JPH05125086A - Aqueous solution of phosphate ester salt - Google Patents

Abstract

PURPOSE:To obtain the subject aqueous solution which is useful as a base for body cleaner with excellent stability to long-term storage without deterioration in smell and hue by using a specified phosphate monoester salt, a specified phosphate diester salt and a specified monosaccharide at a specific ration. CONSTITUTION:The objective aqueous solution comprises (A) 1 to 80wt.% of a phosphate monoester salt of formula I (R<1> is 8 to 16 C alkyl, alkenyl; M<1>, M<2> are each H, alkali metal ion or the like), (B) 0 to 80wt.% of a phosphate diester salt of formula II (R<2> is R<1>; M is alkali metal ion, ammonium) and (C) 0.1 to 40wt.% of at least one selected from the group consisting of monosaccharides such as glucose, disaccharide such as sucrose, ascorbic acid or its salt, glycerol, polyglycerol, propylene glycol, pentaerythritol and trimethylolpropane. It is preferred that a phenolic antioxidant is further added to the aqueous solution by 0.0001 to 10wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous solution of a phosphoric acid ester salt which is useful as a base for a personal cleansing agent, and more particularly to a phosphoric acid ester salt which does not deteriorate in odor and hue even after long-term storage. Regarding aqueous solutions.

[0002]

2. Description of the Related Art Specific alkyl or alkenyl phosphate ester salts (such as those obtained by the method described in Japanese Examined Patent Publication No. 3-27558) are hereinafter simply referred to as "phosphate ester salts".
When used as a detergent in the neutral to weakly alkaline range, it has excellent detergency and foaming power, less skin irritation, excellent biodegradability, and excellent surface chemical properties such as craft point. (Fragrance Journal No. 68, page 2 (1984)) and is widely used as a base for household cleaning agents.

However, such a phosphoric acid ester salt has no problem with respect to odor and hue immediately after production, but has a drawback that it deteriorates and emits odor and changes in hue when stored for a long period of time. It was

On the other hand, conventionally, ditertiary butyl hydroxytoluene (BH
T), antioxidants such as citric acid, and antifungal agents such as benzoic acids are known.

However, when these antioxidants or mildewproofing agents were added to the phosphoric acid ester salt, deterioration of odor could be suppressed, but deterioration of hue could not be improved.

On the other hand, a method of storing the phosphoric acid ester salt aqueous solution in an atmosphere of inert gas and nitrogen can be considered, but the handling of the aqueous solution is inconvenient and equipment is required.
This is a costly method and is not a satisfactory method.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a phosphoric acid ester salt aqueous solution which is stable for a long period of time, does not require facilities and troubles, and does not cause deterioration of odor and hue.

[0008]

In view of the above situation, the inventors of the present invention have conducted diligent research, and as a result, have found that a specific component having two or more hydroxy groups such as monosaccharides in a monophosphate ester salt and a diphosphate ester salt. It was found that a stable solution can be obtained without adding an odor and a hue, and the present invention has been completed.

That is, the present invention provides the following component (a),
(B) and (c) (a) The following general formula (1)

[0010]

[Chemical 3]

(In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, and M ¹ and M ^1
2 represents a hydrogen atom which may be the same or different, an alkali metal ion, an ammonium group or an alkanol ammonium group having a total carbon number of 2 to 9. However, the case where both M ¹ and M ² are hydrogen atoms is excluded) 1 to 80% by weight of monophosphate ester salt (b) The following general formula (2)

[0012]

[Chemical 4]

(In the formula, R ² represents a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, and M represents an alkali metal ion, an ammonium group or an alkanol ammonium group having 2 to 9 carbon atoms in total. ) Diphosphoric acid ester salt represented by 0) to 80% by weight (c) one selected from the group consisting of monosaccharides, disaccharides, ascorbic acid and its salts, glycerin, polyglycerin, propylene glycol, pentaerythritol and trimethylolpropane Or two or more kinds.
An aqueous solution of a phosphoric acid ester salt containing 1 to 40% by weight is provided.

The general formula (1) of the component (a) used in the present invention
As the monophosphate ester moiety of the monophosphate ester salt represented by, those having a linear or branched chain, for example, monooctyl phosphate, monodecyl phosphate, monododecyl phosphate, monotetracosyl phosphate, monooctacosyl phosphate, Monooctenyl phosphoric acid, monooctadecenyl phosphoric acid, monotetracocenyl phosphoric acid, mono-2-octylundecyl phosphoric acid, mono-2-tetradecyl octadecyl phosphoric acid, and the like, and as salts thereof, Examples thereof include sodium salt, potassium salt, ammonium salt, monoethanolammonium salt, diethanolammonium salt, triethanolammonium salt, monoisopropanolammonium salt, diisopropanolammonium salt and triisopropanolammonium salt.

The diphosphate ester moiety of the diphosphate ester salt of the component (b) represented by the general formula (2) has a straight chain or branched chain, for example, dioctyl phosphate, didecyl phosphate, didodecyl phosphate, Ditetracosyl phosphoric acid, dioctacosyl phosphoric acid, dioctenyl phosphoric acid, dioctadecenyl phosphoric acid, ditetracocenyl phosphoric acid, di-2-octylundecyl phosphoric acid, di-2-tetradecyl octadecyl phosphoric acid, etc. Examples of these salts include the same salts as the monophosphate ester (1).

The phosphoric acid ester salts of the above components (a) and (b) can be produced, for example, by the method described in JP-B-3-27558.

The component (c) used in the present invention is as described above. Among them, monosaccharides include glucose, inosit, pencit, sorbit and the like, and disaccharides include sucrose and maltose. Can be mentioned. Among the components (c), glycerin and propylene glycol are particularly preferable.

The amount of the component (c) added varies depending on the concentrations of the components (a) and (b), but the aqueous solution of the present invention contains 1 to 80% by weight of the component (a) and 0 of the component (b). ~ 80
When it is contained in an amount of 0.1 to 40% by weight (hereinafter,
Simply indicated by "%") is suitable. If this amount is less than 0.1%, the hue deteriorates, and if it exceeds 40%, the amount of other components to be blended is limited when commercializing a body wash or the like, which is not preferable.

By further using a known antioxidant in the phosphoric acid ester salt aqueous solution of the present invention, storage stability can be further enhanced and odor and hue deterioration can be suppressed. Examples of such an antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, a phosphoric acid-based antioxidant, and the like, but a phenol-based antioxidant is preferable. Examples include ditertiary butyl hydroxytoluene (BHT), ditertiary butyl hydroxyanisole (BHA), propyl gallate, and the like.
The blending amount of these known antioxidants may be appropriately determined according to the purpose, but is preferably about 0.0001 to 10%.

The phosphoric acid ester salt aqueous solution of the present invention can be produced by mixing and stirring by a conventional method, and can be used as a raw material for blending various detergents. When used as a base for such a detergent, the amount used is usually 1 to 90 weight (active ingredient conversion). In the above, other components can be used in combination, and examples of such a usable combination include general anionic surfactants (alkyl sulfate ester salts, alkyl ether sulfate ester salts, α
-Olefin sulfonates, alkyl sulfonates, taurine-based surfactants, sarcosinate-based surfactants, isethionate-based surfactants, N-acyl acidic amino acid-based surfactants, higher fatty acid salts, acylated polypeptides, etc.); Amphoteric surfactants (alkyl betaine type surfactants, amidopropyl betaine type surfactants, imidazolinium betaine type surfactants, sulfobetaine type surfactants, phosphobetaine type surfactants, sodium laurylaminopropionate, etc. Amino acid type surfactant);
Nonionic surfactants (coconut oil fatty acid diethanolamide, stearic acid monoglyceride, lauryl dimethylamine oxide, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, etc.); cationic interface Activators (stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate), conventionally known moisturizers, thickeners, polymer compounds (carboxyethyl cellulose, hydroxyethyl cellulose, cationized cellulose, etc.) ), Fragrances, preservatives and the like.

[0021]

The phosphoric acid ester salt aqueous solution of the present invention is stable as it is stored for a long period of time and has no deterioration of odor and hue. Therefore, it is extremely useful as a blending raw material for various cleaning agents, especially body cleaning agents. Is.

[0022]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of monododecyl phosphate: 242 g of n-dodecyl alcohol and 242 g of n-hexane were charged into a four-necked flask (equipped with a cooler, a thermometer and a stirrer), and 7
After adding 607 g of 105% polyphosphoric acid prepared from 5% H ₃ PO ₄ and P ₂ O ₅ , reaction was carried out at reflux temperature for 12 hours. Then, after adding 61 g of water, the mixture was further refluxed at 3
A time reaction was performed. After completion of the reaction, n-hexane 242
g, water 90 g, isopropyl alcohol 90 g,
After stirring at 50 ° C. for 30 minutes, the mixture was left standing. Next, after removing the aqueous layer, isopropyl alcohol was removed from the n-hexane layer to obtain crude crystals of the target substance. The obtained crystals were recrystallized using n-hexane to obtain 340 g of the target compound.

Synthesis Example 2 Synthesis of didodecyl phosphate: n-dodecyl alcohol 447 g and P ₂ O ₅ 115 g were charged into a four-necked flask (with a condenser, a thermometer and a stirrer) and reacted at 80 ° C. for 10 hours. went. Then, after adding 45 g of water, the mixture is mixed at 85 ° C.
A time reaction was performed. After completion of the reaction, the same amount of ethanol as the reaction product was added and recrystallization was carried out to obtain 278 g of a target crystal.

Examples 1 to 5 Using the monododecyl phosphate ester and the didodecyl phosphate ester obtained in the synthesis examples, the phosphate ester salt aqueous solutions shown in Table 1 were prepared. These were placed in a hot air dryer adjusted to 40 ° C., and after 1 to 6 months, the hue and the odor were investigated. The results are shown in Table 2. The evaluation was based on the following criteria.

Hue: Indicated by Klet number. The smaller the value is, the better the hue is, and when the value is 30 or less, the hue is good. Odor: The presence or absence of an offensive odor was judged by 10 panelists.
The judgment was based on the following criteria. A: No offensive odor is observed. ◯: Slight offensive odor is observed. Δ: A slightly strong offensive odor is recognized. X: A strong offensive odor is recognized.

[0027]

[Table 1]

[0028]

[Table 2]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 6, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] (In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, and M ¹ and M ² may be the same or different, a hydrogen atom, an alkali metal ion, an ammonium group or a total group. A phosphoric acid monoester salt represented by a C2-C9 alkanolammonium group, provided that both M ¹ and M ² are hydrogen atoms.
1-80 wt% (b) The following general formula (2)

[Chemical 2] (In the formula, R ² represents a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, and M represents an alkali metal ion, an ammonium group, or an alkanol ammonium group having 2 to 9 carbon atoms). Phosphoric acid diester
Salt 0 to 80% by weight (c) Monosaccharide, disaccharide, ascorbic acid and its salt, glycerin, polyglycerin, propylene glycol, pentaerythritol, and one or more kinds selected from the group consisting of trimethylolpropane.
Aqueous phosphoric acid ester salt solution containing 1 to 40% by weight.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

[0008]

In view of the above circumstances SUMMARY OF THE INVENTION The present inventors have as a result of intense research, the hydroxy group of the monosaccharides such as phosphoric acid monoester salts及<br/> beauty phosphodiester salt 2 The present invention has been completed by finding that a stable solution without odor and deterioration of hue can be obtained by adding a specific component having at least one of them.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

(In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, and M ¹ and M ^1
2 represents a hydrogen atom which may be the same or different, an alkali metal ion, an ammonium group or an alkanol ammonium group having a total carbon number of 2 to 9. However, monophosphoric acid represented by (excluding the case where both M ¹ and M ² are hydrogen atoms)
1-80% by weight of ester salt (b) The following general formula (2)

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

(In the formula, R ² represents a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, and M represents an alkali metal ion, an ammonium group or an alkanol ammonium group having 2 to 9 carbon atoms in total. ) Phosphoric acid
Diester salt 0 to 80% by weight (c) Monosaccharide, disaccharide, ascorbic acid and its salt, glycerin, polyglycerin, propylene glycol, pentaerythritol, and one or more kinds selected from the group consisting of trimethylolpropane.
An aqueous solution of a phosphoric acid ester salt containing 1 to 40% by weight is provided.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

The general formula (1) of the component (a) used in the present invention
Phosphoric acid phosphoric monoester salt monoester represented in
The moiety having a straight chain or a branched chain, for example, monooctyl phosphate, monodecyl phosphate, monododecyl phosphate, monotetracosyl phosphate, monooctacosyl phosphate, monooctenyl phosphate, monooctadeceni Ruphosphoric acid, monotetracocenylphosphoric acid, mono-2-octylundecylphosphoric acid, mono-2-tetradecyloctadecylphosphoric acid and the like. Examples of these salts include sodium salt, potassium salt, ammonium salt, Examples include monoethanolammonium salt, diethanolammonium salt, triethanolammonium salt, monoisopropanolammonium salt, diisopropanolammonium salt, triisopropanolammonium salt and the like.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

The phosphodiester portion of the phosphodiester salt of component (b) represented by the general formula (2) has a straight or branched chain, for example, dioctylphosphoric acid, didecylphosphoric acid, didodecylphosphoric acid, Ditetracosyl phosphoric acid, dioctacosyl phosphoric acid, dioctenyl phosphoric acid, dioctadecenyl phosphoric acid, ditetracocenyl phosphoric acid, di-2-octylundecyl phosphoric acid, di-2-tetradecyl octadecyl phosphoric acid, etc. Examples of these salts include the same salts as the phosphoric acid monoester (1). ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 17, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

The phosphoric acid ester salt aqueous solution of the present invention can be produced by mixing and stirring by a conventional method, and can be used as a raw material for blending various detergents. When used as a base for such a detergent, the amount used is usually 1 to 90 % (as active ingredient conversion). In the above, other components may be used in combination, and examples of such a usable combination include general anionic surfactants (alkyl sulfate ester salt, alkyl ether sulfate ester salt, α-
Olefin sulfonate, alkyl sulfonate, taurine-based surfactant, sarcosinate-based surfactant, isethionate-based surfactant, N-acyl acidic amino acid-based surfactant, higher fatty acid salt and acylated polypeptide, etc.); Amphoteric Surfactants (alkyl betaine type surfactants, amidopropyl betaine type surfactants, imidazolinium betaine type surfactants, sulfobetaine type surfactants, phosphobetaine type surfactants, sodium laurylaminopropionate, etc. Amino acid type surfactant);
Nonionic surfactants (coconut oil fatty acid diethanolamide, stearic acid monoglyceride, lauryl dimethylamine oxide, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, etc.); cationic interface Activators (stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate), conventionally known moisturizers, thickeners, polymer compounds (carboxyethyl cellulose, hydroxyethyl cellulose, cationized cellulose, etc.) ), Fragrances, preservatives and the like.

Claims (4)

[Claims] 1. The following components (a), (b) and (c) (a) The following general formula (1): (In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, and M ¹ and M ² may be the same or different, hydrogen atom, alkali metal ion, ammonium group or total A monophosphate ester salt represented by a C2-C9 alkanolammonium group, provided that both M ¹ and M ² are hydrogen atoms).
1-80 wt% (b) The following general formula (2): (In the formula, R ² represents a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, and M represents an alkali metal ion, an ammonium group, or an alkanol ammonium group having 2 to 9 carbon atoms). Diphosphate ester salt 0 to 80% by weight (c) 1 type or 2 types selected from the group consisting of monosaccharides, disaccharides, ascorbic acid and salts thereof, glycerin, polyglycerin, propylene glycol, pentaerythritol and trimethylolpropane Above 0.
Aqueous phosphoric acid ester salt solution containing 1 to 40% by weight. 2. The phosphoric acid ester salt aqueous solution according to claim 1, wherein the component (c) is propylene glycol. 3. The phosphoric acid ester salt aqueous solution according to claim 1, further comprising 0.0001 to 10% by weight of an antioxidant other than (d) ascorbic acid or a salt thereof. 4. The phosphoric acid ester salt aqueous solution according to claim 3, wherein the antioxidant as the component (d) is a phenolic antioxidant.