|Publication number||US3415753 A|
|Publication date||Dec 10, 1968|
|Filing date||Jun 18, 1965|
|Priority date||Jun 26, 1964|
|Also published as||DE1254798B|
|Publication number||US 3415753 A, US 3415753A, US-A-3415753, US3415753 A, US3415753A|
|Inventors||Horst Baumann, Werner Stein, Wilfried Umbach|
|Original Assignee||Henkel & Cie Gmbh|
|Export Citation||BiBTeX, EndNote, RefMan|
|Non-Patent Citations (1), Referenced by (23), Classifications (13)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,415,753 LIQUID AND PASTE DETERGENT CONCENTRATES Werner Stein, Erkrath-Unterbach, and Wilfried Umbach and Horst Baumann, Hilden, Germany, assignors to Henkel & Cie, GmbH., Dusseldorf, Germany, a corporation of Germany No Drawing. Filed June 18, 1965, Ser. No. 465,164 10 Claims. (Cl. 252-121) ABSTRACT OF THE DISCLOSURE There is disclosed a novel method for reducing the viscosity of liquid and/or paste detergent concentrates containing an olefin monosulfonate. The process lies in the finding that by incorporating into the paste and/or liquid detergent concentrate a surface active olefin disulfonate the viscosity of the concentrate is significantly reduced and in addition the wetting and cleansing activity of the wash active materials present in the detergent are enhanced. The invention also includes the resultant concentrates characterized by reduced viscosity.
This invention relates to a method and composition for the reduction of the viscosity of liquid or paste detergent concentrates by means of an olefin disulfonate.
Liquid or paste detergent concentrates are not only used in compounded form as liquid washing, cleaning or rinsing agent, but also are regularly used as intermediates in the industrial production of corresponding washing powders. Such concentrates frequently have a high viscosity which makes their industrial utilization difficult, especially their conveyance or admixing with other components, as well as handling them in daily use upon dosaging or diluting with water. These difliculties encountered with high viscosity are particularly noticeable in detergent concentrates containing surface-active monoolefin sulfonates. Surface-active monoolefin sulfonates include sulfonation products obtained from the reaction of aliphatic monoolefins of a chain length of C to C with strong sulfonating agents such as oleum, chlorosulfonic acid or sulfur trioxide followed by hydrolysis, the manufacture of which is described, for instance, in US. Patents 2,061,617 to 2,061,620 and 2,094,- 451.
It has been attempted frequently to improve the viscosity of liquid or paste detergents by adding anionic hydrotropic substances such as the sulfonates of benzene, toluene or xylene. These substances, although they increase the water-sol'ubility of the wash-active substances and materials admixed with detergent solutions or pastes, have only a slight viscosity-reducing effect on the concentrated aqueous pastes; and furthermore, they do not exert any washing or wettingaction in contrast to the surface-active monoolefin sulfonates and disulfonates.
It is therefore an object of this invention to overcome these and other difficulties in addition to providing a method and composition for reducing the viscosity of liquid or paste detergent concentrates. It is a further object of this invention to provide a method and composition for the viscosity-reduction of olefin sulfonates or olefin sulfonates in combination with other wash-active materials. It is a further object of this invention to pro vide a method and composition for facilitating conveying, dosaging, admixing or diluting liquid or paste detergent compositions. It is a further object of this invention to assist the wetting and cleaning action of wash-active materials present in liquid or paste detergent concentrates.
These and other objects have been achieved by the method and composition of the present invention, in
3,415,753 Patented Dec. 10, 1968 which an olefin disulfonate is used to reduce the viscosity of liquid or paste detergent concentrates, especially those concentrates in which an olefin sulfonate is employed. The surface-active olefin disulfonates of this invention cannot only substantially reduce the viscosity of the concentrated solutions and pastes, but it also assists the wetting and cleaning action of the wash-active materials present in the detergent concentrate.
The composition of the present invention comprises liquid or paste detergent concentrates containing monoolefin a-sulfonates of a chain length of C to C and preferably of C to C and at least one other anionic or non-ionic wash-active material characterized by a total content of surface-active, wash-active material of 10 to 60 percent by weight and an amount of 0.5 to 25 percent by weight, preferably 1 to 15 percent by weight of olefin disulfonate referred, in each case, to the Weight of solution or paste. The monoolefin disulfonates, which serve to reduce the viscosity of the aqueous detergent concentrate are characterized by a chain length of C to C and preferably C to C and by two sulfonate groups in the molecule, and are obtained by reacting monosulfonates of monoolefins with sulf-ur trioxide.
The preparation of the monoolefin sulfonates of this invention is effected through sulfonation of monoolefins with S0 or chlorosulfonic acid and subsequent saponification, which is generally described in US. Patents 2,061,617 to 2,061,620 and 2,094,451. By using 0.5 to 1 mol S0 referred to 1 mol of monoolefin, essentially monosulfonates are formed, whereas, by using 2.2 to 2.6 mols S0 referred to 1 mol of monoolefin, disulfonates are almost exclusively formed.
The total concentration of organic wash-active material in the liquid detergent concentrates and pastes of the invention can lie within the range of 10 to 60, and preferably 10 to 50 percent by weight, referred to the weight of the entire solution or paste. The quantitative ratio by weight of olefin sulfonate to olefin disulfonate is advisedly between 20:1 and 1:4, and preferably between 10:1 and 1:2. In the preferred range, the viscosity-reducing action of the olefin disulfonates is particularly effective. The total content of sulfonated and disulfonated olefins in the concentrates should be 5 to 40 percent by weight.
In addition to the olefin sulfonate and olefin disulfonate, the concentrates also contain at least one other anionic or non-ionic surface-active wash-active material such as alkali soaps of fatty acids as well as wash-active materials of the sulfate or sulfonate type, such as primary or secondary alkyl sulfonates, sulfated alkyl polyglycolethers, sulfate alkyl phenol polyglycol ethers, alkyl benzene sulfonate, oz sulfo fatty acid esters, and the like. Suitable non-ionic wash-active materials are alkyl polyglycol ethers, alkyl phenol polyglycol ethers and fatty acid condensation products comprising esters and amides. The amount of such wash-active materials in the concentrates is at least 5 percent by weight and preferably 10 to 45 percent by weight, referred to the weight of the solution or paste.
The olefin monosulfonates, olefin disulfonates and the other anionic wash-active raw materials contained in the concentrates can be used as sodium, potassium or ammonium salts or else as salts of organic bases, such as mono-, dior triethanolamine. The said salts or cations can also be present in mixture, which is frequently ad vantageous for the preparation of highly concentrated clear solutions.
Due to their reduced viscosity, the detergent concentrates in accordance with the invention, are particularly suitable for the incorporation of components and addition substances customarily used in washing and cleaning agents. These include the wash-alkalis such as carbonates and pyro-, polyand metaphosphates, as well as the silicates of alkalis. The known organic chelate formers, e.g., ethylenediamine-tetracetic acid and its equivalents, can also be incorporated in the concentrates of the invention. Finally, organic high-molecular colloid substances, particularly water-soluble derivatives of cellulose or of starch as well as water-soluble salts of polyacrylic acid or polymethacrylic acid can be added to them. If the concentrates are to be used directly as detergent or cleaning agents, they can also contain known solvents, such as monohydric or polyhydric alcohols, polyglycols or polyglycerins. As additional components, there enter into consideration coloring substances and perfumes, optical brighteners, skin-protecting substances and stabilizers.
The following non-limiting examples are given as certain preferred embodiments of the invention and are not to be construed as narrowing the novel viscosity-reducing method and composition.
These examples illustrate the viscosity-reducing efiect of the diolefin s-ulfonates on various detergent concentrates.
Various combinations of olefin disulfonates and olefin sulfonates with wash-active substances are prepared with water and the viscosity of the various combinations measured. The nature of the compositions thus prepared benzene sulfonate being maintained constant in Example II and the concentration of the alkyl benzene sulfonate and of the olefin sulfonate being maintained constant in Example III. From Examples II, VIII and IX, it can be seen that the viscosity of detergent solutions can rise considerably upon the addition of olefin sulfonates. This phenomenon is only partly due to the increase in the concentration of the wash-active material in the solution. For example, the viscosity of the 40-percent alkyl benzene sulfonate solution is 4650 centipoises and that of a 40-percent olefin sulfonate solution is 1100 centipoises. A solution containing percent alkyl benzene sulfonate and 10 percent olefin sulfonate would theoretically have to have, by application of the mixture rule, a viscosity of about 3700 centipoises, as compared to an actually found value of 9000 centipoises. In the same manner as in all other examples, an addition of disulfonate or a replacement of monosulfonate by disulfonate led in this case also to a strong drop in the viscosity of the aqueous detergent solutions, which was not predictable from the viscosities of solutions of the individual wash-actve components of the mixture. The visc-osity-reducng effect obtaned according to the invention, therefore, is synergistic.
and the results obtained are reported in the tables below. EX, 1551, fihfite, i gfilg e, Viscosity m The monoolefin sulfonates and monoolefin disulfonates qggs percent percent used in the following Examples I to IX contain 14 to p 18 carbon atoms in the molecule (average chain length I C and are in the form of sodium Salts. A Na-alkyl 3 20 s 1:660 benzene sulfonate havng an unbranched alkyl chain 58 4 6 3 gg (average chain length C was also used. Th lky II 30 ""16""131:112133113: 9:000 sulfate of Example VI comprises the sodium salt of a 3g 2 g kggg sulfated fatty alcohol of a chain length of C to C1 15 15 670 (average chain length C The Texapon N (regism Z 23 tered trademark) of Examples IV and V is the sodium salt of a coconut fatty alcohol of an average chain length of 12 to m, which is reacted with 2 mols of ethylene Ex. No. ii r t suiiii ri aiie, disgiriiiiirte, Viscosity cp. oxide and thereupon sulfated. The alkyl polyglycol ether percent percent of Examples VII and IX is obtained by addition 0f 3O 2300 10 mols of ethylene oxide to a fatty alcohol of a chain IV 20 10 '260 length of C to C and an iodine number of 50. The 28 2 2 2g sulfo-ester of Example VIII is the sodium salt of an V 10 20 5s a-sulfo-fatty acid methyl ester from hydrogenated palm 2 125 $12 nut fatty acid. The soap of Example IX is a sodium soap of saturated fatty aclds of a cham length of C Olefin olefin to C22 (average chain length C18). Ex. No. sulfate, sulfonate, disulfonate, Viscosity, op.
The viscosity of the aqueous solutions is measured in Percent Parcelt 119mm each case at a temperature of 20 C. after standing for 30 three weeks, by means of a Hoppler drop-ball viscosim- VI gg eter (DIN 53,015) in Examples I, III to V and VII t0 15 5.5 9.5 6.7 XI, and with an Epprecht rotary viscosimeter [I. R. van ,solid Wazer et al., Viscosity and Flow Measurement, Inter- Mk 1 science Publishers, (New York 1963) pp. 129-135] in o1 Olefin Olefind- Examples II and VI. The percentages set forth 1n the Ex. N0 l slflogatg, sulfonatc Viscosity, cp.
1 6D GICGH tables are percentages by weight. percent P P The alkyl benzene sulfonate/olefin sulfonate/olefin d1- sulfonate system is examined in different mixture ratios, VII 32 228 the concentration of the total solution being maintained 3 4 106 constant in Example I, the concentration of the alkyl 5 31 Sulfo- Olefin Olefin di- Ex. No. ester, NazS04, sulionate, sulfonate, Viscosity, cp.
percent percent percent percent 30 10 354 VIII 30 10 5 1, 970 30 10 4 1 1, 490 30 10 2 3 534 Alkyl- Soap, poly- Olefin Olefin di- Ex. No. percent glycol sulfonate, sulfonate, Viscosity, cp.
ether, percent percent percent 3.9 1.4 1 IX a. 9 1. 4 $1228 3.9 1.4 4 1 1,280 3.9 1,4 6 2 940 Thus, there has been described a novel composition and method for reducing the viscosity of liquid or paste detergents by means of an olefin disulfonate comprising from 8 to 24 carbon atoms. These disulfo-nates are particularly effective when used in combination with detergent solutions or pastes that also contain monoolefin sulfonates.
Although the invention has been described with reference to certain preferred embodiments, it is not the intent of the applicant to be limited thereby, and certain modifications of the novel composition and method are intended to be included Within the broad scope of the invention, as embodied in the following claims.
What is claimed is:
1. A paste or liquid detergent concentrate consisting essentially of an wmonoolefin monosulfonate containing 8 to 24 carbon atoms and an a-olefin disulfonate containing 8 to 24 carbon atoms as viscosity reducing agent, said a-olefin disulfonate being present in an amount of from 0.5 to 25% by weight of said detergent concentrate.
2. A paste or liquid detergent concentrate according to claim 1 wherein said u-olefin disulfonate is present in an amount of from 1 to 15% by weight of said detergent concentrate.
3. A paste or liquid detergent concentrate according to claim 1 wherein said a-monoolefin monosulfonate and said OL-OlGfil'l disulfonate each contain 10 to 20 carbon atoms.
4. A paste or liquid detergent concentrate according to claim 1 additionally containing at least one other wash active material selected from the group consist-ing of organic anionic and nonionic detergents, the total amount of monosulfonate and disulfonate and wash active trnaterials present in said concentrate amounting to 10 to 60% by Weight of said concentrate.
5. A paste or liquid detergent concentrate accord-ing to claim 4 wherein the total amount of surface active and Wash active materials amounts to 50% by weight of said concentrate.
6. A paste or liquid detergent concentrate according to claim 4 wherein said a-monoolefin monosulfonate and said a-olefin disulfonate are present in a total amount of 5 to by weight of said concentrate.
7. A paste or liquid detergent concentrate according to claim 4 wherein said a-olefin monosulfonate and said a-olefin disulfonate are present in a ratio of from 20:1 to 1:4 by weight.
8. A paste or liquid detergent concentrate according to claim 4 wherein said u-olefin monosulfonate and said u-olefin d-isulfonate are present in a ratio of from 10:1 to 1:2 by weight.
9. A paste or liquid detergent concentrate according to claim 4 wherein said additional wash active material is at least one member selected from the group consisting of alkali soaps of fatty acids, alkyl sulfates, alkyl polyglycol ether sulfates, alkyl benzene sulfonates, asulfo fatty acid esters, alkyl polyglycol ethers and alkyl phenol polyglycol ethers.
10. A paste or liquid detergent concentrate according to claim 4 additionally including at least one further member selected from the group consisting of alkali metal carbonate, organic chelating agent, a water-soluble derivative of cellulose or starch, water-soluble salts of polyacrylic acid or polymethacrylic acid, a solvent, a perfume, and an optical brightener.
No references cited.
IJEON D. ROSDOL, Primary Examiner.
B. BETTIS, Assistant Examiner.
US. Cl. X.R. 252-138, 161
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,415 753 December 10 1968 Werner Stein et al.
It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
In the heading to the printed specification, after line 8,
insert Claims priority, application Germany, June 26, 1964,
H 53,097 Column 2, line 50, "sulfonates" should read sulfates line 51, "sulfate" should read sulfated Column 3, line 31, "havng" should read having line 52, "XI" should read IX Column 4, lines 22 and 23, "obtaned" should read obtained Signed and sealed this 10th day of March 1970.
WILLIAM E. SCHUYLER, JR.
Edward M. Fletcher, Jr.
Commissioner of Patents Attesting Officer
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3755203 *||Apr 29, 1971||Aug 28, 1973||Jefferson Chem Co Inc||Detergent slurry compositions|
|US3852221 *||Aug 19, 1971||Dec 3, 1974||Jefferson Chem Co Inc||Liquid olefin sulfonate detergent|
|US4003857 *||Dec 17, 1973||Jan 18, 1977||Ethyl Corporation||Concentrated aqueous olefins sulfonates containing carboxylic acid salt anti-gelling agents|
|US4006111 *||Jul 11, 1973||Feb 1, 1977||Lever Brothers Company||Production of alkane: olefin sulfonate mixtures by sequential sulfonation and sulfitation|
|US4139498 *||Dec 16, 1976||Feb 13, 1979||The Lion Fat & Oil Co., Ltd.||Process of manufacturing high-concentration olefin sulfonate solution|
|US4239641 *||Jul 23, 1979||Dec 16, 1980||Basf Aktiengesellschaft||Use of polyhydric alcohols, carboxylic acids, hydroxy-carboxylic acids and/or their esters with polyhydric alcohols as viscosity regulators|
|US4279786 *||Dec 12, 1979||Jul 21, 1981||The Lion Fat & Oil Co., Ltd.||Homogeneous aqueous alpha-olefin sulfonate composition|
|US4532076 *||Oct 19, 1983||Jul 30, 1985||Henkel Kommanditgesellschaft Auf Aktien||Aqueous anionic surfactant concentrates containing viscosity reducing agents|
|US4537253 *||Mar 31, 1983||Aug 27, 1985||Lion Corporation||Micellar slug for oil recovery|
|US4555351 *||Mar 31, 1983||Nov 26, 1985||Lion Corporation||Micellar slug for oil recovery|
|US4556108 *||Mar 31, 1983||Dec 3, 1985||Lion Corporation||Micellar slug for oil recovery|
|US4597879 *||Mar 31, 1983||Jul 1, 1986||Lion Corporation||Micellar slug for oil recovery|
|US4804491 *||Nov 3, 1986||Feb 14, 1989||The Clorox Company||Aqueous based acidic hard surface cleaner|
|US4820448 *||Sep 8, 1987||Apr 11, 1989||Henkel Kommanditgesellschaft Auf Aktien||Surfactant mixtures and their use|
|US4895669 *||Oct 26, 1988||Jan 23, 1990||The Clorox Company||Aqueous based acidic hard surface cleaner|
|US4911238 *||Dec 19, 1988||Mar 27, 1990||Shell Oil Company||Gas flooding with surfactants enriched in olefin disulfonate|
|US4957646 *||Aug 26, 1987||Sep 18, 1990||Shell Oil Company||Steam foam surfactants enriched in alpha olefin disulfonates for enhanced oil recovery|
|US5069802 *||Nov 9, 1990||Dec 3, 1991||Shell Oil Company||Gas flood surfactants enriched in olefin disulfonate|
|US5110487 *||Dec 5, 1990||May 5, 1992||Chevron Corporation||Enhanced oil recovery method using surfactant compositions for improved oil mobility|
|US5446188 *||Mar 12, 1992||Aug 29, 1995||Henkel Kommanditgesellschaft Auf Aktien||Process for the production of highly concentrated fatty alcohol sulfate pastes|
|US5538669 *||Apr 19, 1995||Jul 23, 1996||Henkel Kommanditgesellschaft Auf Aktien||Stabilized surfactant paste|
|EP0243927A2 *||Apr 28, 1987||Nov 4, 1987||Kao Corporation||Liquid detergent composition|
|WO1992016606A1 *||Mar 12, 1992||Oct 1, 1992||Henkel Kgaa||Process for producing highly concentrated fatty alcohol sulphate pastes|
|International Classification||C11D1/37, C11D17/00, C11D1/14, C11D1/02|
|Cooperative Classification||C11D1/143, C11D1/37, C11D17/003, C11D17/0008|
|European Classification||C11D1/14B, C11D1/37, C11D17/00B6, C11D17/00B|