JPH0978085A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition, comprising a specific glycine derivative (salt), a metallic chelating agent and an antioxidant in a specific proportion, causing low irritation without deteriorating a color tone even when preserved at a high temperature, excellent in feeling of use and suitable as a detergent, etc., for bodies. SOLUTION: This detergent composition comprises (A) 2-90wt.% glycine derivative (salt) of the formula (R<1> is a 5-21C alkyl, an alkenyl or a hydroxyalkyl) such as sodium N-lauroyl-N-carboxyethylglycinate, (B) 0.01-1wt.% metallic chelating agent such as ethylenediaminetetraacetic acid and (C) 0.05-1wt.% antioxidant such as dibutylhydroxytoluene. Furthermore, the pH of an aqueous solution when diluting the detergent composition to a weight of 10 times with water is preferably 4-8.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a detergent composition containing a specific glycine derivative, which contains a metal chelating agent and an antioxidant to provide low irritation and excellent usability, and its color tone and odor. The present invention relates to a cleaning composition that prevents deterioration of the composition.

[0002]

2. Description of the Related Art Body cleansing compositions generally contain an anionic surfactant as a main component. Soaps, that is, higher fatty acid salts, are used for cleansing the skin, and alkyl sulfates and alkyl sulfones are used for cleaning the hair. The acid salt is mainly used. However, soaps used for skin cleansing have the drawback of producing squeaky and taut during rinsing. Alkyl sulfates and alkyl sulfonates used for hair washing have excellent detergency but are irritating. I had a problem with.

Therefore, it has been studied to use a specific glycine derivative as a main base of a detergent as a surfactant having an excellent feeling of use and a low irritation. However, it is colored and smelled at high temperature storage. However, it is still unsatisfactory as a surfactant for detergent compositions.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a cleaning composition which can prevent the coloring and the deterioration of the odor even at high temperature storage while utilizing the characteristics of the glycine derivative.

[0005]

Under the circumstances, the present inventor has conducted earnest studies to eliminate the above-mentioned drawbacks with respect to a detergent composition using a specific glycine derivative, and as a result, the following general formula (1) The glycine derivative represented by
The present invention has been completed by finding that a detergent composition in which coloration and odor deterioration during storage at high temperature are prevented can be obtained by blending a metal chelating agent and an antioxidant.

That is, the present invention provides the following component (A):
(B) and (C): (A) General formula (1)

[0007]

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(Wherein R ¹ represents a linear or branched alkyl group, alkenyl group, or hydroxyalkyl group having 5 to 21 carbon atoms) or a glycine derivative represented by the formula: 2 to 90% by weight, The present invention provides a detergent composition containing 0.01 to 1% by weight of a metal chelating agent and 0.05 to 1% by weight of (C) an antioxidant.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the present invention is a glycine derivative represented by the general formula (1) or a salt thereof. In the formula, examples of the linear or branched alkyl group, alkenyl group, or hydroxyalkyl group having 5 to 21 carbon atoms represented by R ¹ include, for example, n-pentyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decyl group,
Examples include n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-heptadecyl group, methylhexadecyl group, ethylpentyl group, heptadecenyl group and hydroxyundecyl group. . Of these, carbon number 7 to
An alkyl group and an alkenyl group having 17 carbon atoms are preferable, and those having 9 to 15 carbon atoms are particularly preferable.

The salt of the glycine derivative represented by the general formula (1) is, for example, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, a mono-, di- or trialkanolamine salt having 1 to 22 total carbon atoms, 1 to 22 carbon atoms
Alkyl group or alkenyl group-substituted pyridinium salt, a polyalkylene polyamine salt having a total carbon number of 2 to 500 and a total amino number of 2 to 250, a basic amino acid salt, and the like,
For example, sodium salt, potassium salt, magnesium salt, calcium salt, ammonium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt,
Examples thereof include ethylenediamine salt, propylenediamine salt, arginine salt, histidine salt and lysine salt. Of these, alkali metal salts, trialkanolamine salts,
Basic amino acid salts are preferable, and sodium salt, potassium salt, triethanolamine salt, arginine salt, and sodium salt and potassium salt are particularly preferable.

The salt of the glycine derivative represented by the general formula (1) does not necessarily have to be blended as a salt, but the grind derivative and the base forming such a salt are separately blended to obtain a composition. The salt may be formed therein. Examples of bases that form such salts include alkali metal hydroxides, alkaline earth metal hydroxides, ammonia, mono-, di- or trialkanolamines having 1 to 22 carbon atoms, and alkyl groups having 1 to 22 carbon atoms. Or alkenyl group-substituted pyridine, total carbon number 2 to 500 and total amino number 2 to
Examples of the polyalkylene polyamine of 250, basic amino acids and the like, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, arginine, Histidine, lysine, etc. are mentioned.

The component (A) is N-lauroyl-N.
-Carboxyethylglycine sodium salt, N-lauroyl-N-carboxyethylglycine potassium salt, N-
Lauroyl-N-carboxyethylglycine triethanolamine salt, N-myristoyl-N-carboxyethylglycine sodium salt, N-myristoyl-N-carboxyethylglycine potassium salt, N-myristoyl-
N-carboxyethylglycine triethanolamine salt, N-myristoyl-N-carboxyethylglycine arginine salt, N-coconut oil fatty acid acyl-N-carboxyethylglycine sodium salt, N-coconut oil fatty acid acyl-N-carboxyethylglycine potassium salt Salt is preferred.

Such a glycine derivative (1) or a salt thereof can be produced, for example, according to the reaction formula shown below.

[0014]

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That is, glycine represented by the general formula (2) or a salt thereof is reacted with acrylonitrile to obtain a glycine derivative (3) or a salt thereof (step A), which is hydrolyzed and, if necessary, a salt. Glycine derivative (6) or a salt thereof is obtained by exchanging (step B), and then this is reacted with acid chloride (4), and salt exchange is carried out if necessary (step E) to give glycine as the component (A). Derivative (1)
Alternatively, its salt can be obtained. Further, the glycine derivative (3) or salt thereof obtained in step A is reacted with an acid chloride (4), and if necessary, salt exchange is performed to obtain a glycine derivative (5) or salt thereof (step C), Then, the glycine derivative (1) as the component (A) or a salt thereof can be obtained by hydrolyzing the salt and exchanging the salt as necessary (step D).

Each step will be described below. (Step A) In this step, glycine (2) or a salt thereof is reacted with acrylonitrile to obtain a glycine derivative (3) or a salt thereof. Glycine or a salt thereof as a raw material, and acrylonitrile may be produced by known methods, any commercially available one may be used, but if necessary, recrystallization, purification by distillation, etc. You may use.

Specific examples of glycine (2) or a salt thereof 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 (2) or a salt thereof and 0.5 to 10 equivalents of acrylonitrile are added in water at a suitable temperature of 10 to 100 ° C., preferably 30 to 70 ° C., and 0.5 to 100. The glycine derivative (3) or a salt thereof can be obtained by reacting for a time, preferably 1 to 3 hours, and if necessary, by exchanging a counter ion with an electrodialyzer or the like. When the reaction time is longer than 100 hours, side reactions such as hydrolysis of the cyano group occur concurrently, which is not preferable. During the reaction, it is preferable to carry out a treatment such as gradually adding acrylonitrile to an aqueous solution of glycine (2) or a salt thereof, because side reactions such as polymerization of acrylonitrile are significantly suppressed and the yield is improved. The glycine derivative (3) or a salt thereof obtained in this step can be used as it is in the next step, but if necessary, it may be recrystallized using a solvent such as water, methanol, ethanol, etc. It can also be a product.

(Step B) In this step, the cyano group of the glycine derivative (3) or salt thereof obtained in step A is hydrolyzed, preferably in the presence of a basic substance, to give the glycine derivative (6) or its salt. This is the step of obtaining salt. Examples of the basic substance used here include alkali metal hydroxides and alkaline earth metal hydroxides, and specific examples include sodium hydroxide, potassium hydroxide, magnesium hydroxide,
Examples thereof include calcium hydroxide and barium hydroxide.

In this step, the glycine derivative (3)
Or a salt thereof in the presence of 0.1 to 30 equivalents of a basic substance,
In an aqueous solution, if necessary, water and methanol, ethanol,
In a mixed solution with a polar solvent such as isopropanol, acetone, 1,3-propanediol, and propylene glycol, the reaction is carried out at a suitable temperature of 50 to 100 ° C., preferably 70 to 100 ° C. for 0.5 to 100 hours, If necessary, by exchanging counterions with an electrodialyzer,
Glycine derivative (6) or a salt thereof can be obtained.
The glycine derivative (6) or a salt thereof obtained in this step can be used as it is in the next step, but if necessary, it may be recrystallized using a solvent such as water, methanol, ethanol, etc. It can also be a product.

(Step C) In this step, the glycine derivative (3) or salt thereof obtained in step A is reacted with an acid chloride (4), preferably in the presence of an alkaline substance, to give a glycine derivative (5) or This is the step of obtaining the salt. As the acid chloride (4) as a raw material, any of those produced by a known method and those commercially available may be used, but those obtained by purification such as distillation may be used if necessary.
Specific examples of the acid chloride (4) include hexanoic acid chloride, octanoic acid chloride, decanoic acid chloride,
Dodecanoic acid chloride, tetradecanoic acid chloride, hexadecanoic acid chloride, octadecanoic acid chloride,
Examples thereof include fatty acid chlorides having a single composition such as 2-ethylhexanoic acid chloride, isostearic acid chloride and oleic acid chloride, and fatty acid chlorides having a mixed composition such as coconut oil fatty acid chloride and tallow fatty acid chloride.

In this step, the glycine derivative (3)
Or its salt and 0.8-5.0 equivalent normally, Preferably it is 0.
9 to 1.3 equivalents of acid chloride (4) 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, 0-10
0.5-at a suitable temperature of 0 ° C, preferably 10-50 ° C
The glycine derivative (5) or a salt thereof can be obtained by reacting for 100 hours and exchanging a counter ion with an electrodialyzer or the like if necessary. If the amount of the acid chloride (4) used is less than the above range, a large amount of the glycine derivative (3) or a salt thereof remains in the reaction product. A large amount of fatty acid is by-produced from the acid chloride (4), which is not preferable.

In this step, in order to secure the reactivity and allow a certain reaction to proceed, an alkaline substance is added to the reaction system to bring the pH in the system to the alkaline side, preferably pH 9.0 to 9.0.
It is desirable to keep it in the range of 11.0. When the pH of the reaction system is lower than this range, hydrochloric acid, which is a by-product of the reaction, forms a salt with the unreacted glycine derivative (3) and the reaction does not proceed sufficiently, while the pH is higher than this range. In this case, the decomposition of acid chloride (4) is promoted and a large amount of fatty acids are 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 an amount that maintains the system pH within the above range.

The glycine derivative (5) or a salt thereof obtained in this step can be used as it is in the next step. If necessary, a solvent such as water, methanol or ethanol may be used for recrystallization or hydrochloric acid. After treatment with a strong acid such as sulfuric acid, an acid type product of glycine derivative (5) is obtained and recrystallized using a solvent such as acetone, hexane, petroleum ether, methanol, ethanol, butanol,
It is also possible to obtain a glycine derivative (5) or a salt thereof again by using an appropriate neutralizing agent to obtain a highly purified product.

(Step D) In this step, the cyano group of the glycine derivative (5) or its salt obtained in step C is hydrolyzed, preferably in the presence of a basic substance, to give a glycine derivative (1) or its salt. This is the step of obtaining salt. Examples of the basic substance used here include alkali metal hydroxides and alkaline earth metal hydroxides, and specific examples include sodium hydroxide, potassium hydroxide, magnesium hydroxide,
Examples thereof include calcium hydroxide and barium hydroxide.

In this step, the glycine derivative (5)
Or a salt thereof in the presence of 0.1 to 30 equivalents of a basic substance,
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, and propylene glycol, 50 to 100 ° C, preferably 70 to 100 ° C. By reacting for 0.5 to 100 hours at various temperatures, and if necessary by exchanging counterions using an electrodialyzer or the like,
Glycine derivative (1) or a salt thereof can be obtained.

The glycine derivative (1) or a salt thereof obtained in this step can be used as it is in a detergent composition. If necessary, a solvent such as water, methanol or ethanol is used for recrystallization, or After treatment with a strong acid such as hydrochloric acid or sulfuric acid, an acid type product of glycine derivative (1) was obtained,
By recrystallizing it using a solvent such as acetone, hexane, petroleum ether, methanol, ethanol, butanol, and again using an appropriate neutralizing agent to give the glycine derivative (1) or its salt, a higher purity can be obtained. It can also be a purified product of

(Step E) In this step, the glycine derivative (6) or salt thereof obtained in step B is reacted with an acid chloride (4), preferably in the presence of an alkaline substance, to give a glycine derivative (1) or This is the step of obtaining the salt. As the acid chloride (4) as a raw material, the same one as in step C may be used.

In this step, the glycine derivative (6)
Or its salt and 0.8-5.0 equivalent normally, Preferably it is 0.
9 to 1.3 equivalents of acid chloride (4) 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, 0-10
0.5-at a suitable temperature of 0 ° C, preferably 10-50 ° C
The glycine derivative (1) or a salt thereof can be obtained by reacting for 100 hours and exchanging the counter ion with an electrodialyzer or the like if necessary. If the amount of the acid chloride (4) used is less than the above range, a large amount of the glycine derivative (6) or a salt thereof remains in the reaction product. A large amount of fatty acid is by-produced from the acid chloride (4), which is not preferable.

In this step, in order to secure the reactivity and allow a certain reaction to proceed, an alkaline substance is added to the reaction system to bring the pH in the system to the alkaline side, preferably pH 9.0 to 9.0.
It is desirable to keep it in the range of 11.0. When the pH of the reaction system is lower than this range, hydrochloric acid, which is a by-product of the reaction, forms a salt with the unreacted glycine derivative (6) and the reaction does not proceed sufficiently, while the pH is higher than this range. In this case, the decomposition of acid chloride (4) is promoted and a large amount of fatty acids are by-produced. Specific examples of the alkaline substance used here 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, but sodium hydroxide and potassium hydroxide are particularly practical. The amount of these alkaline substances used is an amount that maintains the system pH within the above range.

The glycine derivative (1) or a salt thereof obtained in this step can be used as it is in the detergent composition. It can also be a product.

The glycine derivative or the salt thereof as the component (A) can be used alone or in combination of two or more kinds. The blending amount of the component (A) in the detergent composition of the present invention varies depending on the formulation of the detergent and the like, but is 2-9 in the total composition.
0 wt% (hereinafter, simply indicated by%) is compounded. In the case of a liquid, it is preferable to add 5 to 50%, particularly 10 to 40% in the whole composition, and in the case of a paste, to add 10 to 80%, especially 15 to 40% in the whole composition. In the case of solid form, it is preferable to add 40 to 90%, especially 70 to 90% in the total composition. When the content is within these ranges, foaming is more excellent and a refreshing feeling can be obtained, which is preferable.

The metal chelating agent of the component (B) used in the present invention is not particularly limited as long as it has the ability to chelate metal ions. For example, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid. , Phosphonic acids such as nitrilotriacetic acid, triethylenetetraminehexaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, tripolyphosphoric acid, ethylene glycol bis (2
-Aminoethyl ether) tetraacetic acid, citric acid, maleic acid, polyacrylic acid, isoamylene-maleic acid copolymer, silicic acid, gluconic acid, hydroxybenzyliminodiacetic acid, iminodiacetic acid and salts thereof.
Among them, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, citric acid, tripolyphosphoric acid and salts thereof are particularly preferred.

The compounding amount of the metal chelating agent as the component (B) is
0.01 to 1% in the total composition, preferably 0.02 to 0.
5%. If the blending amount is less than 0.01%, (C) will be described later.
Even when used in combination with the component antioxidant, it is not possible to prevent coloration and deterioration of odor. On the other hand, if it exceeds 1%, the odor of the metal chelating agent itself deteriorates, and deterioration of odor cannot be prevented. .

Examples of the antioxidant as the component (C) used in the present invention include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like. Of these, dibutylhydroxytoluene is represented by the following formula (7).

[0036]

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The content of the antioxidant as the component (C) is 0.05 to 1%, preferably 0.1 to 0.5% in the total composition. If the blending amount is less than 0.05%, the coloring and odor deterioration cannot be prevented. On the other hand, if the blending amount exceeds 1%, the effect of preventing the coloring and odor deterioration reaches an almost equilibrium level even when used in combination with the metal chelating agent. It is not preferable because it will end up.

The detergent composition of the present invention includes other surfactants such as alkyl sulfates, alkyl sulfonates, polyoxyethylene alkyl sulfates, alkylbenzene sulfonates, N-acyl-N-methyltaurine salts. , Alpha olefin sulfonates, alkyl ether acetates, polyoxyethylene alkyl ether acetates and other anionic surfactants; fatty acid amides, polyoxyethylene alkyl ethers, sugar ester-based, sugar ether-based, sugar amide-based nonions Anionic surfactants; amphoteric surfactants such as imidazoline-based and betaine-based surfactants can be optionally used in combination as long as the effects of the present invention are not impaired.

Further, as other additives, components usually used in detergents, for example, moisturizing agents such as propylene glycol, sorbitol and glycerin, carboxyvinyl polymer, methyl cellulose, ethanol, polyoxyethylene glycol distearate and the like viscosity adjustment. Agents, pearlizing agents, fragrances, dyes, ultraviolet absorbers, antioxidant aids, bactericides, anti-inflammatory agents and the like can be optionally added within a range that does not impair the effects of the present invention.

The detergent composition of the present invention can be produced by a conventional method. In addition, the dosage form is not particularly limited, and may be any dosage form such as liquid, paste, cream, solid, and powder. Liquid, paste, and cream are preferable, In particular, it is preferable to use a liquid. In the case of a liquid state, it is preferable to use water as a liquid medium, and the amount of water is 50% in the total composition.
Preferably it is ~ 90%. Further, the cleansing composition of the present invention is suitable as a cleansing agent for the body such as skin and hair, and is particularly preferably used for cleansing the skin.

In the detergent composition of the present invention, the pH of the aqueous solution when diluted 10 times by weight with water is preferably 4 to 8, particularly 5 to 7. 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).

[0042]

The detergent composition of the present invention has low irritation, excellent feeling in use, and has no deterioration in color tone and odor even when stored at high temperature, and is practically advantageous.

[0043]

Next, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the embodiments described below.

Example 1 A detergent composition having the composition shown in Tables 1 and 2 below was produced by a conventional method. The obtained cleaning composition was evaluated for the effect of preventing coloration and the effect of preventing deterioration of dough odor based on the following methods and criteria. The results are shown in Tables 1 and 2.

(Evaluation Method) (1) Coloring Prevention Effect: Each detergent composition was stored under accelerated test conditions at 50 ° C. for 20 days, and the coloring degree was compared with that immediately after preparation according to the following evaluation criteria. It was judged with the naked eye. ◯: Good with no change in color tone. Δ: Unusable due to change in color tone. ×: Unusable due to remarkable change in color tone.

(2) Deterioration effect of dough odor: Each cleaning composition was stored under accelerated test conditions at 50 ° C. for 20 days, and judged immediately after preparation by sensory evaluation by odor panelists. ◯: Good with no change in odor. Δ: Smell changed, but usable. ×: Unusable due to significant change in odor.

[0047]

[Table 1]

[0048]

[Table 2]

As is clear from the results shown in Tables 1 and 2, the products of the present invention were superior to the comparative products in the effect of preventing coloring and the effect of preventing deterioration of the dough odor. In addition, there was low irritation and the feeling of use was good.

Example 2 A liquid detergent composition having the following composition was produced by a conventional method.
The obtained liquid detergent composition was less irritating, was excellent in usability, and was excellent in stability of color tone and odor during storage at high temperature.

[0051]

Table 3 (Components) (%) (1) N-cocoyl-N-carboxyethylglycine sodium 25 (2) 1-hydroxyethylidene-1,1-diphosphonic acid 0.1 (3) dibutylhydroxytoluene 0.2 (4) Triethanolamine laurate 5 (5) Perfume 0.5 (6) Purified water balance

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C11D 3/37 C11D 3/37 // A61K 7/50 A61K 7/50

Claims (6)

[Claims] 1. The following components (A), (B) and (C): (A) General formula (1) (In the formula, R ¹ represents a linear or branched alkyl group, alkenyl group or hydroxyalkyl group having 5 to 21 carbon atoms) or a glycine derivative represented by the formula: 2-90 wt%, (B) metal A cleaning composition containing 0.01 to 1% by weight of a chelating agent and (C) 0.05 to 1% by weight of an antioxidant. 2. The detergent composition according to claim 1, wherein the salt of the glycine derivative represented by the general formula (1) is an alkali metal salt, a trialkanolamine salt or a basic amino acid salt. 3. In the general formula (1), R ¹ has 7 carbon atoms.
The cleaning composition according to claim 1 or 2, which is an alkyl group or an alkenyl group of -17. 4. The cleaning composition according to any one of claims 1 to 3, wherein the pH of the aqueous solution when diluted 10 times by weight with water is 4 to 8. 5. A liquid form according to any one of claims 1 to 4.
9. The cleaning composition according to item 7. 6. The cleansing composition according to claim 1, which is a body cleansing agent.