JPH062221B2 - Method for producing surfactant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a surfactant containing N-alkylbetaine as a main component from a conchiolin hydrolyzate obtained from a shell of a shell having a nacre and / or pearls. It relates to a method of manufacturing.

[Conventional technology]

As the amphoteric surfactant, betaine-type amphoteric surfactant,
Glycine-type amphoteric surfactants and alanine-type amphoteric surfactants are known. Also, lauryl dimethylamino acetic acid betaine is known as an amphoteric surfactant.

Since this surfactant has an atomic group having two types of ions that are opposite to each other as hydrophilic groups in the molecule, it has different properties from ordinary surfactants. In a neutral bath, the molecule has the same properties as in the case of amino acids. Although it acts neutrally by internal salt formation, the amino group in the acidic bath forms a salt and acts as if it were a cationic surfactant, and in the alkaline bath it forms a carboxylate salt to form an anionic surfactant. Shows the following properties. It has good stability to hard water at a concentration that can be used, has considerable stability to heat, has good foaming power and wetting power, and has a low surface tension and other surface activity. It is about the same as the drug.

This aqueous solution is transparent, has almost no toxicity, and is extremely easily soluble in water and alcohol.

Unlike reverse soap, it rarely forms an insoluble precipitate with protein and reduces its effect. Also, even if it coexists with reverse soap, anionic surfactant, and nonionic surfactant, it also coexists with other metal ions. However, since it does not change to an inactive state, it is used for food processing, surgery, obstetrics and gynecology in combination with the fact that some have a strong bactericidal action.

It is generally mild in nature, has little skin irritancy, has no protein coagulation action, and is used in shampoos, rinses and the like.

Thus, the current amphoteric surfactant has no problem in safety for use in cosmetics, but it is natural that a safer raw material is required.

On the other hand, pearls have been used for medicinal purposes since ancient times, and their effectiveness on the skin has been particularly recognized.

It is also known that conchiolin, which is a protein that forms pearls or shells, is the active ingredient.

JP-A-62-223104, JP-A-62-221
It has been used as a raw material for cosmetics as described in Japanese Patent No. 612.

However, this alone has a narrow range of use, and a wider range of uses is desired.

[Problems to be Solved by the Invention]

An object of the present invention is to provide a method for producing a highly safe novel amphoteric surfactant, using conchiolin, which is a protein forming pearls or shells, as a raw material. Is to provide.

[Means for Solving the Problems]

Although amines and fatty acids are usually used to produce amphoteric surfactants, the present inventor uses amino acids as raw materials, and in particular, by using amino acids obtained by hydrolyzing conchiolin, a more safe amphoteric surfactant is obtained. An activator could be obtained.

That is, the present invention is a conchiolin hydrolyzate obtained by hydrolyzing a conchiolin obtained by pulverizing or demineralizing a shell and / or pearl of a shell having a nacre and halogenating a small amount of water. Alkyl (4 to 1 carbon atoms
The method for producing a surfactant is characterized by reacting 2) and then reacting with halogenated methane.

As a kind of shellfish having a nacre, pearl oyster, (Pinctada
martensii) is preferred.

For conchiolin, pearls and nacres of shells are decalcified and hydrolyzed so that they are more easily reacted. The method is disclosed in JP-A-62-223104 and JP-A-62-2.
The method disclosed in Japanese Patent No. 21612 may be used.

When conchiolin is used, a low molecular weight peptide is contained and most of it is decomposed in the subsequent reaction, but a surfactant having a structure different from that when a part of amino acid is used as a raw material can be obtained.

This hydrolyzate of conchiolin is reacted with an alkyl halide in an aqueous solution of a strong strong alkali such as sodium hydroxide or potassium hydroxide. As the alkyl halide, one having 4 to 12 carbon atoms is used in consideration of the properties of the generated surfactant and the easiness of reaction.

At this time, the alkyl halide is insoluble in water, and the conchiolin hydrolyzate is in the aqueous solution, so that it is difficult to react. Therefore, it is necessary to heat and react for a long time. Therefore, the reaction becomes faster when the amount of water is as small as possible.

Methane halide is added to the reaction product and heated.

The type of halogen may be iodine, bromine or chlorine, but in the case of bromine or chlorine, it is necessary to pressurize. In the case of iodine, it is also effective to use a reflux condenser or to stir in order to improve the reaction when pressure is not applied. After that, it is distilled to remove halogenated methane, and is further dissolved in an organic solvent such as ethanol, methanol, or acetone to remove unreacted substances, and then passed over. In addition, H-type strong acid cation exchange resin, such as Dowex 50W series, Amberlite IR-100
Adsorb to series etc.

0.5-2.0 which melt | dissolved this in the mixed liquid of the organic solvent and water
Elute with specified sodium chloride. Examples of the organic solvent include ethanol, methanol, acetone and the like.

Desalinate from this solution to obtain the desired product. As a desalting method, a mosaic charged membrane or an electrodialysis device can be used.

The infrared absorption spectrum of the surfactant produced from the conchiolin of the present invention is shown in FIG.

On the other hand, FIG. 2 shows the infrared absorption spectrum of lauryldimethylaminoacetic acid betaine which is a known similar amphoteric surfactant.

Thus, it is clear that the structure is different from that of the surfactant produced from amino acid as a raw material.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 100 g of conchiolin hydrolyzate was added to and dispersed in a solution of 40 g of sodium hydroxide dissolved in 80 g of purified water.

To this, 300 g of octane iodide was added, and heated at 120 ° C. for 20 hours in a reaction vessel equipped with a reflux device and a stirrer and stirred.

Thereafter, 500 g of iodomethane was added, and the mixture was heated at 80 ° C. for 20 hours and refluxed.

After distilling this to remove methane iodide, ethanol 1
It dissolved in the liter and passed.

Strong acid cation exchange resin (DOWEX 50W
) To 50% of 1N sodium chloride
It was eluted with an aqueous ethanol solution.

This solution was passed through a mosaic charged membrane MC-55B (manufactured by Tosoh Corporation) to desalt and dried.

The yield was 25 g.

(Formulation example-1) Rinse (numerical value is% by weight) A Stearyl trimethyl chloride 5.0 Ammonium Activator obtained in Example-1 5.0 Glyceryl monostearate 1.5 Jojoba oil 1.5 Cetanol 3.0 Preservative Agent 0.1 B Purified water 77.5 Propylene glycol 5.0 Conchiolin hydrolyzate 1.0 (5% aqueous solution) Preservative 0.2 C Fragrance 0.2 A and B are dissolved by heating at about 80 ° C. To do.

While stirring A, B was gradually added, and C was added at about 60 ° C.

(Formulation Example-2) Shampoo A Polyoxyethylene (2 moles) 35.0 Natrium lauryl ether sulfate Lauroyl methylalanine 10.0 Sodium ethylene distearate 2.0 Glycol Active agent obtained in Example-1 5.0 Myristin Octyldodecyl acid 0.5 Disodium edetate 0.1 Preservative 0.1 B Purified water 40.9 1,3 Butylene glycol 5.0 Conchiolin hydrolyzate 1.0 (5% aqueous solution) Preservative 0.2 C Fragrance 0.2 A product was obtained by the same operation as in Prescription Example-1.

(Prescription example-3) Hair treatment A Distearyl dimethyl chloride 5.0 Ammonium palmityl trimethyl chloride 2.5 Ammonium Activator obtained in Example-1 2.5 Isopropyl myristate 2.0 Cetanol 5.0 Preservative 0 .1 B Purified water 74.5 1,3 Butylene glycol 5.0 Cochiolin hydrolyzate 3.0 (5% aqueous solution) Preservative 0.2 C Fragrance 0.2 The product was prepared by the same operation as Formulation Example-1. .

(Formulation Example-4) Hair conditioner A Distearyl dimethyl chloride 2.5 Ammonium stearyl trimethyl 2.5 Ammonium Activator obtained in Example-1 1.0 Glyceryl monoisostearate 1.0 Cetanol 2.0 Preservative 0.1 B Purified water 64.5 Hydroxyethylcellulose 20.0 (2.5% aqueous solution) 1,3 Butylene glycol 5.0 Conchiolin hydrolyzate 1.0 (5% aqueous solution) Preservative 0.2 C Fragrance 0 .2 The product was manufactured by the same operation as in Prescription Example-1.

(Safety Test) The surfactant obtained in Example 1 and lauryldimethylaminoacetic acid betaine having a similar molecular formula were tested for safety against human skin by the following cytotoxicity test method.

Cytotoxicity test method A human skin-derived cultured cell line {Japan Tissue Culture NO.17 (JTC-17)} having an epithelial morphology was used.

The test sample is a water-soluble raw material or product.

Oil-soluble and polymeric raw materials have a limited working concentration.

Samples with a pH of 6.5 to 7.5 are used as they are, but other samples are adjusted in pH with NaOH or HCl before use.

The test method is to put a cover glass on a 6 cm Petri dish and use Eag.
5 ml of le MEM (fetal bovine serum 20%) medium was dispensed, 300,000 JTC-17 cell suspension was added, and the cells were cultured in a CO incubator for 48 hours. The cells were washed twice with PBS (-), 3 ml of a sample diluted to each concentration with PBS (-) was added, and the mixture was incubated at 36 ° C for 60 minutes.

Further, 7 ml Eagle MEM (fetal bovine serum 20%) medium was added, and the cells were cultured in a CO incubator for 48 hours.

The sample was fixed and stained, and evaluated according to the following criteria.

(1 of judgment criteria) Judgment by cell number (including abnormal cell number) Score 0: Same as control 1: Almost same as control (slightly inferior staining density) 2: 2 / 3rd of control (visible to the naked eye) (Decrease) 3: Almost half of control (decrease to a large extent) 4: 1/3 of control (the number of cells is very small) 5: No cells are observed (no or almost no) (criteria 2) ) Judgment based on cell morphology Score 0: normal image 1: abnormal cells are slightly observed. (Normal cells 80% or more) 2: Abnormal cells are recognized (normal cells 50% or more) 3: Many abnormal cells are recognized (normal cells 20 to 50% or so) 4: Almost abnormal cells (normal cells 10%) 5: No normal cells are observed.

Table 1 shows the results of criteria 1 and 2 (in parentheses) when the concentration (%) of the surfactant was changed.

(Use test results) Comparative examples 1 and 2 were prepared by substituting the lauryldimethylaminoacetic acid betaine for the prescription examples 1 and 2 (the active agent obtained in Example 1), and 100 adults (34 men, 66 women) Name) and used it for the size of foam, moist feeling, dryness, good combing, no squeaking, etc., and the results are as shown in Tables 2 and 3. Is.

Shampoo (Example 2 and Comparative Example 2) [Effects of the Invention] The surfactant of the present invention, which is prepared by hydrolyzing conchiolin as an amino acid, is a known amphoteric surfactant lauryldimethylamino when it is incorporated into a cytotoxicity test or cosmetics such as shampoo and rinse. Compared to betaine acetate,
From the viewpoints of moist feeling, dry feeling, combing, squeaking, etc., significant differences were observed, which proved to be excellent. Providing a highly safe amphoteric surfactant, pearl,
It is a significant invention that provides a high degree of utilization of conchiolin, which is a shell-forming protein.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of a surfactant produced from the conchiolin of the present invention. FIG. 2 is an infrared absorption spectrum of lauryldimethylaminoacetic acid betaine.

Claims (2)

[Claims] 1. A conchiolin hydrolyzate obtained by hydrolyzing a conchiolin obtained by pulverizing or demineralizing a pearl shell-containing shell and / or pearl without pulverizing, and a small amount of water. Alkyl halides (4 to 1 carbon atoms
A method for producing a surfactant, which comprises reacting 2) and then reacting with halogenated methane. 2. A kind of shellfish having a nacre is a pearl oyster (Pinc
The method for producing a surfactant according to claim 1, which is tada martensii).