JPH06172522A - Amphoteric surfactant - Google Patents

Abstract

PURPOSE:To provide an amphoteric surfactant excellent in surface activities, such as foaming ability and an ability to reduce surface tension, and in safety from, e.g. denaturation of protein, and suitable for perfumed articles such as a shampoo, a rinse, a cosmetic, a lotion and a cream. CONSTITUTION:An amphoteric surfactant comprising a compound obtained by saponifying with an acid or alkali an adduct of 1mol of a polyethyleneimine of an average molecular weight of 200 to 100,000 with an 8-22C fatty acid in an amount of 1 to (the degree of polyethyleneimine X1) mol and an unsaturated ester or nitrile monomer in an amount of 1 to (the degree of polymerization of polyethyleneimine X1) mol.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an amphoteric surfactant. More specifically, it has a surface activity such as foamability and surface tension lowering ability, and has no skin irritation, does not cause skin roughness or eczema, and does not damage the hair. The present invention relates to an amphoteric surfactant suitable for cosmetics such as highly safe shampoos, rinses, cosmetics, lotions and creams.

[0002]

2. Description of the Related Art Amphoteric surfactants are emulsifying agents, dispersing agents, solubilizing agents, foaming agents, penetrating agents, antibacterial agents, lubricating agents, rust preventive agents, slow dyeing agents, level dyeing agents, and friable agents. Excellent in properties such as antistatic property, as a yield enhancer for paper strength enhancer, paper quality improver, sizing agent, various fillers, pigments, dyes, etc. in the paper industry, adhesion promoter in the adhesive industry, textile industry Improvement of dyeability of various fibers in the field, shrinkage prevention, flameproofing treatment, antistatic treatment, etc., cosmetic composition, detergent composition,
Widely used as a lubricant additive, rust preventive, antifogging agent, etc.

Conventionally, as an amphoteric surfactant, an imidazoline type amphoteric surfactant (USP2528378) obtained by amphoterizing a condensate of aminoethylethanolamine and a fatty acid with sodium monochloroacetate, a fatty acid polyhydric alcohol ester and a polyamine There is known a betaine-type amphoteric surfactant (JP-A-53-122689) obtained by reacting an unsaturated aliphatic monocarboxylic acid with a reaction product thereof with an ester after addition of epoxyalkane to polyethyleneimine. A polymeric amphoteric surfactant obtained by adding an ethylenically unsaturated monomer having a bond or a nitrile group and then saponifying with an acid or an alkali (Japanese Patent Publication No. 2-9
623) and the like are known.

[0004]

However, these conventionally known products have various problems. For example, imidazoline-type amphoteric surfactants and betaine-type amphoteric surfactants have excellent surface activity such as foaming property, but their protein denaturing property that damages skin or hair is soap or phosphate ester type. High compared to surfactants. Protein denaturability is a standard for comparing the safety of raw materials used in the cosmetics field, and it is known that high protein denaturability results in low safety and is not suitable for cosmetics and the like. On the other hand, although a high molecular weight amphoteric surfactant is excellent in safety such as protein denaturation, it has poor surface activity such as foaming property and does not exhibit sufficient performance as a surfactant.

The present invention has been made in view of the above points, and an object thereof is to provide an amphoteric surfactant which is excellent in safety such as protein denaturing property and has good surface activity such as foaming property. To do.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that compounds obtained by reacting a specific polyethyleneimine with a fatty acid and then amphoteric have excellent protein denaturing properties and the like. It has been found that the present invention has properties and can exhibit good surface activity such as foamability, and thus completed the present invention.

That is, the present invention has an average molecular weight of 200 to 1
An unsaturated monomer having an ester bond or a nitrile group (hereinafter referred to as It is an amphoteric surfactant composed of a compound obtained by adding 1 mol of an unsaturated monomer referred to as “monomer A” to a polymerization degree of polyethyleneimine × 1 mol and saponifying with an acid or an alkali. .

The amphoteric surfactant of the present invention can be manufactured as follows. First, polyethylenimine is reacted with a fatty acid to obtain poly-N-acylpolyethyleneimine. The reaction of polyethyleneimine and fatty acid can be carried out by mixing both or adding one to the other and heating at 100 to 200 ° C. for 1 to 10 hours. In this reaction, when polyethyleneimine having a molecular weight of 200 to 20,000 is used, the reaction can be carried out without a solvent, but when polyethyleneimine having a molecular weight of 20,000 to 100,000 is used. It is preferable to carry out the reaction in the presence of a solvent.

Next, a monomer A is added to the obtained poly-N-acyl polyethyleneimine, and an ester group or a nitrile group is saponified to provide an amphoteric interface having an acidic group and a basic group and having a large molecular weight. An activator is obtained. The reaction between the poly-N-acyl polyethyleneimine and the monomer A is carried out by adding the monomer A to the poly-N-acyl polyethyleneimine in the presence or absence of a solvent, and adding the monomer A to 50 to 15%.
It can be performed by heating at 0 ° C. for 1 to 10 hours. After further adding the monomer A, an aqueous solution of an alkali or an acid is added thereto and reacted at 50 to 150 ° C. for 1 to 10 hours to saponify the ester group or nitrile group introduced by the monomer A. It can be performed. Examples of the alkali used for saponification include sodium hydroxide and potassium hydroxide, and examples of the acid include hydrochloric acid and sulfuric acid.

Among the above-mentioned monomers A, those having an ester bond include acrylic acid alkyl ester, methacrylic acid alkyl ester, crotonic acid alkyl ester, itaconic acid alkyl ester, maleic acid alkyl ester, fumaric acid alkyl ester and the like. Named
The alkyl group constituting the ester group preferably has 1 to 6 carbon atoms. Examples of those having a nitrile group include acrylonitrile and methacrylonitrile.

After adding a fatty acid and a monomer A to polyethyleneimine and then performing a saponification reaction, either as it is or after removing the solvent if necessary can be used as an amphoteric surfactant, and calcium chloride and magnesium chloride can be used. For example, it can be used in the form of a calcium salt or a magnesium salt, or purified with hexane, dioxane, acetone or the like.

In each of the above reactions, the reaction ratio of polyethyleneimine, fatty acid, and monomer A is such that 1 mol of the fatty acid is 1 mol or more per 1 mol of the polyethyleneimine, and the number of mols is not more than the degree of polymerization of polyethyleneimine. The amount of the monomer A is preferably 1 mol or more and not more than the number of mols represented by the degree of polymerization of polyethyleneimine × 1, and the amphoteric surfactant obtained by reacting in this range has a balance between hydrophilicity and lipophilicity. Exhibits good and good amphoteric surfactant activity.
The amount of fatty acid added to 1 mol of polyethyleneimine is 1
When the amount is less than the molar amount, the amphoteric surfactant obtained has low lipophilicity, and cannot be added exceeding the degree of polymerization of polyethyleneimine × 1 mol. When the addition amount of the monomer A is less than 1 mol per 1 mol of polyethyleneimine, the hydrophilicity becomes poor, and the addition cannot exceed the degree of polymerization of polyethyleneimine × 1 mol.

The molecular weight of the polyethyleneimine used in the present invention is preferably 200 to 100,000, and the fatty acid and the monomer A can be added uniformly,
An amphoteric surfactant having a well-balanced hydrophilicity and lipophilicity is obtained. When the molecular weight of polyethyleneimine is less than 200, an amphoteric surfactant having a well-balanced hydrophilicity and lipophilicity cannot be obtained, and when it exceeds 100,000, its viscosity is too large to uniformly disperse the fatty acid and monomer A. Is difficult to add and is not preferable.

The fatty acid used in the present invention is preferably one having a total carbon number of 8 to 22, which is dissolved in water and has excellent foaming property, emulsifying property, dispersibility, detergency and the like, and low surface activity and protein denaturation rate. An amphoteric surfactant exhibiting excellent skin irritation alleviation properties such as If the total number of carbon atoms in the fatty acid is less than 8, it will be an amphoteric surfactant that is inferior in foaming properties, detergency and skin irritation, and if it exceeds 22, it will be difficult to dissolve in water, and the appearance of the compound itself will tend to be uneven. However, the commercial value is lowered, which is not preferable. As the fatty acid, one having a total carbon number in the above range can be used alone, or two or more kinds can be mixed and used. As the fatty acid having 8 to 22 carbon atoms, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid,
Tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid,
Examples include arachidic acid, behenic acid, decenoic acid, undecenoic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid, eicosenoic acid, linoleic acid, linolenic acid, and arachidonic acid. The fatty acids may be branched or branched, and these fatty acids may be used alone or in combination of two or more kinds.

Examples of the solvent that can be optionally used in the reaction of the fatty acid and the reaction of adding the monomer A include methanol, ethanol, isopropyl alcohol, butanol and the like. These may be used alone or in admixture of two or more. Can be used.

The amphoteric surfactant of the present invention is used as a yield enhancer for paper strength enhancer, paper quality improver, size improver, various fillers, pigments, dyes, etc. Dyeability improving agents for various fibers in the textile industry, anti-shrink agents, anti-flame processing agents, anti-static agents, cosmetic compositions, detergent compositions, lubricant additives, rust preventives, anti-fog agents Since it has a low protein denaturation rate and high safety, it is suitable as a base for cosmetics and the like.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these as long as the gist thereof is not exceeded. Hereinafter, "%" represents "% by weight".

【Example】

Example 1 30 g of lauric acid (0.15 mol) was added to 150 g (0.5 mol) of polyethyleneimine having an average molecular weight of 300 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) under stirring and under a nitrogen stream at 120 to 18 ° C. ) Was added and reacted at the same temperature for 5 hours. Next, the liquid temperature was kept at 85 ° C., and 86 g (1 mol) of acrylic acid methyl ester was added dropwise thereto over 2 hours.
The reaction was carried out at 80 ° C for 1 hour. After the reaction, add 95 g (0.95 mol) of a 40% strength caustic soda aqueous solution, and add 4 at 95 ° C.
The saponification reaction is performed for 3 hours to give the amphoteric surfactant of the present invention.
A 0% aqueous solution was obtained. The foamability and foam stability of the obtained amphoteric surfactant, surface tension and protein denaturation rate were measured,
The results are shown in Table 1.

Foaming property and foam stability test method The foaming property and foam stability are measured according to JIS-K-3362-6.5.
In accordance with (Rosmaisul method), pH 6.0 of aqueous solution,
Amphoteric surfactant concentration (concentration of solid content excluding salt) 1.
It was performed at 0% and a liquid temperature of 25 ° C.・ Surface tension test method The surface tension is JISK-3362-6.4 (Dunui method).
According to the above, the pH was 6.0 in the aqueous solution, the concentration of the amphoteric surfactant (concentration of solid content excluding sodium chloride) was 0.1%, and the solution temperature was 25 ° C.・ Protein denaturability test method The protein denaturability is determined by the HPLC method (Miyazaki et al., J. Soc. Cosm
et.Chem.Japan.Vol.18.No.2), the protein denaturation rate was measured using an amphoteric surfactant concentration (solid content concentration excluding sodium chloride) of 0.1% and ovalbumin.

Example 2 171.8 g of lauric acid was added to 150 g (0.25 mol) of polyethyleneimine having an average molecular weight of 600 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) under stirring and under a nitrogen stream at 120 to 180 ° C. (0.86 mol) was added, and the mixture was reacted at the same temperature for 5 hours. Next, the liquid temperature was maintained at 80 ° C., and 100 g (1.0 mol) of acrylic acid ethyl ester was added dropwise thereto over 2 hours, and the mixture was reacted at 80 ° C. for 1 hour. After the reaction, 4
95 g (0.95 mol) of 0% concentration caustic soda aqueous solution was added, and saponification reaction was carried out at 95 ° C. for 4 hours to obtain a 30% aqueous solution of the amphoteric surfactant of the present invention. The amphoteric surfactant thus obtained was used to measure the foamability, foam stability, surface tension and protein denaturation rate in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 150 g (0.075 mol) of polyethyleneimine having an average molecular weight of 2000 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) and 150 g of toluene were charged, and the mixture was stirred and under a nitrogen stream.
Oleic acid 42.5g, keeping at 20-180 ℃
(0.15 mol) was added, and the mixture was reacted at the same temperature for 5 hours. Next, the liquid temperature was maintained at 80 ° C., and 129 g (1.5 mol) of acrylic acid methyl ester was added dropwise thereto over 2 hours,
The reaction was carried out at 0 ° C for 1 hour. After the reaction, 142.5 g (1.43 mol) of a 40% strength caustic soda aqueous solution was added, and a saponification reaction was carried out at 95 ° C. for 4 hours to obtain a 30% aqueous solution of the amphoteric surfactant of the present invention. The amphoteric surfactant thus obtained was used to measure the foamability, foam stability, surface tension and protein denaturation rate in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 150 g (0.015 mol) of polyethyleneimine having an average molecular weight of 10,000 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) and 150 g of toluene were charged, and the mixture was stirred and under a nitrogen stream.
Stearic acid 4.28 while maintaining at 120-180 ° C
(0.015 mol) was added, and the mixture was reacted at the same temperature for 5 hours.
Next, the liquid temperature was maintained at 80 ° C., and 172 g (2.0 mol) of acrylic acid methyl ester was added dropwise to this over 8 hours to give 8
The reaction was carried out at 0 ° C for 2 hours. After the reaction, 190 g (1.9 mol) of a 40% strength aqueous caustic soda solution was added, and a saponification reaction was carried out at 80 ° C. for 4 hours to give 30% of the amphoteric surfactant of the present invention.
% Aqueous solution was obtained. The amphoteric surfactant thus obtained was used to measure the foamability, foam stability, surface tension and protein denaturation rate in the same manner as in Example 1, and the results are shown in Table 1.

Example 5 150 g (0.0015 mol) of polyethyleneimine having an average molecular weight of 100,000 (manufactured by Nippon Shokubai Chemical Industry Co., Ltd.)
And 200 g of toluene were charged, and 2 g of lauric acid was added while maintaining the temperature at 120 to 180 ° C. under stirring and under a nitrogen stream.
(0.01 mol) was added, and the mixture was reacted at the same temperature for 5 hours. Next, the liquid temperature was maintained at 80 ° C., and 86 g (1.0 mol) of acrylic acid methyl ester was added dropwise over 2 hours to 80 ° C.
And reacted for 1 hour. After the reaction, 95 g (0.95 mol) of a 40% aqueous caustic soda solution was added, and a saponification reaction was carried out at 95 ° C. for 4 hours to obtain a 30% aqueous solution of the amphoteric surfactant of the present invention. Example 1 using the obtained amphoteric surfactant
The foamability, foam stability, surface tension and protein denaturation rate were measured in the same manner as in, and the results are shown in Table 1.

Comparative Example 1 Polyethyleneimine having an average molecular weight of 600 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) (150 g, 0.25 mol) was treated with stirring and under a nitrogen stream at 75 to 85 ° C. while maintaining a total carbon number of 12 20.5 g (0.1 mol) of a mixture of 14 1,2-epoxyalkanes in a ratio of 1: 1 was added dropwise over 1 hour and reacted at the same temperature for 4 hours. Next, in another reaction kettle,
Sodium monochloroacetate 1223 g (10.5 mol)
Was dissolved in 1742 g of water, 510 g of 40% caustic soda dissolved in advance was added, and the mixture was uniformly mixed. Then, 199.5 g of an epoxyalkane addition reaction product of polyethyleneimine that had been reacted was added, and the mixture was heated at 70 to 80 ° C. 1
After reacting for 30 minutes, 480 g of 40% caustic soda
(4.8 mol) was added and reacted for 5 hours to obtain a 45% aqueous solution of an amphoteric surfactant. The amphoteric surfactant thus obtained was used to measure the foamability, foam stability, surface tension and protein denaturation rate in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 Polyethyleneimine having an average molecular weight of 600 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) (150 g, 0.25 mol) was added with stirring and under a nitrogen stream at 75 to 85 ° C. while maintaining a total carbon number of 12. 154 g (0.75 mol) of a mixture of 14: 1, 2-epoxyalkane in a ratio of 1: 1 was added dropwise over 1 hour, and the mixture was reacted at the same temperature for 4 hours. Example 1 using the obtained poly-N-hydroxyalkyl polyethyleneimine
The foamability, foam stability, surface tension and protein denaturation rate were measured in the same manner as in, and the results are shown in Table 1.

Comparative Example 3 1223 g (10.5 mol) of sodium monochloroacetate
Was dissolved in 1896 g of water, 510 g (5.1 mol) of 40% caustic soda that had been dissolved in advance was added, and the mixture was uniformly mixed, and then polyethyleneimine having an average molecular weight of 600 (manufactured by Nippon Shokubai Chemical Co., Ltd.) 150 g ( 0.25
Mol) and after reacting at 70 to 80 ° C. for 1 hour and 30 minutes,
Further, 480 g (4.8 mol) of 40% caustic soda was added and reacted for 5 hours to obtain a 35% aqueous solution of an amphoteric surfactant. The amphoteric surfactant thus obtained was used to measure the foamability, foam stability, surface tension and protein denaturation rate in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 4 The foamability, foam stability, surface tension and protein denaturation rate were measured in the same manner as in Example 1 using lauric acid amidopropyldimethyl acetic acid betaine, and the results are shown in Table 1.

Comparative Example 5 Polyethyleneimine having an average molecular weight of 600 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) (150 g, 0.25 mol) was added with a total carbon number of 12 while maintaining the temperature at 75 to 85 ° C. under stirring and under a nitrogen stream. 191.5 g (0.93 mol) of a mixture of 14 1,2-epoxyalkanes in a ratio of 1: 1 was added dropwise over 1 hour, and the mixture was reacted at the same temperature for 4 hours. Next, 180.8 g of methyl acrylate was added dropwise at 75 to 80 ° C. for 1 hour, and the reaction was performed at the same temperature for 3 hours, then heated to 95 to 100 ° C., and 92.4 g of 40% caustic soda aqueous solution was added in 2 hours. After dropping, the mixture was aged at the same temperature for 2 hours to obtain a 20% aqueous solution of an amphoteric surfactant. The foaming property, foam stability, surface tension and protein denaturation rate of the resulting amphoteric surfactant were measured, and the results are shown in Table 1.

Comparative Example 6 Polyethyleneimine having an average molecular weight of 600 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) (150 g, 0.25 mol) was charged with methyl acrylate 120. 5 g was added dropwise at 75 to 80 ° C. for 1 hour and the reaction was carried out at the same temperature for 3 hours, then heated to 95 to 100 ° C., 61.6 g of 40% aqueous sodium hydroxide solution was added dropwise for 2 hours, and after the addition, After aging for 2 hours at temperature, a 30% aqueous solution of an amphoteric surfactant was obtained. The foaming property, foam stability, surface tension and protein denaturation rate of the resulting amphoteric surfactant were measured, and the results are shown in Table 1.

Comparative Example 7 Using a polyethyleneimine having an average molecular weight of 600 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.), foaming property, foam stability, surface tension and protein denaturation rate were measured in the same manner as in Example 1.
The results are shown in Table 1.

[0030]

[Table 1]

[0031]

As described above, the amphoteric surfactant of the present invention has an acyl group having 8 to 22 carbon atoms, an amino group and a carboxymethyl group in its molecule, and the acyl group has lipophilicity, Amino group and carboxymethyl group express zwitterionic hydrophilicity, and compared to conventionally known zwitterionic surfactants, lipophilicity and hydrophilicity are well balanced, and protein denaturation without skin irritation Excellent surface activity such as excellent foaming property.

Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09K 15/20 C11D 1/10 D06M 15/61 D21H 17/46 // C09K 3/18 8318-4H 21/14 8318-4H C10M 149/12 9159-4H D06P 1/52 9160-4H C10N 10:02 20:04 30:00 A 8217-4H

Claims (1)

[Claims] 1. A polyethyleneimine having an average molecular weight of 200 to 100,000 and 1 mol of a fatty acid having 8 to 22 carbon atoms to a degree of polymerization of polyethyleneimine × 1 mol.
An amphoteric surfactant characterized by comprising a compound obtained by subjecting an unsaturated monomer having an ester bond or a nitrile group to an addition reaction of 1 mol to a polymerization degree of polyethyleneimine × 1 mol and saponifying with an acid or an alkali. Agent.