US3332876A - Detergent composition - Google Patents

Detergent composition Download PDF

Info

Publication number
US3332876A
US3332876A US561374A US56137466A US3332876A US 3332876 A US3332876 A US 3332876A US 561374 A US561374 A US 561374A US 56137466 A US56137466 A US 56137466A US 3332876 A US3332876 A US 3332876A
Authority
US
United States
Prior art keywords
alkyl
sulfonate
carbon atoms
detergent
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US561374A
Inventor
Walker Arthur Polden
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to GB1050848D priority Critical patent/GB1050848A/en
Priority to CA776614A priority patent/CA776614A/en
Priority to FI2285/65A priority patent/FI44927B/fi
Priority to FR34851A priority patent/FR1457000A/en
Priority to CH1413365A priority patent/CH485842A/en
Priority to AT931665A priority patent/AT257784B/en
Priority to BE670913D priority patent/BE670913A/xx
Priority to DE19651467663 priority patent/DE1467663A1/en
Priority to DK526865AA priority patent/DK127071B/en
Priority to NL6513298A priority patent/NL6513298A/xx
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US561374A priority patent/US3332876A/en
Application granted granted Critical
Publication of US3332876A publication Critical patent/US3332876A/en
Priority to US27096D priority patent/USRE27096E/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • This invention relates to detergent compositions having outstanding sudsing and detergent properties, based on synergistic ternary mixtures of olefin sulfonates, alkyl benzene sulfonates and alkyl ether sulfates.
  • olefins having a free hydrogen atom on a carbon in the alpha-position can be sulfonated directly using vigorous sulfonating agents.
  • the sulfo radical attaches to the terminal carbon atom and the double bond remains intact, but may migrate from the alpha position.
  • the olefins have suitable molecular weight,
  • the sulfonates have detergent properties.
  • ternary mixtures of olefin sulfonates, alkyl aryl sulfonates and alkyl ether sulfates are synergistic, and have sudsing and cleaning power better than would be expected from a knowledge of their performance when used alone, and, in particular, better than would be expected from a knowledge of the performance of binary mixtures, especially mixtures of alkyl benzene sulfonates and alkyl ether sulfates, without the third component, and of the third component alone.
  • a detergent composition comprising a synergistic ternary mixture of (A) an olefin sulfonate having 12 to 16 carbon atoms in the molecule, (B) an alkyl benzene sulfonate having an alkyl chain containing 10 to 18 carbon atoms and (C) an alkyl ether sulfate having the formula RO(C H O),,SO M wherein R is an alkyl chain having 10 to 18 carbon atoms, x is l to 5, and M is a cation.
  • olefin sulfonates is used herein to mean compounds which can be produced by the sulfonation of alpha olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have .been formed in the reaction are hydrolysed to give the preferably 12 to 14 carbon atoms. Preferably, they are straight chain olefins. Olefin sulfonates having more than 16 carbon atoms do not give the desired high lathering performance in the mixtures according to the invention; those with fewer than 12 carbon atoms having reduced detergent properties.
  • the olefin sulfonates 3,332,876 Patented July 25, 1967 ice may contain minor amounts of other materials, arising from impurities in the original olefin stock and from side reactions during the sulfonation process.
  • a preferred embodiment of the present invention is the use herein of the olefin sulfonate compositions which are described completely in a patent application Ser. No. 516,139, filed Dec. 23, 1965, by Phillip F. Pflaumer and Adriaan Kessler and titled, Detergent Composition.
  • the alkyl aryl sulfonates are preferably alkyl benzene sulfonates, and the alkyl chain preferably has 12 to 16 carbon atoms.
  • the alkyl chain may be derived, for example, from branched or straight chain olefins, such as tetraor penta-propylene polymers or mixtures thereof, straight chain alpha-olefins obtained from petroleum cracking or by the polymerization of ethylene, or from halogenated paraffins.
  • An alkyl chain which is a straight chain containing 12 carbon atoms is generally very suitable.
  • the alkyl ether sulfates can be made by the condensation by known methods of ethylene oxides on to monohydric alcohols having 10 to 18 carbon atoms.
  • R has 12 to 14 carbon atoms.
  • the alcohols may be derived from fats, e.g., coconut oil, or they may be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred. Such alcohols are reacted with 1 to 5, and especially 3, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
  • the cation in the case of all the detergent ingredients may be alkali metal, ammonium or a substituted ammonium radical, or (as further explained below) may be in part magnesium, or may be an alkaline earth metal. It may be a mixture of any two or more of these.
  • olefin sulfonates While the addition of even small amounts of the olefin sulfonates to any mixtures of the alkyl aryl sulfonates and the alkyl ether sulfates provides synergistic. mixtures, preferred mixtures comprise 5 to of the olefin sulfonate, by weight of the ternary mixture and to 25% of a mixture comprising the alkyl aryl sulfonate and the alkyl ether sulfate in a ratio from 9:1 to 3:7 by Weight.
  • ternary mixtures containing 5 to 50% of the olefin sulfonate, and 95 to 50% of a mixture of the alkyl aryl sulfonate and the alkyl ether sulfate in a ratio of from 8.5 :15 to 1:1 by Weight.
  • the synergistic properties of the ternary mixtures of the invention are most marked when the compositions are used in hard water. Accordingly, where they may be used in soft water, it is advantageous to include some of a source of water hardness in the composition. This may be done by including a source of magnesium ion in the composition, either by adding a soluble magnesium salt, such as the sulfate or chloride or by incorporating one of the detergent ingredients at least partly in the form of its magnesium salt.
  • compositions may contain any of the other ingredients usual in detergent compositions such as alkaline builder salts, bleaches, optical brighteners, sequestering agents, soil suspending agents, colors, perfumes, bacteriocides and the like.
  • Other organic detergents may be present in minor proportions provided that they do not impair the performance of the ternary mixture of the invention.
  • lather stabilizers while usually unnecessary, may be added; examples are fatty acyl ethanolamides, especially lauric monoethanolamide.
  • the ternary mixtures are useful in solid, pasty or liquid detergent compositions, and are particularly well suited to liquid ones.
  • liquid compositions they are dispersed or dissolved in a liquid medium, preferably water, optionally containing solubilizing agents such as lower monohy'dric alcohols having 1 to 4 carbon atoms, or hydrotropic salts such as toluene or xylene sulfonates, etc.
  • a frame was provided in which a number, for example six, 500 ml. cylinders could be placed and rotated about an axis perpendicular to their long axis.
  • a solution of the detergent composition in water at 115 F. the concentration being selected according to the information required from the test.
  • 3 ml. of a standard soil load namely, a liquid edible shortening based mainly on marine oils.
  • the cylinders were then rotated in the frame for 1 minute at 20 r.p.m. They were then stood upright, the stoppers were removed, and the lather height above the clear liquid was measured. A further addition of 3 ml. of the soil was made and the procedure was repeated until substantially no lather remained.
  • the sum of the measured lather heights is reported as the lather height.
  • Example I Several diflerent liquid detergent compositions were made, each containing a total of 40% by weight of active detergent consisting of olefin sulfonates derived from alpha-olefin having 14 carbon atoms, tetra-propylene alkyl benzene sulfonate, and coconut alkyl trie-thylene glycol ether sulfate, all in the form of their sodium salts.
  • the proportions of these components in each composition are indicated in the table below.
  • the remainder of each composition consisted primarily of water, containing sufficient solubilizing agent (lower alcohol and, if necessary, hydrotrope) to give a homogeneous composition.
  • Each composition was dissolved in hard water (18) to give a solution containing 0.26% of the composition, and tested for lather power by the method described above. The results are given in the following table:
  • compositions f and g were according to the invention, the others being .included for comparison.
  • Composition 1 had better lather power than the best binary mixtures e.
  • Composition g had better lather power than would be expected of a 1:1 mixture of half the detergent ingredients of compositions a and d, which would have the same formula.
  • compositions according to the invention had excellent detergent properties.
  • Example II Composition Olefin Lather Serial sulfonate Height Allryl benzene Alkyl ether (Inches) ulionate Sulfate 40 0 O 7. 55 0 40 0 2. 00 0 0 40 2. 33 0 2O 20 9. 56 10 20 10 10. 81 20 10 1O 10. 87
  • compositions e and 1 were according to the invention, the others being included for comparison. Both e and f had better lather power than was provided by the best binary mixture of alkyl benzene sulfonate and alkyl ether sulfate, composition d. Moreover, composition 1 had better lather power than would be expected of a 1:1 mixture of half the detergent ingredients of compositions a and d, which would have the same formula.
  • compositions according to the invention had excellent detergent properties.
  • the ternary mixture may be used in any desired proportion. If the proportion is very small, for example less than 10% by weight of the composition, then inconveniently large amounts of the composition may have to be transported and used in order to achieve a given amount of cleaning. If the proportion is very great, then there may not be sufficient place for all other desired ingredients of the composition (such as builder salts in the case of solid compositions), or it may be difiicult to achieve a stable composition (in the case of liquid compositions). Suitable proportions of the ternary mixture will often be found to be within the range from 10 to 60%, by weight of the composition. Proportions within the range from 20 to 50% are preferred for liquid compositions.
  • a detergent composition consisting essentially of a synergistic ternary mixture of (A) a straight chain monoolefin sulfonate having 12 to 16 carbon atoms in the molecule, (B) an alkyl benzene sulfonate having an alkyl chain containing 10 to 18 carbon atoms and (C) an alkyl ether sulfate having the formula RO(C H O) SO M wherein R is an alkyl chain of 10 to 18 carbon atoms, x is a value from 1 to about 5, the cation of said sulfonate compounds and the cation M of said sulfate compound being selected from the group consisting of alkali metal, ammonium, magnesium and alkaline earth metal, the proportion of said mono-olefin sulfonate being from about 5 to 75% of the ternary mixture and to 65% of a mixture of said alkyl aryl sulfonate and said alkyl ether sulfate in
  • a detergent composition according to claim 1 wherein said mono-olefin sulfonate has chain length of 12 to 14 carbon atoms.
  • a detergent composition according to claim 1 wherein the alkyl benzene sulfonate has an alkyl chain of 12 to 16 carbon atoms.
  • a detergent composition according to claim 1 wherein the alkyl ether sulfate has an alkyl chain of 12 to 14 carbon atoms and is derived from coconut alcohols.
  • a detergent composition according to claim 6 wherein the alkyl ether sulfate has the formula where Rrepresents an alkyl group having 12 to 14 carbon atoms.
  • a detergent composition according to claim 1 which References Cited UNITED STATES PATENTS 2,061,617 11/1936 Downing et a1. 260-513 2,086,215 7/1937 DeCroote 252338 2,846,402 8/1958 Lew 252-152 2,972,583 2/1961 Hewitt 252-161 FOREIGN PATENTS 704,288 2/1954 Great Britain.

Description

United States Patent 3,332,876 DETERGENT COMPOSITION Arthur Pold'en Walker, Whitley Bay, England, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio NoDrawing. Continuation of application Ser. No.
423,298, Jan. 4, 1965. This application June 29,
1966, Ser. No. 561,374
Claims. (Cl. 252-152) This application is a continuation of Ser. No. 423,298, filed Jan. 4, 1965, by Arthur Polden Walker, entitled,
Detergent Composition.
This invention relates to detergent compositions having outstanding sudsing and detergent properties, based on synergistic ternary mixtures of olefin sulfonates, alkyl benzene sulfonates and alkyl ether sulfates.
Mixtures of alkyl benzene sulfonates and alkyl ethylene glycol or polyethylene glycol ether sulfates have previously been used in combination detergent compositions and have synergistic properties. Thus the detergent power and sudsing power of mixtures of these detergents are I greater than would be expected from consideration of their performance when used alone.
It is also known that olefins having a free hydrogen atom on a carbon in the alpha-position can be sulfonated directly using vigorous sulfonating agents. The sulfo radical attaches to the terminal carbon atom and the double bond remains intact, but may migrate from the alpha position. When the olefins have suitable molecular weight,
the sulfonates have detergent properties.
It has now been found that ternary mixtures of olefin sulfonates, alkyl aryl sulfonates and alkyl ether sulfates are synergistic, and have sudsing and cleaning power better than would be expected from a knowledge of their performance when used alone, and, in particular, better than would be expected from a knowledge of the performance of binary mixtures, especially mixtures of alkyl benzene sulfonates and alkyl ether sulfates, without the third component, and of the third component alone.
According to the invention therefore there is provided a detergent composition comprising a synergistic ternary mixture of (A) an olefin sulfonate having 12 to 16 carbon atoms in the molecule, (B) an alkyl benzene sulfonate having an alkyl chain containing 10 to 18 carbon atoms and (C) an alkyl ether sulfate having the formula RO(C H O),,SO M wherein R is an alkyl chain having 10 to 18 carbon atoms, x is l to 5, and M is a cation.
The term olefin sulfonates is used herein to mean compounds which can be produced by the sulfonation of alpha olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have .been formed in the reaction are hydrolysed to give the preferably 12 to 14 carbon atoms. Preferably, they are straight chain olefins. Olefin sulfonates having more than 16 carbon atoms do not give the desired high lathering performance in the mixtures according to the invention; those with fewer than 12 carbon atoms having reduced detergent properties.
In addition to the true alkene sulfonates and a proportion of hydroxy-alkane sulfonates, the olefin sulfonates 3,332,876 Patented July 25, 1967 ice may contain minor amounts of other materials, arising from impurities in the original olefin stock and from side reactions during the sulfonation process.
A preferred embodiment of the present invention is the use herein of the olefin sulfonate compositions which are described completely in a patent application Ser. No. 516,139, filed Dec. 23, 1965, by Phillip F. Pflaumer and Adriaan Kessler and titled, Detergent Composition.
The alkyl aryl sulfonates are preferably alkyl benzene sulfonates, and the alkyl chain preferably has 12 to 16 carbon atoms. The alkyl chain may be derived, for example, from branched or straight chain olefins, such as tetraor penta-propylene polymers or mixtures thereof, straight chain alpha-olefins obtained from petroleum cracking or by the polymerization of ethylene, or from halogenated paraffins. An alkyl chain which is a straight chain containing 12 carbon atoms is generally very suitable.
The alkyl ether sulfates can be made by the condensation by known methods of ethylene oxides on to monohydric alcohols having 10 to 18 carbon atoms. Preferably, R has 12 to 14 carbon atoms. The alcohols may be derived from fats, e.g., coconut oil, or they may be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred. Such alcohols are reacted with 1 to 5, and especially 3, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
The cation in the case of all the detergent ingredients may be alkali metal, ammonium or a substituted ammonium radical, or (as further explained below) may be in part magnesium, or may be an alkaline earth metal. It may be a mixture of any two or more of these.
While the addition of even small amounts of the olefin sulfonates to any mixtures of the alkyl aryl sulfonates and the alkyl ether sulfates provides synergistic. mixtures, preferred mixtures comprise 5 to of the olefin sulfonate, by weight of the ternary mixture and to 25% of a mixture comprising the alkyl aryl sulfonate and the alkyl ether sulfate in a ratio from 9:1 to 3:7 by Weight. Especially good performance is given by ternary mixtures containing 5 to 50% of the olefin sulfonate, and 95 to 50% of a mixture of the alkyl aryl sulfonate and the alkyl ether sulfate in a ratio of from 8.5 :15 to 1:1 by Weight.
It is found that the synergistic properties of the ternary mixtures of the invention are most marked when the compositions are used in hard water. Accordingly, where they may be used in soft water, it is advantageous to include some of a source of water hardness in the composition. This may be done by including a source of magnesium ion in the composition, either by adding a soluble magnesium salt, such as the sulfate or chloride or by incorporating one of the detergent ingredients at least partly in the form of its magnesium salt.
The compositions may contain any of the other ingredients usual in detergent compositions such as alkaline builder salts, bleaches, optical brighteners, sequestering agents, soil suspending agents, colors, perfumes, bacteriocides and the like. Other organic detergents may be present in minor proportions provided that they do not impair the performance of the ternary mixture of the invention. In particular, lather stabilizers, while usually unnecessary, may be added; examples are fatty acyl ethanolamides, especially lauric monoethanolamide.
The ternary mixtures are useful in solid, pasty or liquid detergent compositions, and are particularly well suited to liquid ones. In such liquid compositions they are dispersed or dissolved in a liquid medium, preferably water, optionally containing solubilizing agents such as lower monohy'dric alcohols having 1 to 4 carbon atoms, or hydrotropic salts such as toluene or xylene sulfonates, etc.
The following examples serve to illustrate the invention. In these examples, the latherin'g power of the detergent compositions was measured by the following test.
A frame was provided in which a number, for example six, 500 ml. cylinders could be placed and rotated about an axis perpendicular to their long axis. Into each cylinder was placed 100' ml. of a solution of the detergent composition in water at 115 F., the concentration being selected according to the information required from the test. To each solution was added 3 ml. of a standard soil load, namely, a liquid edible shortening based mainly on marine oils. The cylinders were then rotated in the frame for 1 minute at 20 r.p.m. They were then stood upright, the stoppers were removed, and the lather height above the clear liquid was measured. A further addition of 3 ml. of the soil was made and the procedure was repeated until substantially no lather remained.
The sum of the measured lather heights is reported as the lather height.
Example I Several diflerent liquid detergent compositions were made, each containing a total of 40% by weight of active detergent consisting of olefin sulfonates derived from alpha-olefin having 14 carbon atoms, tetra-propylene alkyl benzene sulfonate, and coconut alkyl trie-thylene glycol ether sulfate, all in the form of their sodium salts. The proportions of these components in each composition are indicated in the table below. The remainder of each composition consisted primarily of water, containing sufficient solubilizing agent (lower alcohol and, if necessary, hydrotrope) to give a homogeneous composition. Each composition was dissolved in hard water (18) to give a solution containing 0.26% of the composition, and tested for lather power by the method described above. The results are given in the following table:
Composition Olefin Lather Serial Snltonate Height Alkyl benzene Alkyl ether (Inches) sulfonate Sulfate Compositions f and g were according to the invention, the others being .included for comparison. Composition 1 had better lather power than the best binary mixtures e. Composition g had better lather power than would be expected of a 1:1 mixture of half the detergent ingredients of compositions a and d, which would have the same formula.
The compositions according to the invention had excellent detergent properties.
Example II Composition Olefin Lather Serial sulfonate Height Allryl benzene Alkyl ether (Inches) ulionate Sulfate 40 0 O 7. 55 0 40 0 2. 00 0 0 40 2. 33 0 2O 20 9. 56 10 20 10 10. 81 20 10 1O 10. 87
Compositions e and 1 were according to the invention, the others being included for comparison. Both e and f had better lather power than was provided by the best binary mixture of alkyl benzene sulfonate and alkyl ether sulfate, composition d. Moreover, composition 1 had better lather power than would be expected of a 1:1 mixture of half the detergent ingredients of compositions a and d, which would have the same formula.
The compositions according to the invention had excellent detergent properties.
In the compositions of the present invention, the ternary mixture may be used in any desired proportion. If the proportion is very small, for example less than 10% by weight of the composition, then inconveniently large amounts of the composition may have to be transported and used in order to achieve a given amount of cleaning. If the proportion is very great, then there may not be sufficient place for all other desired ingredients of the composition (such as builder salts in the case of solid compositions), or it may be difiicult to achieve a stable composition (in the case of liquid compositions). Suitable proportions of the ternary mixture will often be found to be within the range from 10 to 60%, by weight of the composition. Proportions within the range from 20 to 50% are preferred for liquid compositions.
What is claimed is:
1. A detergent composition consisting essentially of a synergistic ternary mixture of (A) a straight chain monoolefin sulfonate having 12 to 16 carbon atoms in the molecule, (B) an alkyl benzene sulfonate having an alkyl chain containing 10 to 18 carbon atoms and (C) an alkyl ether sulfate having the formula RO(C H O) SO M wherein R is an alkyl chain of 10 to 18 carbon atoms, x is a value from 1 to about 5, the cation of said sulfonate compounds and the cation M of said sulfate compound being selected from the group consisting of alkali metal, ammonium, magnesium and alkaline earth metal, the proportion of said mono-olefin sulfonate being from about 5 to 75% of the ternary mixture and to 65% of a mixture of said alkyl aryl sulfonate and said alkyl ether sulfate in a ratio of from 9:1 to 3 :7 by weight.
2. A detergent composition according to claim 1 wherein said mono-olefin sulfonate has chain length of 12 to 14 carbon atoms.
3. A detergent composition according to claim 1 wherein the alkyl benzene sulfonate has an alkyl chain of 12 to 16 carbon atoms.
4. A detergent composition according to claim 3 wherein the alkyl group of the alkyl benzene sulfonate is derived from the group consisting of tetrapropylene, pentapropylene, and mixtures thereof.
5. A detergent composition according to claim 3 wherein the alkyl group of the alkyl benzene sulfonate is a straight chain having 12 carbon atoms.
6. A detergent composition according to claim 1 wherein the alkyl ether sulfate has an alkyl chain of 12 to 14 carbon atoms and is derived from coconut alcohols.
7. A detergent composition according to claim 6 wherein the alkyl ether sulfate has the formula where Rrepresents an alkyl group having 12 to 14 carbon atoms.
8. A detergent composition according to claim 1 wherein the proportion of said mono-olefin sulfonate is from 5 to 50% of the ternary mixture and the ratio of said alkyl benzene sulfonate to said alkyl ether sulfate is from 85:15 to 1:1.
9. A detergent composition according to claim 1 which References Cited UNITED STATES PATENTS 2,061,617 11/1936 Downing et a1. 260-513 2,086,215 7/1937 DeCroote 252338 2,846,402 8/1958 Lew 252-152 2,972,583 2/1961 Hewitt 252-161 FOREIGN PATENTS 704,288 2/1954 Great Britain.
6 OTHER REFERENCES Chem. Ber., 97, #10, 2903-13 (October 1964); Higher Molecular Aliphatic Sulfonic Acids. I. Z-Hydroxy-l-n- Alkanesulfonic Acids, F. Pushel and Claus Kaiser.
Chem. Ber. 97, #10, 2917- (October 1964); Higher Molecular Aliphatic Sulfonic Acids. II. S-Hydroxy-l-n- Alkanesulfonic Acids and Their Inner Esters (1,3-Sultones). F. Puschel and Claus Kaiser.
Chem. Ber. 97, #10, 2926-33 (October 1964); Higher Molecular Unsaturated Sulfonic Acids and the Hydrolysis of 1,3-Alkanesultones. F. Puschel and Claus Kaiser.
Chem. Ber. 98, 735-742 (1965); Higher Molecular Aliphatic Sulfonic Acids. IV. Sulfonation of Unbranclied Alpha-Olefins with S0 F. Puschel and Claus Kaiser.
Stupel, Manufacturing Chemist, Combination of Raw Materials Improves Synthetic Detergents, March 1952, pp. 99-102.
LEON D. ROSDOL, Primary Examiner.
S. E. DARDEN, Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,332,876 July 25, 1967 Arthur Polden Walker It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 4, line 51, 65% should read 25% Signed and sealed this 14th day of April 1970.
(SEAL) Edward M. Fletcher, Jr.
Commissioner of Patents Attesting Officer

Claims (1)

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A SYNERGISTIC TERNARY MIXTURE OF (A) A STRAIGHT CHAIN MONOOLEFIN SULFONATE HAVING 12 TO 16 CARBON ATOMS IN THE MOLECULE, (B) AN ALKYL BENZENE SULFONATE HAVING AN ALKYL CHAIN CONTAINING 10 TO 18 CARBON ATOMS AND (C) AN ALKYL ETHER SULFATE HAVING THE FORMULA R(C2H4O)XSO2M WHEREIN R IS AN ALKYL CHAIN OF 10 TO 18 CARBON ATOMS, X IS A VALUE FROM 1 TO ABOUT 5, THE CATION OF SAID SULFONATE COMPOUNDS AND THE CATION M OF SAID SULFATE COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL, AMMONIUM, MAGNESIUM AND ALKALINE EARTH METAL, THE PROPORTION OF SAID MONO-OLEFIN SULFONATE BEING FROM ABOUT 5 TO 75% OF THE TERNARY MIXTURE AND 95 TO 65% OF A MIXTURE OF SAID ALKYL ARYL SULFONATE AND SAID ALKYL ETHER SULFATE IN A RATIO OF FROM 9:1 TO 3:7 BY WEIGHT.
US561374A 1964-10-15 1966-06-29 Detergent composition Expired - Lifetime US3332876A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
GB1050848D GB1050848A (en) 1964-10-15
CA776614A CA776614A (en) 1964-10-15 Detergent composition
FI2285/65A FI44927B (en) 1964-10-15 1965-09-24
FR34851A FR1457000A (en) 1964-10-15 1965-10-13 Detergent compositions
CH1413365A CH485842A (en) 1964-10-15 1965-10-13 Detergents and cleaning agents
BE670913D BE670913A (en) 1964-10-15 1965-10-14
AT931665A AT257784B (en) 1964-10-15 1965-10-14 Detergent mix
DE19651467663 DE1467663A1 (en) 1964-10-15 1965-10-14 Detergent mix
DK526865AA DK127071B (en) 1964-10-15 1965-10-14 Detergent.
NL6513298A NL6513298A (en) 1964-10-15 1965-10-14
US561374A US3332876A (en) 1964-10-15 1966-06-29 Detergent composition
US27096D USRE27096E (en) 1964-10-15 1968-11-15 Best available copy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB4211264 1964-10-15
US561374A US3332876A (en) 1964-10-15 1966-06-29 Detergent composition

Publications (1)

Publication Number Publication Date
US3332876A true US3332876A (en) 1967-07-25

Family

ID=26264823

Family Applications (2)

Application Number Title Priority Date Filing Date
US561374A Expired - Lifetime US3332876A (en) 1964-10-15 1966-06-29 Detergent composition
US27096D Expired USRE27096E (en) 1964-10-15 1968-11-15 Best available copy

Family Applications After (1)

Application Number Title Priority Date Filing Date
US27096D Expired USRE27096E (en) 1964-10-15 1968-11-15 Best available copy

Country Status (11)

Country Link
US (2) US3332876A (en)
AT (1) AT257784B (en)
BE (1) BE670913A (en)
CA (1) CA776614A (en)
CH (1) CH485842A (en)
DE (1) DE1467663A1 (en)
DK (1) DK127071B (en)
FI (1) FI44927B (en)
FR (1) FR1457000A (en)
GB (1) GB1050848A (en)
NL (1) NL6513298A (en)

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3513099A (en) * 1966-12-06 1970-05-19 Purex Corp Ltd Las detergents containing primary and secondary alkoxy alkanol ammonium sulfates
US3676374A (en) * 1969-11-25 1972-07-11 Procter & Gamble Enzyme-containing liquid detergent compositions
US3780860A (en) * 1971-05-17 1973-12-25 Stephan Chem Co Flotation of copper sulfide ores
US3827557A (en) * 1971-05-17 1974-08-06 Stepan Chemical Co Method of copper sulfide ore flotation
JPS49108110A (en) * 1972-11-13 1974-10-15
US3852221A (en) * 1971-08-19 1974-12-03 Jefferson Chem Co Inc Liquid olefin sulfonate detergent
JPS5012104A (en) * 1972-11-13 1975-02-07
JPS5033488B1 (en) * 1969-07-10 1975-10-31
US3944663A (en) * 1971-06-16 1976-03-16 Colgate Palmolive Company Mild light duty detergent containing homopolymers of ethylene oxide
US4013577A (en) * 1972-04-14 1977-03-22 Colgate-Palmolive Company Heavy duty dry biodegradable detergent composition
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
US4024078A (en) * 1975-03-31 1977-05-17 The Procter & Gamble Company Liquid detergent composition
US4064076A (en) * 1973-04-09 1977-12-20 Colgate-Palmolive Olefin sulfonate detergent compositions
US4092272A (en) * 1975-09-16 1978-05-30 Kao Soap Co., Ltd. Liquid detergent composition
US4129515A (en) * 1976-09-13 1978-12-12 The Procter & Gamble Company Heavy-duty liquid detergent and process
US4166048A (en) * 1975-09-22 1979-08-28 Kao Soap Co., Ltd. High foaming detergent composition having low skin irritation properties
US4235758A (en) * 1977-12-22 1980-11-25 Lever Brothers Company Clear liquid detergent composition containing MgABS and alkyl polyether sulphates
US4435317A (en) 1980-04-24 1984-03-06 The Procter & Gamble Company Dishwashing liquid including alkyl sulfate, alkyl ether sulfate, alkylbenzene sulfonate and magnesium
US4536317A (en) * 1982-04-26 1985-08-20 The Procter & Gamble Company Foaming surfactant compositions
US4554099A (en) * 1983-04-19 1985-11-19 Lever Brothers Company Opaque general-purpose cleaning composition comprising alcohol esterified resin copolymers
US4601844A (en) * 1984-08-31 1986-07-22 The Procter & Gamble Company Granular automatic dishwasher detergent with alkyl phosphate and calcium ion source
US4614612A (en) * 1977-12-22 1986-09-30 Lever Brothers Company Liquid detergent composition
US4842767A (en) * 1986-09-10 1989-06-27 Colgate-Palmolive Company Heavy duty built aqueous liquid detergent composition containing stabilized enzymes
US5912222A (en) * 1994-08-26 1999-06-15 Colgate Palmolive Company Microemulsion light duty liquid cleaning compositions
EP2380956A1 (en) * 2010-04-19 2011-10-26 The Procter & Gamble Company Process for making a detergent
US8183196B2 (en) 2010-04-23 2012-05-22 The Procter & Gamble Company Detergent composition
US8357650B2 (en) 2010-04-23 2013-01-22 The Procter & Gamble Company Aminocarboxylic builder particle
US8455422B2 (en) 2010-04-23 2013-06-04 The Procter & Gamble Company Process for making a methyl glycine diacetic acid particle
EP3388504A4 (en) * 2015-12-10 2019-08-07 Kao Corporation Surfactant composition

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5950200B2 (en) 1978-02-17 1984-12-06 ライオン株式会社 Improved liquid cleaning composition
NZ206213A (en) 1982-11-16 1985-12-13 Unilever Plc Foaming liquid detergent compositions containing alkylbenzenesulphonates and alkyl ether sulphates

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2061617A (en) * 1936-11-24 Stllphonic acid derivatives of aii
US2086215A (en) * 1936-12-24 1937-07-06 Tret O Lite Company Processes for breaking petroleum emulsions
GB704288A (en) * 1950-12-08 1954-02-17 Sandoz Ltd Detergents
US2846402A (en) * 1958-08-05 Alkyl sulfate detergent compositions
US2972583A (en) * 1956-05-17 1961-02-21 Colgate Palmolive Co Detergent cake and method of making same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2061617A (en) * 1936-11-24 Stllphonic acid derivatives of aii
US2846402A (en) * 1958-08-05 Alkyl sulfate detergent compositions
US2086215A (en) * 1936-12-24 1937-07-06 Tret O Lite Company Processes for breaking petroleum emulsions
GB704288A (en) * 1950-12-08 1954-02-17 Sandoz Ltd Detergents
US2972583A (en) * 1956-05-17 1961-02-21 Colgate Palmolive Co Detergent cake and method of making same

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3513099A (en) * 1966-12-06 1970-05-19 Purex Corp Ltd Las detergents containing primary and secondary alkoxy alkanol ammonium sulfates
JPS5033488B1 (en) * 1969-07-10 1975-10-31
US3676374A (en) * 1969-11-25 1972-07-11 Procter & Gamble Enzyme-containing liquid detergent compositions
US3780860A (en) * 1971-05-17 1973-12-25 Stephan Chem Co Flotation of copper sulfide ores
US3827557A (en) * 1971-05-17 1974-08-06 Stepan Chemical Co Method of copper sulfide ore flotation
US3944663A (en) * 1971-06-16 1976-03-16 Colgate Palmolive Company Mild light duty detergent containing homopolymers of ethylene oxide
US3852221A (en) * 1971-08-19 1974-12-03 Jefferson Chem Co Inc Liquid olefin sulfonate detergent
US4013577A (en) * 1972-04-14 1977-03-22 Colgate-Palmolive Company Heavy duty dry biodegradable detergent composition
JPS5012104A (en) * 1972-11-13 1975-02-07
JPS49108110A (en) * 1972-11-13 1974-10-15
US4064076A (en) * 1973-04-09 1977-12-20 Colgate-Palmolive Olefin sulfonate detergent compositions
US4024078A (en) * 1975-03-31 1977-05-17 The Procter & Gamble Company Liquid detergent composition
US4018720A (en) * 1975-07-14 1977-04-19 The Procter & Gamble Company Laundry detergent compositions in emulsion/suspension
US4092272A (en) * 1975-09-16 1978-05-30 Kao Soap Co., Ltd. Liquid detergent composition
US4166048A (en) * 1975-09-22 1979-08-28 Kao Soap Co., Ltd. High foaming detergent composition having low skin irritation properties
US4129515A (en) * 1976-09-13 1978-12-12 The Procter & Gamble Company Heavy-duty liquid detergent and process
US4235758A (en) * 1977-12-22 1980-11-25 Lever Brothers Company Clear liquid detergent composition containing MgABS and alkyl polyether sulphates
US4614612A (en) * 1977-12-22 1986-09-30 Lever Brothers Company Liquid detergent composition
US4435317A (en) 1980-04-24 1984-03-06 The Procter & Gamble Company Dishwashing liquid including alkyl sulfate, alkyl ether sulfate, alkylbenzene sulfonate and magnesium
US4536317A (en) * 1982-04-26 1985-08-20 The Procter & Gamble Company Foaming surfactant compositions
US4554099A (en) * 1983-04-19 1985-11-19 Lever Brothers Company Opaque general-purpose cleaning composition comprising alcohol esterified resin copolymers
US4601844A (en) * 1984-08-31 1986-07-22 The Procter & Gamble Company Granular automatic dishwasher detergent with alkyl phosphate and calcium ion source
US4842767A (en) * 1986-09-10 1989-06-27 Colgate-Palmolive Company Heavy duty built aqueous liquid detergent composition containing stabilized enzymes
US5912222A (en) * 1994-08-26 1999-06-15 Colgate Palmolive Company Microemulsion light duty liquid cleaning compositions
EP2380956A1 (en) * 2010-04-19 2011-10-26 The Procter & Gamble Company Process for making a detergent
WO2011133286A1 (en) * 2010-04-19 2011-10-27 The Procter & Gamble Company Process for making a detergent
US8183196B2 (en) 2010-04-23 2012-05-22 The Procter & Gamble Company Detergent composition
US8357650B2 (en) 2010-04-23 2013-01-22 The Procter & Gamble Company Aminocarboxylic builder particle
US8455422B2 (en) 2010-04-23 2013-06-04 The Procter & Gamble Company Process for making a methyl glycine diacetic acid particle
EP3388504A4 (en) * 2015-12-10 2019-08-07 Kao Corporation Surfactant composition

Also Published As

Publication number Publication date
BE670913A (en) 1966-04-14
FI44927B (en) 1971-11-01
USRE27096E (en) 1971-03-23
CA776614A (en) 1968-01-23
FR1457000A (en) 1966-07-08
CH485842A (en) 1970-02-15
GB1050848A (en)
AT257784B (en) 1967-10-25
NL6513298A (en) 1966-04-18
DE1467663A1 (en) 1969-05-22
DK127071B (en) 1973-09-17

Similar Documents

Publication Publication Date Title
US3332876A (en) Detergent composition
US4681704A (en) Detergent composition containing semi-polar nonionic detergent alkaline earth metal anionic detergent and amino alkylbetaine detergent
US4435317A (en) Dishwashing liquid including alkyl sulfate, alkyl ether sulfate, alkylbenzene sulfonate and magnesium
US4052342A (en) Secondary alkyl sulfate: alcohol ethoxylate mixtures
US4302364A (en) Liquid detergent compositions comprising anionic, nonionic and cationic surfactants
JPH09505088A (en) Liquid synthetic detergent composition having alpha-sulfonated fatty acid methyl ester and anionic surfactant
US4235758A (en) Clear liquid detergent composition containing MgABS and alkyl polyether sulphates
CZ53393A3 (en) Liquid or jellylike cleansing agent and method of washing dishes therewith
US3755206A (en) Detergent compositions
US3085982A (en) Liquid detergent composition
US3192166A (en) Liquid detergent composition
ES554587A0 (en) PROCEDURE FOR THE OBTAINING OF LIQUID DETERGENTS EXEMPT FROM SALT COADJUVANTS WITH SOFTENING PROPERTIES OF CLOTHING
US3231504A (en) Liquid detergent compositions
EP0157443B1 (en) Detergent composition containing semi-polar nonionic detergent, alkaline earth metal anionic detergent, and amidoalkylbetaine detergent
KR940010123B1 (en) Detergent composition
CA1217112A (en) Liquid detergent compositions
EP0178006B1 (en) Liquid detergent compositions
EP0241073B1 (en) Liquid detergents containing anionic surfactant, succinate builder and fatty acid
US3640880A (en) Hard surface cleaner
US3179599A (en) Detergent composition
US6214783B1 (en) High foaming, grease cutting light duty liquid detergent
US4102826A (en) Liquid detergent
US3836484A (en) Phosphate-free detergent concentrates containing sulfated and sulfonated linear alkylphenols
US3332875A (en) Detergent composition
US3544475A (en) Detergent compositions based on mixtures of alpha-olefin sulfonates and dimer olefin sulfonates