JPH08199187A - Liquid detergent composition - Google Patents

Abstract

PURPOSE: To obtain a liquid detergent composition having low irritation to the skin of hand, face and body, and hair, etc., and excellent detergency, foamability, foam quality and use feeling, useful as a detergent, etc., by containing a specific ether sulfonate. CONSTITUTION: This liquid detergent composition contains (A) an ether sulfonate expressed by formula I [R<1> is an 8-36C alkyl or alkenyl; X<1> is O, COO, CONR<2> (R<2> is H or a 1-4C alkyl), S or SO2 , etc.; Y and Z are each H or a 1-2C alkyl; M<1> is H or an alkali metal, etc.; (n) is 0-10] and more preferably (B) a sulfobetaine of formula II [R<3> is an 8-18C alkyl or alkenyl; X<2> is (OR<8> )n (R<8> is a 2-4C alkylene), etc.; R<4> and R<5> are each a 1-2C alkyl]. The mixing amount of the component B is preferably 1-100wt.% based on the component A and pH of the composition is preferably in a range of 3.5-7.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition useful as a detergent for hands, face, body skin, hair and the like.
More particularly, it relates to a liquid detergent composition which is stable in a weakly acidic region, has excellent detergency, foamability, foam quality and feeling of use, and has very low irritation to skin and hair.

[0002]

2. Description of the Related Art Alkyl (or alkenyl) ether sulfonates (hereinafter simply referred to as "ether sulfonates"), which are anionic surfactants, have excellent detergency and foaming power when used in a neutral region, and also have a strong scum dispersive power. In addition, it is characterized by mild skin irritation (JP-A-62-25199, JP-A-62-195).
097 publication).

However, such surfactants such as ether sulfonates have at least one hydroxyl group in the molecule, and due to this hydrogen bonding force, they have a very high crystallinity and a high Kraft point, so that they become liquid detergents. Is poor in compoundability and is mainly used for solid detergents such as solid soap.

Therefore, it is desired to develop a liquid detergent while taking advantage of the characteristics of ether sulfonate. One such attempt is to use an alkyl polyoxyethylene ether sulfonate in which the crystallinity of ether sulfonate is reduced (Japanese Patent Laid-Open No. 52-147582). This compound is foamed with an increase in polyoxyethylene chain length. And a decrease in detergency were observed, which was not a preferable cleaning component. In addition, those having oxoalcohol at the raw material site of the alkyl chain (Shell: AGE product)
S / NEGS) is also known, but since this compound has a relatively high linearity of the alkyl chain of about 80 to 85%, it has a low solubility in water when used under weak acidity and is not suitable as a liquid detergent. There wasn't. On the other hand, recently, attempts have been made to improve the solubility by using a lower alkyl ether sulfonate having a short chain length or a hydrotrope agent (WO9216609, WO9109931).

However, the ether sulfonate having a lower alkyl group has an odor derived from unreacted raw materials and is not suitable as a base for a detergent used for the body and hair.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to achieve the above-mentioned properties while taking advantage of the characteristics of the ether sulfonate type surfactant, which have excellent detergency, foaming power, feeling of use and little skin irritation. It is an object of the present invention to provide a stable ether sulfonate-containing liquid detergent composition which does not have such drawbacks.

[0007]

In view of such circumstances, the inventors of the present invention have conducted diligent research and as a result, as a result, an alkyl, alkenyl or (poly) oxyalkylene group represented by the following general formula (1) having a high branching ratio. The present inventors have completed the present invention by finding that an aqueous ether sulfonate solution having a is stable liquid even under weak acidity, and that it is extremely useful as a liquid detergent because the characteristics of the ether sulfonate surfactant are utilized.

That is, the present invention has the following general formula (1):

[0009]

Embedded image

[In the formula, R ¹ is a linear or branched carbon atom number 8
To 36 alkyl or alkenyl groups, X ¹ is an oxygen atom COO, CONR ² (wherein R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), PO ₄ M ² , a sulfur atom or SO. ₂ is shown, and Y and Z are hydrogen atom or carbon number 1
2 represents an alkyl group, except when both Y and Z are alkyl groups. M ¹ and M ² represent a hydrogen atom, an alkali metal, ammonium, an alkylammonium having 2 to 9 carbon atoms or an alkanolammonium having 2 to 9 carbon atoms, and n represents an average addition mole number of 0 to 10. However, when n is 0 or both Y and Z are hydrogen atoms, the branching ratio of the alkyl or alkenyl group for R ¹ is 40.
~ 100%. ] The liquid detergent composition containing the ether sulfonate represented by these is provided.

The ether sulfonate used in the present invention is represented by the above general formula (1). The alkyl or alkenyl group represented by R ¹ in the formula (1) is represented by n in the formula.
Is 0 or both Y and Z are hydrogen atoms,
It has a branching ratio of 40 to 100% and a carbon number of 8 to 36. Here, the branching ratio means the weight% of the branched alkyl or alkenyl groups in all R ¹ alkyl or alkenyl groups.
Say. The branching rate is more preferably 45 to 100%, particularly preferably 80 to 100%. When the branching ratio is less than 40%, the Kraft point is high under weak acidity, and it is difficult to obtain a stable liquid composition, and when used as a liquid detergent, the characteristics of the ether sulfonate type surfactant, such as foaming, It is not preferable because performance such as feeling of use is deteriorated.

The branched alkyl group represented by R ¹ is
2-pentyldecyl group, 2-butylundecyl group, 2-
Examples thereof include a propyldecyl group, a 2-ethylnonyl group, a 2-methyloctyl group, a 2-hexyldecyl group and a 2-octyldecyl group. Examples of the branched alkenyl group include a 2-methyloctenyl group and a 2-octyldecenyl group. Can be mentioned.

The straight-chain alkyl group represented by R ¹ includes octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Examples thereof include a nonadecyl group, an eicosyl group, a heneicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, and a hexatriacontyl group. Examples of the straight-chain alkenyl group include an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, an eicosenyl group, a heneicosenyl group, and docosenyl. Group, tricocenyl group, tetracocenyl group, pentacocenyl group,
Examples thereof include a hexacocenyl group, a heptacocenyl group, an octacocenyl group, a nonacocenyl group, a triacontenyl group, and a hexatriacontenyl group.

Among these alkyl or alkenyl groups having a branching ratio of 40 to 100%, those having 10 to 20 carbon atoms, particularly 11 to 16 carbon atoms are preferable. An alkyl group is more preferable than an alkenyl group.

X ¹ is O, COO, CONR ² , P
O ₄ M ² , S or SO ₂ is shown, where R ² has 1 carbon atom.
As the alkyl group of ~ 4, methyl group, ethyl group, n-
Examples thereof include propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group. Of these X ^1, an oxygen atom is particularly preferable.

Y and Z are a hydrogen atom or an atom having 1 to 2 carbon atoms.
Alkyl group, ie methyl group, ethyl group, preferably water
Although it is an elementary atom or a methyl group, both Y and Z are
Unless it is a radical. Either Y or Z is
And Y and Z are both hydrogen atoms than in the case of the alkyl group.
R¹Is preferably branched from the viewpoint of production. M ¹
And M²Is a hydrogen atom; sodium, potassium, etc.
Alkali metal; ammonium; monoethylammonium
System, diethylammonium, triethylammonium, etc.
Alkyl ammonium; monoethanol ammoniu
System, diethanol ammonium, triethanol ammonium
Such as ammonium and monoisopropyl alcohol ammonium
Alkanol ammonium can be mentioned, but
Potassium metal, ammonium is preferred, especially sodium,
Preference is given to potassium and ammonium. n is the average addition mole
Indicates a number, and 0 to 10 is preferable, 0 to 5 is particularly preferable, and 0 to 3 is particularly preferable.
Good.

The ether sulfonate (1) is, for example, U
SP2260753, USP2327053, USP2
989547, Kuwamura et al., Journal of Industrial Chemistry, 63 (4), 5
95 (1960), ibid. 64 (11), 1958 (196)
It can be produced by the method described in 1) or the like. Specifically, for example, it can be produced according to the following reaction formula.

[0018]

[Chemical 4]

[In the formula, R ¹ is the same as above] That is, an epichlorohydrin is reacted with alcohol in the presence of tin tetrachloride to form a halohydrin compound, and an alkali such as sodium hydroxide is allowed to act on it. The desired ether sulfonate (1a) can be obtained by reacting with an epoxide derivative and a sulfonating agent such as sulfite such as sodium sulfite or sodium hydrogen sulfite.

In this reaction, the alcohol represented by R ¹ OH as a raw material is, for example, a highly branched oxo alcohol (Diadol 115L, etc .: Mitsubishi Chemical, Rial 123, etc .: Unichema, Exar, etc .: Exxon, etc., tridecanol: Kyowa Hakko et al.), A distillate mainly containing a branched portion of oxo alcohol having a high linear rate (Dovanol 231: Mitsubishi Kagaku etc.), Guerbet alcohol (β-branched alcohol), and the like.

Specific examples of the above reaction formula include the following.

[0022]

Embedded image

When an adduct of propylene oxide with a higher alcohol is used, X ¹ = 0 in the general formula (1),
Compounds with n = 1 to 10 are obtained.

A compound in which X ¹ is COO or CONR ² can be obtained by the method described in the literature [C
S195794 (1982), IN121696 (19
71)]. Those in which X ¹ is S or SO ₂ can be produced by using a branched alkyl type higher mercaptan such as t-dodecyl mercaptan as a raw material, and those in which X ¹ is PO ₄ M ² are disclosed in JP-A 62-123
It can be obtained from a branched higher alcohol according to the method described in Japanese Patent No. 191.

In the present invention, the following general formula (2) is used for the purpose of further stabilizing the liquid detergent composition.

[0026]

[Chemical 6]

[Wherein R³Is a straight chain having 8 to 18 carbon atoms or
Represents a branched chain alkyl or alkenyl group, X²Is (O
R⁸)_n(Where R⁸Is a straight or branched chain having 2 to 4 carbon atoms
Represents an alkylene group, and n represents a number of 0 to 10) or
CON (R⁶) R⁷-(Where R ⁶Is hydrogen atom or carbon number
1 to 4 alkyl groups, R⁷Is an alkane having 1 to 5 carbon atoms
Represents a xylene group), R^FourAnd R^FiveHas 1 to 2 carbon atoms
[Showing the alkyl group of]
Is preferred.

In the general formula (2), the alkyl group having 8 to 18 carbon atoms represented by R ³ is, for example, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group. Group, heptadecyl group, octadecyl group, and alkenyl groups include octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group. These may be linear or branched. Specific examples of those having a branched chain include 2-ethylhexyl, 2-pentyldecyl, 2-butylundecyl, 2-propyldecyl, 2-ethylnonyl and 2-methyloctyl groups. Among these, those having 10 to 16 carbon atoms, particularly those having 12 carbon atoms are preferable. Further, a straight chain is preferred to a branched chain, and an alkyl group is more preferred than an alkenyl group.

In the general formula (2), R ⁴ and R ⁵ are
A methyl group or an ethyl group can be mentioned, but a methyl group is preferable. Further, as the alkyl group of R ⁶ , a methyl group,
Examples thereof include ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group. R ⁷
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group.
^As the alkylene group of ⁸ , a methylene group, an ethylene group,
A propylene group and a butylene group are mentioned, but an ethylene group is preferable. Among the above X ² , the preferable one is (O
R ⁸ ) _n can be mentioned, and among these, the case where n = 0 is particularly preferable.

Among the sulfobetaines represented by the general formula (2), the following compounds are preferred.

[0031]

[Chemical 7]

In the composition of the present invention, the content of the ether sulfonate (1) is preferably 1 to 60% by weight, particularly 3 to 40% by weight, more preferably 5 to 30% by weight. It is preferable in order to raise.

On the other hand, the blending amount of sulfobetaine (2) is
It is preferably 1 to 100% by weight, preferably 10 to 90% by weight, particularly preferably 20 to 80% by weight, based on the ether sulfonate (1). If this amount is less than 1% by weight relative to (1), the stability of the aqueous solution will not be improved so much, and the meaning of blending will be small, and if it exceeds 100% by weight, high viscosity will occur. May occur, which is not preferable.

If necessary, the liquid detergent composition of the present invention may further contain a general anionic active agent (alkyl sulfate ester salt, which is used in soaps, facial cleansers, dishwashers, shampoos, body shampoos, cosmetics, etc.). Alkyl ether sulfate, α-olefin sulfonate, acylated taurine-based surfactant, acylated glycine-based surfactant, acylated sarcosine-based surfactant, acylated isethionate,
N-acyl acidic amino acid surfactant, higher fatty acid salt,
And acylated polypeptides), amphoteric surfactants (alkyl betaine type surfactants, amidopropyl betaine type surfactants, imidazolium betaine type surfactants, where betaine is carbobetaine, sulfobetaine, phosphobetaine. Non-ionic surfactant (coconut oil fatty acid diethanolamide, stearic acid monoglyceride, lauryl dimethylamine oxide, polyoxyethylene alkyl ether, polyoxyethylene fatty acid sorbitan ester, alkyl glycoside, acylated glucamine, etc.), cationic activity Agents (distearyl dimethyl ammonium chloride, lanolin fatty acid aminopropylethyl dimethyl ammonium sulphate), solvents (ethanol, propylene glycol, etc.), higher alcohols, polymers (thickeners) Antioxidants, preservatives, disinfectants, ultraviolet inhibitor, pearling agent, may be formulated oil, chelating agents, in the range that does not impair the effects of the present invention a perfume or the like.

These optional components may be used alone or in combination of two or more, and the compounding amount is not particularly limited, but in the composition of the present invention, it is in the range of 0 to 40% by weight, particularly 0 to 30% by weight. It is preferable to set the inside.

The composition of the present invention can be produced by mixing the above-mentioned components and water by a conventional method. Also,
The composition of the present invention can be adjusted to a desired pH with an organic acid, an inorganic acid, an organic base or an inorganic base, and the pH range is 3.5 to 7.0, particularly 4.0 to 6.5. , 4.5 more
From the viewpoint of the effect of the present invention, it is preferable to set it to 6.0.

[0037]

EFFECT OF THE INVENTION The liquid detergent composition of the present invention is excellent in liquid stability particularly under weak acidity, has good foaming, detergency and feeling of use and is low in irritation. Therefore, it is extremely useful as a weakly acidic detergent that can be used as a detergent that comes into direct contact with the skin, such as a detergent for kitchen, as well as a shampoo, a body shampoo and a face wash.

[0038]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
In addition, "%" means "weight%" below.

Synthesis Example 1 (Synthesis of n-dodecyl glyceryl ether sulfonic acid sodium salt):

[0040]

Embedded image

372 g of n-dodecyl alcohol (2 mo
l), epichlorohydrin 416g (4.5mol), tetrabutylammonium bromide 64g (0.2mol)
Was charged into a four-necked flask (with a condenser, a thermometer, and a stirrer), and 667 g (8 mol) of 48% NaOH was added to 5 times.
The mixture was added dropwise at 0 ° C and reacted at 50 ° C for 10 hours. After completion of the reaction, the product was washed with an aqueous NaCl solution and excess epichlorohydrin was distilled off to obtain 480 g of n-dodecyl glycidyl ether. (Reaction rate of alcohol: 93%) 145 g (0.6 mo) of n-dodecyl glycidyl ether
l), ethanol, NaHSO ₃ 94 g (0.9 mol),
25 g (0.2 mol) of Na ₂ SO ₃ and water were charged into a four-necked flask (with a cooling tube, a thermometer and a stirrer), and the reaction was carried out at 80 ° C. for 10 hours. After the reaction is completed, ethanol is added to desalt, and recrystallization is performed from an ethanol aqueous solution to obtain the target product, n-dodecyl glyceryl ether sulfonate Na.
210 g of salt (glycidyl ether reaction rate: 97%) was obtained.

Synthesis Examples 2 to 10 According to the method of Synthesis Example 1, the ether sulfonates shown in Table 1 were obtained.

[0043]

[Table 1]

Example 1 An aqueous surfactant solution was prepared using the ether sulfonates obtained in Synthesis Examples 1 to 10 and an alkyl sulfobetaine * 3 of the following formula. However, at that time, the pH of the aqueous solution was made weakly acidic by using a dilute hydrochloric acid aqueous solution. The appearance properties, liquid stability, foaming amount (20 ° C., 40 ° C.), and detergency of these aqueous solutions were evaluated by the following methods. The results are shown in Table 2 and Table 3.
Shown in

[0045]

[Chemical 9]

(Exterior Properties) After adjusting the 5% aqueous solution of each sample, the appearance properties were observed at 25 ° C. (heating the samples that are difficult to dissolve to dissolve them).

(Liquid stability) -Preparation of 5% aqueous solution of each sample, followed by 1 day at each temperature (-5
It was allowed to stand at 0 ° C., 0 ° C., 5 ° C., 25 ° C.) and the appearance was observed. ◯: Clear solution. X: Crystals are precipitated and are in a floating or precipitation state.

(Amount of foaming) -After preparing a 2% aqueous solution of each sample, 100 ml of this solution is poured into a graduated cylinder at a liquid temperature (20 ° C, 40 ° C). Then, the stirring blade was left in the above solution, and the volume ml of the foam generated 30 seconds after the start of stirring was measured.
The amount of foam was evaluated. 200 ml or more: good ○, 200 to 100 ml: slightly insufficient Δ, less than 100 ml: insufficient × The rotation speed of the stirring blade was 1000 rpm and it was reversed every 5 seconds.

(Cleaning power) -Comedo sebum (melting point 42 ° C) containing carbon black was applied to the forearm of a person, left for 5 minutes, foamed with a 5% aqueous solution, massaged 10 seconds 20 times, washed with water, and then blackened. The degree of fall was evaluated. Almost no residue: ○, obviously remaining: △,
Almost no fall: ×

[0050]

[Table 2]

[0051]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C11D 1/94 // (C11D 1/94 1:16 1:28 1:92)

Claims (4)

[Claims] 1. The following general formula (1): [In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 36 carbon atoms, X ¹ represents an oxygen atom, CO
O, CONR ² (wherein R ² is a hydrogen atom or a carbon number 1
~ 4 alkyl groups), PO ₄ M ² , sulfur atom or S
O ₂ is shown, and Y and Z are a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, except when both Y and Z are alkyl groups. M ¹ and M ² are hydrogen atom, alkali metal,
Ammonium, alkyl ammonium having 2 to 9 carbon atoms or alkanol ammonium having 2 to 9 carbon atoms, n
Represents a number of 0 to 10 in terms of the average number of moles added. However, when n is 0 or both Y and Z are hydrogen atoms, R
The branching ratio of the alkyl or alkenyl group of ¹ is 40 to 100
%. ] The liquid detergent composition containing the ether sulfonate represented by these. 2. The following general formula (2):[In the formula, R³Is a linear or branched alkane having 8 to 18 carbon atoms.
Represents a kill or alkenyl group, X²Is (OR⁸)_n(This
R here⁸Is a linear or branched alkylene having 2 to 4 carbon atoms
Group, n is a number from 0 to 10) or CON
(R⁶) R⁷-(Where R ⁶Is a hydrogen atom or 1 to 4 carbon atoms
Represents an alkyl group of R,⁷Is an alkylene having 1 to 5 carbon atoms
Represents a group)^FourAnd R^FiveIs an al having 1 to 2 carbon atoms
A sulfobetaine represented by
The liquid detergent composition according to claim 1, wherein 3. The liquid detergent composition according to claim 2, wherein the blending amount of sulfobetaine represented by the general formula (2) is 1 to 100% by weight based on the ether sulfonate represented by the general formula (1). Stuff. 4. The method according to claim 1, which has a pH of 3.5 to 7.0.
The liquid detergent composition according to any one of 1.