a saturated fatty acid derived from the lauric acid fat group with a staturated monovalent aliphatic alcohol having 1-4 carbon atoms.

9. A wash agent according to claim 1 having improved foaming properties in which said sulfonated fatty acid ester salt constitutes the salt of an ester of a saturated fatty acid having from 12-14 carbon atoms and a saturated monovalent aliphatic alcohol having 1-4 carbon atoms.

10. A wash agent according to claim 1 having improved washing properties and a low foaming capacity in which said sulfonated fatty acid ester salt constitutes the salt of an ester of a saturated fatty acid having from 16- 18 carbon atoms and a saturated monovalent aliphatic alcohol having l-4 carbon atoms.

11. A wash agent according to claim 1 containing 33 weight percent of a mixture of tetrapropylene benzene sulfonate and a sulfonated palmitic acid ethyl ester salt', and

67 weight percent of sodium sulfate.

12. A wash according to claim 1 containing 30 weight percent of a mixture of a sulfated cur-C fatty alcohol and a sulfonated palmitic acid butyl ester salt; and

70 weight percent sodium sulfate.

13. A wash agent according to claim 1 containing 30 weight percent of a mixture of tetrapropylene benzene sulfonate, a sulfated C -C fatty alcohol, and a sulfonated ester salt of palmitic acid butyl ester; and

70 weight percent of sodium sulfate.

14. A wash agent according to claim 1 in the form of a mixture in which said first and second components together constitute (a) -75 weight percent thereof with 12 the remainder of (b) 25-95 weight percent being composed of (i) 0-20 weight percent of a foam improving agent selected from the group consisting of fatty acid amides and their addition products with ethylene oxide,

(ii) 0-70 weight percent of a wash alkali selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, and alkali metal silicates,

(iii) 0-70 weight percent of an anhydrous alkali metal phosphate selected from the group consisting of ortho phosphates, and polyphosphates,

(iv) 03.5 weight percent of an alkali metal perborate compound constituting an active oxygen carrier, (v) 0-15 weight percent of MgSiO, as stabilizer for said active oxygen carrier compound,

(vi) 0-20 weight percent of a weak acid reacting compound selected from the group consisting of'boric acid, citric acid, oxalic acid, lactic acid, glycolic acid, tartaric acid, amido-sulfonic acid, and acid salts of strong inorganic acids, and

(vii) 0-2 weight percent of a soil removing agent selected from the group consisting of water-soluble sizes, gelatin, salts of ether carboxylic acids of cellulose, salts of ether carboxylic acids of starch, salts of ether sulfonic acids of cellulose, salts of ether sulfonic acids of starch, salts of acid sulfuric acid esters of cellulose and salts of acid sulfuric acid esters of starch.

References Cited UNITED STATES PATENTS 2,043,476 6/1936 Guenther et al. 260-400 2,303,212 11/1942 Kjse et al 252-121 2,460,968 2/1949 Bert et al. 260400 2,806,044 9/1957 Weil et al. 260-400 2,876,200 3/1959 Strain et al 252-99 X 2,972,583 2/1961 Hewitt 252-152 X 3,338,838 8/1967 Wilson 252-161 OTHER REFERENCES Stirton et al., Surface Active Properties of Salts of Alpha-Sulfonated Acids and Esters, J. Amer. Oil. Chem. Soc., vol. 31, p. 13, 1955. Library of Congress TP 1.05 (4 pages).

The Condensed Chemical Dictionary, 7th edition, Rose, Reinhold, New York, 1967, pp. 874, 867, 868.

LEON D. ROSDOL, Primary Examiner.

S. E. DARDEN, Assistant Examiner.

gg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,413,221 Dated November 26, 1968 Patent No.

Inventor) Ernst Gotte, Werner Stein and Herbert Weiss It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

' Column 10, line 70, cancel "in the alkyl radical"; line 71, after "atoms" and before the period insert --in the alkyl radica1 SIGNED AND SEALED EB3 4979 (SEAL) I Am mum: E. sum. 33. EdwardMFletchmI Gommissioner of Patents Attesting Officer