JP2000072730A - Surfactant composition containing n-substituted-beta- alanine or its salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surfactant composition having good odor and color in spite of the use of an N-substituted-β-alanine by including a specific N- substituted-β-alanine (salt) and a specific sulfur compound. SOLUTION: The objective composition contains (A) an N-substituted-β-alanine (salt) of formula RNXCH2CH2COOM [R is a (substituted) 6-25C hydrocarbon group; X is H or (CH2)2COOH; M is H, an alkali metal, an alkaline earth metal or the like] and (B) 0.05-50 wt.%, preferably 5-20 wt.% (based on the component A) of a sulfur compound selected from sulfurous acid (salt) (e.g. sodium sulfite), acidic sulfurous acid (salt) (e.g. sodium bisulfite), persulfuric acid (salt) (e.g. sodium persulfate), dithionous acid (salt) (e.g. sodium dithionite) and thiosulfuric acid (e.g. sodium thiosulfate). The component A is preferably produced by reacting an aliphatic primary amine with an acrylic acid derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a surfactant composition containing an N-substituted β-alanine or a salt thereof, and a detergent composition containing the surfactant composition.

[0002]

2. Description of the Related Art Recently, amino surfactants have been used as mild surfactants. N-substituted β-alanine represented by the following general formula (I) or a salt thereof is classified as an amino acid-based amphoteric activator, and is described in US Pat.
No. 33, JP-A-6-116596 and JP-A-9-3
No. 485 specifically describes this.

RNXCH ₂ CH ₂ COOM (I) (wherein, R represents a carbon number of 6 to 25 which may have a substituent.
Indicates a hydrocarbon group, X is a hydrogen atom or a - (CH _{2) 2} CO
Represents OH, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium cation, an alkanolamine cation or a basic amino acid cation)

As described in US Pat. No. 2,787,633, N-substituted β-alanine is obtained by subjecting an aliphatic primary amine to Michael addition of acrylic acid, acrylate ester, acrylonitrile, etc., and optionally obtaining an addition product. It is known that it can be produced by hydrolysis of

JP-A-6-116596 discloses a detergent composition comprising an N-substituted β-alanine activator and a hydroxycarboxylic acid, and JP-A-9-3485 discloses an N-substituted β-alanine activator. A detergent composition comprising a combination of a surfactant and an ether carboxylic acid-based activator is described.

[0006]

However, the conventional N-substituted β-alanine-based surfactant has a problem that when used as a detergent or a surfactant composition, it has a bad odor and gives color over time. ing. In particular, when used as a kitchen cleaner, a hair cleaner, or a skin cleaner, stability becomes a problem, and the value as a product is significantly impaired.

An object of the present invention is to provide a surfactant composition comprising an N-substituted β-alanine having good odor and hue.

[0008]

In the present invention, it has been found that the object of the present invention is achieved by adding a specific sulfur compound to N-substituted β-alanine, and the present invention has been completed.

That is, the present invention provides (A) an N-substituted β-alanine represented by the following general formula (I) or a salt thereof, and (B) sulfurous acid, acidic sulfite, persulfate, dithionite, thiosulfate and Provided is a surfactant composition comprising, as an essential component, at least one sulfur compound selected from the group consisting of salts thereof.

RNXCH ₂ CH ₂ COOM (I) (wherein, R represents a carbon number of 6 to 25 which may include a substituent.
Indicates a hydrocarbon group, X is a hydrogen atom or a - (CH _{2) 2} CO
Represents OH, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium cation, an alkanolamine cation or a basic amino acid cation)

In the surfactant composition of the present invention, it is preferable that the N-substituted β-alanine or a salt thereof is obtained by reacting an aliphatic primary amine with an acrylic derivative.

Further, the present invention provides a detergent composition comprising the above-mentioned surfactant composition and an anionic surfactant as essential components.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) in the surfactant composition of the present invention is an N-substituted β represented by the above general formula (I).
Alanine or a salt thereof.

In R in the general formula (I), the hydrocarbon group may be linear or branched, saturated or unsaturated, and may optionally contain a substituent such as a hydroxyl group. As the hydrocarbon group of carbon vinegar 6 to 25, an alkyl group or alkenyl group having 6 to 25 carbon atoms is preferable. Examples of the alkyl group include hexyl, heptyl, octyl, nonyl, decyl, undecyl, 2-ethyldecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and nonadecyl. Group, eicosyl group, heneicosyl group, docosyl group and the like. Examples of the alkenyl group include a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, a 2-ethyldecenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, and a nonadecenyl group. No. Among them, R is particularly preferably a straight-chain alkyl group having 8 to 18 carbon atoms.

In M in the general formula (I), examples of the alkali metal include lithium, potassium and sodium, and examples of the alkaline earth metal include calcium and magnesium. As the alkanolamine cation, a lower alkanolamine cation is preferable, and examples thereof include cations such as triethanolamine, diethanolamine, and monoethanolamine. Examples of the basic amino acid cation include cations such as lysine and arginine. M is preferably a hydrogen atom, an alkali metal,
Alkanolamine cation, particularly preferably
Hydrogen atom, potassium, sodium, triethanolamine cation. These may be a mixture of two or more.

As a method for producing the N-substituted β-alanine of the component (A) or a salt thereof, the following method is preferable.
First, an aliphatic primary amine is reacted with an acrylic derivative,
It is an addition reaction product. Acrylic derivatives include acrylic acid, acrylates and acrylonitrile.

In this addition reaction, the acrylic derivative is reacted with the aliphatic primary amine in a molar ratio of 1 to 2 at a temperature of usually 20 to 100 ° C., preferably 40 to 90 ° C. When the temperature is lower than 20 ° C., the reaction takes a long time, and when the temperature is higher than 100 ° C., the odor and hue of N-substituted β-alanine deteriorate. When the molar ratio of the acrylic derivative to the aliphatic primary amine increases, a large amount of unreacted acrylic derivative remains, and moreover, a large amount of 2-mol adduct is undesirably produced as a by-product. On the other hand, if the molar ratio is small, unreacted aliphatic primary amine increases, which is not preferable. As for the reaction time, the acrylic acid derivative is preferably added dropwise over 0.1 to 2 hours, and aging is preferably performed for 1 to 12 hours.

Further, a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol and butyl alcohol or water may be added to promote the reaction. This lower alcohol or water may be distilled off from the addition reaction product under reduced pressure, if necessary, or may remain. The use amount of the lower alcohol or water is preferably 1 to 50 parts by weight based on 100 parts by weight of the aliphatic primary amine.

When an acrylate or acrylonitrile is used as the acrylic derivative, the resulting N-substituted aminopropionate or N-substituted aminopropionitrile is further hydrolyzed with an alkali or acid to obtain the above-mentioned general formula (I). An N-substituted β-alanine represented by I) is obtained.

The hydrolysis temperature is usually 50 to 100 ° C, preferably 60 to 90 ° C. As for the hydrolysis time,
It is preferable to add an alkali or an acid dropwise over 0.5 to 2 hours and ripen it for 1 to 6 hours. After the hydrolysis, if necessary, the pH of the product may be adjusted to 6 to 12 with an acid. The acid used is a commonly used inorganic acid or organic acid, such as hydrochloric acid, sulfuric acid, benzoic acid, and paratoluenesulfonic acid. The temperature is preferably from 20 to 90 ° C. When the pH is adjusted after the hydrolysis, an inorganic salt or an organic salt is generated corresponding to the inorganic or organic acid to be used, but may be removed by a desalting method such as electrodialysis if necessary.

(B) in the surfactant composition of the present invention
The component is one or more sulfur compounds selected from the group consisting of sulfurous acid, acidic sulfurous acid, persulfuric acid, dithionous acid, thiosulfuric acid and salts thereof.

Examples of the sulfite include sodium sulfite, potassium sulfite, barium sulfite, calcium sulfite, and ammonium sulfite. Examples of the acid sulfite include sodium bisulfite, potassium bisulfite, calcium bisulfite, and ammonium bisulfite. Examples of the persulfate include sodium persulfate, potassium persulfate, and ammonium persulfate; examples of the dithionite include sodium dithionite and hydrosulfite; examples of the thiosulfate include sodium thiosulfate, potassium thiosulfate, and thiosulfate. Barium, ammonium thiosulfate and the like, preferably sodium sulfite, potassium sulfite, sodium hydrogen sulfite, sodium persulfate, sodium dithionite, sodium thiosulfate, more preferably sodium sulfite, sulfite Sodium acid hydrogen sodium dithionite.

The surfactant composition of the present invention contains the above components (A) and (B) as essential components. The content ratio of the component (A) to the component (B) is preferably such that the component (B) is in the range of 0.05 to 50% by weight, more preferably 5 to 20% by weight, based on the component (A). is there. When the content of the component (B) exceeds 50% by weight, an excessive sulfur compound is decomposed to generate a sulfur odor, whereas when the content is less than 0.05% by weight, an effect sufficient to improve the odor is observed. I can't.

Preferably, a predetermined amount of (B) a sulfur compound is added to the solution of (A) N-substituted β-alanine obtained by the above production method. (B) The sulfur compound may be oxidized with hydrogen peroxide or the like to form sulfate ions, if necessary, in amounts other than those used to improve odor and hue.

The surfactant composition of the present invention is a compound that has achieved the initial object of having a good odor and not giving color over time, and is therefore extremely suitable as a surfactant used for various uses. is there.

Among them, body cleaners, kitchen cleaners,
Use of various cleaning agents such as hard surface cleaning agents is
It is very preferable because the advantages of substituted β-alanine such as high detergency and high mildness can be positively utilized.

When used as a detergent, the surfactant composition of the present invention can be suitably used either singly or as a mixture with another surfactant. When mixed, alkyl sulfate, alkyl ethoxy sulfate, α-olefin sulfonate, α-sulfofatty acid ester salt, alkylbenzene sulfonate, soap, alkyl ether carboxylate, alkyl sulfosuccinate, alkyl phosphorus Anionic surfactants represented by acid ester salts, amino acid derivatives such as alkyl alaninate and alkyl taurate, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, fatty acid alkanolamides, alkyl polyglucosides, and short-chain alkyls Nonionic surfactants represented by glucoside long-chain fatty acid esters, alkylmethylglucamides, sucrose fatty acid esters, etc .; alkylamine oxides; alkylcarbobetaines; Amphoteric and amphoteric surfactants represented by tines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylimidazolines or derivatives thereof, and the like are preferred. Among these surfactants, anionic surfactants are particularly preferred in terms of high detergency and foam performance. The mixing ratio of these surfactants is N-substituted β-alanine 100
It is preferably from 10 to 1000 parts by weight based on parts by weight.

When used as a detergent, components other than surfactants usually used in ordinary detergents, such as alcohol-based hydrotropes such as lower alcohols and polyalkylene glycols, toluene sulfonic acid, Xylene sulfonic acid, cumene sulfonic acid,
Hydrotropes such as benzoic acid and salicylic acid; low molecular aromatic compounds used as antibacterial agents; chelating agents such as citric acid, malic acid and EDTA; dyes, fragrances, viscosity modifiers, and functional substances such as inorganic compounds Can be suitably mixed.

[0029]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following examples, “parts” and “%” are “parts by weight”, respectively.
And "% by weight".

Examples 1 to 12 and Comparative Examples 1 and 2 N-alkyl β-alanine shown in Table 1 was mixed with a sulfur compound shown in Table 1 in a composition having an addition amount shown in Table 1 (mixing ratio to N-alkyl β-alanine). , Pure water and N-alkyl β
A 30% alanine solution was obtained to obtain a surfactant composition. Table 2 shows the results of the evaluation of odor and hue according to the following evaluation criteria.

(Evaluation of Odor) A sensory test was conducted, and the odor was evaluated according to the following criteria. ：: No odor and good odor. Δ: Slight odor and bad odor. ×: Off-flavor is strong and remarkably bad.

(Evaluation of Hue) The hue was visually evaluated according to the following criteria. ：: Hue change is slight. Δ: Color change is observed with a change in hue. X: Color change is noticeable with a remarkable change in hue.

[0033]

Table 1 Kinds of N-substituted β-alanine Kinds and addition amounts (%) of sulfur compounds Example 1 N lauryl β-alanine sodium sulfite 20.0 Example 2 N lauryl β-alanine sodium sulfite 0.05 Example 3 N lauryl β-alanine sodium bisulfite 5.00 Example 4 N Lauryl β-alanine Sodium Dithionite 5.00 Example 5 N Stearyl β Alanine Sodium Sulfite 5.00 Example 6 N Palm ^* β Alanine Sodium Sulfite 5.00 Example 7 N Lauryl β Alanine Barium Sulfite 5.00 Example 8 N Lauryl β Alanine potassium thiosulfate 5.00 Example 9 N lauryl β-alanine sodium sulfite 15.0 Example 10 N lauryl β-alanine sodium sulfite 10.0 Example 11 N lauryl β-alanine sodium sulfite 100.0 Example 12 N lauryl β-alanine sodium persulfate 5.00 Comparative example 1 N Lauri No β-alanine added- Comparative Example 2 N lauryl β-alanine sodium sulfate 1.00 * Fatty acid residue derived from coconut fatty acid

[0034]

[Table 2] Odor (initial) Odor (after storage at 50 ° C for 1 month) Hue (after storage at 50 ° C for 1 month) Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Example 4 ○ ○ ○ Example 5 ○ ○ ○ Example 6 ○ ○ ○ Example 7 ○ ○ ○ Example 8 ○ ○ ○ Example 9 ○ ○ ○ Example 10 ○ ○ ○ Example 11 ○ × ○ Example 12 ○ ○ ○ Comparative Example 1 △ × × Comparative Example 3 △ × ×

From the results shown in Table 1, the surfactant composition of the present invention to which a predetermined amount of a sulfur compound has been added is excellent in both hue and odor stability over time. However, there was a tendency for the system not added and the system added excessively to deteriorate over time. No effect was observed with sodium sulfate, which was the same as without addition.

Next, examples in which the surfactant compositions produced in the above Examples and Comparative Examples are used as detergents will be described.

Examples 13 to 17 and Comparative Examples 3 to 4 Liquid detergent compositions shown in Table 3 were prepared, and the compositions were evaluated for detergency, skin irritation, odor and hue. Table 3 shows the results. Odor and hue were evaluated in the same manner as described above, and skin irritation and detergency were evaluated by the following methods. In addition, all the compounding amounts in Table 3 are% by weight, and the composition was adjusted to pH 6.5.

(Evaluation of skin irritation) Surfactant composition 1
% Aqueous solution (35 ° C.) was evaluated by an immersion test by hand of 10 testers. That is, the immersion-drying operation was performed 15 times every minute, and the degree of skin roughness of the hand after 24 hours was visually judged according to the following criteria.

：: Almost no skin roughness Δ: Signs of rough skin such as dry desquamation and red spot change are observed on a part of the keratinous surface of the skin. ×: Hand rough symptoms such as dry desquamation and red spot change are clearly observed.

(Evaluation of Detergency) After dissolving 10 g of soybean oil and 10 g of tallow as specified in the Japanese Pharmacopoeia in 60 ml of chloroform, 0.1 g of oil red is added and mixed well to prepare a dirty solution. A glass plate is immersed in this solution to contaminate it, and air-dried at a temperature of 25 ° C. for 30 minutes or more to remove chloroform to prepare a contaminated piece (contamination amount: 20 to 30 mg /
Sheet). Six of these contaminated pieces were placed at 25 ° C. and 700 ml of 0.15
After washing by stirring at a rotation speed of 20 rpm for 3 minutes in a% detergent solution, the sample was air-dried, the weight was measured, and the oil removal rate after washing was calculated by the following equation (1) to obtain the detergency.

Detergency (%) = {1− (W ₂ −W ₀ ) / (W ₁ −W ₀ )} × 100 (1) (where W ₀ represents the weight of the glass plate,
W ₁ is the weight of the glass plate after contamination, W ₂ denotes the weight of the glass plate after washing air dry)

[0042]

Example 3 Comparative Example 13 14 15 16 17 3 4 Surfactant Composition of Example 1 10 Surfactant Composition of Example 2 10 Surfactant Composition of Example 3 10 Interface of Example 4 Surfactant Composition 10 Surfactant Composition of Example 5 10 Surfactant Composition of Comparative Example 1 10 Surfactant Composition of Comparative Example 2 10 POE (n = 3) Sodium Lauryl Sulfate 5.5 5 C ₁₄ α-Olefin sulfonic acid Na salt 5.55 POE (n = 10) lauryl ether 5.55 5.5 lauric acid diethanolamide 5.55 5.5 purified water Remaining Remaining Remaining Remaining Remaining Remaining Remaining detergency>90>90>90> 90 >90>90> 90 Skin irritation ○ ○ ○ ○ ○ ○ ○ Odor after storage at 50 ℃ for one month ○ ○ ○ ○ ○ × × Hue after storage at 50 ℃ for one month ○ ○ ○ ○ ○ × × In 3, POE represents polyoxyethylene, and n represents the average number of moles of ethylene oxide added.

As is clear from Table 3, all of the prepared cleaning compositions show excellent mildness and cleaning performance, but the cleaning compositions of the present invention (Examples 13 to 17) show 50%.
The odor and hue after storage at 50 ° C. for one month are good, whereas the comparative detergent compositions (Comparative Examples 3 and 4) have the problem that the odor and hue after storage at 50 ° C. for one month are poor. Have.

[0044]

The surfactant composition of the present invention does not contain impurities such as odorous components, and has excellent properties such as high foaming power, high detergency, and low skin irritation. Yes,
Moreover, it is an excellent base material that does not cause coloring or abnormal odor even when it is formulated as a liquid detergent and has a good odor and is stored, especially for kitchen detergents, hair detergents, It is very suitable as a skin cleanser.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Fumio Wakui 1-3-7 Honjo, Sumida-ku, Tokyo Lion Inside (72) Inventor Tomomichi Okano 1-3-7 Honjo, Sumida-ku, Tokyo Incorporated (72) Inventor Noriko Sugimoto 1-3-7 Honjo, Sumida-ku, Tokyo Lion F-term in incorporated company (reference) 4D077 AB10 BA07 BA13 DB07Y DB10Y DC02Z DC26Y DC26Z DC28Y DC43Z DC50Y 4H003 AB08 AB15 AB31 AC08 AC13 BA12 DA02 DA17 EA02 EA03 EA12 ED02 FA02 FA14 FA18 FA25 4H006 AA03 AB68 AB70 BS10 BS70 BU32

Claims (3)

[Claims] (A) N represented by the following general formula (I)
Substituted β-alanine or a salt thereof, and (B) one or more sulfur compounds selected from the group consisting of sulfurous acid, acidic sulfurous acid, persulfuric acid, dithionous acid, thiosulfuric acid and salts thereof as essential components. A surfactant composition. RNXCH ₂ CH ₂ COOM (I) (wherein, R represents a carbon number of 6 to 25 which may include a substituent.
Indicates a hydrocarbon group, X is a hydrogen atom or a - (CH _{2) 2} CO
Represents OH, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium cation, an alkanolamine cation or a basic amino acid cation) 2. The surfactant composition according to claim 1, wherein the N-substituted β-alanine or a salt thereof is obtained by reacting an aliphatic primary amine with an acrylic derivative. 3. A detergent composition comprising the surfactant composition according to claim 1 and an anionic surfactant as essential components.