JPH04298600A - Surfactant composition and detergent composition - Google Patents

Abstract

PURPOSE:To reduce irritation to hair and scalp, improve foaming and decrease coloring with the lapse of time by mixing specified aminoamic acid surfactant composition and phosphorous acid compound. CONSTITUTION:The title composition is prepared by adding 0.03 to 15% phosphorous acid compund represented by formula III (wherein R<4>, R<5> and R<6> each represent hydrogen, Na, K or ammonium) to an aminoamic acid surfactant composition comprising at least one member selected from the group consisting of aminoamic acid compounds represented by formula I and II (wherein R<1> represents a substituted or unsubstituted aliphatic hydrocarbon group; R<2> and R<3> each represent hydrogen or 1 to 4C hydroxyalkyl; and M represents one member selected from the group consisting of hydrogen, Na, K and triethanolamine, and 3.5 to 45% polyaclyric acid or its water-soluble salt.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a surfactant composition containing an amide amino acid type surfactant containing polyacrylic acid and a phosphorous acid compound as essential components, and a surfactant composition containing the surfactant composition. The present invention relates to a characteristic cleaning composition.

0002

[Conventional technology] Recently, it has become more gentle and less irritating to the hair and scalp.
Amidoamino acid type amphoteric surfactants have been frequently used as cleansing agent bases for shampoos, facial cleansers, etc., which lather well. However, since these amphoteric surfactants use monochloroacetic acid, monochloropropionic acid, etc. in the amphoteric reaction, they have the disadvantage that salt is produced as a by-product. The presence of common salt impairs the compatibility with other surfactants and conditioning agents such as cationized cellulose, often causing problems in formulations. As an amide amino acid type amphoteric surfactant that does not contain salt, there is a method in which an amide amine compound is reacted with acrylic acid. (Tokuko Showa 60-48
However, the amide amino acid type amphoteric surfactant produced by this method is mild to the hair and scalp, has good lathering, and does not contain salt, so it is difficult to mix with other surfactants. Although it has the advantage that it can be used freely, it has the disadvantage that it becomes colored over time, making it difficult to incorporate it into shampoos and the like. As a method to prevent this coloration over time, methods such as adding sodium borohydride and treating with activated carbon have been tried, but the former only results in temporary decolorization.
In the latter method, activated carbon is encapsulated in surfactant micelles and cannot be filtered out, and is not satisfactory as an industrial production method for improving the drawbacks.

0003

[Problems to be solved by the present invention] The purpose of the present invention is to create an amide amino acid type surfactant that is mild to the hair and scalp, has good foaming properties, shows little coloring over time, and does not contain any salt. The object of the present invention is to provide a composition, and also to provide a cleaning composition containing the surfactant composition as an essential component.

0004

[Means for Solving the Problems] That is, the present invention solves the problems by formulas (1) and (2)

[Chemical 7] (1)

[Formula 8] (2) (wherein, R1 represents a saturated or unsaturated aliphatic hydrocarbon group having 7 to 21 carbon atoms, and R2 and R3
represent a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms, and may be the same or different, and M is one selected from a hydrogen atom, sodium, potassium, and triethanolamine. represents. ), and polyacrylic acid or a water-soluble salt thereof.

[C9
] (3) (In the formula, R4, R5, R6 represent a hydrogen atom, sodium, potassium or ammonium group, and may be the same or different.) At least one phosphorous acid compound represented by They are a surfactant composition characterized in that the following three components (A), (B), and (C) are added as essential components. (A) One or more amide amino acid type surfactants selected from amide amino acid compounds represented by the following general formulas (1) and (2).

[Chemical formula 10] (1)

[Formula 11] (2) (wherein, R1 represents a saturated or unsaturated aliphatic hydrocarbon group having 7 to 21 carbon atoms, and R2 and R3
represent a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms, and may be the same or different; M represents a hydrogen atom, sodium, potassium, and triethanolamine; represent. ) (B) Polyacrylic acid or a water-soluble salt thereof. (C) At least one phosphorous acid compound represented by the following general formula (3).

embedded image (3) (In the formula, R4, R5, and R6 represent a hydrogen atom, sodium, potassium, or ammonium group, and may be the same or different.)

The amide amino acid type amphoteric surfactant composition containing polyacrylic acid used in the present invention can be easily produced by the method described in Japanese Patent Publication No. 60-4871. That is, the following general formula (4)

[Chemical formula 13] (4) (wherein, R1 represents a saturated or unsaturated aliphatic hydrocarbon group having 7 to 21 carbon atoms, and R2 and R3 are a hydrogen atom or a hydrogen atom having 1 to 4 carbon atoms. The amidoamine compound represented by the formula (representing a hydroxyalkyl group, which may be the same or different) and an equimolar amount or more of acrylic acid are reacted to form the following general formulas (1) and (2).

[Chemical formula 14] (1)

embedded image (2) (wherein, R1, R2, and R3 are the same as defined above)
This is a method for producing an amide amino acid type surfactant composition, in which an amide amino acid compound represented by is produced, and then a polymerization initiator is added to the reaction mixture to polymerize the remaining acrylic acid.

The amidoamine compound represented by the general formula (4) can be produced by condensing a fatty acid or fatty acid ester with an ethylenediamine derivative, or by hydrolyzing an imidazoline compound.

Specific examples of the amide amino acid compounds represented by the general formulas (1) and (2) include N-cocoyl-N'-(2-hydroxyethyl)-N'-(carboxyethyl)ethylenediamine, N-cocoyl-N'-(2-hydroxyethyl)-N'-(carboxyethyl)ethylenediamine, -Lauroyl-N'-
(2-hydroxyethyl)-N'-(carboxyethyl)ethylenediamine, N-caproyl-N'-(2-hydroxyethyl)-N'-(carboxyethyl)ethylenediamine, N-stearoyl-N'-(2-hydroxy ethyl)-N'-(carboxyethyl)ethylenediamine, N-cocoyl-N-(2-hydroxyethyl)-
N',N'-bis(carboxyethyl)ethylenediamine, N-lauroyl-N-(2-hydroxyethyl)-
N',N'-bis(carboxyethyl)ethylenediamine, N-stearoyl-N-(2-hydroxyethyl)
-N',N'-bis(carboxyethyl)ethylenediamine, N-cocoyl-N-(2-hydroxyethyl)-
N'-(carboxyethyl)ethylenediamine, N-lauroyl-N-(2-hydroxyethyl)-N'-(carboxyethyl)ethylenediamine, N-caproyl-
N-(2-hydroxyethyl)-N'-(carboxyethyl)ethylenediamine, N-lauroyl-N',N'
-bis(carboxyethyl)ethylenediamine, N-lauroyl-N'-(carboxyethyl)ethylenediamine, N-lauroyl-N-(2-hydroxyethyl)-
Examples include N'-(2-hydroxyethyl)-N'-(carboxyethyl)ethylenediamine and the sodium salts, potassium salts, and triethanolamine salts of these compounds.

The content of polyacrylic acid or its water-soluble salt in the amide amino acid type surfactant composition is in the range of 3.5 to 45% based on the total amount of the amide amino acid compound and polyacrylic acid (active ingredients). Preferably within.

The other component of the present invention, the general formula (3
) The phosphorous acid compounds represented by are specifically exemplified as follows:
Examples include phosphorous acid, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, ammonium phosphite, and ammonium hydrogen phosphite. The blending amount of the phosphorous acid compound is 0.03- to the active ingredient of the amide amino acid type surfactant composition.
15%, preferably 0.1-10%. 0.03
If the amount is less than 15%, the effect of preventing coloring will be small, and if it is more than 15%, it is not necessary.

The surfactant composition of the present invention can be applied to shampoos, body shampoos, baby shampoos, pet shampoos, facial cleansers, kitchen detergents, and the like. When blended into these detergent compositions, the following components can be used in combination with the surfactant composition of the present invention within a range that does not impair its performance. Namely, fatty acid soap, higher alcohol sulfate ester salt, polyoxyethylene higher alcohol sulfate ester salt, higher alcohol phosphate ester salt, polyoxyethylene higher alcohol phosphate ester salt, sulfosuccinate ester salt, α-olefin sulfonate, mono Anionic surfactants such as alkyl phosphate ester salts, acylmethyl taurate salts, acyl isethionates, amphoteric surfactants such as alkylimidazolinium betaine type, amidopropyl betaine type, fatty acid diethanolamide, fatty acid monoethanolamide, alkyl amines Examples include nonionic surfactants such as oxides and polyoxyethylene higher alcohol ethers, and cationic surfactants such as quaternary ammonium salt type cationic surfactants.

[0011] If necessary, solubilizers such as glycols, emollients such as ester oil, preservatives such as hyaluronic acid, chitin, and chitosan, cell activators such as aloe extract and placenta extract, and allantoin may be used. , anti-inflammatory agents such as glycyrrhizinate, anti-dandruff agents such as zinc pyrithione and piroctone olamine, fragrances, pigments, etc. can also be added.

[0012] The present invention will now be explained in more detail with reference to Examples.

[Example] Production example-1 N-cocoyl-N'-(2-hydroxyethyl)-N'
-Production of (sodium carboxyethyl)ethylenediamine 305g (1.0 mol) of N-cocoyl-N'-(2-hydroxyethyl)ethylenediamine and 611g of water were mixed, heated to 85°C, and 93.7g (1.0mol) of acrylic acid was mixed. .3 mol) was added dropwise for 1 hour. After further aging at the same temperature for 2 hours, the reaction solution was cooled to 30°C to obtain an aqueous solution of N-cocoyl-N'-(2-hydroxyethyl)-N'-(carboxyethyl)ethylenediamine. Next, add 35% to this aqueous solution.
% hydrogen peroxide solution was added, and the mixture was kept at 55 to 60°C for 12 hours to polymerize unreacted acrylic acid. Next, 411 g of sodium hydroxide aqueous solution with a concentration of 12.6%
was added to neutralize the mixture to obtain 1390 g of an aqueous solution of the title compound. The active ingredient of this product was 30.1%, and the polyacrylic acid was 8.7% based on the active ingredient.

Production Example-2 Production of N-lauroyl-N'-bis(sodium carboxyethyl)ethylenediamine 242 g (1.0
mol) and 839 g of water were mixed, heated to 85°C, and then 216.2 g (3.0 mol) of acrylic acid was added dropwise over 1.5 hours. After further aging at 85 to 90°C for 2 hours, the reaction solution was cooled to 30°C. Next, add 3
Add 16.1g of 5% hydrogen peroxide solution and heat to 60 to 70°C.
The mixture was kept for 15 hours to polymerize unreacted acrylic acid, and after the reaction, an alkali was added to neutralize it to obtain 1270 g of an aqueous solution of N-lauroyl-N'-bis(sodium carboxyethyl)ethylenediamine and polyacrylic acid. The active ingredient in this product was 30.2%, and the polyacrylic acid was 34.7% based on the active ingredient.

Production example-3 N-cocoyl-N'-(2-hydroxyethyl)-N'
-(sodium carboxyethyl)ethylenediamine and N-cocoyl-N-(2-hydroxyethyl)-N'-
Preparation of a mixture of (sodium carboxyethyl)ethylenediamine 2-coconut alkyl-N-(2-hydroxyethyl)-2
- A mixture of N-cocoyl-N'-(2-hydroxyethyl)ethylenediamine obtained by hydrolyzing 43 g (0.15 mol) of imidazoline, N-cocoyl-N-(2-hydroxyethyl)ethylenediamine, and water. 163g
After heating to 80° C., 32.4 g (0.45 mol) of acrylic acid was added dropwise over 1 hour. Further add 80 to 90% of the reaction solution.
After aging at 0°C for 2 hours, the reaction solution was cooled to 30°C and 35%
Add 0.78g of hydrogen peroxide solution and heat at 50 to 60°C.
The unreacted acrylic acid was kept for 5 hours to polymerize, and after the reaction, an alkali was added to neutralize it, resulting in N-cocoyl-N'-(2-hydroxyethyl)-N'-(sodium carboxyethyl)ethylenediamine and N-cocoyl. 192 g of an aqueous solution of a mixture of -N-(2-hydroxyethyl)-N'-(sodium carboxyethyl)ethylenediamine and polyacrylic acid was obtained. The active ingredient of this product is 30.4%
, polyacrylic acid was 30.8% based on the active ingredient.

Examples 1 to 20, Comparative Examples 1 to 5 Production Examples 1 to 5
Amidoamino acid type surfactant composition 100 obtained in 3.
A test was conducted in which a phosphorous acid compound or the like was added to g and left at 50° C. for 10 days, and the change in color before and after the test was measured. The hue was measured by the Gardner method, which is defined as a standard oil and fat analysis method. Table 1 shows the test conditions and test results. In the table, the number in parentheses next to the amount of phosphorous acid compound added represents the addition rate of the phosphorous acid compound to the active ingredient of the amide amino acid type surfactant composition.

[Table 1]

Example 21 Body shampoo

Lauric acid
5.0% by weight
Composition of Production Example-1
10.0 Phosphorous acid
0.2 (6.2
%) Amidopropyl dimethylamino laurate
betaine acetate

5.0 Lauric acid diethanolamide 3.0
potassium hydroxide
Amount to adjust pH to 8
glycerin
3.0
Methylparaben
0.1
purified water

Zanko's body shampoo lathered well, was gentle on the skin, and did not discolor over time.

Example 22 Hair shampoo Polyoxyethylene (3) lauryl ether - Sodium sulfate

10.0% by weight Composition of Production Example-1

40.0 Phosphorous acid

1.0 (7.7%)
Sodium lauroylmethyl-β-alanine
2.0 Sodium lauroylmethyltaurate 2.
0 Coconut oil fatty acid diethanolamide
1.0
cationized cellulose
0.5 citric acid
Amount to make pH 7
Edetate disodium
0.1
Methylparaben
0.1
purified water

This hair shampoo lathered well, was gentle on the hair and skin, and did not stain over time.

Example 23 Facial cleansing agent Myristic acid
24
．． 0% by weight lauric acid

5.0 Stearic acid

4.0 Composition of Production Example-1
5.0 Sodium hydrogen phosphite
0.1 (9.1%) Potassium hydroxide
4.8
Polyoxyethylene (5) coconut oil fatty acid

monoethanolamide
7.0
ethylene glycol distearate
3.0 Glycerin
4.0 Polyethylene glycol 400
3.0 Hyaluronic acid
0.5 Methylparaben
0.1 Purified water
This facial cleanser foamed well, gave a gentle and moist feeling to the skin, and did not discolor over time.

Example 24 Kitchen detergent Composition of Production Example-1
50.0% by weight phosphorous acid

1.0 (6.2%) Potassium phosphite
0.2 (1.2%)
α-Olefin sulfonic acid soda
5.0 Laurylamine oxide
3.0 Methylparaben

0.2 Purified water

This kitchen detergent foamed well, had good cleaning power, was gentle on the skin, and did not stain over time.

[0020]

[Effects of the invention] The present invention provides excellent foaming and cleaning power.
An amide amino acid type surfactant composition that is gentle on the skin and hair, does not cause coloration over time, and does not contain salt, so it can be formulated with high flexibility, and a cleaning composition containing the surfactant composition as an essential ingredient. can be manufactured.

Claims (2)

[Claims] Claim 1 General formulas (1) and (2) Represents a hydrocarbon group, R2 and R3
represent a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms, and may be the same or different; M represents a hydrogen atom, sodium, potassium, and triethanolamine; represent. ) An amide amino acid type surfactant composition containing one or more amide amino acid compounds represented by the general formula (
3) [Chemical formula 3] (3) (In the formula, R4, R5, and R6 represent a hydrogen atom, sodium, potassium, or ammonium group, and may be the same or different.) Phosphous acid represented by A surfactant composition characterized in that at least one compound is added thereto. [Claim 2] The following three components (A), (B), (C)
A cleaning composition characterized by having as an essential ingredient. (A) One or more amide amino acid type surfactants selected from amide amino acid compounds represented by the following general formulas (1) and (2). [Chemical Formula 4] (1) [Chemical Formula 5] (2) (In the formula, R1 represents a saturated or unsaturated aliphatic hydrocarbon group having 7 to 21 carbon atoms, and R2 and R3
represent a hydrogen atom or a hydroxyalkyl group having 1 to 4 carbon atoms, and may be the same or different; M is a hydrogen atom, a type obtained from sodium, potassium, and triethanolamine; represents. ) (B) Polyacrylic acid or a water-soluble salt thereof. (C) At least one phosphorous acid compound represented by the following general formula (3). embedded image (3) (In the formula, R4, R5, and R6 represent a hydrogen atom, sodium, potassium, or ammonium group, and may be the same or different.)