JPS59106409A - Cosmetic containing chitin compound - Google Patents

Abstract

PURPOSE:A cosmetic for providing the skin and hair with flexibility and gloss with wettness and smoothness, preventing fine wrinkles, improving combing properties, containing a water-soluble chitin compound of glycol chitin, carboxymethyl chitin, or chitin sulfate. CONSTITUTION:A cosmetic containing glycol chitin having a repeating unit shown by the formula I , carboxymethyl chitin having a repeating unit shown by the formula II, or chitin sulfate having a repeating unit shown by the formula III. The chitin compound is soluble in water, and its solution shows water retention and lubricating properties, improved adsorbing properties on the surface tissue of the skin and hair, enhances waving effect on permed hair, improves its durability, and provides hair with antistatic effects. The compound can be prepared from inexpensive chitin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel cosmetic containing a water-soluble chitin compound.

The chitin compound according to the present invention is soluble in water, and its solution exhibits water-retaining slipperiness and excellent adsorption to the surface tissues of the skin and hair. Gives a moist and smooth skin and prevents fine wrinkles. On the other hand, it enhances the waving effect of permanent hair, improves its durability, exhibits antistatic effect, and combs easily.

Until now, there have been no examples of using chitin or chitin derivatives in cosmetics, and the present inventors have focused on the polymer structure of chitin and have been investigating ways to use it. However, chitin is hardly soluble in water, and therefore, when applying chitin in cosmetics, one of the important points is the means to solubilize it. On the other hand, when we investigated substances with a structure similar to chitin, we found that chitosan was found.We also investigated whether chitosan is also insoluble in water and investigated its application to cosmetics. -1904, the same publication = 54-95740.

According to this, it was found that chitosan was solubilized using acetic acid, formic acid, and hydrochloric acid and used in cosmetics. However, the drawback is that the pH range of cosmetics is limited by the relationship with the acid used, and the cosmetics are soluble under any conditions over a wide range of pn' values of 3.5 to 10.
The combination is overpriced. Therefore, the present inventors took these points into consideration, and in addition to the water solubilization method of chitin, the present inventors also developed a method for adding (blending) chitin to cosmetics over a wide pH range.
As a result of continued research to obtain stability, they succeeded in using water-soluble chitin derivatives such as glycol chitin, carboxymethyl chitin, and chitin sulfate.

This will be specifically described below using examples and the like.

Chitin is a well-known polymer compound that exists in large quantities as a component in the outer shells of aquatic crustaceans and insects such as arthropods shrimp and crabs.In Japan, chitin is a byproduct obtained from shrimp and crabs. Although various ways of using it have been studied, it has not yet been used effectively. The essence of chitin is a polysaccharide in which N-acetylated glycosamine is bonded to β-U, type 4, and strong hydrogen bonds are observed between the molecules due to the acetylamino groups in the molecule. It hardly dissolves in water or any other organic solvent, and it has the property of not being easily affected by other divine agents.

This can be expressed as a general formula as follows. The difference between chitin and chitosan is that chitosan is obtained by hydrolyzing the acetamide group at the second position of chitin with an alkali and deacetylating it.

〔Kitchen〕

The water-soluble chitin derivatives of the present invention include glycol chitin, which is made water-soluble by glycolizing the 6-position of chitin, carboxymethyl chitin, which is made water-soluble by carboxymethylating chitin, and sulfuric acid esterification of chitin. The purpose is to use three water-soluble chitin sulfate compounds.

Of course, these water-soluble chitin compounds have never been applied to cosmetics, and have only been provided as analytical reagents, such as glycol chitin or substrates for the enzymes lysozyme and chitinase. . In other words, the present inventors, when using chitin in cosmetics,
Commercially available chitin is obtained, several derivatives are prepared based on it, and those with excellent water solubilization, pH stability, and effectiveness are selected to produce cosmetics, which is the object of the present invention. This made it possible to use it for

Since materials other than chitin are commercially expensive, the present inventors used inexpensive chitin as a starting material to produce each water-soluble chitin compound. The manufacturing method is shown below, and although these compounds and the manufacturing method themselves are well known, not much research has been done on their uses until now.
Griwar Chitin 76ij: Commercially available chitin was pulverized using a pulverizer, 20 pieces of this were taken, and immersed in 42% caustic soda 400i. In order for the caustic soda solution to penetrate into the inside of the chitin powder, it was left under reduced pressure for about 8 hours, and then left at room temperature under normal pressure for 2 days and nights. Then, using a cryogen, add 1009 pieces of thin ice under conditions of 0° C. or lower while stirring. The alkaline chitin solution obtained in this way was transferred to a sealable container, cooled again below 0°C, and 30g of ethylene oxide was added.
, and after about 30 minutes have passed, add 30 g of ethylene oxide and leave at room temperature for 2 to 3 hours to complete the reaction. Next, using a cellophane membrane, dialysis was carried out in running water for 3 hours, and insoluble matter precipitated after completion of the dialysis was filtered and removed, concentrated under reduced pressure, and then freeze-dried to obtain glycol chitin 1 in the form of a water-soluble white powder.
I got 50 ri.

(2) Method for producing carboxymethyl chitin Commercially available chitin is pulverized using a pulverizer, and 20 ml of the powder is immersed in 400 ml of 42% caustic soda. In order to allow the caustic soda solution to penetrate well into the inside of the chitin powder, it was left under reduced pressure for about 8 hours, and then left at room temperature under normal pressure for 2 days and nights. Thereafter, 1,000 g of thin ice is added while stirring at a temperature of 0° C. or lower using a cryogen. Next, 600 ml of 4M monochloroacetic acid soda is added little by little. Next, stirring was continued at room temperature overnight, and after the reaction was completed, the mixture was dialyzed against running water for 3 days using a cellophane membrane. After completing the dialysis, the precipitated insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure and lyophilized to obtain about 1202 carboxymethyl chitin in the form of white powder.

(3) Production method of chitin sulfate 8 g of dried chitin was heated at a humidity of 10° under dry nitrogen filling.
1O07 kept in C! of dichloroethane and 207n
j! of chlorsulfonic acid and reacted with stirring in a constant temperature bath at 25°C for about 2 hours. After removing unreacted chlorsulfonic acid, the remaining
0- dichloroethane and stir for about 5 minutes. Next, after discarding the dichloroethane layer, 100-dichloroethane was added again, and the bath was cooled to 0°C until the temperature reached 2.
Triethylamine 70%/!, taking care not to rise above 0℃! and then 40 fnl of water.

Add 320 liters of isopropyl alcohol to this thread, evaporate the supernatant, wash again with 1507 nl of isopropyl alcohol, dissolve the syrupy substance in 75% ethyl alcohol, discard the supernatant, and remove the reaction mixture. is added to an appropriate amount of water, dialyzed in running water, the dialysate is concentrated under reduced pressure, and then freeze-dried to obtain 4 g of powder.

〔safety〕

Regarding skin safety, we tested each animal in accordance with the safety test method specified by FD, including skin irritation, secondary irritation,
Eye mucosal irritation, phototoxicity, contact allergy, etc. were tested using an aqueous solution containing 20% glycol chitin, carboxylmethyl chitin, and chitin sulfate, but no abnormalities were observed. Based on this result, regarding healthy human skin - secondary irritation test (patch test),
Ten men and women (20 to 45 years old) were treated with an aqueous solution containing 5% each of glycol chitin, carboxylmethyl chitin, and chitin sulfate, and no abnormalities were observed after 24 hours. It didn't work out.

Next, regarding each chitin water-soluble compound mentioned above,
Regarding the use in cosmetics or hair products, examples of formulations will be shown and effects will be described.

[Prescription example (1): Lotion] Glycerin 9. Life...Fist...Φ 5.0%1.3-Fthylene gelicol...3. 0 Oleyl Alcohol Twin 2Q...Q...Life...@1
．． 5 span 20...fist...Φ...
・ 0.5 paraben (methyl) @@@@@・・・・
...0.05 glycol chitin or carboxylmethyl chitin or chitin sulfate...0.1-20
Purified water・・・・・・・・・・・・All @ 1 0
Set to 0.

(For the above formulation, it is easier to dissolve uniformly by adding water-soluble chitin in purified water or a mixture of purified water and glycerin in advance to create a solution.) [Formulation example ( 2), Lotion] A solution in which glycol chitin, carboxylmethyl chitin, or chitin sulfate is dissolved in purified water (content: 1
~20%)...5.0 %tlow...@
・・Shizuka@・・・・Fist・・・・ 2.0 Mitsuro
U...φ...fist...fist...0 fistΦ...l
'6.0 Liquid paraffin 11111141111@11
111111φ11@・46.5 cetyl alcohol・1
1 @, -・Conflict e...0・ 2.0 Pow sand ** @ em *
***mmamaa*am**'maa 1. QFragrance and paraben (methyl)... Bring the total amount to 100 with an appropriate amount of purified water.

[Formulation example (3): Vanishing cream] Stearic acid
...11I...Fist...16. ○ % Sorbitan monostearate 2.0 polyoxyethylene sorbitan monostearate...Φ...e...
...Fist...l11111...1.5 Fragrances and parabens...Aqueous solution containing an appropriate amount of glycol chitin, carboxylmethyl chitin, or chitin sulfate at a total of 5.0%.・・・・・・・・・・・・
...3.5-4.5 propylene glycol...Φ
・---6.0 With purified water, make the total 100.

[Prescription example (4): Cold cream beeswax...ψ...1■,Φ...Fist Φ10
．． ○% Ceresin eIIe...Fist...-
・Sha・・mine 10.0 Vaseline・e・e＠■・・・・
・Fist－・－・・・15.0 Lanolin・・・・・・・＠
Φe...1・@war・5.0 sulfur paraffin・・
...*@@@@@@@@...17.5 Brown rice oil (Oryza oil S-1)...l O,0 glycol chitin or force/lz-boxymethyl chitin or chitin sulfate 1
Aqueous solution containing -woO, 1-20%...
・・・・・・↓、○〜4.0 Incense sticks and preservatives・・・・・・
・・・・・・・・・ With appropriate amount of purified water, total B100
Tozuro.

[Prescription example (5), cosmetic soap (transparent type)] Coconut oil...
1・11-・11 fight... fight ■・skewer・・fist・・l 9.
0% beef tallow・・・・・・・・・・・・・・・・・・
...17. ○Castor oil・轡・・・Fist・Φ・−・
1...Fist...9.8.0NaOH (35+5%)
−−−−−−−−−−23.0 Add 40% glycol chitin, carboxylmethyl chitin, or chitin sulfate to a mixture of 4% glycerin and purified water.
Containing aqueous solution・・・・・・・・・・・・・・・ 8
．． 0 ethanol・・・・・・・・・Φ−”−”−
15.0 Purified water・・・・・・・・・・・・・・・・・・
...6.0 [Prescription example (6), liquid shampoo] Na lauryl sulfate (30% liquid) 0.0% amizole LDE...11I...6.0 Ethoxylation / Phosphorus Alcohol 2.0 A solution containing 40% of the chitin water-soluble compound used in Prescription Example (5).
...0.5-20 Add purified water to make the total amount 100.

[Formulation example (7): Hair rinse] Trietha lauryl sulfate/-luamine---15.0%
Aqueous solution containing 20% of lauric acid jetanolamide 5.0 chitin sulfate 3.
0 Parabens (methyl and propyl)・0. ].

Make the total volume to 100 with purified water.

[Formulation example (8), hair cream] (A,) Liquid paraffin Φ・・φ5ees・11・・43.0
%cetanol--・--・--・e・・・・・・・e
2.0 Stearic acid - Oo...
6.0(B) Triethanolamine--Threat... 1.5
% of the chitin water-soluble compound used in formulation example (5).
Solution containing 0%・・・・・・・・・1.0-3.
0 parabens (methyl and propyl), 0.2 fragrance...
・・・・・・・・・・・・・・・・・・ Add an appropriate amount of purified water to make the total volume 100.

*Prescriptions of (A) and CB) are desirably prepared by heating them separately at 70 to 80°C and gradually adding (A) to (B) while stirring and emulsifying them.

[Viscosity and thermal stability]

Many of the substances in cosmetics that have a moisturizing and lubricating effect decrease in viscosity when heated or heated. Therefore, assuming the heating conditions when compounding into cosmetics, for example, carboxymethyl chitin was measured based on an aqueous solution containing 25% O in a constant temperature bath at 70°C and 100'O, as shown in Table 1. As shown, the thermal stability was also good, and it was found that it could be satisfactorily maintained under the heating conditions during the normal manufacturing process of cosmetics.

On the other hand, when the pH stability is set to 4.0 or less, the viscosity gradually decreases, and the moisture retention and slippery filling also decrease. In addition, the concentration of water-soluble chitin compounds added to cosmetics and the moisturizing and slippery filling effect are 0.1% or more when converted to powder.

[Antistatic effect on hair]

The advantages of using water-soluble chitin compounds in hair materials include maintaining the hair's stability and flexibility due to its water-retaining lubricity, as well as its antistatic effect against tV, as shown in Table 2. I found out that This is a great advantage for hair cosmetics. In addition, the antistatic effect was measured using a rotary static tester at Kyoto University Kaken2 in an environment of 20°C and 60% humidity (lol).
0 [Moisturizing Effect] The water-soluble chitin compound according to the present invention is characterized in that when it is dissolved in water, a high viscosity and non-sticky lubricity effect can be obtained. Such a slippery effect and viscosity are similar to those of hyaluronic acid, a mucopolysaccharide. Therefore, we thought that hyaluronic acid may have a strong moisturizing effect similar to that shown by hyaluronic acid. Using an aqueous solution, 1 Drcp was dropped and spread over a 4 cm circle, and then measured over time using a skin stratum corneum moisture meter manufactured by Company S. The results were as shown in Figure 1. Yes, it does not have a strong moisturizing effect like hyaluronic acid, but the moisturizing effect when used at low concentrations with general moisturizers such as glycerin and propylene glycol is equivalent to this. It was found that it shows.

[Comb effect on hair]

Water-soluble chitin compounds according to the present invention, glycol chitin, carboxymethyl chitin, chitin sulfur-1.
Add 10% of each of these three types dissolved in water to 10% in a standard rinse agent formulation, rinse your hair according to the normal rinse method, and check whether the hair combs smoothly or not. A sensory test was conducted on 20 women regarding things such as hair thinning. The results shown in Table 3 were obtained.

In the test according to Table 3, after washing with a commercially available shampoo, rinsing once with the rinse agent of A~]), twice with warm water, moderately scrubbing,
After washing the pampas grass and drying it with hot air, each person was asked to judge the smoothness of the comb and the dryness of the hair. , about 10% of the total (2 out of 20 people). All of the other BD (rinse containing chitin compounds) had better results than A.

[Brief explanation of drawings]

Figure 1 shows the moisturizing effect of a water-soluble chitin compound.1 is water containing 0.25% glycol chitin.Aqueous solution 2 contains 0.25% carboxymethyl chitin.Aqueous solution 3 contains 5.0% propylene glycol6. teeth,
Seijinsui patent applicant

Claims (1)

[Claims] Cosmetics characterized by containing one or more chitin compounds selected from glycol chitin, carboxymethyl chitin, and chitin sulfate.