JPS6031359B2 - liquid cleaning agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stable liquid detergent containing an anionic surfactant and a cationic surfactant.

In recent years, in the field of household detergents, there has been an increasing demand for liquid detergents containing an anionic surfactant and a cationic surfactant in order to provide both a cleaning effect and a softening effect at the same time.

However, in general, when an anionic surfactant and a cationic surfactant coexist in an aqueous solution, they form a water-insoluble complex and precipitate out, making it difficult to obtain a stable solution.

In order to solve such problems, using a combination of an anionic surfactant and a cationic polymer compound, or a combination of a cationic surfactant and an anionic polymer compound,
A method to make a homogeneous aqueous solution under specific conditions, or a method to prevent complex precipitation by using an alkyl ether sulfate as an anionic surfactant and a mono-long chain alkyl type quaternary ammonium salt as a cationic surfactant. (Japanese Unexamined Patent Publication No. 52-35203) has been proposed.

However, all of these methods are limited in the cationic surfactants or anionic surfactants that can be used.
It has the disadvantage that it cannot be applied to a wide range of surfactants.

The present inventors have conducted intensive research on a method of coexisting a cationic surfactant in a stable homogeneous solution using any anionic surfactant. It was discovered that the object could be achieved by using it in combination with alcohol, and based on this knowledge, the present invention was completed.

That is, the present invention provides (10 to 3% by weight of anionic surfactant, (o) general formula [in which at least one of R and R2 is the formula (where R is an alkyl group having 8 to 24 carbon atoms, R ' is a hydrogen atom or a methyl group, n is an integer of 0 or 1 to 5),
The rest are lower alkyl groups, lower hydroxyalkyl groups, or penzyl groups, R3 and R4 are lower alkyl groups, lower hydroxyalkyl groups, or penzyl groups, and X is a monovalent anion. Quaternary ammonium salt 0.1 to 8% by weight and represented by the general formula (in the formula, R5 is a lower alkyl group, R6 is a hydrogen atom or a lower alkyl group, and R7 is a lower alkyl group or a lower hydroxyalkyl group) 0.1-1% by weight of alcohol
The present invention provides a liquid cleaning agent consisting of an aqueous solution containing.

The anionic surfactant used as the component (A) of the present invention is a commonly used sulfonic acid type or sulfuric acid ester type anionic surfactant, such as Q having 10 to 20 carbon atoms.
-Olefin sulfonate, alkyl sulfate having 8 to 18 carbon atoms, alkyl ether sulfate derived from an alkyl ether obtained by adding an average of 0.5 to 10 moles of ethylene oxide to an alcohol having 8 to 20 carbon atoms, and 9 to 16 carbon atoms
These include alkylbenzene sulfonates having an alkyl group, paraffin sulfonates having 10 to 20 carbon atoms, and the like.

These may be used alone or as a mixture of two or more. The content of this component (i) is within the range of surfactant content in common liquid detergents, and is generally selected in the range of 10 to 3% by weight.

Next, the 'o} component of the present invention is a quaternary ammonium salt represented by the general formula (1), which includes the general formula (R'2 in the formula is the same as R3, R4 and same meaning 4
0) and compounds represented by are included.

This quaternary ammonium salt is produced by, for example, reacting a higher alcohol or an ether obtained by adding an alkylene oxide to a higher alcohol with epihalohydrin.
Reacting with a secondary amine or tertiary amine, or reacting a higher alcohol or an ether obtained by adding an alkylene oxide to a higher alcohol with a tertiary amine or quaternary ammonium salt having a glycidyl group. It can be manufactured by

The higher alcohol used in this case is preferably an alcohol whose main component is one having 12 to 18 carbon atoms, such as beef tallow alcohol and coconut oil alcohol.

Examples of the quaternary ammonium salt represented by the general formula (la) include 3-stearoxy2-hydroxypropyltrimethylammonium chloride, 31(8stearoxyethoxy)12-hydroxypropyltrimethylammonium chloride, and 31/f-lumitoxy. Examples include 2-hydroxypropyltrimethylammonium chloride.

Examples of the quaternary ammonium salt represented by the general formula (lb) include bis(3-stearoxy-2-hydroxypropyl)-dimethylammonium chloride, bis[3-(Bstearoxyethoxy)-2-hydroxypropyl ]-Dimethylammonium chloride, etc. It is important to use such a specific quaternary ammonium salt as the component (o) of the present invention.

The content of this (o} component is selected in the range of 0.1 to 8% by weight. If this amount is less than this, the expected effects of using this [o} component, such as softening effect and hair washing. Effects such as ease of subsequent combing cannot be obtained sufficiently, and if the amount exceeds this value, it becomes difficult to maintain a uniform solution state.Furthermore, the amount of this {o} component is
It is preferable to reduce the amount to 1/2 or less of the {i} component. Moreover, the first component of the present invention is a monoalcohol or glycol represented by the above general formula (b).

Examples of such alcohols include tert-amyl alcohol, 2-ethyl-1,3-hexanediol,
Examples include 2-butanol, 3-bentanol, 2-hexanol, and 6-methyl-2,4-hebutanediol. It is necessary to use such a specific alcohol as a component; if other alcohols are used, it is difficult to form a uniform aqueous solution.

The content of this component is selected within the range of 0.1 to 1% by weight.

If this amount is less than this, a sufficient stabilizing effect will not be obtained, and if it is too much, the water-removal properties of this component will be low, so no improvement in the stabilizing effect can be expected. , which is not preferable because it may reduce stability in some cases. Furthermore, one component of this is t.

} Advantageously, it is used in an amount equal to or greater than the amount of the component. The liquid detergent of the present invention is prepared by dissolving one of the above-mentioned components in water and thoroughly dispersing it in accordance with a conventional method.

In addition to the above-mentioned essential components, auxiliary additives commonly used in ordinary liquid detergents can be added to the liquid detergent of the present invention as desired. Examples of such additives include inorganic acid salts, organic acid salts, ethanol, perfumes, pigments, preservatives, and the like. The liquid cleansing agent of the present invention is a stable, transparent, homogeneous solution containing an anionic surfactant and a quaternary ammonium salt, and when used to clean hair, it foams well during use and leaves the hair dry after use. The effect of the quaternary ammonium salt makes it fluffy and supple, and when used for washing dishes, it has the advantage of being less irritating to the skin and lathering well.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 As the anionic surfactant, Q-olefin sulfonic acid sodium salt (Lion Oil Co., Ltd., Liporan 1400),
Using dodecyl sulfate sodium salt, lauryl ether sodium sulfate (average number of moles added with ethylene oxide: 3 moles), or alkylbenzenesulfonic acid sodium salt, and as a quaternary ammonium salt, 3-stearoxy 2
-Hydroxypropyltrimethylammonium chloride or bis(3-stearoxy-2-hydroxypropyl)dimethylammonium chloride were used in combination to prepare liquid cleaning agents, and their low temperature stability was investigated.

As the alcohol, rt-amyl alcohol was used, and the contents of each component were 15% by weight of anionic surfactant, 2% by weight of quaternary ammonium salt, and 2% by weight of alcohol. Table 1 shows the stability results for each combination after standing for two weeks at -5°C.

For comparison, a case where distearyldimethylammonium chloride was used as the quaternary ammonium salt is also shown. The meanings of the symbols in the table are as follows.

○...Completely melted △...turbidity x...precipitate Table 1 Note) SOTMAC: 3-stearoxy 2-hydroxyf.

Lopyltrimethylammonium chloride ODMAC; bis(3-stearoxy-2-hydroxypropyl)-dimethylammonium chloride DSDMAC; distearyldimethylammonium chloride Example 2 Except for using 2-ethyl-1,3-hexanediol as the alcohol. The low temperature stability of the liquid detergent prepared in the same manner as in Example 1 was investigated using the same machine as in Example 1, and the results are shown in Table 2.

Table 2 Note: Abbreviations and evaluation symbols for quaternary ammonium salts have the same meanings as in Table 1.

Comparative Example When an attempt was made to prepare a liquid detergent containing an anionic surfactant and a quaternary ammonium salt using the same combination as in Example 1 without adding an alcohol component, all of the liquid detergents became turbid or precipitated and were not uniform. It was not possible to prepare a suitable aqueous solution.

Example 3 15% by weight of Q-olefin sulfonic acid sodium salt was used as the anionic surfactant, and 3-stearoxy-2-hydroxyph was used as the quaternary ammonium salt.

By combining different amounts of lopyltrimethylammonium chloride, bis(3-stearyloxy-2-hydroxypropyl)-dimethylammonium chloride, or distearyldimethylammonium chloride, and using the same amount of 2-ethyl-1,3-hexanediol together. Various liquid cleaning agents were prepared. These were examined for low temperature stability in the same manner as in Example 1, and the results are shown in Table 3. 3 Note) Abbreviations and evaluation symbols for quaternary ammonium salts have the same meanings as in Table 1.

As is clear from this table, by using 2-ethyl-1,3-hexanediol in combination, up to 8% by weight of quaternary ammonium salt can be blended without any problem.

In the case of BSODMAC, turbidity is observed at 8% by weight, but it can be completely dissolved by increasing the amount of 2-ethyl-1,3-hexanediol to 1% by weight.

Example 4 Bis(3-stearoxy-2-hydroxypropyl)-dimethylammonium chloride was used as the quaternary ammonium salt in an amount of 5% by weight, and as alcohol 2-ethyl-1,3-hexanediol was used in an amount of 5% by weight. Liquid detergents were prepared by using the same combination and varying the amount of Q-olefin sulfonic acid sodium salt.

These were examined for low temperature stability in the same manner as in Example 1, and the results are shown in Table 4. 4 Note: The evaluation symbols have the same meanings as in Table 1. As is clear from this table, transparent and stable products can be obtained by increasing the amount of anionic surfactant to at least twice the amount of quaternary ammonium salt. A liquid cleaning agent is obtained.

Example 5 15% by weight of Q-olefin sulfonic acid sodium salt was used as the anionic surfactant, and bis(3-stearoxy-2-hydroxyph) was used as the quaternary ammonium salt.

Various liquid cleaning agents were prepared by using 2-ethyl-1,3-hexanediol as the alcohol and 2-ethyl-1,3-hexanediol as the alcohol, and varying the blending ratio of both. These were examined for low temperature stability in the same manner as in Example 1, and the results are shown in Table 5. Table 5 Note) Evaluation symbols have the same meanings as in Table 1. As is clear from this table, when the amount of quaternary ammonium salt blended is relatively small (2% by weight or less), 1/2 amount of 2-ethyl-1,3 per quaternary ammonium salt
- By using hexanediol in combination, a transparent solution can be obtained.

However, as the amount of quaternary ammonium salt increases, the amount of alcohol required to obtain a clear solution increases, and when the amount of quaternary ammonium salt increases to 6% by weight, the same amount of alcohol is required. Become.

Furthermore, at 8% by weight, a clear solution cannot be obtained even if the same amount of alcohol is added. Example 6 Table 6 shows the results of a foaming test on a liquid detergent containing a predetermined amount of Q-olefin sulfonic acid sodium salt and bis(3-stearoxy-2-hydroxypropyl)-dimethylammonium chloride or distearyldimethylammonium chloride. show.

Note that this liquid cleaning agent contains the same amount of 2-ethyl-1,3-hexanediol as the quaternary ammonium salt.
Foaming was measured by the Roth-Miles method under the conditions of 25q○, pH 6, and anionic surfactant concentration of 0.25% (W/V).

Table 6 The numbers in this table indicate foaming (ribs).

Furthermore, the abbreviations for quaternary ammonium salts have the same meanings as in Table 1. As is clear from this table, foaming is improved when an anionic surfactant and Shigeru ODMAC are used in combination.

On the other hand, in the case of DSDMAC, foaming is reduced. Example 7 Shampoo W containing peace (3-stearoxy-2-hydroxypropyl)-dimethylammonium chloride and 2-ethyl-1,3-hexanediol as an anionic surfactant, 2-ethyl-1,3-hexane A shampoo containing only diol (B} and a shampoo containing neither diol (C}) were prepared according to the formulations shown in Table 7, respectively.

Table 7 These three types of shampoo were used in combinations of ■-(C) and (B}-[C}, and were tested by 15 women each to evaluate their performance.

The results are shown in Table 8. In the evaluation results items in Table 8, Kaze-(C} represents the value obtained by subtracting the number of people who found ``Ku'' to be superior to the number of people who found ``Kyou'' to be superior, and {
B}-{C)' From the number of people who think that {B} is better{
It shows the value obtained by subtracting the number of people who said that C} was excellent. Table 8 As is clear from this table, by blending BSODMAC, a shampoo with excellent performance in terms of smoothness, softness, and ease of hair application can be obtained.

Example 8 Bis(3-stearoxy2) as a cationic surfactant
-Hydroxypropyl)-dimethylammonium chloride and 2-ethyl-1,3-hexanediol as the alcohol, the liquid detergent was prepared according to the formulation shown in Table 9.
' was prepared.

For comparison, }' was prepared without adding a cationic surfactant. Table 9 These two types of liquid cleaning compositions were subjected to a dipping test by 20 women, and the degree of roughness of their hands was clinically evaluated.

The test method was as follows. That is, for 10 people, their right hand was immersed in the aqueous solution of composition A' and their left hand was immersed in the aqueous solution of composition ○, and for the remaining 10 people, their right hand was immersed in the aqueous solution of composition ○ and their left hand was immersed in the aqueous solution of composition A', and a pairwise comparison was performed. The composition concentration was 1%, the soaking temperature was 4000°C, and the soaking time was 3 times a day. A soaking test was conducted for 2 consecutive days, and the results were evaluated the next morning. The judgment results are shown in the first table. Table 10 The numbers in this table represent the number of people who had less rough hands in A' minus the number of people who had less rough hands in ○.

Therefore, from the results in this table, it can be seen that in any combination, the cleaning agent of composition A' causes less rough hands.

Claims (1)

[Claims] 1 (a) Anionic surfactant 10 to 30% by weight, (b) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [At least one of R_1 and R_2 in the formula is the formula ▲ Numerical formula,
There are chemical formulas, tables, etc.▼ (However, R has 8 to 24 carbon atoms.
an alkyl group, R' is a hydrogen atom or a methyl group, n is an integer of 0 or 1 to 5), and the remainder is a lower alkyl group, a lower hydroxyalkyl group, or a benzyl group,
R_3 and R_4 are a lower alkyl group, a lower hydroxyalkyl group, or a benzyl group, and There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_5 is a lower alkyl group, R_6 is a hydrogen atom or a lower alkyl group, and R_7 is a lower alkyl group or a lower hydroxyalkyl group) 0.
A liquid cleaning agent consisting of an aqueous solution containing 1 to 10% by weight. 2. The liquid detergent according to claim 1, wherein the amount of component (B) relative to component (A) is 1/2 or less. 3. A liquid cleaning agent in which the amount of component (C) is at least equal to component (B).