JPH10139889A - Conjugate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a conjugate excellent in moisture-absorbing power, water- absorbing power, moisture retention and skin-touching property and useful as an additive for cosmetics, etc., antibacterial and/or antifungal agent, soil improving agent, etc., by crosslinking a conjugate formed of a water-soluble chitin, etc., and amino acid homopolymer, etc. SOLUTION: This conjugate is obtained by crosslinking a conjugate formed of (A) a water-soluble chitin and/or water-soluble chitosan, e.g. deacetylated chitin having 45-55% deacetylation ratio and (B) an amino acid homopolymer such as polyglutamic acid and/or a cellulose derivative such as carboxymethyl cellulose by using a crosslinking agent such as glutaraldehyde. Furthermore, a molar ratio of the component A to the component B used is (20/1) to (1/20), preferably 10/1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid powdery hygroscopic agent for use as a detergent, a skin cosmetic, an antiperspirant, a hair cosmetic, and the like.
It relates to moisturizers, skin protection agents, and slip agents.

[0002]

2. Description of the Related Art Chitin is obtained by extracting from shrimp and crab shell, and chitosan is obtained by deacetylating the chitin. Its function is biocompatibility,
It is used in the development of artificial skin, coagulants, antibacterial / antifungal agents, and cosmetics because of its metal ion collecting properties, antibacterial / antifungal properties, moisturizing properties, and the like. Chitosan can be dissolved in aqueous acidic solutions, but becomes insoluble in neutral and alkaline regions. Utilizing this property, Japanese Patent Application Laid-Open Nos. 61-40337 and 58-5
Nos. 7401 and 56-16532 disclose a method for producing granular chitosan. However, even if the form is collapsed or crosslinked in an acidic solution, an acidic substance, a surfactant and additives remain. If they are present, there is a disadvantage that they cause coloring and that sufficient cross-linking cannot be performed. On the other hand, a method of obtaining a complex by a polyelectrolyte complex formation method using a water-soluble chitin or chitosan derivative in a neutral aqueous solution instead of an acidic aqueous solution of chitosan is disclosed, but in this case, the composite powder is crosslinked. Since the morphology is maintained only by electrostatic bonding, not by bonding, the resulting composite powder can exist only in a narrow neutral pH range,
If it is less than 6.5 or more than 8, morphological change may occur or disappear. When such a composite powder is used as a solid cosmetic additive, a detergent, or the like, it is easily affected by the ionic atmosphere due to other ingredients, compositions, and moisture, and the composite powder flows / flows out.
They have the disadvantage of causing morphological changes, which impair the desired moisturizing properties and skin feel.

[0003]

SUMMARY OF THE INVENTION The present invention solves the conventional drawbacks of morphological instability due to a pH change, a decrease in moisturizing power, and a change in coloring, and provides a moisturizer for cosmetics, a detergent, an antiperspirant, and hair. An object of the present invention is to obtain a chitin / chitosan complex suitable for additives such as cosmetics and bath additives, antibacterial / antifungal agents, and soil conditioners.

[0004]

According to the present invention, a complex formed from (A) water-soluble chitin and / or water-soluble chitosan and (B) an amino acid homopolymer and / or a cellulose derivative is crosslinked. It provides a complex. The (A) water-soluble chitin and water-soluble chitosan used in the present invention are water-soluble polyelectrolytes, and these may be derivatives, for example, partially deacetylated chitin or partially acetylated chitosan. . In the present invention, in order for the obtained complex to be homogeneous in shape and composition, deacetylated chitin having the best water solubility and having a deacetylation rate of about 45 to 55% (reference: M
akromol. Chem. , 176, 1191-111
95 (1975)) is suitable. In the present invention, the deacetylation ratio indicates the percentage of the number of NH2 groups / (the number of NH2 groups + the number of NHCOCH3 groups). In addition, water-soluble chitin and water-soluble chitosan preferably have a lower weight molecular weight in order to form a powder.
2,000 to 200,000 is preferred. If the weight average molecular weight is too high, the composite to be formed is not a powdery or short fibrous one but a hard long fibrous one, which may make it difficult to process the additive for cosmetics or the like. However, the short fiber form can be used as it is as an additive for cosmetics or the like, or can be made into a powder form by adding a pulverization step to a subsequent step. Normally, chitin and chitosan have a weight average molecular weight of 100 to 1,000,000 or more, so that chitin and chitosan before derivatization can be reduced in molecular weight by enzymatic decomposition or chemical treatment, if necessary.

Further, the water-soluble chitin or water-soluble chitosan used in the present invention includes carboxyacylation, carboxymethylation, phosphorylation, sulfated hydroxyacylation, carboxylation (above, negative charge) of chitin or chitosan. Grade, aminoalkylation (more positive charge), acylation, hydroxyacylation, diethylaminoethylation,
Includes those that have become water-soluble as a result of derivatization such as introduction of a sugar side chain, hydroxylation, and alkali chloride (above, neutral charge). Further, in order to increase the water solubility of chitin and chitosan, or to control the charge state of chitin and chitosan, the derivatization may be performed plural times, and if the water solubility of chitin and chitosan can be maintained, the same ionic species may be used. May be mixed.

In the present invention, the amino acid homopolymer (B) includes polyglutamic acid and polyaspartic acid with a negative charge, polylysine and polyhistidine with a positive charge.
Polyarginine and the like can be mentioned. The weight average molecular weight of the amino acid homopolymer is usually 1,000 to 500,000. Examples of the cellulose derivative having a negative charge include carboxymethylated cellulose, sulfonated cellulose, hydroxypropyl cellulose, and phosphorylated cellulose, and those having a positive charge include aminoalkylated cellulose. The weight average molecular weight of the cellulose derivative is usually 1,000 to 500,000. In the present invention, as the component (B), in addition to the amino acid homopolymer and the cellulose derivative, hyaluronic acid, alginic acid, collagenan, pectin, chondroitin sulfate, gelatin, xanthan gum, galaconic acid,
Negatively charged water-soluble polymers such as sulfonated lignin, tannic acid, acidic polysaccharides and salts of acidic polysaccharides, and sericin, fibroin, collagen, dextran salts, polygalactosamine, basic polysaccharides, and salts of basic polysaccharides Such a water-soluble polymer having a positive charge can be used in combination. These water-soluble polymers can be used in combination as long as they have the same charge and can maintain water solubility. Further, a derivative of a water-soluble polymer may be used for improving the water solubility and adjusting the charge amount. Here, the derivatization may include the same reaction as the component (A).

In the present invention, the crosslinking agent (C) comprises (A)
A functional group of water-soluble chitin or water-soluble chitosan,
(B) It can be selected according to the type of functional group possessed by the amino acid homopolymer or the cellulose derivative. For example, dialdehydes such as glutaraldehyde, 1-ethyl-3-
(3-dimethylaminopropyl) -carbodiimide hydrochloride, or water-soluble carbodiimides such as 1,3-dicyclohexylcarbodiimide, cyanogen bromide, acid azide, diisocyanates, epoxy compounds, epichlorohydrin, dichloride, Woodward reagent, Coupling agents and the like can be mentioned.

[0008] The complex of the present invention comprises water-soluble chitin or water-soluble chitosan as component (A) (hereinafter referred to as component (A)).
And (B) an amino acid homopolymer or a cellulose derivative (hereinafter referred to as component (B)) in an aqueous medium to synthesize a polyelectrolyte complex, and then obtain a polymer electrolyte complex by adding a crosslinking agent. . The concentration of the component (A) in the reaction solution for synthesizing the polymer electrolyte complex is usually 0.001 to 10% by weight, preferably 0.01 to 10% by weight.
The concentration of the component (B) is preferably 0.0001 to 20% by weight, more preferably 0.001 to 20% by weight.
15% by weight. The proportion of the component (A) and the component (B)
Although it depends on the charge amount of each component, usually, component (A): component (B) = 20: 1 to 1:20, preferably 10:
1 (molar ratio). The components (A) and (B) may be separately prepared as aqueous solutions and then mixed. (A)
The mixing of the component and the component (B) is preferably carried out by adding one aqueous solution instantaneously while stirring one aqueous solution with a stirrer or the like. The temperature at which the component (A) and the component (B) are reacted is usually 0 to 100 ° C, preferably 0 to 80 ° C, and the reaction time is several tens seconds to several tens of seconds.
Minutes. Next, a cross-linking agent is added to a reaction solution of the component (A) and the component (B). The amount of the cross-linking agent added is (cross-linking agent concentration) / (concentration of the functional group of component (A)) 0.00
It may be 1 to 50, more preferably 0.01 to 10. The concentration of the functional group is determined by titration, FT-IR
It can be determined by a method or an NMR measurement method.
Here, an inorganic salt of several weight% may be added to the above mixture.

After a predetermined amount of the crosslinking agent is added, 0 to 100
The complex of the present invention can be obtained by reacting at about ° C for 30 minutes to several hours. The obtained complex may be centrifugally washed 2 to 4 times with ion-exchanged water or purified water, and further centrifugally washed 1 to 2 times with an organic solvent mixed with water, such as ethanol, methanol, or acetone. The composite of the present invention can be used while being dispersed in water, but is usually dried to a powder. Drying of the composite may be vacuum drying or hot air drying, but the drying temperature is preferably from 40C to 90C. When the composite of the present invention is made into a powder, the particle size is usually 1 to 30 μm, and the shape is irregular.

[0010]

EXAMPLES Examples of the present invention are shown below, but the present invention is not limited to the scope of the examples. The evaluation method of the complex is as follows. [Water absorption] 0.1 g of the composite powder is wrapped in a non-woven fabric, the mouth is closed, and water is immersed for 12 hours. Thereafter, draining is performed for 30 minutes while the entire nonwoven fabric is suspended in the room. The sample containing water is measured as the weight before drying, and dried at 105 ° C. for 6 hours. After drying, measure the weight. Water absorption = [weight before drying (g)-weight after drying (g)] /
Weight after drying (g) [Moisturizing rate] After warm air drying at 70 ° C for 6 hours, vacuum drying was performed at room temperature for 5 hours, and an appropriate amount of water and H0g were added to an appropriate amount of the composite powder. The hydrated sample before measurement is weighed to be w0 g. The sample is allowed to stand in a room, weighed every hour, and the weight at which the weight of the water-containing sample becomes constant is defined as w. All operations during measurement were performed at room temperature 23 ° C and humidity 50
Performed in a room adjusted to%. Moisturizing rate = 1-[(w0-w) / H0] [Hygroscopicity] After drying with hot air at 70 ° C. for 6 hours and then vacuum drying at room temperature for 5 hours, an appropriate amount of composite powder was weighed, and the weight before measurement was measured. And The sample is allowed to stand in a room, weighed every hour, and when the moisture-absorbed sample has a constant weight, weighed as the weight after moisture absorption. All operations during measurement were performed at room temperature 23 ° C.
The test was performed in a room adjusted to a humidity of 50%. Moisture absorption = [weight after moisture absorption (g) −weight before measurement (g)] /
Weight before measurement (g) [Evaluation of insolubilization of acid and alkali] After adding 100 ml of purification to 1 g of the same kind of complex, 1N hydrochloric acid aqueous solution so as to have a pH of 2 or 1N hydroxylation so as not to have a pH of 12 respectively. After adding an aqueous sodium solution and stirring for 1 hour, the complex was collected by centrifugation and dried. When the recovery rate of the complex when purified water was added was set to 100, the recovery rate in the case of an aqueous acid or alkali solution was determined. [Skin feel] The obtained composite powder was put on the back of the hand to examine the feel. The results were shown as good: excellent feeling or poor: bad feeling.

Example 1 γ-Methyl-L-glutamic acid-N-carboxylic anhydride was subjected to ring-opening polymerization at room temperature for 3 days in dichloromethane using triethylamine as a polymerization initiator. 0.7 g to 1.5 g of the obtained poly-γ-methyl-L-glutamic acid (PMLG)
100 ml of a 5% by weight sodium hydroxide / ethanol (1: 3 (weight)) solution is added, and the mixture is subjected to a hydrolysis reaction at 45 ° C. for 1 hour, and then purified and dried by a usual method to obtain poly-L-glutamic acid (PLG). Was obtained (weight average molecular weight: 20,000). 400 mg of the synthesized PLG was dissolved in 40 ml of purified water in a beaker, and further stirred for 1 hour.
A 40% by weight aqueous acetylated chitosan aqueous solution (commercially available; manufactured by Koyo Chemical Co., Ltd.) was added instantaneously.
A white powdery precipitate formed. Subsequently, after stirring for 30 minutes, 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride (water-soluble carbodiimide;
WSC) was added thereto, and the mixture was reacted at room temperature for 2 hours to obtain a complex. The resulting complex is washed twice with purified water at 8000 r.
After centrifugal washing at pm, further centrifugal washing with ethanol, and recovery, the product was dried with hot air at 105 ° C. for 3 hours and subsequently dried under vacuum at room temperature for 3 hours. Table 1 shows the yield, colorability, water absorption, moisture absorption, and water retention of the obtained composite, Table 2 shows the skin feel, and Table 3 shows the acid and alkali insolubility evaluation.

Example 2 In Example 1, a water-soluble polycarbodiimide (WS
A complex was produced in the same manner as in Example except that 25 μl of glutaraldehyde (20% by weight aqueous solution; GA) was added instead of C). Yield of the obtained complex,
Table 1 shows the coloring property, water absorption, moisture absorption and water retention, Table 2 shows the skin feel, and Table 3 shows the acid and alkali insolubility evaluation. Example 3 Microcrystalline cellulose (trade name: Avical SF, manufactured by Asahi Kasei Corporation) 1
g, dissolved in 60 g of tetraethylammonium chloride / dimethylsulfoxide (1: 3 (by weight)) at 90 ° C., returned to room temperature, and cooled to 1.50 ml of sulfur trioxide.
/ Dimethylsulfoxide 75 ml of sulfur trioxide complex was added, and after 1 hour of reaction, neutralized with aqueous sodium hydroxide solution,
Methanol washing, dialysis against purified water, freeze drying,
A sulfonated cellulose sodium salt (SCN) was obtained.
As a result of titration, the sulfonation ratio was 0.6. SCN20
0 mg was dissolved in 40 ml of purified water, and 1
A 40% by weight aqueous acetylated chitosan aqueous solution was instantaneously added to produce a white fibrous powder. Subsequently, after stirring for 30 minutes, 25 μl of glutaraldehyde (20% by weight aqueous solution; GA) was added, and the mixture was reacted at room temperature for 2 hours. After obtaining a complex, the mixture was centrifugally washed and dried in the same manner as in Example 1. After crushing with milk stick, the same evaluation as in Example 1 was performed.
The results are shown in Tables 1, 2 and 3.

Example 4 5 mg of SCN was dissolved in 40 ml of purified water, and 40 ml of a 1% by weight aqueous acetylated chitosan aqueous solution was dissolved with stirring.
When 1 was added instantaneously, a white powdery precipitate formed. Subsequently, after stirring for 30 minutes, 25 μl of glutaraldehyde (20% by weight aqueous solution; GA) was added, and the mixture was reacted at room temperature for 2 hours. After obtaining a complex, the mixture was centrifugally washed and dried in the same manner as in Example 1. After pulverization with milk stick, the same evaluation as in Example 1 was performed, and the results are shown in Tables 1, 2 and 3. Example 5 Sodium carboxymethylcellulose (commercial product; CM
40 ml of an aqueous solution in which C) was dissolved to 1% by weight was prepared, and 40 ml of a 1% by weight aqueous acetylated chitosan aqueous solution was instantaneously added thereto with stirring, whereby a white fibrous powder was produced. Subsequently, after stirring for 30 minutes, 25 μl of glutaraldehyde (20% by weight aqueous solution; GA) was added and reacted at room temperature for 2 hours to obtain a complex.
The centrifugal washing and drying were performed in the same manner as in Example 1. After pulverization with milk stick, the same evaluation as in Example 1 was performed, and the results are shown in Tables 1, 2 and 3.

Comparative Example 1 400 mg of chitosan having a weight average molecular weight of 30,000 or less (trade name: water-soluble chitosan, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 40 ml of 1% by weight aqueous acetic acid solution, and 1% by weight of carboxymethyl cellulose (1% by weight) was stirred. CMC) An aqueous solution (40 ml) was added instantaneously to produce a brownish fibrous powder. Continue 30
After stirring for 25 minutes, 25 μl of glutaraldehyde (20% by weight aqueous solution; GA) was added, and the mixture was reacted at room temperature for 2 hours. After obtaining a complex, the mixture was centrifugally washed and dried in the same manner as in Example 1.
After drying, it turned dark green. After pulverization with milk stick, the same evaluation as in Example 1 was performed, and the results are shown in Tables 1, 2 and 3. Comparative Examples 2 to 4 Composites were prepared in the same manner as in Examples 1, 4 and 5, except that WSC or GA as a crosslinking agent was not added. The acid and alkali insolubility was evaluated, and the results are shown in Table 3.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

[Table 3]

[0018]

Industrial Applicability The composite of the present invention is excellent in moisture absorption, water absorption, moisture retention and skin feel, and has additives such as cosmetics, cleaning agents, antiperspirants, hair cosmetics, bath agents, and antibacterial / antibacterial agents. Fungicides,
It can also be applied to soil conditioners.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A61K 7/06 A61K 7/06 7/50 7/50

Claims (1)

[Claims] 1. A complex obtained by cross-linking a complex formed from (A) water-soluble chitin and / or water-soluble chitosan and (B) an amino acid homopolymer and / or a cellulose derivative.