KR20010010761A - beta chitin which is water-soluble without skin-trouble and viscosity-regulated and the cosmetics comprising it - Google Patents

Abstract

PURPOSE: A viscosity-controlled water-soluble beta-chitin without skin irritation provided, which is adequate as a cosmetic substance by water-soluble property without skin irritation, and is controlled to have adequate viscosity. A cosmetic composition containing the beta-chitin is also provided. CONSTITUTION: A process for the preparation of water-soluble beta-chitin comprises the steps of: cutting squid backbone into pieces, and soaking into 1N sodium hydroxide; washing with water, and putting into 1N HCl and shaking for 1hr at room temperature; washing with water, and putting in 1N sodium hydroxide and shaking at 90deg.C for 1hr; washing fully with water, and drying to get pure beta-chitin particles; pulverizing the refined beta-chitin, and pouring to 50%(w/v) sodium hydroxide; storing in a freezer after shaking for 1hr to get alkali beta-chitin with sodium-substituted No.6 carbon; adding isopropane to the alkali beta-chitin, and shaking; adding monochloroacetic acid while maintaining the temperature at below 10deg.C to get water-soluble beta-chitin with carboxymethyl-substituted No.6 carbon; adding ethanol, filtering, and adding 4% NaCl; adding ethanol slowly to get precipitates; and washing with ethanol, and drying to get the objective water-soluble beta-chitin.

Description

Beta chitin which is water-soluble without skin-trouble and viscosity-regulated and the cosmetics comprising it}

The present invention relates to a water-soluble beta chitin and a cosmetic comprising the same, the viscosity is adjusted without the skin irritation. More specifically, in order to prepare a water-soluble beta chitin without skin irritation, the method comprising the step of stirring the beta chitin at 40 ℃ or more aqueous sodium hydroxide solution below 10 ℃ and storing below 0 ℃ 24 hours or more The present invention relates to the preparation of alkaline beta chitin, an intermediate of water-soluble beta chitin. In addition, in order to prepare a water-soluble beta chitin having a viscosity suitable for cosmetics, the alkali beta chitin according to the present invention is reacted with monochloroacetic acid, the ratio of monochloroacetic acid to purified beta chitin is 3-7 (g / It relates to a water-soluble beta chitin prepared as g).

Chitin is a polysaccharide composed of amino sugars (amino derivatives of sugars) in which N-acetylglucosamine is polymerized by β-1,4 bonds. Chitin is a white powder, insoluble in water and poorly reactive. It has a chemical structure similar to cellulose but is more stable than cellulose.

Chitin is an important component of the cell walls of fungi, as well as building the hard epidermis or shell of arthropods. The amount of chitin present on the planet is surprisingly high, and even a single group of crustaceans, the kelp, produces hundreds of billions of tons of chitin a year.

In the past, proteins attached to the shells of crustaceans were not only odorous due to decay, but also were treated as industrial waste due to their poor solubility due to strong hydrogen bonds between chitin molecules. Much research has been done on chitin in terms of processing issues and resource use (see Seichi Kataoka, Kobunshi Ronbunshu, 39,759 (1982), S. Hattori, et al J. Colloid and Interface Sci. 104, 72 (1985)).

On the other hand, the materials currently used as moisturizers in cosmetics are mostly only functions as a moisturizer and no other functions. In particular, hyaluronic acid (hyaluronic acid), which is currently used as a representative moisturizer of cosmetics, is widely distributed in animal and plant systems, but it is known that there is no effect other than the moisturizer.

Chitin, like hyaluronic acid, is a biocompatible polymer, which forms a film when it is applied to the skin in solution, and also contains hydroxyl groups in the molecule, thus exhibiting a moisturizing function by minimizing moisture loss in the skin. . In addition, beta chitin has been reported to have superior physiological activity in wound healing, cell regeneration, and immune function activation, unlike alpha chitin (Vaccine vol. 4, 151-156 (1986), Carbohydrate Res. Vol. 146,251-258). (1986), US Pat. No. 4,427,654, US Pat. No. 5,698,228).

However, until now, there has been no case in which beta chitin having excellent function as described above has been developed as a cosmetic without skin irritation.

Therefore, the present invention is to develop beta chitin excellent in skin physiological activity as a functional raw material suitable for cosmetics. In other words, the water-insoluble beta chitin is solubilized to be suitable as a cosmetic ingredient, but the solubility process is developed so as not to cause skin irritation, and the properties of beta chitin are properly adjusted to retain various effects of the original beta chitin. At the same time, to improve the moisturizing feeling when applying the skin.

The present invention relates to a water-soluble beta chitin and a cosmetic comprising the same, the viscosity is adjusted without the skin irritation. More specifically, in order to prepare a water-soluble beta chitin without skin irritation, the method comprising the step of stirring the beta chitin at 40 ℃ or more aqueous sodium hydroxide solution below 10 ℃ and storing below 0 ℃ 24 hours or more The present invention relates to the preparation of alkaline beta chitin, an intermediate of water-soluble beta chitin. In addition, in order to prepare a water-soluble beta chitin having a viscosity suitable for cosmetics, the alkali beta chitin according to the present invention is reacted with monochloroacetic acid, the ratio of monochloroacetic acid to purified beta chitin is 3-7 (g / It relates to a water-soluble beta chitin prepared as g).

In order to apply beta chitin to cosmetics, it is preferable to prepare beta chitin in a soluble form in the formulation. Accordingly, the present invention seeks to prepare a water soluble beta chitin that can be dissolved in the aqueous phase, the largest portion of the formulation.

That is, in the present invention, in order to apply beta chitin to cosmetics, first, beta chitin (formula 1) purified from natural products is converted to alkali beta chitin (Formula 2) in which hydrogen located at carbon 6 is substituted with sodium group sodium hydroxide. Then, the sodium group of the alkali beta chitin is substituted with a carboxymethyl group to provide carboxymethyl beta chitin (Formula 3) which is a water-soluble beta chitin. Such carboxymethyl beta chitin has increased hydrophilicity to exhibit water-soluble properties.

Hereinafter, the present invention will be described in detail by dividing the process of purifying beta chitin, converting the purified natural beta chitin into an alkali beta chitin, and making the alkali chitin into a water-soluble beta chitin.

[Betachitin Tablets]

The collected squid backbone is finely cut and then stirred in 1 ~ 3N sodium hydroxide aqueous solution at 60 ~ 90 ° C. for 1 ~ 5 hours to remove the protein. Then, washed sufficiently with water to remove sodium hydroxide, and then deposited at 0.1 to 1 N hydrochloric acid at room temperature to remove calcium. At this time, the reaction should be performed at room temperature to prevent the reduction of the chitin molecular weight. If necessary, repeat this process two to three times.

In particular, in order to obtain a high molecular weight water-soluble chitin, in the present invention, the concentration of hydrochloric acid is adjusted to 0.1 to 1N and the temperature is set to room temperature. This is because high concentrations of hydrochloric acid and high temperatures break down the chain of beta chitin, leading to a decrease in molecular weight.

On the other hand, the purified beta chitin is preferably passed through more than 30 mesh (mesh), particularly preferably through 30-40 mesh. When the particles of beta chitin are larger than 30 mesh, the sodium group cannot be sufficiently substituted with the hydrogen of beta chitin 6 carbon in comparison with the particles smaller than 30 mesh in the production of alkali beta chitin. This is because the final product may become a colloidal state that is poorly soluble in water.

[Preparation of Alkali Beta Chitin]

To convert beta chitin into alkaline beta chitin, the beta chitin must be reacted with an aqueous sodium hydroxide solution to replace hydrogen located at carbon 6 of the beta chitin with the sodium group sodium hydroxide.

On the other hand, the conventional method for producing an alkali beta chitin [Vaccine vol. 4, 151-156 (1986)] adds 0.1-0.2% of sodium dodecyl sulfate to a high concentration of sodium hydroxide solution in order to have a smooth contact during the reaction between chitin and sodium hydroxide solution. However, sodium dodecyl sulphate remains in the final product, causing skin irritation.

Therefore, in the present invention, instead of using sodium dodecyl selpet in the production of alkali beta chitin, the beta chitin was stirred in an aqueous sodium hydroxide solution at a low temperature of 10 ℃ or less as a reaction condition, and then at 0 ℃ or less for a long time more than 24 hours It is left (see Experiment 3).

The reason why the reaction temperature was kept at a low temperature of 10 ° C. or lower during stirring was because sodium hydroxide reacts with the acetylamide group of the beta chitin to free the acetyl group, thereby producing chitosan converted to the amine group. On the other hand, at low temperatures, sodium ions of sodium hydroxide react with the sixth carbon to produce alkali beta chitin.

On the other hand, in order to prepare an alkaline beta chitin intermediate suitable for preparing the final product of the present invention water-soluble beta chitin, the concentration of aqueous sodium hydroxide solution should be at least 40%, the reaction time should be at least 24 hours [see Experiment 2] ]. This is because the alkali beta chitin of the present invention is not formed when the concentration of the sodium hydroxide aqueous solution is 40% or less or the reaction time is 24 hours or less. In addition, the yield of alkali chitin is different depending on the reaction time even at the same concentration of sodium hydroxide aqueous solution. Preferably the concentration of sodium hydroxide is at least 50%, the reaction time is preferably at least 48 hours.

[Production of Water-soluble Beta Chitin]

The alkali beta chitin prepared according to the present invention is reacted with monochloroacetic acid to prepare a water-soluble beta chitin in which carbon 6 of the alkali beta chitin is substituted with a carboxymethyl group.

At this time, isopropanol is added to the alkali beta chitin and stirred, and monochloroacetic acid is added to form a water-soluble beta chitin substituted with a carboxymethyl group. At this time, since the heat of reaction is generated to maintain the temperature below 10 ℃ using cooling water.

The ratio of monochloroacetic acid to purified beta chitin is preferably 3 to 7 (g / g). This is because the viscosity of the water-soluble beta chitin varies depending on the amount of motochloroacetic acid added (see Experiment 1). When the ratio of monochloroacetic acid to purified beta chitin is 3 (g / g) or less, the yield of water-soluble beta chitin is lowered. In other words, the yield is usually 80% under the conditions of 3 or more, but the yield drops rapidly to 60 to 70% under the conditions of 3 or less. On the other hand, when the ratio of monochloroacetic acid to the purified beta chitin is 7 (g / g) or more, the viscosity is almost constant at 400 to 350 cps. Therefore, the addition of the ratio of monochloroacetic acid of 7 or more is insignificant and inefficient. In this case, there is a problem that salt formation may occur and cause skin irritation.

In particular, the ratio of monochloroacetic acid to beta chitin is most preferably 4 (g / g). This is because having a high viscosity as much as possible indicates a feeling of use suitable for cosmetics.

At this time, the reason for adding isopropanol is as follows. First, isopropanol acts as a swelling agent, so that alkali beta chitin can be swollen to facilitate the reaction with monochloroacetic acid. Second, pigments and proteins present in trace amounts in chitin can be removed. Third, the viscosity of the mixture of alkali beta chitin and sodium hydroxide may be lowered to facilitate stirring during the reaction with monochloroacetic acid. In addition, monochloroacetic acid can easily participate in the reaction because it is easily released into chloride and acetic acid in isopropanol solution.

On the other hand, the reason for maintaining the reaction temperature below 10 ° C is to prevent the conversion to chitosan due to the heat of reaction.

Furthermore, to separate the water-soluble beta chitin prepared by the reaction process as described above and make it into a powder, the following reaction step may be added.

After the reaction to prepare the water-soluble beta chitin was terminated, dehydrated by centrifugation to remove isopropanol, and ethanol was added thereto and stirred. This is to facilitate the cleaning because the product is in the form of lumps.

Then, after sufficient washing, the product is dissolved in water. After complete dissolution, the insolubles were removed by filtration, and then 2 to 4% of sodium chloride was added, and 1.5 to 2 times of ethanol was slowly added to the filtrate while stirring to obtain a precipitate. After washing three times with ethanol again and then vacuum-dried, water-soluble beta chitin can be separated into a powder state.

The water-soluble beta chitin prepared according to the present invention may be prepared from 0.5% (w / v) aqueous solution to 1% (w / v) aqueous solution (including preservatives) and applied to cosmetics.

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

[Example 1; Beta Chitin Tablet]

Collected squid backbone (squid backbone) was cut to a size of about 4 ~ 5cm using a cutter. Squid bone was immersed in 1N aqueous sodium hydroxide solution and stirred at about 90 ° C for 1 hour. Then, washed with water sufficiently to remove sodium hydroxide and stirred again for about 1 hour in 1N hydrochloric acid diluted at room temperature.

After washing sufficiently with water again, the mixture was stirred for 1 hour at 90 DEG C in 1N aqueous sodium hydroxide solution. Then, the mixture was washed with water sufficiently and dried to obtain pure beta chitin particles from which proteins and calcium were removed.

[Example 2; Alkali beta chitin production]

Purified beta chitin in Example 1 was ground and passed through 30 mesh. 10 g of the resulting beta chitin particles were added to 100 ml of an aqueous sodium hydroxide solution at a concentration of 50% (w / v), followed by stirring while maintaining the temperature at 10 ° C or lower. After stirring for about 1 hour and stored in a freezer at 0 ℃ or less for one day. Then, an alkali beta chitin in which hydrogen of carbon 6 is substituted with a sodium group can be obtained.

[Example 3; Preparation of Water Soluble Beta Chitin]

1 L of isopropanol was added to the alkaline beta chitin in the slurry prepared in Example 2, followed by stirring to sufficiently mix. Then 40 g of monochloroacetic acid was added. At this time, since heat of reaction was generated, the temperature was maintained at 10 ° C. or lower using cooling water. This produced a water-soluble beta chitin in which a carboxymethyl group was bonded to carbon 6 of chitin.

After completion of the reaction, isopropanol was removed, and about 0.5 L of ethanol was added and stirred. Then, after sufficient washing, the product was dissolved in water. After complete dissolution, the insolubles were removed by filtration, and then 4% sodium chloride was added, and 1.5 times ethanol of the filtrate was slowly added with stirring to obtain a precipitate. After washing three times with ethanol again, and vacuum-dried to separate the water-soluble beta chitin substituted carboxymethyl group.

<Experiment 1; Viscosity Measurement of Water Soluble Betachitin>

1) After pulverizing the purified beta chitin and passing through 30 mesh, 10 g of purified beta chitin was deposited in 50% (w / v) sodium hydroxide solution and stored at -1 ° C. for at least 24 hours, and alkali beta chitin Switched to

2) After adding 1 L of isopropanol and stirring it sufficiently, 30 g, 40 g, 50 g, and 70 g of monochloroacetic acid were added to each sample for reaction.

3) After completion of the reaction, each sample was added to 0.5 L ethanol, stirred, completely dissolved in deionized water, and 4% sodium chloride was added thereto. Ethanol was slowly added to a volume of 1.5 times to obtain a precipitate. This was again washed three times with ethanol, filtered and dried to obtain the final product, water-soluble betanchitin.

4) After preparing the 0.5% (w / v) aqueous solution by sampling each final product, the viscosity was measured using a viscometer (Brrokfield viscometer, spindle NO.2, RPM30). The results are shown in Table 1.

Mass of monochloroacetic acid charged Viscosity (spindle NO2, 25 ° C, RPM30) 30 g 544cps 40 g 900 cps 50 g 656cps 70 g 412cps

As shown in Table 1 above, it is possible to control the viscosity of the water-soluble beta chitin produced by adjusting the input ratio of monochloroacetic acid. The viscosity was the highest when the amount of monochloroacetic acid was 40 g with respect to 10 g of beta chitin. Therefore, the present invention intends to adjust the ratio of beta chitin and monochloroacetic acid to 1: 4 for the preparation of water-soluble beta chitin with high viscosity as a raw material suitable for cosmetics.

On the other hand, when the amount of monochloroacetic acid was made 30 g or less with respect to 10 g of beta chitin, the yield of water-soluble beta chitin fell. In other words, the yield was usually 80% under the conditions of 30g or more, but rapidly decreased to 60-70% under the conditions of 30g or less. Therefore, the minimum amount of monochloroacetic acid for sufficient reaction with alkali beta chitin is 30 g.

When the amount of monochloroacetic acid is 70 g or more with respect to 10 g of beta chitin, the viscosity is almost constant at 350 to 400 cps. Therefore, the addition of more than 70g of monochloroacetic acid is meaningless and inefficient, in this case, there is also a problem that can cause salt generation to cause skin irritation.

<Experiment 2; Concentration and Reaction Time of Aqueous Sodium Hydroxide Solution for the Preparation of Alkali Betachitin>

The beta chitin was reacted with an aqueous sodium hydroxide solution at a temperature lower than 10 ° C. to prepare an alkaline chitin in which hydrogen located at carbon 6 of the beta chitin was substituted with a sodium group.

As shown in Table 2 below, by varying the concentration and reaction time of the sodium hydroxide aqueous solution, the concentration and reaction time of sodium hydroxide aqueous solution, which is optimal for preparing alkali chitin, an intermediate of water-soluble beta chitin, the final product, was determined. .

Whether or not the alkaline chitin of the present invention was prepared was determined by dissolving the final product in ionized water after reacting the alkali chitin and monochloroacetic acid at a ratio of 1: 4.

Sodium hydroxide solution concentration (w / v) 30% 40% 50% 60% Reaction time 10 hours × × × × 24 hours × × ○ ○ 48 hours × × ○ ○

(×: no reaction, ○: reaction)

Looking at the results of Table 2, it can be seen that when the concentration of the aqueous sodium hydroxide solution is less than 40%, alkali chitin is not formed as an intermediate of the water-soluble beta chitin as the final product.

When the concentration of the aqueous sodium hydroxide solution is 50%, 60%, it can be seen that when the reaction time is 24 hours, 48 hours, the alkali chitin of the present invention is formed.

On the other hand, the final yield of the alkali chitin of the present invention was higher at 48 hours than at 24 hours. This may be because the amount of alkali chitin produced varies depending on the reaction time even at the same concentration.

Therefore, in the production of alkali chitin, it can be seen that it is preferable to adjust the reaction time at a concentration of 50% or more and at least 48 hours.

<Experiment 3; Intradermal safty test>

Comparative Example 1

The purified beta chitin was pulverized and passed through a 30 mesh to recover 10 g, and then immersed in 100 ml of 50% sodium hydroxide aqueous solution containing 0.2% sodium dodecyl sulfate, stirred at 10 ° C. or less, and then -1. It was stored for 12 hours at ℃. Then, 40 g of monochloroacetic acid was slowly added, followed by stirring while stirring. Thereafter, the reaction solution was stored in a refrigerated state for 24 hours, ethanol was added thereto to disperse the reaction product, and then filtered and dissolved in an aqueous 4% (w / v) sodium chloride solution. After complete dissolution, ethanol was slowly added to 1.5 times the solution volume to obtain a final product. After filtration separated and dried to obtain a powder (sample 1).

Example 4

Purified beta chitin was pulverized and passed through 30 mesh to recover 10 g, and then immersed in 100 ml of 50% aqueous sodium hydroxide solution, stirred at 10 ° C. or less, and then stored at −1 ° C. for 48 hours. Then, 40 g of monochloroacetic acid was slowly added, followed by stirring while stirring. Thereafter, the reaction solution was stored in a refrigerated state for 24 hours, and then ethanol was added to disperse the reaction product, filtered, and dissolved in 4% (w / v) aqueous sodium chloride solution. After complete dissolution, ethanol was added slowly to 1.5 times the solution volume to obtain the final product. After filtration separated and dried to obtain a powder (sample 2).

Intradermal safty tests were performed on the final product samples 1 and 2 obtained in Comparative Example 1 and Example 4, respectively.

The test method is as follows.

1) 4 ml / kg of 1% Evans blue was intravenously injected into rabbits.

2) Immediately, 0.1 ml of sample 1 or 2 was injected subcutaneously and lethal after 1 hour.

3) The back skin was peeled off and examined.

The results are shown in Table 3.

Test substance density n = 1 n = 2 Average Judgment Sample 1 (Comparative Example 1) 2% in saline 5.0 (5.0) 5.0 (5.0) 5.0 River 1% in saline 4.5 (4.0) 3.5 (3.5) 4.0 River Sample 2 (Example 2) 2% in saline 0.5 (0.5) 0.5 (0.5) 0.5 radish 1% in saline 0.5 (0.5) 0.5 (0.5) 0.5 radish

* (): Reaction after 24 hours

Criteria

0-0.9: non-irritant, 1.0-1.9: light irritant,

2.0-2.9: Mild irritant, 3.0 and above: Severe irritant

n = 1, n = 2 are numbers of animals used in the experiment

As can be seen in Table 3, the surfactant sodium dodecyl sulfate contained when preparing the alkaline chitin according to the conventional method (Comparative Example 1) causes skin irritation. Accordingly, the present invention has developed a process using no surfactant as in Example 4. That is, as in Example 4, the beta chitin was stirred in an aqueous sodium hydroxide solution at low temperature, and then left at 0 ° C. or less for a long time to prepare alkali beta chitin without a surfactant.

The water-soluble beta chitin prepared by the present invention has water-soluble properties without causing skin irritation, and thus is suitable as a raw material for cosmetics and has been adjusted to have a viscosity suitable for cosmetics.

In addition, the water-soluble beta chitin prepared by the present invention retains various effects such as wound healing, cell regeneration, and immune function activation of the original beta chitin, and improves the moisturizing feeling during skin application.

Claims (9)

In the alkali beta chitin of formula (2) in which hydrogen located at carbon 6 of the beta chitin of formula (1) is substituted with sodium group of sodium hydroxide, Alkali beta chitin, characterized in that the beta chitin prepared by the method comprising the step of stirring at 10 ° C or less with an aqueous solution of sodium hydroxide at least 40% and 24 ° C or less. The alkali beta chitin according to claim 1, wherein the concentration of sodium hydroxide is at least 50%, and the storage time is at least 48 hours. According to claim 1, wherein the beta chitin is an alkali beta chitin, characterized in that passed through a mesh of 30 or more. According to claim 3, wherein the beta chitin alkali beta chitin, characterized in that passed through 30 to 40 mesh. In the water-soluble beta chitin of Formula 3 wherein the sodium group of carbon 6 of the alkali beta chitin of Formula 2 is substituted with a carboxymethyl group, A water-soluble beta chitin prepared by the method comprising the step of reacting the alkali beta chitin prepared by any one of claims 1 to 4 with monochloroacetic acid. 6. The water-soluble beta chitin according to claim 5, wherein the input ratio of monochloroacetic acid is 3 to 7 (g / g) based on the beta chitin of Formula 1. 6. The water-soluble beta chitin according to claim 5, wherein the reaction temperature is maintained at 10 DEG C or lower. In the method for separating the water-soluble beta chitin prepared by any one of claims 5 to 7, Dehydrating the water-soluble beta chitin by centrifugation to remove isopropanol and stirring by adding ethanol, Dissolving the product in water after washing to remove insolubles through filtration; And A method for separating water-soluble beta chitin, comprising adding 2-4% sodium chloride and separating the water-soluble beta chitin while stirring 1.5 to 2 times ethanol in the filtrate. A cosmetic comprising a water-soluble beta chitin according to any one of claims 5 to 7, or containing a water-soluble beta chitin isolated by claim 8.