JPH05214362A - Anionic surfactant and detergent composition containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject surfactant having low protein denaturation ratio, excellent foaming properties, low-temperature stability and mildness, comprising a mixture of specific ether carboxylate. CONSTITUTION:The objective surfactant comprising a mixture of an ether carboxylate of formula I (R<1> is 8-20C alkyl or alkenyl; M is alkaline (earth metal, ammonium or alkanolamine; n is 0 or 1) wherein the average value n (av) of addition molar number of ethylene oxide contained in the ether carboxylate constituting the mixture is 1-10, the content of an ether carboxylate is <=10wt.% when the addition molar number (n) of ethylene oxide is 0 and the mixture has a weight distribution of the ether carboxylate to satisfy a formula II (Yi shows ratio % of the ether carboxylate when the addition molar number of ethylene oxide is i mol and P is addition molar number of ethylene oxide to the ether carboxylate having the highest content in the mixture).

Description

Detailed Description of the Invention

[0001]

The present invention relates to an anionic surfactant having excellent foamability and stability at low temperature, and having a very low protein denaturation rate, which gives a mild feeling to the skin, and a detergent containing the same. It relates to a composition.

[0002]

2. Description of the Related Art The general formula R--O-(CH ₂ C
H ₂ O) nCH ₂ COOM (wherein R is a higher alkyl group or an alkenyl group, n is an integer, and M is a salt-forming cation) are known.
This ether carboxylate is ethoxylated by adding ethylene oxide to higher alcohol R-OH having active hydrogen in the presence of an oxide catalyst, and then obtaining an adduct (higher alcohol ethoxylate) as an intermediate. It is prepared by reacting monochloroacetic acid with carboxylation and then forming a salt. by the way,
The ether carboxylate represented by the above general formula is widely used as an anionic surfactant. But,
The ether carboxylate obtained as described above contains unreacted higher alcohol, a compound obtained by adding ethylene oxide to this unreacted higher alcohol, a compound obtained by condensing monochloroacetic acid with this higher alcohol, and the like. Since the number n of added moles of was distributed over a wide range, it was not yet satisfactory in its surfactant performance and low temperature stability. Therefore, when such a conventional ether carboxylate is used as a body shampoo, a hair shampoo, a cleaning agent for kitchen, etc., its compounding amount is inevitably large, which is disadvantageous in terms of cost, and further low temperature There was also a problem such as poor storage properties.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above problems found when an ether carboxylate salt is used as a surfactant, and provides an anionic surfactant excellent in surfactant performance and low temperature stability. It is an object of the present invention to provide an anionic surfactant having an extremely low protein denaturation rate and an excellent mildness to the skin, and a detergent composition containing the same, as well as to provide an agent and a detergent composition containing the same. And

[0004]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, the general formula R ¹ —O— (CH ₂ CH ₂ O) nCH ₂ COOM (1) (wherein R ¹ is a higher alkyl group or alkenyl group having an average carbon number of 8 to 20) And M is an alkali metal, an alkaline earth metal, ammonium or an alkanolamine, and n is an integer of 0 or 1 or more), and an ethercarboxylic acid that constitutes the mixture. The average value n (av) of the added mole number n of ethylene oxide contained in the salt is in the range of 1 to 10, and the content of the ether carboxylate component having the added mole number n of ethylene oxide of 0 is 10% by weight. And further, the mixture has the following formula:

[Equation 1] (In the formula, Yi represents the weight% of the ethercarboxylic acid salt in which the number of moles of ethylene oxide added is i mole, and P represents the number of moles of ethylene oxide added in the ethercarboxylic acid salt having the highest content in the mixture). Provided are anionic surfactants characterized by having a satisfactory weight distribution of ether carboxylates and detergent compositions containing the same.

The anionic surfactant of the present invention comprises a mixture of ether carboxylates represented by the above-mentioned general formula (I) (hereinafter also referred to as mixture A). In this case, the ethercarboxylic acid salt components constituting this mixture A differ in the number of carbon atoms of R ¹ representing the higher alkyl group or alkenyl group and the number n of added moles of ethylene oxide (hereinafter abbreviated as EO). Higher alkyl group or alkenyl group R contained in ether carboxylate
The average carbon number of ¹ is 8 to 20, preferably 12 to 16. In this mixture A, the average addition mole number n (av) of EO contained in the ether carboxylate is preferably in the range of 1 to 10, more preferably in the range of 2 to 5. .. The average number of added moles of this EO n (a
When v) is less than 1, it is not preferable because the foaming performance as a surfactant is inferior and the "slimy feeling" is increased. Further, when n (av) exceeds 10, the hydrophilicity becomes too large, which causes problems such as deterioration of detergency, which is not preferable. In addition, in the mixture A, the content of the ether carboxylate component having an EO addition mole number n of 0 is 1
It is preferable to define it in the range of 0% by weight or less, preferably 0 to 3% by weight. If this content exceeds 10% by weight,
It is not preferable because it is inferior in foam performance and low temperature stability.

Further, in the mixture A, the weight distribution with respect to the number of moles n of EO addition of the ether carboxylate contained in the mixture A is preferably as sharp as possible, and the surfactant ability and the sliminess at the time of washing and mildness to the skin are preferable. From the viewpoint of the properties and stability at low temperature, it is necessary that the mixture A satisfies the above formula (I). Formula (I)
When the number of moles of EO addition of the ether carboxylate having the highest content is P, the number of moles of EO addition n is (P-2).
It shows the total content Y (% by weight) of the ether carboxylates in the range from (P + 2) to (P + 2). The larger the total content Y, the sharper (narrower) the weight distribution with respect to the EO-added mole number n of the ether carboxylate contained in the mixture A is. In the present invention, the total content Y is maintained at 55% by weight or more, preferably 65% by weight or more. When the total content Y is smaller than the above range, sliminess at the time of washing, mildness to skin, and low temperature stability are deteriorated, which is not preferable. Further, in the mixture A of the present invention, it is preferable that the EO addition mole number P of the ether carboxylate having the highest content and the average addition mole number n (av) of EO contained in the ether carboxylate are as close as possible. , Generally, the absolute value of the difference between the two | P
It is preferable that -n (av) | is in the range of 0 to 2.
A conventional ethercarboxylic acid salt mixture used as an anionic surfactant has an EO-added mole of the ethercarboxylic acid salt contained in the mixture, even if its n (av) is in the range of 1 to 10. The weight distribution for the number n is broad, the difference between P and n (av) becomes large, and EO
The content of the ether carboxylate having the added mole number n of 0 is the largest, and the value of P is usually 0. Such an ether carboxylic acid salt mixture is inferior in surfactant performance and low temperature stability, causes sliminess during washing, and is also inferior in mildness to the skin.

The anionic surfactant according to the present invention can be manufactured by a conventionally known method. For example, when reacting EO with higher alcohol ROH,
A magnesium oxide catalyst added with metal ions such as aluminum and gallium as a reaction catalyst while controlling the amount of EO added and reacted (JP-A-1-164437)
When the reaction is carried out using, the average number of moles of addition of EO n (av) is in the range of 1 to 10, the content of unreacted alcohol in which the number of moles of addition of EO is zero is about 10% by weight or less and the higher alcohol obtained A reaction intermediate having a sharp weight distribution with respect to the number of moles of EO-added ethoxylate is produced, and then this reaction intermediate is reacted with monochloroacetic acid in the presence of a hydrogen chloride binder (eg, alkali hydroxide). Then, the obtained carboxylated product is reacted with a base to form a salt.

If necessary, the anionic surfactant comprising the mixture A of the present invention may be used in combination with another anionic surfactant. In this case, the surfactant to be used in combination is used. The agents usually reduce the mildness to the skin. The present inventors have examined other preferable surfactants that can be used in combination with the surfactant of the present invention without deteriorating the lumildity to the skin, which is a feature of the surfactant. As a result, the following two kinds of anionic surfactants were found to be good. (A) Polyoxyethylene sulfate ester salt represented by the following general formula (2) R ² —O— (CH ₂ CH ₂ O) m-SO ₃ M (2) In the formula, R ² has 8 to 16 carbon atoms. Is an alkyl group or an alkenyl group, M is an alkali metal such as Na or K, an alkaline earth metal such as Mg, ammonium or an alkanolamine (for example, diethanolamine, 1-ethanolamine, especially triethanolamine), and m is 1 It is an integer of -6, especially an integer of 2-4. (B) Myristic Acid Salt Examples of the cation forming the salt include alkali metals such as Na and K, alkaline earth metals such as Mg, ammonium, and alkanolamine. The addition amount of the polyoxyethylene alkyl sulfate ester salt and / or myristic acid salt to be used in combination with respect to the mixture A is represented by the content rate in the entire mixture and is as follows. (A) Polyoxyethylene alkyl sulfate ester salt 0.1 to 20% by weight, preferably 0.1 to 5% by weight. (B) Myristic acid salt 0.1 to 20% by weight, preferably 0.1 to 10% by weight. When the amount of the (a) polyoxyethylene alkyl sulfate and / or (b) myristic acid is less than 0.1% by weight, no effect of using these surfactants in combination is observed, while those (a) And / or (b) the amount of the surfactant added exceeds 20% by weight, which is not preferable because the mildness to the skin decreases.

The detergent composition of the present invention comprises an anionic surface active agent comprising the above-mentioned mixture A or a mixture obtained by adding the above-mentioned (a) polyoxyethylene alkyl sulfate ester salt and (b) myristic acid salt to this mixture A. It contains an agent. The content of this anionic surfactant in the detergent composition is 1 to 50% by weight, preferably 5 to 40% by weight. If it is less than 1% by weight, the cleaning performance is poor and the intended purpose cannot be achieved. On the other hand, a content of more than 50% by weight is not preferable because it is difficult to liquefy with water, for example, when using.

The detergent composition of the present invention contains various additives and auxiliary agents used in ordinary detergent compositions in order to obtain a product form suitable for the purpose of use, such as shampoo, body shampoo and kitchen detergent. The components can be contained within the range without particularly impairing the object of the present invention. Examples of these additives include water, ethanol, isopropanol, solvents such as propylene glycol, and high molecular compounds such as polyethylene glycol, polyethylene oxide, higher alcohol ethoxylates, chitosan, carrageenan, and cellulose derivatives. You can Further, the detergent composition of the present invention, it is also possible to add higher fatty acids, acylated amino acid salts, betaine alkyldimethylaminoacetate, activators such as alkyldimethylaminohydroxypropylsulfobetaine in an appropriate ratio, Furthermore, sequestering agents such as ethylenediaminetetraacetic acid and citric acid, antifungal agents such as benzoic acid, dyes and fragrances may be added. These additives and auxiliary ingredients are 9
It can be used in the range of 9 to 50% by weight, preferably 97 to 60% by weight. The cleaning composition of the present invention is a solid,
It can be used in the form of various cleaning agents such as liquid and paste. When used as a liquid or paste-like cleaning agent, it has improved low-temperature stability as compared with conventional cleaning agents of the same type.

The anionic surfactant of the present invention can be used as various detergent components in the same manner as conventional ones. However, by utilizing the property of being well foamed and mild to the skin, shampoo is particularly useful. It is ideal as a body cleanser for body shampoos, cleansing cosmetics, etc. Further, since it is mild to the hand and has little "slimming" feeling, it is also suitable as a kitchen detergent.

[0012]

EXAMPLES Next, the present invention will be described in more detail by way of examples. All% and parts shown below are based on weight.

The contents of the test item evaluation methods shown below are as follows. (1) Foaming property 1% of the test liquid is placed on a wet towel, and the towel is grabbed on an empty washbasin until bubbles disappear, and the volume of bubbles generated at that time is measured with a graduated cylinder. (2) Protein denaturation rate This is one of the criteria for evaluating the mildness to the skin and is measured as follows. The detergent composition was diluted with a buffer solution having the following composition so that the concentration of the surfactant was 1%, and the mixture was allowed to stand at 40 ° C. for 24 hours, and then the denaturation rate of ovalbumin was measured by a chromatography method. The mildness was evaluated according to the following criteria. (Buffer solution formation) NaH ₂ PO ₄ · 12H ₂ O: 0.02 mol / l NaHPO ₄ · 2H ₂ O: 0.03 mol / l Na ₂ SO ₄ : 0.15 mol / l (liquid chromatographic conditions) 1) Transfer Layer: Buffer solution 2) Injection amount: 4 μl 3) Column temperature: room temperature 4) Column: TSK-GER G3000SWXL (manufactured by Tosoh Corporation) 5) Flow rate: 0.8 ml / min (calculation of protein denaturation rate) (Evaluation Criteria for Mildness to Skin) A: Protein denaturation rate of 30% or less B: Protein denaturation rate of 31 to 70% C: Protein denaturation rate of 71% or more (3) Low temperature stability A detergent composition is kept at a constant temperature of -5 ° C. If the condition when left in the tank for 1 month is the same as the initial value, it is ○, if the appearance is slightly changed, it is △, and if it is significantly changed, it is ×.
Evaluated as.

Example 1 A predetermined amount of anionic surfactant listed in Table 1 was added to Table 1
Add the additives listed as other ingredients to 100% of the total amount.
The detergent composition thus obtained was used to test its foamability, protein denaturation rate and low temperature stability. The results are shown in Table 1.

Example 2 and Example 3 To a predetermined amount of the anionic surfactant shown in Table 1, a predetermined amount of polyoxyethylene sulfate / triethanolamine salt or myristate triethanolamine salt was added. The additives listed in Table 1 as other components were added to this mixture to make the total amount 100%, and the foaming property, protein denaturation rate and low temperature stability were tested using the detergent composition thus obtained. The results are shown in Table 1.

Comparative Example A detergent composition having the same composition as in Example 1 was prepared.
However, in this case, the content of the by-product (carboxylate of unreacted higher alcohol) in the anionic surfactant was higher than that in Example 1 and was 9% by weight, and the EO addition of the ether carboxylate was performed. The weight distribution with respect to the number of moles was broad, and its N (av) was 4, but the number of moles P with EO of the ether carboxylate giving the highest content was 1. Further, the value represented by the formula (I) is 41
% By weight. Foamability, protein denaturation rate and low temperature stability were also tested using this composition, and the results are shown to be inferior to the composition of Example 1 as shown in Table 1.

[0016]

[Table 1]

[0017]

EFFECT OF THE INVENTION The anionic surfactant of the present invention and the detergent composition containing the same have a foaming property,
Both the protein denaturation rate and the low temperature stability are improved. Also, the combination of polyoxyethylene sulfate and myristic acid salt shows excellent performance. The detergent composition of the present invention has good foamability, has an extremely low protein denaturation rate and is mild to the skin, and thus is not only useful as a skin detergent for hair shampoos, body shampoos, etc., but also a kitchen detergent. It is also useful as it brings a mild feeling to the hand.

Front Page Continuation (72) Inventor Fumio Wakui 1-3-7 Main Office, Sumida-ku, Tokyo Lion Corporation

Claims (3)

[Claims] 1. A compound represented by the general formula R ¹ —O— (CH ₂ CH ₂ O) nCH ₂ COOM (1) (wherein R ¹ is a higher alkyl group or alkenyl group having an average carbon number of 8 to 20, Is an alkali metal, alkaline earth metal, ammonium or alkanolamine, and n is an integer of 0 or an integer of 1 or more), and is contained in the ether carboxylate constituting the mixture. The average value n (av) of the added mole number n of ethylene oxide is in the range of 1 to 10, and the content of the ether carboxylate component having the added mole number n of ethylene oxide is 0 is 10% by weight or less. , And the mixture has the following formula: (In the formula, Yi represents the weight% of the ethercarboxylic acid salt in which the number of moles of ethylene oxide added is i mole, and P represents the number of moles of ethylene oxide added in the ethercarboxylic acid salt having the highest content in the mixture). An anionic surfactant characterized by having a satisfactory weight distribution of ether carboxylate. 2. A detergent composition containing the anionic surfactant according to claim 1. 3. An anionic surfactant according to claim 1, and at least one surfactant selected from the following anionic surfactants (a) and (b). Body cleaning agent or kitchen cleaning agent. (A) polyoxyethylene sulfates _{^{R 2 -O- (CH 2 CH 2}} O) m-SO 3 M (2) ( wherein represented by the following general formula (III), R ² is 8 to 16 carbon atoms Is an alkyl group or an alkenyl group of M is an alkali metal, an alkaline earth metal,
Ammonium or alkanolamine, m is 1
(B) myristic acid salt (provided that the cation forming the salt is an alkali metal, an alkaline earth metal, ammonium or an alkanolamine).