JPH02134308A - Skin cosmetic - Google Patents

Abstract

PURPOSE:To obtain a skin cosmetic improved in feeling of use by blending a chitosan derivative, prepared by reacting chitosan or low-molecular chitosan with saccharides having reducing terminals and excellent in viscosity and gelling properties as a water-soluble high polymer with other ingredients. CONSTITUTION:A skin cosmetic obtained by blending a chitosan derivative prepared by reacting chitosan or low-molecular chitosan with saccharides, e.g., glucose, N-acetylglucosamine, lactose, arabinose or maltose, having reducing terminals using reaction for reducing a Schiff base in an amount of 0.01-10wt.%, especially 0.05-2wt.% based on the final composition in a skin cosmetic, such as toilet water, cream, milky lotion or foundation, and having excellent touch. Furthermore, the above-mentioned chitosan derivative has excellent touch in blending with water or an aqueous solution of an alcohol and forms solutions with hardly any stringiness, viscous solutions or gelatinous solutions.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a skin cosmetic product obtained by blending a derivative obtained by reacting chitosan or low-molecular-weight chitosan with a saccharide having a reducing end. It is something.

[Conventional technology and its problems]

Traditionally, water-soluble polymers, whether natural or synthetic, have utilized their properties to be used as thickeners, gelling agents, stabilizers, dispersants, film-forming agents, water retention agents, flocculants, etc. It is used in a wide variety of fields. Among these, those used in skin cosmetics are desired to have a suitable viscosity, be non-sticky, have no stringiness, and have a good feel during use and after use. However, many of the various natural and synthetic polymers that have been developed to date have a poor feel (stickiness) and film feel, and natural polysaccharide polymers that have a good feel are viscous, At present, it is not possible to provide sufficient gelling properties, and there is no satisfactory product.

[Failure to solve the problem]

The present inventors have conducted various studies on water-soluble polymers that have appropriate viscosity, are not stringy, and are comfortable to use, and have found that chitosan derivatives or low-molecular-weight chitosan derivatives subjected to addition reaction with saccharides are superior. It has been found that it has viscosity and gelling properties, and that when it is blended into skin cosmetics, it can impart an excellent feel, leading to the present invention.

That is, the present invention relates to a skin cosmetic containing a chitosan derivative obtained by reacting chitosan or low-molecular-weight chitosan with a saccharide having a reducing end.

Chitosan is usually obtained by deacetylating chitin obtained from the shells of crabs, shrimps, etc. by alkali treatment, enzyme treatment, etc. However, in the present invention, to distinguish between chitin and chitosan, those with a degree of deacetylation of 40% or more are defined as chitosan, and those with a degree of deacetylation of 40% or more are defined as chitin.

In addition, low-molecular-weight chitosan can be produced by, for example, treating chitosan with concentrated hydrochloric acid or chlorine gas, sodium perborate, or hydrogen peroxide, or treating chitin with an acid or alkali to cause deacetylation and glycosidic decomposition at the same time. It can be obtained by a method of hydrolysis using an enzyme such as chitinase.

Examples of sugars having a reducing end include aldoses, ketoses such as glucose, galactose, mannose, arabinose, xylose, erythrose, glyceraldehyde, heptulose, hexulose, pentulose, and amine sugars such as glucosamine, N-acetylglucosamine, and galactosamine. Examples of monosaccharides include deoxy sugar, branched sugar, etc. In addition, trisaccharides and polysaccharides containing these monosaccharides as constituents, such as maltose, isomaltose, maltotriose, lactose, various oligosaccharides, and natural polysaccharides such as pullulan, inulin, amylose, amylopectin, dextran, dextrin, and starch. and their decomposition products, isomerization products, and derivatives. One or more of these saccharides are used in the reaction.

In the present invention, the reaction between chitosan or low-molecular-weight chitosan and a saccharide having a reducing end means a reaction that reduces Schiff base. Normally, a Toschiff base is formed in which an amine group and an aldehyde coexist, but since the Schiff base is unstable (decomposes in the presence of water, acid, base, etc.), it is further stabilized by reduction.

As the reducing agent, considering reactivity and selectivity, sodium cyanoborate (NH3BH3) or amine borane reducing agent, such as ammonia borane (NH3BH3
), monomethylamine borane ((CH3)NH2BH3
), dimethylamine Bohr :/ ((CH,) 2
NHBH3), trimethylamine borane ((CL)3)
NBH3) and pyridine borane (C5H3NBI+3) are preferably used as reducing agents. One or more of these reducing agents are used in the reaction.

In addition, derivatives in which the primary alcohol at the 6th position of chitosan into which a sugar side chain has been introduced are further modified, such as oxyethylene, oxypropylene addition, carboxymethylation, phosphorylation, sulfation, dihydropropylation, or the 2nd position It is also possible to use a derivative in which a primary amine has not yet been added with a sugar side chain or a secondary alcohol at the 3-position has been modified.

The chitosan derivative obtained as described above can be further purified by solvent washing, precipitation formation, etc., gel filtration, ion exchange column chromatography, etc.

When these chitosan derivatives are blended with water or an aqueous alcohol solution, they form a solution with a good feel and less stringiness, a viscous solution, or a gel-like solution.

According to the present invention, by formulating these chitosan derivatives as they are or as a solution into a skin cosmetic, a skin cosmetic with a good feel can be made. Examples of skin cosmetics include lotions, creams, milky lotions, foundations, etc., and the feel of these products can be improved by incorporating the chitosan derivative of the present invention.

There is no particular restriction on the blending ratio of the chitosan derivative of the present invention in these skin cosmetics, but it is preferable to blend the chitosan derivative of the present invention in a proportion of 0.01 to 10% by weight, particularly 0.05 to 2% by weight in the final composition. preferable.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to these examples.

Example 1 Chitosan [manufactured by Katokichi ■, chitosan 9B, degree of deacetylation 90%, viscosity 300 cps (0.5% 10.5% acetic acid, 20°C, B type viscometer)) Ig was 300 ml! Add 100 mj' of a mixed solvent of methanol/1% acetic acid = 1/l, stir thoroughly and dissolve, then add 5 g of glucose and dissolve, then add 2.0 g of dimethylamine borane while stirring. , and allowed to react at room temperature for 24 hours. As the reaction progressed, the reaction system turned into a gel and then turned white. After the reaction was completed, it was washed several times with 300mj' of methanol, and then washed with 300rn of a 90% ethanol aqueous solution.
It was washed several times with l and dried. Yield was 1.3g.

Similarly, derivatives of Examples 2 to 5 were produced by changing the types of saccharides as shown in Table 1.

The compounds shown in Examples 1 to 5 were dissolved in 1% aqueous solution or became viscous solutions or gel-like solutions.

Example 6 Low-molecular chitosan [Kimitsuki Chitosan F1 manufactured by Kimitsu Chemical Industry ■, degree of deacetylation 84.5%, viscosity 11 cps
(0.5% 10.5% acetic acid, 20°C, B type viscometer)]
1g of methanol/1% acetic acid = 1/1 mixed solution 60ml
I! 5g of N-acetylglucosamine
Add and dissolve. Furthermore, 2.0 g of pyridine borane was added, and the mixture was reacted at room temperature for 8 hours. As the reaction progressed, the system gelled. After the reaction, acetone/water = 5/1 mixed solvent 300-10. IN NaOH/ethanol/acetone = 1/2/1 mixed solvent 300ml and diethyl ether 300mf! After washing, it was dried. Collection f
f11.5g.

Similarly, Example 7 shown in Table 1 by changing the type of saccharide
~The derivative of Example 10 was obtained. The compounds shown in Examples 6 to 10 were dissolved in 1% aqueous solution or became viscous solutions or gel-like solutions.

Example 11 Chitosan [Chitosan CLH, manufactured by Yaizu Suisan Kagaku Kogyo ■,
Degree of deacetylation 85%, viscosity 200 cps (0.5% 1
0.5% acetic acid, 20°C, B type viscometer)) 150 in lOg
After adding m1' of water and stirring and dispersing, the pH was adjusted to 11 with an aqueous sodium hydroxide solution, and the mixture was heated to 70°C. Add 5.25-hydrogen peroxide solution (commercially available concentration approximately 35%),
Allowed time to react. After the reaction is complete, remove the reaction solution, wash with water,
After drying, low molecular weight chitosan was obtained. Its degree of deacetylation is 8
9%, viscosity 5 cps (0.5% 10.5% acetic acid, 20
℃, Type B viscometer), and the yield was 8.1 g. 1 g of this low-molecular-weight chitosan was placed in a 300-mm Erlenmeyer flask, and 50-ml of methanol/1% acetic acid aqueous solution was added to dissolve the mixture, 5 g of maltose was added and dissolved, and sodium cyanoborohydride .5 g was added and reacted for 5 hours. After the reaction is completed, 300 rnl of acetone/water-5/l mixed solvent and 300 rnl of ether! Washed with
Dry. The yield was 11.6g.

Similarly, derivatives of Examples 12 to 14 were produced by changing the type of saccharide as shown in Table 1. Examples 11 to 14
The material shown in Example 14 was dissolved in a 1% aqueous solution, or became a viscous solution or a gel-like solution.

Example 15 (Skin cream) Stearic acid
2.0% stearyl alcohol
6.0% reduced lanolin
2.0% squalane 4,
0% octyldodecanol 5.0% glyceryl monostearate 3.0% fragrance, preservative suitable chitosan derivative of Example 1 0.2% propylene glycol
5.0% purified water 68.8
%Apply 0.2g of the above cream to your face and spread it well. Compared to creams containing no chitosan derivatives, the cream felt less sticky and had a light texture. Similar results were obtained when the chitosan derivatives of Examples 2 to 14 were blended.

Example 16 (Lotion) Chitosan derivative of Example 1 0.2% Sorbit 2.0% 1.3-butylene glycol 4.0% Polyoxyethylene oleyl ether (25) 2.0% Ethanol 15.0% Flavorings and preservatives Appropriate amount Purified water
76.8% 0.2 mf of the above lotion was applied to the back of the washed hand. It gave a light and smooth feel compared to a lotion without the addition of chitosan derivatives.

Similar results were obtained when the chitosan derivatives of Examples 2 to 14 were blended.

Example 17 (Emulsion) Microcrystalline wax 1.0% beeswax 2.0% lanolin
2.0% liquid paraffin
30.0% fragrance, preservatives
Appropriate amount of glycerin 8.0
% Chitosan derivative of Example 1 0.15% Purified water 51.85% 0.3 g of the above emulsion was applied to the upper arm and spread well. It felt lighter and smoother than the emulsion without the addition of chitosan derivatives. Similarly, the results were also good when the chitosan derivatives of Examples 2 to 10 were blended.

Example 18 (Milk foundation) Stearic acid 2.0%-L 0.2
% 2.0% 2゜0% Bill 9.0% 8.0% 4.0% Adequate amount 0.5% 5.0% Cetostearyl alcohol Liquid lanolin Liquid paraffin Myristate Isoprooxide Titanium talc Color pigment, fragrance, preservative Agent Bentonite Propylene Glycol Chitosan Derivative of Example 1 % Purified Water 65.1% 0.1 g of the above emulsion foundation was placed on a sponge and spread on the cheeks. It had better adhesion and a lighter feel than the one without the addition of chitosan derivatives. Similarly, the results were also good when the chitosan derivatives of Examples 2 to 10 were blended.

Test Example 1 The skin creams and lotions shown in Examples 15 and 16 were subjected to sensory evaluation by 15 professional female panelists. The evaluation was expressed as the average of the panel evaluation scores. As a control, one to which the Example composition was not added was used. The results are shown in Table-2.

(Evaluation points) Cream evaluation for skin JFF Presence of stickiness/+3 absent to -3 present Presence or absence of lightness/+3 present to -3 absent Spreadiness when applying / +3 good to -3 bad lotion rating Presence or absence of lightness/+3 present to -3 absent Presence of smooth feeling/+3 Each of the above items 3/I feel it very much compared to the control.

2/Compare with the control.

l/Slightly felt compared to the control.

0/same as control I went to that point.

3. Degree of undisclosed wood substitution: The rate of addition of chitosan to primary amino groups was determined by potentiometric titration.

table

Claims (1)

[Claims] A skin cosmetic containing a chitosan derivative obtained by reacting chitosan or low-molecular-weight chitosan with a saccharide having a reducing end.