US3929680A - Liquid detergent composition - Google Patents

Abstract

A liquid detergent composition containing as active ingredients anionic surfactants or non-ionic surfactants and at least two kinds of solubilizing agents. The composition contains as one solubilizing agent 3 to 30%, based on the surfactant, of an aliphatic saturated hydrocarbon having 6 to 14 carbon atoms on the average or an alkyl benzene containing an alkyl group having 6 to 14 carbon atoms on the average.

Description

Unite lf States atent Aral et al.

[ Dec. 30, 1975 LIQUID DETERGENT COMPOSITION Inventors: Haruhiko Arai, Narashino;

Kyozaburo Tachibana, Sakura; Yoshinori Naganuma, Tokyo; Moriyasu Murata, Narashino, all of Japan Assignee: Kao Soap Co., Ltd., Tokyo, Japan Filed: Apr. 17, 1973 Appl. No.: 352,053

Foreign Application Priority Data Apr. 20, 1972 Japan 47-039886 US. Cl. 252/542; 252/89; 252/139; 252/153; 252/170; 252/171; 252/172; 252/173; 252/363.5; 252/536; 252/539; 252/550; 252/551; 252/554; 252/555; 252/558; 252/DIG. 13; 252/DIG. 14

Int. CL C11D 3/18; C11D 3/43; C11D 3/44; C11D 17/08 Field of Search 252/118, 122, 126, 127, 252/132,139,153,162,170,172, 363.5,

558, 559, DIG. 13, DIG. 14, 173, 542, 544

[56] References Cited UNITED STATES PATENTS 2,901,433 8/1959 Spring 252/118 3,533,955 10/1970 Pader..... 252/153 3,658,985 4/1972 Olson...,...' 424/70 Primary ExaminerDennis E. Talbert, Jr.

Assistant ExaminerDennis L. Albrecht Attorney, Agent, or Firm-Woodhams, Blanchard and Flynn [57] ABSTRACT 4 Claims, N0 Drawings LIQUID DETERGENT COMPOSITION BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a liquid detergent composition. More particularly, this invention relates to a liquid detergent composition having excellent low temperature stability and containing an anionic surfactant and- /or a non-ionic surfactant, and solubilizing agents.

2. Description of the Prior Art Known liquid detergent compositions comprise, for instance, an alkyl benzene sulfonate and, incorporated therein, one or more solubilizing agents, for instance, lower alcohols such as ethanol, benzene sulfonates, lower alkyl benzene sulfonates such as p-toluene sulfonates, glycols such as propylene glycol, acetyl benzene sulfonates, acetamides, pyridine carboxylic acid amides, benzoates and urea. However, these detergent compositions are inevitably defective in that white turbidity or phase separation is brought about at low temperatures.

SUMMARY OF THE INVENTIONv Accordingly, the object of this invention is to provide a liquid detergent composition which possesses excellent low temperature stability, and the gist of this invention resides in a liquid detergent composition comprising as active ingredients at least one member selected from anionic surfactants and non-ionic surfactants and at least two solubilizing agents, characterized in that as one solubilizing agent there is used about 3 to about 30% by weight, based on the amount of the above surfactants, of an aliphatic saturated hydrocarbon having 6 to 14 carbon atoms on the average or an alkyl benzene containing an alkyl group having 6 to 14 carbon atoms on the average.

The aliphatic saturated hydrocarbon used as one embodiment of the indispensable solubilizing agent in the composition of this invention contains 6 to 14 carbon atoms on the average, and it may be of either the normal form or the iso-form or a mixture thereof. As specific examples, there may be mentioned hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, etc. Still further, kerosene, fluid paraffin and petroleum fractions containing as the main component such saturated hydrocarbon as mentioned above can be used.

The alkyl benzene used as the other embodiment of the indispensable solubilizing agent in the composition of this invention contains a straight or branched alkyl group having 6 to 14 carbon atoms on the average. As specific examples, there may be mentioned hexyl benzene, octyl benzene, nonyl benzene, dodecyl benzene and tetradecyl benzene.

All of the heretofore known solubilizing agents can be used as the other solubilizing agent in the composition of this invention. For instance, there may be employed lower alcohols such as methanol, ethanol and isopropyl alcohol; benzene sulfonates, p-toluene sulfonates, xylene sulfonates and acetyl benzene sulfonates; glycols such as ethylene glycol and propylene glycol; acetamides; pyridine dicarboxylic acid amides; aromatic carboxylic acid salts such as benzoates and salicylates; and urea. The salts included in this group, i.e. the various sulfonates and aromatic carboxylic acid salts, are usually alkali metal salts (sodium or potassium), ammonium salts or amine salts.

As the anionic surfactant that the composition of this invention can contain, there can be mentioned, for instance, straight or branched alkyl benzene sulfonates, alkyl sulfuric acids ester salts, alkane sulfonates, a-olefin sulfonates, salts of polyoxyethylene alkyl or alkylphenyl ether sulfuric acid esters, and ether carboxylates expressed by the general formula R-O(CH C- H O),,R'COOM in which R is an alkyl or alkenyl group having 8 to 22 carbon atoms or an alkyl phenyl group in which the alkyl group has 6 to 17 carbon atoms, R is an alkylene group having 1 to 4 carbon atoms, M stands for a water-soluble cation, and n is a number from 1 to 30. The anionic surfactant is an alkali metal salt such as sodium or potassium, ammonium salt or an alkanolamine salt such as mono-, dior triethanolamine.

As the non-ionic surfactant, there may be exemplified polyoxyethylene alkyl ethers in which the alkyl group has 8 to 18 carbon atoms and 4 to 14 oxyethylene units and polyoxyethylene alkyl phenyl ethers in which the alkyl group has from 8 to 12 carbon atoms and 6 to 12 oxyethylene units.

The hydrocarbon (aliphatic saturated hydrocarbon or alkyl benzene as defined above) to be used as the indispensable solubilizing agent in the composition of this invention is incorporated in an amount of about 3 to about 30% (by weight; the same will apply hereinafter) based on the amount of the surfactant(s), and the weight ratio of said hydrocarbon solubilizing agent to the other solubilizing agent should be preferably from 1/40 to 2/1. In case the hydrocarbon solubilizing agent is incorporated in an amount such as specified above, the low temperature stability of the detergent composition is highly improved as compared with the case where such hydrocarbon is not added, and the incorporation of the hydrocarbon solubilizing agent does not adversely affect the foaming property or rinsing ability of the composition but tends to increase the detergency. Accordingly, the composition of this invention is useful as a detergent for foodstuffs and table wares, a shampoo and a heavy or light duty liquid detergent for clothes.

This invention will now be illustrated in more detail by reference to Referential Example and Examples, in which the white turbidity-separation temperature was determined in the following manner:

Namely, about l5 ml of a sample aqueous solution was taken into a test tube, and the solution was cooled at a rate of 1C per minute while gently agitating the solution in the vertical direction by means of a stirring rod. When the white turbidity or phase separation was caused to occur, the temperature was read. The so read temperature was defined as the white turbidity-separation temperature.

REFERENTIAL EXAMPLE Sodium straight-chain dodecyl benzene 20% sulfonate Solubilizing agent indicated in Table l ater 5% balance Results are shown in Table l Table 1 Turbidity-Separation Formulation: So b iZing Agent Temperature (C) Sodium straight-dodecyl benzene sulfonate 20% N dd d 5 (purity 89.6%; sodium sulfate 9.7%;

ot a e 3 dodecyl benzene 0.7%) Sodium benzoate separation occurred at room Urea 5% temperature (15C) Hydrocarbon indicated in Table 3 1% Sodium p-toluene same as above water balance sulfonate Soxium xylene sulfonate 9 Table 3 Urea 2 i Triethanol amine l 10 Hydrocarbon P l l 0 zggz fi g ycol 8 temperature C) n-HeXane 5 Not added -2 n-Dodecane separation occurred at room n-Hexane 4.5

temperature (C) n-Dodecane n-Hexadecane same as above 15 n-Tetradecane Mineral oil* same as above Mineral oil -5 Kerosene same as above (same as indicated in Table l) Dodecyl benzene same as abovve Kemsflne Xylene same as above n-Hexyl benzene 3 Benzene 13 Doodecyl benzene (n iso= 40:60) 55 Note: n-Tetradecyl benzene -3 *:b.p.= l77-l88C, specific gravity=0.76 (156C), isoparaffin (Cw hydrocar- Squalene separation occurred at bons= 50%. C hydrocarbons=20%. others= 30%). room temperature (15C) Benzene same as above Xylene same as above As will be apparent from the above data, the hydrocarbon solubilizing agent of this invention do not exhibit an effect of improving the low temperature stabil- AS Wm be P Y P b the ity when used alone; drocarbon of this invention exhibits a very high effect of im rovin the low tem erature stabilit in the co- P g P Y EXAMPLE 1 presence of urea. Turbidity-separation temperatures of aqueous solu- EXAMPLES 3 o 9 tions of the following formulation including a solubiliz- T f h f H ing agent indicated in Table 2 and n-dodecane were 1 nyseparatllozi temperatures 0 i e O Owmg determined to obtain results shown in Table 2. vanous aqueous so u Ions measure EXAMPLE 3 Formulation: Sodium straight-dodecyl benzene 20% CmPanSo" sulfonate d Sodium straight-dodecyl g' g g. O or 1% benzene sulfonate 16% 16% intTzgsg 1 llZll'lg agent indicated sq sodium nonyi phenyl 40 polyethoxy (3) acetate 4% 4% Water balance Urea 5% 15 Ethanol 5% 5% Table 2 n-Dodecane 0% 0.7%

Turbidity-separation tempera- Turbidity-separation agent ture (C) temperature about 5C below l0C 0% of n-dodecane 1% of ndodecane Not added 3 2 Sodium benzoate separation 13.5 EXAMPLE 4 occurred at room temperature (15C) Comparison This invention gfiggigrzriitg-toluene same as above l0 sodium Bold-m (CH) S dium t 9 l sulfonate 20% 20% 2 em 5 6 2 7 Urea 14% 14% Triethanol amine l 3 Mmera on 0% 07% Propylene glycol 6 2 Turbidity-separation Ethanol 9 2 temperature about 4.5C below 6C :b.p.= I88-ZO8C, specific gravity=0.77 (156C), paraffin (n-C, 27%. iso- Ciz= 35%, others= 38%).

As will be apparent from the above data, addition of n-dodecane is effective for improving the low tempera- EXAMPLE 5 ture stability. Especially when sodium xylene sulfonate, urea and triethanol amine are co-present, the effect of i Comparison This invention n-dodecane is remarkable.

Sodium POE(3) alkyl (C )ether sulfate 20% 20% EXAMPLE 2 Urea lO% 10% Turbidity-separation temperatures of the following lij ggs zf gg 0% 1% formulation including a hydrocarbon indicated in temperailure about -4c below -6C Table 3 were determined to obtain results shown in Table 3.

EXAMPLE 6 Comparison This invention Sodium straight-dodecyl t J, benzene sulfonate 15% 1 5% Sodium nonyl phenyl polyethoxy(3) acetate 5% 5% Sodium xylene sulfonate 14% 14% Ethanol 2% 2% Kerosene 2% Turbidity-separation temperature about 2C below C EXAMPLE 7 Comparison This invention Sodium nonyl phenyl polyethoxy(3) acetate 20% 20% Urea 5% 5% n-Dodecane 0% 1% Turbidity-separation temperature about C below 12C EXAMPLE 8 Comparison This invention Sodium straight-dodecyl benzene sulfonate 20% Ethanol 5% 5% Dodecyl benzene 0% 2.5%

Turbidity-separation temperature about 9C below 4C EXAMPLE 9 Comparison This invention POE(8) dodecyl ether 35% 35% Ethanol 10% 10% Mineral oil (same as indicated in Table 1) 0% 10% Turbidity-separation temperature about -5C below 10C EXAMPLE 10 The following liquid detergents (A) and (B) were prepared.

1. When both the liquid detergents (A) and (B) were allowed to stand still at 5C for 5 days, the phase separation occurred in the detergent (A) but no change was observed in the detergent (B) of this invention.

2. The ability of washing dishes was tested on each of the detergents (A) and (B) in the following manner. 10 g of the detergent and 10 g of water were absorbed in a sponge from which water had been well drained off, and the sponge was crumbled by hands to form foams. Thus, dishes, each beingcoated with 5 g of a mixed oil-fat (consisting of of beef tallow and 10% of rape oil), were washed, and the detergency was evaluated based on the number of dishes washed until foams disappeared. As a result, it was found that each of the detergents (A) and (B) had a detergency of 4 plates of dishes. V

EXAMPLE 1 l The following liquid detergents (C) and (D) were prepared.

Detergent ingredients Comparison (C) This invention Sodium straight-dodecyl 1. When both the detergents (C) and (D) were allowed to stand at 5C for 5 days, the phase separation occurred in the detergent (C) but no change was observed in the detergent (D) of this invention.

2. Naturally contaminated cotton cloths were washed by using the above detergents (C) and (D) under the following conditions. The detergency of the detergent (D) was somewhat superior to that of the detergent (C) but no significant difference was observed.

Washing conditions:

Tester: Terg-O-Tometer Deterent concentration: 0.20% (in city water) Bath ratio: 6 contaminated cloths per 500 cc Washing temperature: 30C

Washing operation: at rpm for 10 minutes Rinsing: once for 5 minutes The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A liquid detergent composition having improved low temperature stability, consisting essentially of an aqueous solution of at least one surfactant selected from the group consisting of anionic surfactants and non-ionic surfactants, the amount of said surfactant being an amount effective for making said detergent composition suitable for washing foodstuffs, tableware or clothes, or as a shampoo; a first solubilizing agent selected from the group consisting of alkanols having one to 3 carbon atoms; benzene sulfonates, p-toluene sulfonates, xylene sulfonates, acetyl benzene sulfonates, glycols, acetamides, pyridine dicarboxylic acid amides, benzoates, salicylates and urea; and a second solubilizing agent selected from the group consisting of hexyl benzene, octyl benzene, nonyl benzene, dodecyl benzene and tetradecyl benzene, said liquid detergent composition containing from about 3 to about 30 percent by weight, based on the weight of said surfactant, of said second solubilizing agent, the weight ratio of said second solubilizing agent to said first solubilizing agent being from l/40 to 2/ 1, whereby to improve the I carboxylates 8 6 to 17 carbon atoms, R is an alkylene group having 1 to 4 carbon atoms, M stands for a water-soluble cation, and n is a number from I to 30.

3. A liquid detergentcomposition according to claim I, in which said non-ionic surfactant is selected from polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers.

4. A liquid detergent composition according to claim 1, in which the amount of said surfactant is from 20 to 35 percent by weight, based on the total weight of said detergent composition.

Claims (4)

1. A LIQUID DETERGENT COMPOSITION HAVING IMPROVED LOW TEMPERATURE STABILITY, CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTION OF AT LEAST ONE SURFACTANTS AND NON-IONIC SURFACTANTS, T CONSISTING OF ANIONIC SURFACTANTS AND NON-IONIC SURFACTANTS, THE AMOUNT OF SAID SURFACTNAT BEING AN AMOUNT EFFECTIVE FOR MAKING SAID DETERGENT COMPOSITION SUITABLE FOR WASHING FOODSTUFFS, TABLEWARE OR CLOTHES, OR AS A SHAMPOO; A FIRST SOLUBILIZING AGENT SELECTED FROM THE GROUP CONSISTING OF ALKANOLS HAVING ONE TO 3 CARBON ATOMS; BENZENE SULFINATES, P-TOLUENE SOLFONATES, XYLENE SULFONATES, ACETYL BENZENE SULFONATES, GLYCOLS, ACETAMIDES, PYRIDINE DICARBOXYLIC ACID AMIDES, BENZOATES, SALICYLATESL AND UREA; AND A SECOND SOLUBILIZING AGENT SELECTED FROM THE GROUP CONSISTING OF HEXYL BENZENE, OCTYL BENZENE, NONYL BENZENE, DODECYL BENZENE AND TETRADECYL BENZENE, SAID LIQUID DETERGENT COMPOSITION CONTAINING FROM ABOUT 3 TO ABOUT 30 PERCENT BY WEIGHT, BASED ON THE WEIGHT BASED ON THE WEIGHT OF SAID SECOND SOLUBILIZING AGENT, THE WEIGHT RATIO OF SAID SECOND SOLUBILIZING AGENT TO SAID FIRST SOLUBILIZING AGENT BEING FROM 1/40 TO 2/1, WHEREBY TO IMPROVE THE LOW TEMPERATURE STABILITY OF THE LIQUID DETERGENT COMPOSITION.

2. A liquid detergent composition according to claim 1 in which said anionic surfactant is selected from the group consisting of straight or branched alkyl benzene sulfonates, alkyl sulfuric acid ester salts, alkane sulfonates, Alpha -olefin sulfonates, salts of polyoxyethylene alkyl or alkylphenyl ether sulfuric acid esters, and ether carboxylates expressed by the general formula R-O-(CH2H2O)n-R''-COOM in which R is an alkyl or alkenyl group having 8 to 22 carbon atoms or an alkyl phenyl group containing an alkyl group having 6 to 17 carbon atoms, R'' is an alkylene group having 1 to 4 carbon atoms, M stands for a water-soluble cation, and n is a number from 1 to 30.

3. A liquid detergent composition according to claim 1, in which said non-ionic surfactant is selected from polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers.

4. A liquid detergent composition according to claim 1, in which the amount of said surfactant is from 20 to 35 percent by weight, based on the total weight of said detergent composition.