JP3223038B2 - Cosmetic containing esterified agar oligosaccharide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to the application of a novel agar-derived oligosaccharide derivative to cosmetics. More particularly, the present invention relates to a cosmetic containing an ester of an enzyme or acid hydrolyzate of agar, which is a polymer of D-galactose and 3,6-anhydro-L-galactose.

[0002]

BACKGROUND OF THE INVENTION The esterified product of agar oligosaccharides used in the present invention is characterized by the properties of the constituent sugars and the degree of polymerization.
Alternatively, the oligosaccharide has hydrophobicity or properties due to the induction of alkyl esterification (chemical modification) of the oligosaccharide. In application to skin external preparations such as cosmetics, for example, compared to alginic acid and its derivatives widely used as moisturizers and thickeners for cosmetics, gum arabic, carboxymethylcellulose, etc. There is almost no sticky feeling at the time of application, and furthermore, it has an appropriate moisturizing property, and an extremely excellent feeling in use can be obtained. Therefore, liquid, gel, cream, powder, or foam, regardless of its form, for example, various hair care products such as shampoo and rinse, hair tonic, hair styling, lotion, cream, emulsion, By mixing and using as a base, emulsion improver, thickener, etc. in various products such as skin cosmetics such as body soaps, or bath cosmetics such as bath additives, it does not give a sticky feeling, A smooth feeling of use and a moist feeling can be obtained. Further, the agar oligosaccharide and its esterified product according to the present invention are not used by general bacteria, and are characterized by little need to worry about preservative measures.

[0003]

2. Description of the Related Art Galactooligosaccharides are not used in intestinal bacteria. For example, lactose-derived galactooligosaccharides have been applied to health foods and the like, but agar oligosaccharides are still rarely used. Anti-aging method (JP-A-62-110955), food preservative method (JP-A-62-10955)
-210974) and so on.

[0004]

Heretofore, for example, alginic acid and its derivatives, or polysaccharides such as gum arabic and carboxymethylcellulose (CMC) have been widely used as humectants and thickeners for cosmetics. Has been
These have many problems such as stickiness and stickiness, and have a drawback that it is difficult to obtain a smooth feeling of use and finish. Under these circumstances, the present inventors, in use,
The purpose of the present invention is to develop a novel cosmetic material which can substantially satisfy the moisturizing property and does not give a sticky feeling, and has been studying hard.

[0005]

Means for Solving the Problems In developing a material to satisfy the above-mentioned problems, the constituent sugars are composed of hydrophobic 3,6-anhydro-L-galactose and hydrophilic D-galactose. Are alternately β-1,4 bonds and α
Agarose (a
garose), and various studies have been made on this. Agarose has a structure similar to that of Chemical Formula 1, and is a main component of agar obtained by extracting hot water from Agaricus or Ogonori. It is a polysaccharide that is very easy to obtain and can be supplied at low cost.

Embedded image As described above, agarose has a unique basic structure in which two types of monosaccharides having contradictory properties are regularly and alternately arranged. If this property is used well, a meaningful result can be obtained as a solution to the problem. It was considered to be obtained.

Accordingly, the present inventors have attempted various chemical inductions using agar, and have evaluated their physicochemical properties, sensory evaluation in application to skin and hair, and usability as cosmetics. As a result, agar oligosaccharides obtained by the action of agarase (β-agarase), agar oligosaccharides obtained by the action of various inorganic and organic acids, and furthermore, the agar oligosaccharides were esterified. The compound, compared to polysaccharides conventionally used as moisturizers and thickeners, has an excellent feel to the skin and a feeling of use, and appropriately imparts moisture necessary for flexibility of skin and hair. I found what I could do. Further, the agar oligosaccharide according to the present invention is not utilized as a carbohydrate by general bacteria, and as a result, it is possible to keep skin and hair clean, and it is extremely advantageous in terms of preservation. Thus, the present invention has been completed. The esterified product in the present invention means, for example, various fatty acids and alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts, carboxymethylated products and the like, which are acceptable as cosmetics. Hereinafter, the present invention will be described in more detail with reference to Examples and the like.

The agarase (β-agarase) used in the present invention is described in Gifu Prefectural Industrial Technology Center Report No. 24, (1).
A new agar-decomposing bacterium obtained from soil near the Yamaoka-cho agar branch of Gifu Prefectural Industrial Technology Research Institute in Yamaoka-cho, Gifu was announced in 992). Not something. β-Agarase is an enzyme that specifically cleaves a β-1,4 bond to produce an oligosaccharide (agar oligosaccharide) having neoagarobiose as a constituent unit. The acid used for acid decomposition in the present invention is sulfuric acid,
In addition, inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as acetic acid, citric acid and lactic acid can also be used. Regarding the hydrolysis reaction of agar, a method generally performed without particular preference may be adopted. In other words, it is only necessary to obtain an agar decomposition product containing neoagarobiose and oligosaccharides having the same as its constituent unit. In addition, the decomposition reaction time may be freely selected according to the intended degree of polymerization of the oligosaccharide. In addition, the esterification of oligosaccharides may be performed by a usual method for esterification of saccharides without particular limitation.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention contains an esterified agar-derived oligosaccharide obtained by decomposing agar extracted from seaweed containing galactan such as tengusa and ogonori with an enzyme or an acid. With cosmetics. The cosmetics herein include all skin cosmetics for the purpose of skin gloss, flexibility, lubricity, etc. and all hair stylings applied for the purpose of softening, glossing, lubricating, and styling effects of hair. .

[0009]

EXAMPLES Example of Production of Agar Oligosaccharides by Enzymatic Decomposition 1 kg of agar powder is prepared at a concentration of 1.5%, heated and dissolved in a boiling water bath, and then cooled to 40 ° C. For this agar solution,
Add 2U of the crude enzyme solution per 1g of agar, and stir at 40 ° C for 15 minutes.
Perform enzymatic degradation reaction for hours. Thereafter, the temperature is raised again to 100 ° C. to inactivate the enzyme and obtain an agar decomposition solution. This is freeze-dried to obtain 1 kg of agar oligosaccharide. FIG. 1 shows an outflow curve by HPLC performed for estimating the molecular weight.

FIG.

[0010]

EXAMPLES Example of Production of Agar Oligosaccharide by Acid Decomposition 1 kg of agar powder is prepared to a concentration of 10%. 100 ml of 1N sulfuric acid is added thereto and dissolved by heating with stirring. Thereafter, heating is continued at 100 ° C. for 2 hours to carry out a hydrolysis reaction to obtain an agar decomposition solution. This is neutralized with 1N sodium hydroxide and freeze-dried or spray-dried to obtain 1 kg of agar oligosaccharide.

[0011]

Example: Production example of agar oligosaccharide esterified product To 1 kg of the agar oligosaccharide obtained in the preceding example, 6 L of dimethylformamide, 1.8 L of pyridine and 7 k of stearic acid chloride were added.
g was added and reacted at 60 ° C. with stirring, and then the solvent was removed. The residue is then washed several times with methanol and dried to give about 3 kg of stearylated agar oligosaccharide.

[0012]

EXAMPLES Sensory Evaluation of Agar Oligosaccharides and Esterified Compounds In the evaluation of the agar oligosaccharides and / or esterified products obtained in the examples, cosmetics having simple formulations as shown in Table 1 were prepared. A use test was performed by 25 panelists. The method comprises preparing each of the same cosmetics prepared in advance by adding the agar oligosaccharide according to the present invention and / or its esterified product and other bases as a comparative object,
Without giving any information to the panelists, we asked them to use each of the two weeks while comparing them freely.

[Table 1] The questionnaire items are as follows. Q1. Please answer for lotion, emollient cream and hair rinse respectively. Please select one of the four used ones that felt less sticky compared to the other ones (the ones that felt a refreshing feel). Q2. Please answer each of lotion, emollient cream and hair rinse. Please select one of the four bottles that you feel used to give a moist feeling compared to the others. Q3. Please answer for lotion, emollient cream and hair rinse respectively. Of the four used each, one that felt smoother than the others
Please choose a type. Q4. Please answer each of lotion, emollient cream and hair rinse. Judging comprehensively, please select one of the four used products that has the best feeling for use as cosmetics. Table 2 shows the results.

[Table 2]

The agar oligosaccharides and the esterified products thereof according to the present invention obtained good results in cosmetics in a simple formulation. Therefore, using various additives and the like generally used, the formulation was tried, and the feeling of use was tried.

[0014]

Example: Soft lotion weight% 1. Sorbitol 2 2.1,3-butylene glycol 2 3. Polyethylene glycol 1000 14. Polyoxyethylene oleyl ether (25EO) 25 5. Agar oligosaccharide and / or esterified product thereof 0.5. Ethanol 15 7. Appropriate amount of flavor 8. Preservative appropriate amount 9. Appropriate amount of pH adjuster 10． The remaining lotion was 100 with purified water. The obtained lotion had a fresh feeling without stickiness.

[0015]

Example: Emollient cream weight% 1. Beeswax 2 2． Stearyl alcohol 5 3. Stearic acid 8 4. Squalane 10 5. Self-emulsifying propylene glycol monostearate 3 6. Polyoxyethylene cetyl ether (20EO) 1 7.1,3-butylene glycol 8 8 8. Agar oligosaccharide and / or esterified product thereof Suitable amount of fragrance 10. Preservatives qs. Residue with purified water 100 The obtained emollient cream has good spreadability, a refreshing feeling and a smooth appearance.

[0016]

EXAMPLES Hair cream weight% 1. Stearic acid 0.5 2. Liquid lanolin 1 3. Squalane 14 Liquid paraffin 42 5. Polyoxyethylene cetyl ether (20EO) 1.5 6. Polyoxyethylene cetyl ether (5EO) 2.5 7. Sorbitan monostearate 1.5 8. Self-emulsifying glyceryl monostearate 0.5 9. Propyl parahydroxybenzoate qs. Triethanolamine appropriate amount 11. Tetrasodium edetate 1 12.1, 3,3-butylene glycol Suitable amount 13. Agar oligosaccharide and / or esterified product thereof 1 14. Perfume appropriate amount 15. The residue was adjusted to 100 purified water. The resulting hair cream had no oiliness, and had a refreshing and moderate hair-styling effect and a soft and firm luster.

[0017]

EXAMPLES Set lotion weight% Acrylic resin alkanolamine solution 2 2. Agar oligosaccharide and / or esterified product thereof 13. Ethanol 30 4. Glycerin 2 5. Dyes, flavors appropriate amount 6. 6. Methyl parahydroxybenzoate qs The residue was adjusted to 100 purified water. The resulting set lotion had a smooth use feeling and a smooth brushing feeling.

[0018]

[Brief description of the drawings]

FIG. 1 shows an HPCH efflux curve of an agar oligosaccharide (enzymatic degradation) obtained in an example. (Analysis conditions) Column Shodex Ionpak KS-802 Column temperature 60 ° C Eluent H ₂ O Flow rate 1 mL / min Pump Shimadzu LC-4A detector Shimadzu differential refractometer RID-2A
S

Claims (1)

(57) [Claims] (1) A galactan (ga) such as tengusa and ogonori.
Cosmetics containing esterified agar-derived oligosaccharides obtained by enzymatically or acid-decomposing agar extracted from seaweeds containing lactan)