JPH06353A - Amphoteric surfactant - Google Patents

Abstract

(57) [Summary] [Purpose] Shampoo, rinse, excellent surface activity such as foaming ability and surface tension lowering ability, and safety such as protein denaturation.
An amphoteric surfactant suitable for cosmetics such as cosmetics, lotions, and creams. [Structure] 1 mol of polyethyleneimine having an average molecular weight of 200 to 100,000 and 1 to 12 having a total carbon number of 12 to 18
1 mole of 2-epoxyalkane is added to the degree of polymerization of polyethyleneimine × 1 mole, and sodium monochloroacetate is added to the degree of polymerization of 1 mole to degree of polymerization of polyethyleneimine × 2 moles.

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 foaming property and surface tension lowering ability, and it is not very sensitive to skin, does not cause skin irritation, does not cause skin irritation, does not damage hair, and is extremely safe for so-called protein denaturation. Highly effective shampoo,
The present invention relates to an amphoteric surfactant suitable for cosmetics such as 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 adding an epoxyalkane to a specific polyethyleneimine and then amphoterizing the compound have excellent protein denaturability. They have found that they have safety and can exhibit good surface activity such as foamability, and completed the present invention.

That is, the present invention has an average molecular weight of 200 to 1
1 mol of 1,2-epoxyalkane having a total carbon number of 12 to 18 per 1 mol of polyethyleneimine of 0,000, the degree of polymerization of polyethyleneimine x 1 mol, and sodium monochloroacetate of 1 mol to the degree of polymerization of polyethyleneimine. × 2
It is an amphoteric surfactant obtained by adding moles.

The amphoteric surfactant of the present invention can be manufactured as follows. First, 1,2-epoxyalkane is added to polyethyleneimine to obtain poly-N-hydroxyalkylpolyethyleneimine. The addition reaction between polyethyleneimine and 1,2-epoxyalkane is carried out by mixing 50 or 15 with dropping one to the other.
It can be performed by heating to 0 ° C. for 1 to 30 hours. In this reaction, when polyethyleneimine having a molecular weight of 200 to 20,000 is used, the reaction can be performed without a solvent, but the molecular weight is 20,000 to 100,000.
When the polyethyleneimine of 00 is used, it is preferable to carry out the reaction in the presence of a solvent.

Then, the obtained poly-N-hydroxyalkyl polyethyleneimine is reacted with sodium monochloroacetate to obtain an amphoteric surfactant having an acidic group and a basic group and having a large molecular weight. The reaction between poly-N-hydroxyalkylpolyethyleneimine and sodium monochloroacetate is carried out by adding sodium monochloroacetate to poly-N-hydroxyalkylpolyethyleneimine in the presence of an alkali in water or a solvent, and adding 1 at 50-100 ° C. ~
It can be performed by heating for 20 hours. In this reaction, sodium monochloroacetate may be added in a necessary amount all at once, but the necessary amount is divided into about 2 times, and when the reaction is started and the pH after the reaction is 9 or less. It is preferable that the addition of the monochloroacetic acid sodium salt is carried out twice, and the addition reaction of sodium monochloroacetate to the amino group can be smoothly carried out.

Polyethyleneimine can be used as an amphoteric surfactant after reacting 1,2 epoxyalkane and sodium monochloroacetate, or can be used as an amphoteric surfactant without modification, and calcium chloride,
It can also be used in the form of calcium salt or magnesium salt with magnesium chloride or the like. Further, these can be used after being purified with hexane, dioxane, acetone or the like.

In each of the above reactions, the reaction ratio of polyethyleneimine, 1,2-epoxyalkane and sodium monochloroacetate was 1 mol of polyethyleneimine.
The 1,2-epoxyalkane is preferably 1 mol or more to the degree of polymerization of polyethyleneimine × 1 mol or less, and the sodium monochloroacetate is 1 mol or more to the degree of polymerization of polyethyleneimine × 2 mol or less. The amphoteric surfactant obtained as described above has a good balance between hydrophilicity and lipophilicity and exhibits good amphoteric surfactant activity.
When the amount of 1,2-epoxyalkane added to 1 mol of polyethyleneimine is less than 1 mol, the resulting amphoteric surfactant has low lipophilicity, and the degree of polymerization of polyethyleneimine must exceed 1 mol. I can't. When the number of moles of sodium monochloroacetate added is less than 1 per 1 mole of polyethyleneimine, the hydrophilicity is poor, and the degree of polymerization of polyethyleneimine cannot exceed 2 moles. Since the reactivity of sodium monochloroacetate is slightly inferior, it is preferably used in an amount of 1 to 1.5 times the number of moles to be added. The amount of alkali when reacting sodium monochloroacetate is 1 / mole of the number of moles of sodium monochloroacetate.
It is preferably 2 mol or less.

The polyethyleneimine used in the present invention preferably has a molecular weight of 200 to 100,000, and it is possible to uniformly add 1,2-epoxyalkane and sodium monochloroacetate, and it has hydrophilicity and lipophilicity. A well-balanced amphoteric surfactant 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, the viscosity is too large,
It is difficult and not preferable to uniformly add 2-epoxyalkane and sodium monochloroacetate.

The 1,2-epoxyalkane used in the present invention preferably has a total carbon number of 12 to 18, and is dissolved in water to have excellent surface activity such as foaming property, emulsifying property, dispersibility and detergency. An amphoteric surfactant exhibiting excellent skin irritation alleviation properties such as low protein denaturation rate can be obtained. 1,
When the total carbon number of 2-epoxyalkane is less than 12, it becomes an amphoteric surfactant which is inferior in foaming property, detergency and skin irritation, and when it exceeds 18, it becomes difficult to dissolve in water, and the appearance of the synthetic product itself is not uniform. Is likely to occur and the commercial value is reduced, which is not preferable. As the 1,2-epoxyalkane, those having a total carbon number within the above range can be used alone or in combination of two or more kinds.

Examples of the solvent that can be optionally used in the reaction for adding 1,2-epoxyalkane and the reaction for adding sodium monochloroacetate include methanol, ethanol, isopropyl alcohol, butanol and the like. A mixture of two or more species can be used.

Examples of the alkali used when reacting sodium monochloroacetate include sodium hydroxide and potassium hydroxide. These alkalis can be used alone or in admixture of two or more.

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 Polyethyleneimine having an average molecular weight of 300 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) (150 g, 0.5 mol) was stirred and under a nitrogen stream while maintaining the temperature at 75 to 85 ° C. while having 1, 12 carbon atoms in total. -Epoxy alkane 102 g (0.55 mol) was added dropwise over 1 hour and reacted at the same temperature for 4 hours. Next, in a separate reaction kettle, sodium monochloroacetate 8
After dissolving 97 g (7.7 mol) in 1350 g of water, 4
310 g (3.1 mol) of 0% concentration caustic soda aqueous solution was added and uniformly mixed, and the epoxyalkane addition reaction product of polyethyleneimine was added thereto, and after reacting at 70 to 80 ° C. for 1 hour and 30 minutes, 40% was further added. Caustic soda 310g
(3.1 mol) was added and reacted for 5 hours to obtain a 45% aqueous solution of the amphoteric surfactant of the present invention. 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.

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 of the aqueous solution was 6.0, the concentration of the amphoteric surfactant (solid content concentration excluding sodium chloride) was 0.1%, and the solution temperature was 25 ° C.・ Testing method for protein denaturing property Protein denaturing property is determined by 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 Polyethyleneimine having an average molecular weight of 600 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) (150 g, 0.25 mol) and 1,2-epoxyalkane having a total carbon number of 12 and 14 were mixed at a ratio of 1: 1. An aqueous solution prepared by dissolving 277 g (1.35 mol) of the dried product, 807 g (6.9 mol) of sodium monochloroacetate in 1500 g of water, and a caustic soda aqueous solution 560 having a 40% concentration.
g (5.6 mol) was used and reacted in the same manner as in Example 1 to obtain a 46% aqueous solution of the amphoteric surfactant of the present invention.
The resulting amphoteric surfactant 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 Polyethyleneimine having an average molecular weight of 2000 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) (150 g, 0.075 mol) and 1,2-epoxyalkane having a total carbon number of 12 and 14 were mixed at a ratio of 1: 1. 108 g (0.53 mol) of the obtained product was dissolved in toluene to carry out an addition reaction, and after the reaction, toluene was removed. Add 443 g of sodium monochloroacetate (3.8
Was used in an aqueous solution of 830 g of water and 300 g (3 mol) of 40% strength caustic soda to react in the same manner as in Example 1 to obtain a 46% aqueous solution of the amphoteric surfactant of the present invention. The resulting amphoteric surfactant 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 Polyethyleneimine having an average molecular weight of 10,000 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.), 150 g (0.015 mol), and 1,2-epoxyalkane having a total carbon number of 12 and 14 were 1: 1.
45 g (0.21 mol) of a mixture of the above, an aqueous solution of 245 g (7 mol) of sodium monochloroacetate dissolved in 500 g of water, and 210 g of a 40% aqueous caustic soda solution.
(2.1 mol) was reacted in the same manner as in Example 3 to obtain a 46% aqueous solution of the amphoteric surfactant of the present invention. Using the obtained amphoteric surfactant, its foaming property, foam stability, surface tension and protein denaturation rate were measured 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 (produced by Nippon Shokubai Kagaku Kogyo Co., Ltd.) and 1,2-epoxyalkane having 16 and 18 carbon atoms were mixed at a ratio of 1: 1. Using 117 g (0.45 mol) of the prepared product, an aqueous solution in which 280 g (2.4 mol) of sodium monochloroacetate was dissolved in 500 g of water, and 200 g (2 mol) of 40% caustic soda, the reaction was carried out in the same manner as in Example 3 to obtain the product. A 52% aqueous solution of the amphoteric surfactant of the invention was obtained. Using the obtained amphoteric surfactant, its foaming property, foam stability, surface tension and protein denaturation rate were measured in the same manner as in Example 1, 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 which 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 resulting amphoteric surfactant 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 mol, 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 1,2-epoxyalkanes 1 and 14 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 Kagaku Kogyo 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 resulting amphoteric surfactant 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 a β-hydroxyalkyl group, an amino group and a carboxymethyl group in its molecule, and the β-hydroxyalkyl 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 the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08G 73/02 NTC 9285-4J C08L 79/02 LQZ 9285-4J C11D 1/10

Claims (1)

[Claims] 1. A mole of polyethyleneimine having an average molecular weight of 200 to 100,000, 1 mole of 1,2-epoxyalkane having a total carbon number of 12 to 18 to a degree of polymerization of polyethyleneimine × 1 mole, and monochloroacetic acid. 1 sodium
An amphoteric surfactant characterized by being obtained by adding the polymerization degree of polyethyleneimine × 2 moles.