JP3315828B2 - Detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition, and more particularly, it has good lathering during washing, has good lather removal when rinsing, and has no irritating effect on the skin. The present invention relates to a detergent composition which is low in storage stability and excellent in storage stability.

[0002]

2. Description of the Related Art Cleaning compositions such as kitchen cleaners, hair cleaners, and body cleaners generally contain an anionic surfactant as a main component, and are mainly composed of higher fatty acid salts (soaps) and alkyl sulfates. , Sulfonates and the like are used. However, when soap is used for skin washing, for example, soap scum (higher fatty acid Ca salt) is generated and adheres to the skin at the time of rinsing, so that the lubricating property of the skin surface is significantly reduced, and creaking and firmness are caused. there were. In addition, when an alkyl sulfate, a sulfonate, or the like is used for washing hair, there are no defects such as squeak and tightness, but poor foam removal and poor lubricity of hair.

[0003] For the purpose of remedying these drawbacks, various attempts have been made to incorporate various auxiliaries such as oils such as higher alcohols and co-activators. Since the effect, the foaming power, the feeling upon use, etc. are reduced, it is easy to be restricted by the prescription, and it has been difficult to obtain a sufficiently satisfactory cleaning agent.

Further, a detergent composition containing an acyl imino dibasic acid type anionic surfactant has been studied (JP-A-2-84496, JP-A-5-117139, JP-A-6-80987). These cleaning agents have a detergency,
Although the foaming power, feeling of use, etc. are improved, the acylimino dibasic acid type anionic surfactant used as a detergent is a derivative from iminodiacetic acid, and it is particularly poor in storage stability at low temperatures. There was a problem.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide good foaming, good foam retention, good foam removal at the time of rinsing, no sliminess, low irritation and low-temperature storage stability. Another object of the present invention is to provide an excellent cleaning composition.

[0006]

Under such circumstances, the present inventors have conducted intensive studies. As a result, when a specific glycine derivative and a fatty acid amide derivative are used in combination, good foaming and good foam retention are obtained during washing. However, the present inventors have found that a cleansing composition can be obtained which has good foam removal during rinsing, does not cause sliminess, has little irritation to the skin, and has excellent low-temperature storage stability.

That is, the present invention relates to (A) the general formula (1)

[0008]

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(Wherein R ¹ represents a linear or branched alkyl group, alkenyl group or hydroxyalkyl group having 7 to 21 carbon atoms, M ¹ and M ² are the same or different and each represents a hydrogen atom, an alkali metal A mono-, di- or trialkanol ammonium having 1 to 22 carbon atoms, or an alkaline earth metal, ammonium, or a basic amino acid), and (B) a glycine derivative represented by the following general formula (2):

[0010]

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Wherein R ² represents an alkyl group having 7 to 21 carbon atoms, and R ³ and R ⁴ are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. hydroxyalkyl group or a - (where m indicates the number of _{2~4) (C 2 H 4 O} ) m H group is to provide a detergent composition containing a fatty acid amide derivative represented by showing a].

The component (A) used in the present invention is a glycine derivative represented by the general formula (1). Where R
^As a linear or branched alkyl group, alkenyl group, or hydroxyalkyl group having 7 to 21 carbon atoms represented by ¹ ,
For example, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-heptadecyl group , Methylhexadecyl group, ethylpentyl group, heptadecenyl group, hydroxyundecyl group and the like. Of these, alkyl and alkenyl groups having 7 to 21 carbon atoms are preferred from the viewpoint of foaming properties and the like, and those having 9 to 15 carbon atoms are particularly preferred.

In the general formula (1), M ¹ and M ² are, for example, hydrogen atom, sodium, potassium, magnesium, calcium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, arginine, histidine, lysine And the like. Of these, sodium, potassium, triethanolammonium and arginine are preferred, and sodium and potassium are particularly preferred.

The glycine derivative (1) as the component (A) includes N-lauroyl-N-carboxyethylglycine sodium salt, N-lauroyl-N-carboxyethylglycine potassium salt, N-lauroyl-N-carboxyethylglycine trisulfate. Ethanol ammonium salt, N-myristyl-N-carboxyethylglycine sodium salt,
N-myristyl-N-carboxyethylglycine potassium salt, N-myristyl-N-carboxyethylglycine triethanolammonium salt, N-myristyl-N-
Carboxyethylglycine arginine salts are preferred.

Such a glycine derivative (1) can be produced, for example, according to the following reaction formula.

[0016]

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(Wherein R ¹ , M ¹ and M ² have the same meaning as described above)

That is, glycine represented by the general formula (3) or a salt thereof is reacted with acrylonitrile to obtain a glycine derivative (4) (step A), which is hydrolyzed,
If necessary, salt exchange is performed to obtain a glycine derivative (7) (Step B), and then reacted with an acid chloride (5),
If necessary, salt exchange (Step E), (A)
The component glycine derivative (1) can be obtained. Further, the glycine derivative (4) obtained in the step A is reacted with an acid chloride (5), and if necessary, salt exchange is performed to obtain a glycine derivative (6) (step C), which is then hydrolyzed. The glycine derivative (1) of the component (A) can also be obtained by subjecting to salt exchange as required (Step D).

Hereinafter, each step will be described. (Step A) In this step, glycine or a salt thereof (3) is reacted with acrylonitrile to obtain a glycine derivative (4). Glycine or a salt thereof, which is a raw material, and acrylonitrile may be any of those manufactured by a known method and those which are commercially available, but if necessary, recrystallized, purified by distillation or the like. May be used.

Specific examples of glycine or its salt (3) include glycine, glycine sodium salt, glycine potassium salt, glycine lithium salt, glycine magnesium salt,
Glycine calcium salt, glycine ammonium salt, glycine ethylenediamine salt, glycine propylenediamine salt and the like can be mentioned, and glycine sodium salt, glycine potassium salt and glycine ammonium salt are particularly preferable.

In this step, glycine or a salt thereof (3) and 0.5 to 10 equivalents of acrylonitrile are dissolved in water at an appropriate temperature of 10 to 100 ° C, preferably 30 to 70 ° C, for 0.5 to 100 ° C. The glycine derivative (4) can be obtained by reacting for a period of time, preferably 1 to 3 hours, and, if necessary, exchanging counter ions using an electrodialyzer or the like. If the reaction time is longer than 100 hours, side reactions such as hydrolysis of a cyano group occur undesirably. At the time of the reaction, if measures such as acrylonitrile are gradually added dropwise to an aqueous solution of glycine or a salt thereof (3), side reactions such as polymerization of acrylonitrile are remarkably suppressed, and the yield is improved. The glycine derivative (4) obtained in this step can be directly used in the next step, but if necessary, recrystallized using a solvent such as water, methanol, ethanol or the like to obtain a highly purified product. You can also.

(Step B) This step is a step of hydrolyzing a cyano group of the glycine derivative (4) obtained in the step A, preferably in the presence of a basic substance, to obtain a glycine derivative (7). . Examples of the basic substance used herein include alkali metal hydroxides and alkaline earth metal hydroxides. Specific examples include sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide.
Barium hydroxide and the like can be mentioned.

In this step, the glycine derivative (4)
In an aqueous solution in the presence of 0.1 to 30 equivalents of a basic substance, if necessary, in a mixed solution of water and a polar solvent such as methanol, ethanol, isopropanol, acetone, 1,3-propanediol, and propylene glycol. At 50
The glycine derivative (7) is obtained by reacting at an appropriate temperature of 100 to 100 ° C, preferably 70 to 100 ° C for 0.5 to 100 hours and, if necessary, exchanging counter ions using an electrodialyzer or the like. Can be. The glycine derivative (7) obtained in this step can be directly used in the next step, but if necessary, recrystallized using a solvent such as water, methanol, ethanol or the like to obtain a highly purified product. You can also.

(Step C) This step is a step of reacting the glycine derivative (4) obtained in the step A with an acid chloride (5) preferably in the presence of an alkaline substance to obtain a glycine derivative (6). is there. As the acid chloride (5) as a raw material, any of those manufactured by a known method, commercially available ones, and the like may be used, but if necessary, purified ones such as distillation may be used. Acid chloride (5)
Examples of the hexanoic acid chloride, octanoic acid chloride, decanoic acid chloride, dodecanoic acid chloride, tetradecanoic acid chloride, hexadecanoic acid chloride, octadecanoic acid chloride, 2-ethylhexanoic acid chloride, isostearic acid chloride, oleic acid chloride and the like Fatty acid chlorides having a mixed composition such as fatty acid chloride having a single composition, coconut oil fatty acid chloride, and tallow fatty acid chloride are exemplified.

In this step, the glycine derivative (4)
And usually 0.8 to 5.0 equivalents, preferably 0.9 to 1.3 equivalents.
Equivalent acid chloride (5) in an aqueous solution, if necessary, in a mixed solution of water and a polar solvent such as methanol, ethanol, isopropanol, acetone, 1,3-propanediol, propylene glycol, etc., at 0 to 100 ° C. The glycine derivative (6) can be obtained by reacting at an appropriate temperature of preferably 10 to 50 ° C. for 0.5 to 100 hours and, if necessary, exchanging counter ions using an electrodialyzer or the like. If the amount of the acid chloride (5) used is less than the above range, a large amount of the glycine derivative (4) remains in the reaction product, and if it is more than the above range, the unreacted acid chloride (4) From 5), a large amount of fatty acids is undesirably produced as a by-product.

In this step, in order to ensure the reactivity and allow a certain reaction to proceed, an alkaline substance is added to the reaction system, and the pH in the system is set to the alkali side, preferably the pH is adjusted to 9.0 to 9.0.
It is desirable to keep in the range of 11.0. If the pH of the reaction system is lower than this range, hydrochloric acid by-produced by the progress of the reaction forms a salt with the unreacted glycine derivative (4) and the reaction does not proceed sufficiently, while the pH is higher than this range. In this case, the decomposition of the acid chloride (5) is promoted, and a large amount of fatty acids is by-produced. Specific examples of the alkaline substance used include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, and sodium carbonate; and organic bases such as triethylamine, pyridine, and 4- (dimethylamino) pyridine. But especially sodium hydroxide,
Potassium hydroxide is practical. The amount of these alkaline substances used is such that the pH in the system is maintained within the above range.

The glycine derivative (6) obtained in this step can be used as it is in the next step. However, if necessary, recrystallization is carried out using a solvent such as water, methanol or ethanol, or hydrochloric acid, sulfuric acid or the like is used. After treatment with strong acid
The acid form of the glycine derivative (6) was obtained, recrystallized using a solvent such as acetone, hexane, petroleum ether, methanol, ethanol, butanol, and then again using a suitable neutralizing agent to obtain the glycine derivative ( By performing 6), a purified product with higher purity can be obtained.

(Step D) This step is a step of hydrolyzing the cyano group of the glycine derivative (6) obtained in Step C, preferably in the presence of a basic substance, to obtain the glycine derivative (1). . Examples of the basic substance used herein include alkali metal hydroxides and alkaline earth metal hydroxides. Specific examples include sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide.
Barium hydroxide and the like can be mentioned.

In this step, the glycine derivative (6)
In an aqueous solution in the presence of 0.1 to 30 equivalents of a basic substance,
If necessary, in a mixed solution of water and a polar solvent such as methanol, ethanol, isopropanol, acetone, 1,3-propanediol, propylene glycol, etc.
The glycine derivative (1) can be obtained by reacting at an appropriate temperature of 100 ° C., preferably 70 to 100 ° C. for 0.5 to 100 hours and, if necessary, exchanging counter ions using an electrodialyzer or the like. it can.

The glycine derivative (1) obtained by this step can be used as it is in a detergent composition. If necessary, recrystallization is carried out using a solvent such as water, methanol or ethanol, or hydrochloric acid or sulfuric acid. After treatment with a strong acid such as glycine derivative (1), an acid form of the glycine derivative (1) is obtained, which is recrystallized using a solvent such as acetone, hexane, petroleum ether, methanol, ethanol, or butanol. By using the glycine derivative (1) with a wetting agent, a purified product with even higher purity can be obtained.

(Step E) This step is a step of reacting the glycine derivative (7) obtained in the step B with an acid chloride (5) preferably in the presence of an alkaline substance to obtain a glycine derivative (1). is there. The same acid chloride (5) as the raw material may be used as in step C.

In this step, the glycine derivative (7)
And usually 0.8 to 5.0 equivalents, preferably 0.9 to 1.3 equivalents.
Equivalent acid chloride (5) in an aqueous solution, if necessary, in a mixed solution of water and a polar solvent such as methanol, ethanol, isopropanol, acetone, 1,3-propanediol, propylene glycol, etc., at 0 to 100 ° C. The glycine derivative (1) can be obtained by reacting at an appropriate temperature of preferably 10 to 50 ° C. for 0.5 to 100 hours and, if necessary, exchanging counter ions using an electrodialyzer or the like. If the amount of the acid chloride (5) used is smaller than the above range, a large amount of the glycine derivative (7) remains in the reaction product. From 5), a large amount of fatty acids is undesirably produced as a by-product.

In this step, in order to ensure reactivity and allow a certain reaction to proceed, an alkaline substance is added to the reaction system, and the pH in the system is shifted to the alkali side, preferably the pH is adjusted to 9.0 to 9.0.
It is desirable to keep in the range of 11.0. When the pH of the reaction system is lower than this range, hydrochloric acid by-produced by the progress of the reaction forms a salt with the unreacted glycine derivative (7) and the reaction does not proceed sufficiently, while the pH is higher than this range. In this case, the decomposition of the acid chloride (5) is promoted, and a large amount of fatty acids is by-produced. Specific examples of the alkaline substance used herein include sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, inorganic bases such as sodium carbonate,
Triethylamine, pyridine, 4- (dimethylamino)
Examples thereof include organic bases such as pyridine, and particularly, sodium hydroxide and potassium hydroxide are practical. The amount of these alkaline substances used is such that the pH in the system is maintained within the above range.

The glycine derivative (1) obtained in this step can be used as it is in a detergent composition. However, if necessary, the same post-treatment as in step D can be carried out to obtain a higher-purity purified product. You can also.

The glycine derivative of the component (A) can be used alone or in combination of two or more. The amount of component (A) in the detergent composition of the present invention varies depending on the type of detergent and the like, but is preferably 2 to 60% by weight (hereinafter simply referred to as%) in the total composition, Especially 5-5
0% is preferable because foaming is good and a refreshing feeling can be obtained.

The component (B) used in the present invention is a fatty acid amide derivative represented by the general formula (2). In the formula, the alkyl group represented by R ² has 7 to 21 carbon atoms, and particularly preferably has 12 to 18 carbon atoms, for example, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, heptadecyl group and the like. The combination of R ³ and R ⁴ is preferably a case where both are a hydroxyalkyl group, particularly a hydroxyethyl group, or a case where one is a hydroxyalkyl group, particularly a hydroxyethyl group and the other is a hydrogen atom. As the fatty acid amide derivative of the component (B), lauric acid monoethanolamide, lauric acid diethanolamide, coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, lauric acid monoisopropanolamide, and coconut oil fatty acid monoisopropanolamide are preferable.

The amount of the component (B) in the cleaning composition of the present invention varies depending on the dosage form, etc.
It is preferable to mix 10% to 10%, and it is particularly preferable to mix 1% to 5% because the foam quality becomes very creamy.

Component (A) in the cleaning composition of the present invention
The mixing ratio of the component (B) and the component (B) is (A) / (B) = 1 by weight.
00/1 to 2/1, particularly preferably 50/1 to 5/1.
The total amount of the components (A) and (B) varies depending on the type of the detergent composition, but in the case of a liquid detergent, 5 to 50% of the composition, and in the case of a paste-like detergent, 15 to 50%. 70%,
In the case of a solid detergent, the content is preferably 40 to 95%.

The detergent composition of the present invention comprises a surfactant other than the above, for example, an anionic surfactant such as N-acyl sarcosine salt, alkyl ether sulfate, polyoxyethylene alkyl ether sulfate, etc .; Nonionic surfactants such as alkyl ethers, sugar esters and sugar amides; amphoteric surfactants such as imidazoline and betaine can also be used in combination as long as the effects of the present invention are not impaired.

As other additives, components usually used in detergents such as carboxyvinyl polymer, methylcellulose, ethanol, polyoxyethylene glycol distearate, etc .; viscosity modifiers; An agent, an antioxidant, a bactericide, an anti-inflammatory agent, a preservative, and the like can be arbitrarily compounded as long as the effects of the present invention are not impaired.

The detergent composition of the present invention can be produced according to a conventional method, and its dosage form is not particularly limited, and it can be prepared in any form such as liquid, paste, cream, solid, and powder. In particular, it is preferable to use a liquid, paste, or cream. In the case of a liquid state, it is preferable to use water as a liquid medium, and it is preferable that the blending amount of water is 50 to 90% in the whole composition. Further, the cleaning composition of the present invention is suitable as a body cleaning agent for skin, hair, and the like, and particularly preferably for skin cleaning.

The detergent composition of the present invention preferably has an aqueous solution having a pH of 4 to 9, particularly 5 to 7, when diluted 10 times by weight with water. In order to obtain a preferable pH, it may be adjusted by adding an acid or an alkali to the detergent composition, and an equimolar ion exchange may be performed on the component (A).

[0043]

EFFECTS OF THE INVENTION The cleaning composition of the present invention has good lathering and lather retention during cleaning, has good lather removal during rinsing, does not cause sliminess, has little skin irritation, and has a low temperature. It is also excellent in storage stability, especially for the body,
Useful as a facial skin cleanser.

[0044]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Example 1 The components having the compositions shown in Tables 1 and 2 were uniformly mixed, and the pH was adjusted with hydrochloric acid to prepare a detergent composition. In addition,
The pH of each detergent composition was prepared by preparing a 10-fold weight-diluted aqueous solution, taking 50 ml of this solution, and at a temperature of 25 ° C.
It measured using HORIBA pH meter F-14.
The obtained cleaning composition was evaluated for storage stability, foaming, and feeling upon use. The results are shown in Tables 1 and 2.

(Evaluation Method) (i) Storage stability: 50 ml of each detergent composition was filled in a glass screw tube, sealed, and stored for one month in a 5 ° C. constant temperature room. One month later, the liquid state of the contents was visually observed and evaluated according to the following criteria. ；: Uniform transparent liquid. X: Crystals precipitated or clouded.

(Ii) Foaming: For each detergent composition,
A 10-fold diluted aqueous solution was prepared, and 100 ml of this aqueous solution (liquid temperature: 40 ° C.) was poured into a graduated cylinder. Next, a stirring blade was installed in the aqueous solution, the blade was rotated, and the volume (ml) of the foam generated 30 seconds after the start of stirring was measured to determine the foaming amount, which was evaluated according to the following criteria. The rotation speed of the stirring blade was 1000 rpm, and was reversed every 5 seconds. ；: Foaming amount 200 ml or more. ；: Bubbling amount 160 ml or more and less than 200 ml. Δ: Foaming amount 120 ml or more and less than 160 ml. ×: Foaming amount less than 120 ml.

(Iii) Feeling of Use: Ten male and female panelists were allowed to wash the body for one week using each cleaning composition, and sensory evaluation was performed on the following items.
In the evaluation, an average value was calculated based on the following criteria, and the average value was 3.
5 or more is very good (◎), 3.5 to 4.4 is good (○), 2.5 to 3.4 is normal (△),
The case of 2.4 or less was determined to be defective (x). (1) Foaming; 5; Good foaming. 4: Slight foaming. 3: Normal. 2: The foaming is slightly poor. 1; Foaming is poor. (2) Foam retention; 5; Good foam retention. 4: Slightly good foam retention. 3: Normal. 2; Slightly poor foam retention. 1; foam retention is poor. (3) Out of bubbles during rinsing; 5; Out of bubbles is good. 4: Slightly defoamed. 3: Normal. 2: The foaming is somewhat poor. 1; foaming is poor. (4) Refreshing feeling when drying the towel; 5; Refreshing. 4: Slightly refreshing. 3: Normal. 2: Slightly slimy. 1;

[0049]

[Table 1]

[0050]

[Table 2]

As is clear from Tables 1 and 2, the cleaning compositions of the present invention were all excellent in storage stability, foaming and feeling upon use. In addition, the cleaning composition of the present invention was excellent in detergency and extremely weak in irritation to hand skin.

Example 2 (Whole body cleaning agent)

(Table 3) (Components) (%) (1) N-lauroyl-N-carboxyethylglycine sodium salt 15 (2) N-myristoyl-N-carboxyethylglycine sodium salt 5 (3) lauric acid diethanolamide 5 (4 ) Methylcellulose 0.1 (5) Fragrance 0.5 (6) Ethanol 3 (7) Purified water balance

After dissolving the components (1) and (2) in purified water heated according to the above composition, the components (3) to (6) are added, mixed and cooled to obtain a transparent liquid detergent composition (whole body). Washes). The pH of a 10-fold dilution aqueous solution of the obtained detergent was 6.0.

When the skin and hair were washed with the obtained detergent, the foaming and rinsing properties were good and a refreshing feeling was obtained, and the feeling of use was excellent. In addition, there was little irritation to the skin and the storage stability was good.

Example 3 (face wash)

(Components) (%) (1) N-lauroyl-N-carboxyethylglycine 12 (2) N-myristoyl-N-carboxyethylglycine 8 (3) arginine 8 (4) coconut oil fatty acid monoethanolamide 5 (5) Glycerin 10 (6) Fragrance 0.5 (7) Purified water balance

According to the above composition, the component (3) is added to heated purified water, then the components (1) and (2) are added and neutralized and dissolved, and then the components (3) to (5) are added. After mixing and cooling, the component (6) was added to obtain a transparent liquid detergent composition (face wash). Of a 10% by weight diluted aqueous solution of the obtained face wash
pH was 6.0.

When the face was washed with the obtained facial cleanser, the foaming and rinsing properties were good, a refreshing feeling was obtained, and further, there was no flat feeling after drying, and the feeling of use was excellent. In addition, there was little irritation to the skin and the storage stability was good.

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Claims (1)

(57) [Claims] (A) General formula (1) (Wherein, R ¹ represents a straight-chain or branched-chain alkyl group, alkenyl group or hydroxyalkyl group having 7 to 21 carbon atoms, and M ¹ and M ² are the same or different and represent a hydrogen atom, an alkali metal, an alkaline earth, A glycine derivative represented by a metal class, ammonium, mono-, di- or trialkanol ammonium having a total carbon number of 1 to 22 or a basic amino acid); and (B) a general formula (2) [Wherein, R ² represents an alkyl group having 7 to 21 carbon atoms;
³ and R ⁴ are the same or different and each represent a hydrogen atom,
3 alkyl group, or hydroxyalkyl group having 1 to 3 carbon atoms _{- (C 2 H 4 O)} m H group (m is a number of 2 to 4) washing containing fatty acid amide derivative represented by showing a] Composition.