Liquid detergent composition

Arai , et al. December 30, 1

Patent Grant 3929680

U.S. patent number 3,929,680 [Application Number 05/352,053] was granted by the patent office on 1975-12-30 for liquid detergent composition. This patent grant is currently assigned to Kao Soap Co., Ltd.. Invention is credited to Haruhiko Arai, Moriyasu Murata, Yoshinori Naganuma, Kyozaburo Tachibana.


United States Patent 3,929,680
Arai ,   et al. December 30, 1975

Liquid detergent composition

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.


Inventors: Arai; Haruhiko (Narashino, JA), Tachibana; Kyozaburo (Sakura, JA), Naganuma; Yoshinori (Tokyo, JA), Murata; Moriyasu (Narashino, JA)
Assignee: Kao Soap Co., Ltd. (Tokyo, JA)
Family ID: 12565446
Appl. No.: 05/352,053
Filed: April 17, 1973

Foreign Application Priority Data

Apr 20, 1972 [JA] 47-039886
Current U.S. Class: 510/111; 252/363.5; 510/119; 510/427; 510/432; 510/421; 510/127; 510/237; 510/340; 510/342; 510/235
Current CPC Class: C11D 3/18 (20130101)
Current International Class: C11D 17/00 (20060101); C11D 3/18 (20060101); C11D 003/18 (); C11D 003/43 (); C11D 003/44 (); C11D 017/08 ()
Field of Search: ;252/118,122,126,127,132,139,153,162,170,172,363.5,558,559,DIG.13,DIG.14,173

References Cited [Referenced By]

U.S. Patent Documents
2901433 August 1959 Spring
3533955 October 1970 Pader
3658985 April 1972 Olson
Primary Examiner: Talbert, Jr.; Dennis E.
Assistant Examiner: Albrecht; Dennis L.
Attorney, Agent or Firm: Woodhams, Blanchard and Flynn

Claims



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 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--(CH.sub.2 H.sub.2 O).sub.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.
Description



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 INVENTION

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, .alpha.-olefin sulfonates, salts of polyoxyethylene alkyl or alkylphenyl ether sulfuric acid esters, and ether carboxylates expressed by the general formula R--O--(CH.sub.2 CH.sub.2 O).sub.n --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-, di- or 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 15 ml of a sample aqueous solution was taken into a test tube, and the solution was cooled at a rate of 1.degree.C 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

Turbidity-separation temperatures of solubilizing agent-containing aqueous solutions of the following formulation were measured.

______________________________________ Sodium straight-chain dodecyl benzene 20% sulfonate Solubilizing agent indicated in Table 1 5% Water balance ______________________________________

Results are shown in Table 1.

Table 1 ______________________________________ Turbidity-Separation Solubilizing Agent Temperature (.degree.C) ______________________________________ Not added 3 Sodium benzoate separation occurred at room temperature (15.degree.C) Sodium p-toluene same as above sulfonate Soxium xylene sulfonate 9 Urea -2 Triethanol amine -1 Propylene glycol 6 Ethanol 9 n-Hexane 5 n-Dodecane separation occurred at room temperature (15.degree.C) n-Hexadecane same as above Mineral oil* same as above Kerosene same as above Dodecyl benzene same as abovve Xylene same as above Benzene 13 ______________________________________ Note * : b. p. = 177 - 188.degree.C, specific gravity = 0.76 (15.6.degree.C), isoparaffin (C.sub.10 hydrocarbons = 50%, C.sub.11 hydrocarbons = 20%, others = 30%).

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 stability when used alone.

EXAMPLE 1

Turbidity-separation temperatures of aqueous solutions of the following formulation including a solubilizing agent indicated in Table 2 and n-dodecane were determined to obtain results shown in Table 2.

______________________________________ Formulation: Sodium straight-dodecyl benzene 20% sulfonate n-Dodecane 0 or 1% Other solubilizing agent indicated in Table 2 5% Water balance Table 2 ______________________________________ Turbidity-separation tempera- agent ture (.degree.C) 0% of n-dodecane 1% of n- dodecane ______________________________________ Not added 3 2 Sodium benzoate separation 13.5 occurred at room temperature (15.degree.C) Sodium p-toluene same as above 10 sulfonate Sodium xylene sulfonate 9 1 Urea -2 -7 Triethanol amine -1 -3 Propylene glycol 6 2 Ethanol 9 2 ______________________________________

As will be apparent from the above data, addition of n-dodecane is effective for improving the low temperature stability. Especially when sodium xylene sulfonate, urea and triethanol amine are co-present, the effect of n-dodecane is remarkable.

EXAMPLE 2

Turbidity-separation temperatures of the following formulation including a hydrocarbon indicated in Table 3 were determined to obtain results shown in Table 3.

______________________________________ Formulation: Sodium straight-dodecyl benzene sulfonate 20% (purity = 89.6%; sodium sulfate = 9.7%; dodecyl benzene = 0.7%) Urea 5% Hydrocarbon indicated in Table 3 1% Water balance Table 3 ______________________________________ Turbidity- Hydrocarbon separation temperature (.degree.C) ______________________________________ Not added -2 n-Hexane -4.5 n-Dodecane -7 n-Tetradecane -3 Mineral oil -3.5 (same as indicated in Table 1) Kerosene -2.5 n-Hexyl benzene -3 Doodecyl benzene (n : iso = 40 : 60) -5.5 n-Tetradecyl benzene -3 Squalene separation occurred at room temperature (15.degree.C) Benzene same as above Xylene same as above ______________________________________

As will be apparent from the above results, the hydrocarbon of this invention exhibits a very high effect of improving the low temperature stability in the co-presence of urea.

EXAMPLES 3 TO 9

Turbidity-separation temperatures of the following various aqueous solutions were measured.

EXAMPLE 3

Comparison This invention ______________________________________ Sodium straight-dodecyl benzene sulfonate 16% 16% Sodium nonyl phenyl polyethoxy (3) acetate 4% 4% Urea 15% 15% Ethanol 5% 5% n-Dodecane 0% 0.7% ______________________________________ Turbidity-separation temperature about -5.degree.C below -10.degree.C ______________________________________

EXAMPLE 4

Comparison This invention ______________________________________ Sodium .beta.-olefin (C.sub.14) sulfonate 20% 20% Urea 14% 14% Mineral oil** 0% 0.7% ______________________________________ Turbidity-separation temperature about -4.5.degree.C below -6.degree.C ** : b.p. = 188 - 208.degree.C, specific gravity = 0.77 (15.6.degree.C), paraffin (n-C.sub.12 = 27%, iso-C.sub.12 = 35%, others = 38%).

EXAMPLE 5

Comparison This invention ______________________________________ Sodium POE(3) alkyl (C.sub.13.5)ether sulfate 20% 20% Urea 10% 10% n-Dodecane 0% 1% Turbidity-separation temperature about -4.degree.C below -6.degree.C ______________________________________

EXAMPLE 6

Comparison This invention ______________________________________ Sodium straight-dodecyl benzene sulfonate 15% 15% Sodium nonyl phenyl polyethoxy(3) acetate 5% 5% Sodium xylene sulfonate 14% 14% Ethanol 2% 2% Kerosene 0% 2% ______________________________________ Turbidity-separation temperature about -2.degree.C below -5.degree.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 15.degree.C below 12.degree.C ______________________________________

EXAMPLE 8

Comparison This invention ______________________________________ Sodium straight-dodecyl benzene sulfonate 20% 20% Ethanol 5% 5% Dodecyl benzene 0% 2.5% ______________________________________ Turbidity-separation temperature about 9.degree.C below 4.degree.C ______________________________________

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 -5.degree.C below -10.degree.C ______________________________________

EXAMPLE 10

The following liquid detergents (A) and (B) were prepared.

______________________________________ Liquid Comparison This invention detergent ingredients (A) (B) ______________________________________ Sodium straight-dodecyl benzene sulfonate 16% 16% Sodium nonyl phenyl polyethoxy (3) acetate 4% 4% Sodium citrate 2% 2% Urea 15% 15% Ethanol 2% 2% Mineral oil (same as used in Example 4) 0% 1.5% ______________________________________

1. When both the liquid detergents (A) and (B) were allowed to stand still at -5.degree.C 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 being coated with 5 g of a mixed oil-fat (consisting of 90% 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.

EXAMPLE 11

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

______________________________________ Detergent ingredients Comparison (C) This invention (D) ______________________________________ Sodium straight-dodecyl benzene sulfonate 15% 15% Sodium .alpha.-olefin (C.sub.14) sulfonate 5% 5% Sodium citrate 15% 5% Sodium metasilicate 5% 5% Sodium xylene sulfonate 4% 4% n-Dodecane 0% 2% ______________________________________

1. When both the detergents (C) and (D) were allowed to stand at -5.degree.C 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: 30.degree.C

Washing operation: at 100 rpm for 10 minutes

Rinsing: once for 5 minutes

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