WO2010049995A1

WO2010049995A1 - Pullulan fatty acid ester soluble in oil solution at room temperature and cosmetic preparation containing the same

Info

Publication number: WO2010049995A1
Application number: PCT/JP2008/069549
Authority: WO
Inventors: 正人井爪; 雄一柿坂; 建剛鈴木; 潤一北澤
Original assignee: 片倉チッカリン株式会社; 讃岐化学工業株式会社
Priority date: 2008-10-28
Filing date: 2008-10-28
Publication date: 2010-05-06
Also published as: JPWO2010049995A1; JP5383696B2

Abstract

Disclosed is a pullulan fatty acid ester which is soluble in an oil solution at room temperature, wherein the substituent introduced into a hydroxy group of pullulan is a myristoyl group and/or a palmitoyl group and the substitution degree of hydroxy group by the substituent is within the range of 1.6-2.4. Also disclosed is a use of such a pullulan fatty acid ester.

Description

Pullulan fatty acid ester that dissolves in oil at room temperature and cosmetics containing the same

The present invention relates to a pullulan fatty acid ester and a cosmetic containing the same. More specifically, the present invention relates to a pullulan fatty acid ester configured to be dissolved in an oily component at room temperature by controlling the substituent and the degree of substitution.

Pullulan, which is a raw material of pullulan fatty acid ester, is a water-soluble natural polysaccharide in which maltotriose is regularly α-1,6-linked. Since a compound in which a fatty acid is ester-bonded to pullulan increases in oil solubility, it can be applied to oil-soluble cosmetics. For example, an acyl group having 2 to 24 carbon atoms and a substitution degree of 0.0001 to 0.5 (in Patent Document 1, the substitution degree is 1 when all three hydroxyl groups are substituted per glucose residue). Patent Document 1 describes that the introduced pullulan fatty acid ester is excellent in film formation, and when used in pack cosmetics, has excellent film strength, and is used in pack cosmetics having quick drying properties and good peelability. ing.

Patent Documents 2 and 3 describe an oil-soluble cream containing a pullulan fatty acid ester, and Patent Document 4 describes an oil-soluble finish cosmetic containing a pullulan fatty acid ester.

However, in the preparation of the pullulan fatty acid ester-containing cosmetic described in Patent Documents 1 to 4, heating was required when the pullulan fatty acid ester was dissolved in the oil. In order to further simplify the production process of cosmetics containing pullulan fatty acid esters, it is desirable to use pullulan fatty acid esters that dissolve in oils without heating, but such pullulan fatty acid esters are still known. Not.
Japanese Patent Laid-Open No. 10-182341 Japanese Patent Publication No. 60-26081 Japanese Patent Publication No. 60-26082 Japanese Patent Publication No. 60-26089

Therefore, an object of the present invention is to provide a pullulan fatty acid ester that dissolves in an oil without heating and a method for using the same.

As a result of intensive studies to solve the above problems, the present inventors have substituted the hydroxyl group of pullulan with myristic acid and / or palmitic acid, and the degree of substitution (here, 3 per glucose residue). The pullulan fatty acid ester obtained by setting the degree of substitution when the hydroxyl groups are all substituted to 3) in the range of 1.6 to 2.4 is highly soluble in oils not only when heated but also at room temperature. As a result, the present invention has been completed.

That is, the present invention relates to a pullulan fatty acid ester that dissolves in an oil at room temperature. In a more specific aspect, the present invention includes:

[1] A pullulan that is soluble in an oil at room temperature, wherein the substituent introduced into the hydroxyl group of pullulan is a myristoyl group and / or a palmitoyl group, and the degree of substitution of the hydroxyl group by the substituent is 1.6 to 2.4 Fatty acid ester.

[2] A cosmetic comprising an oil agent in which the pullulan fatty acid ester according to [1] is dissolved.

In this cosmetic, the oil agent preferably contains hydrocarbon oil and / or ester oil.

In one preferred embodiment, the hydrocarbon oil and / or ester oil comprises isododecane, glyceryl tri-2-ethylhexanoate, neopentyl glycol dicaprate, neopentyl glycol di-2-ethylhexanoate, and diisopropyl malate. It is at least one selected from the group consisting of stearyl.

In a preferred embodiment, such a cosmetic is a water-resistant cosmetic.

[3] A method for producing a cosmetic comprising mixing the pullulan fatty acid ester according to the above [1] in an oil and dissolving it, and blending it into the cosmetic.

In this method, the oil agent preferably contains a hydrocarbon oil and / or an ester oil.

In one embodiment of this method, it is preferred to mix the pullulan fatty acid ester with the oil at room temperature.

In this method, when the pullulan fatty acid ester is mixed with the oil at room temperature, if the pullulan fatty acid ester has a myristoyl group as the substituent, the hydrocarbon oil and / or ester oil contained in the oil may be isododecane, tri- It is preferably at least one selected from the group consisting of glyceryl 2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, diisostearyl malate, and neopentyl glycol dicaprate.

In this method, when the pullulan fatty acid ester is mixed with the oil agent at room temperature in this method, if the pullulan fatty acid ester has a palmitoyl group as the substituent, the hydrocarbon oil and / or ester oil contained in the oil agent may be isododecane and di- It is preferably at least one selected from the group consisting of neopentyl glycol 2-ethylhexanoate.

In a preferred embodiment, the cosmetic produced by this method is a water-resistant cosmetic.

According to the present invention, a cosmetic containing a pullulan fatty acid ester can be produced by a simpler process.

Hereinafter, the present invention will be described in detail.

The pullulan fatty acid ester according to the present invention is a pullulan fatty acid ester that can be dissolved in an oil agent with high solubility even at room temperature.

More specifically, in the pullulan fatty acid ester according to the present invention, the hydroxyl group of pullulan is substituted with a myristoyl group and / or palmitoyl group, and the degree of substitution of the hydroxyl group of pullulan by the myristoyl group and / or palmitoyl group is 1 It is characterized by being in the range of .6 to 2.4.

In the pullulan fatty acid ester according to the present invention, the degree of substitution of the hydroxyl group of pullulan with a myristoyl group and / or palmitoyl group is 1.6 to 2.4, more preferably 2.0 to 2.4.

In the present invention, the “degree of substitution” refers to an acyl group (here, a myristoyl group and / or a hydroxyl group) out of hydroxyl groups (three) per glucose ring (glucose residue) constituting the pullulan in the pullulan fatty acid ester. Or the number of hydroxyl groups substituted with palmitoyl groups). This degree of substitution is calculated as an average value per glucose ring constituting the pullulan fatty acid ester. If all three hydroxyl groups present in the glucose ring are substituted, the degree of substitution is 3. The degree of substitution can be calculated according to the following formula by measuring the hydroxyl value of pullulan fatty acid ester according to the test method of JIS K 0070.
Hydroxyl value = 56.11 × (3-substitution degree) / ((molecular weight of substituent−1.01) × substitution degree + 162.14) × 1000
The test method of JIS K 0070 that can be used in the present invention is a test method for the acid value, hydroxyl value, etc. of a chemical product defined in JIS (Japanese Industrial Standard). The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated, and the test method here is JIS K 0070, 7. 3 The pyridine-acetyl chloride method is adopted, and the outline of the procedure is as follows. That is, a sample (here, pullulan fatty acid ester, which is an amount corresponding to the expected hydroxyl value) is weighed up to three significant digits in a flat bottom flask 200 mL, and 5 mL of pyridine is added and dissolved. To this is added 5 mL of an acetyl chloride-toluene solution (100 g of acetyl chloride dissolved in 1 L of toluene). Immediately heat the flat bottom flask to 65-70 ° C. with a water bath with an air condenser for 5 minutes. Add about 10 mL of water from the top of the air cooling tube to cool it, remove the air cooling tube, plug the flat bottom flask and shake vigorously. Further, after removing the stopper, an air cooling tube is attached and the mixture is boiled on a sand bath or a hot plate for 5 minutes to hydrolyze excess acetyl chloride. After allowing to cool, wash the air cooling tube several times with about 5 mL of water. Add a few drops of phenolphthalein solution (90 g of ethanol (95) to 1.0 g of phenolphthalein and make up to 100 mL with water) as an indicator, and add 0.5 mol / L potassium hydroxide ethanol solution (35 g of potassium hydroxide). Dissolve in 20 mL of water, add ethanol (95) to 1 L, block carbon dioxide, leave it for 2 to 3 days, then remove the supernatant or filter, and obtain the factor separately) Titration is carried out, and the end point is when the indicator is light red for 30 seconds. The blank test is operated in the same way without a sample. Further, the hydroxyl value is calculated according to the following formula.

Hydroxyl value = [(Amount of 0.5 mol / L potassium hydroxide ethanol solution used in blank test (mL)) − (Amount of 0.5 mol / L potassium hydroxide ethanol solution used in titration (mL))] × (Factor of 0.5 mol / L potassium hydroxide ethanol solution) x 28.05 / (mass of sample (g)) + acid value The acid value neutralizes free fatty acid, resin acid, etc. contained in 1 g of sample This is the number of mg of potassium hydroxide required for the test, and the test method here employs the 3.1 neutralization titration method of JIS K 0070, and the outline of the procedure is as follows. That is, a sample (here, pullulan fatty acid ester, which is an amount corresponding to an expected acid value) is weighed into an Erlenmeyer flask. Add 100 mL of solvent (diethyl ether and ethanol (99.5) mixed according to solubility in the solvent) and a few drops of phenolphthalein solution as an indicator, and shake well until the sample is completely dissolved on the water bath . Further, the well-mixed solution is titrated with a 0.1 mol / L potassium hydroxide ethanol solution, and the end point is when the indicator is light red for 30 seconds. Furthermore, an acid value is calculated according to the following formula. The 0.1 mol / L potassium hydroxide ethanol solution was prepared by dissolving 7 g of potassium hydroxide in 5 mL of water, adding ethanol (95) to 1 L, blocking carbon dioxide and leaving it for 2 to 3 days. Or filtered and a separate factor is obtained.

Acid value = (amount of 0.1 mol / L potassium ethanol solution used for titration (mL)) x (factor of 0.1 mol / L potassium ethanol solution) x 5.611 / (mass of sample (g))
The “factor” is a coefficient for correcting a deviation from an accurate density, which is obtained by standardization, as normally understood by those skilled in the art.

The pullulan that can be used as a raw material for producing the pullulan fatty acid ester according to the present invention has the following general formula I:

It is a compound represented by these. This compound is typically produced by culturing Aureobasidium pullulans, which is a kind of black yeast, using starch or the like as a raw material, and maltotriose regularly obtained by secretion into the culture solution. It is an α-1,6-linked water-soluble natural polysaccharide. The pullulan used in the present invention preferably has a weight average molecular weight (Mw) of usually 50,000 or more, preferably 50,000 to 300,000. That is, n in the general formula I is 100 or more, preferably 102 to 618. The pullulan that can be used as a raw material in the present invention may be a pullulan produced by any method, and any commercially available pullulan can be obtained and used. Examples of commercially available pullulan that can be suitably used include the product name “Food Additive Pullulan P-10” (weight average molecular weight of about 100,000) manufactured by Hayashibara Biochemical Research Co., Ltd. sold by Hayashibara Shoji Co., Ltd. “Food additive pullulan” (weight average molecular weight about 200,000) and the like.

The pullulan fatty acid ester according to the present invention is a reaction (myristoylation and / or palmitoylation) of the pullulan as described above according to the present invention with myristic acid and / or palmitic acid, or a halide thereof, which is a fatty acid. ). For example, 100 parts of pullulan, 800 parts of dimethylformamide (DMF) and pyridine (appropriate amount) are mixed and dissolved, and while maintaining the temperature of this solution at 90 ° C., there are myristic acid and / or palmitic acid as fatty acids. Alternatively, the pullulan fatty acid ester according to the present invention is obtained by gradually dropping (for example, over 1 hour) a mixed solution of the halide (halide) and 1000 parts of toluene, stirring, and then performing reprecipitation and washing with methanol or the like. Can be prepared. The precipitate after washing may be dried and pulverized.

Here, the halides of myristic acid and / or palmitic acid (including fluoride, chloride, bromide and iodide) are not particularly limited, but preferred examples include myristoyl chloride and palmitoyl chloride. Those skilled in the art can easily prepare myristic acid and a halide of palmitic acid by ordinary methods, but they can also be obtained as commercial products.

The degree of substitution of the hydroxyl group in the pullulan fatty acid ester according to the present invention can be controlled by adjusting the amount ratio of pullulan to the myristic acid and / or palmitic acid to be reacted or the halide thereof. Specifically, for example, experimentally, the degree of substitution is calculated for a pullulan fatty acid ester obtained in a reaction system in which the quantitative ratio thereof is changed little by little, whereby the degree of substitution falls within the range of 1.6 to 2.4. The mixing ratio of pullulan and myristic acid and / or palmitic acid or its halide can be determined. In one embodiment, myristoyl chloride may be mixed with pullulan in a weight ratio of 2.48 to 3.73 times. In another embodiment, palmitoyl chloride may be mixed with pullulan in a weight ratio of 2.77 to 4.15 times.

The pullulan fatty acid ester according to the present invention thus obtained exhibits easy solubility (good solubility) in the oil agent. In the present invention, an oil agent means one or more oily components or an oily composition containing the same. In the present invention, the solubility of the pullulan fatty acid ester can be confirmed by adding 95 parts of an oil agent to 5 parts of the pullulan fatty acid ester and observing the solution after stirring, as described in Examples below. The high solubility (very good solubility) of the pullulan fatty acid ester according to the present invention can be confirmed by the fact that the mixture exhibits a transparent appearance when mixed with an oil agent. When the mixture with the oil agent becomes slightly cloudy, it can be said that the solubility is slightly reduced but still shows a good solubility, and when it is apparently cloudy or hardly dissolved (slightly soluble) ) May not be soluble.

The pullulan fatty acid ester according to the present invention preferably exhibits solubility in an oil agent in a range of 15 ° C. to 90 ° C., and exhibits excellent solubility in an oil agent in a range of 50 ° C. to 90 ° C. Further, it has an advantageous property in that it is easily dissolved in an oil even at room temperature (in the present invention, “room temperature” is defined as 15 ° C. to 30 ° C.).

Although the oil agent in which the pullulan fatty acid ester according to the present invention is easily soluble is not particularly limited, for example, oily components such as animal and vegetable oils, hydrocarbon oils, higher fatty acids, ester oils, higher alcohols, silicones, or two of them. A mixture of seeds or more can be mentioned. The pullulan fatty acid ester according to the present invention is particularly excellent in solubility in hydrocarbon oils and ester oils. Specific examples of the oil component in which the pullulan fatty acid ester of the present invention is easily soluble include hydrocarbon oils such as liquid paraffin (for example, light liquid paraffin), isododecane and squalane, and glyceryl tri-2-ethylhexanoate. , Neopentyl glycol dicaprate, dipentyl glycol di-2-ethylhexanoate, diisostearyl malate, and dipentaglycol neopentyl glycol myristate, myristyl myristate, glyceryl trimyristate, diisostearyl malate, etc. Examples include ester oils. These oily ingredients are widely used in cosmetics. In addition, glyceryl tri-2-ethylhexanoate is called trioctanoin in the display name established by the Japan Cosmetic Industry Association, and the INCI name (International Nomenclature Cosmetic Ingredient names; this name is obtained from the US Cosmetic, Assigned) is called TRIETHYLHEXANOIN. In addition, di-2-ethylhexanoic acid neopentyl glycol is called neopentyl glycol diethylhexanoate by the name specified by the Japan Cosmetic Industry Association, and NEOPENTYL GLYCOL DIETHYLHEXANOATE by the INCI name.

Examples of the oil component in which the pullulan fatty acid ester according to the present invention is easily soluble include hydrocarbon oils such as isododecane, and ester oils such as glyceryl tri-2-ethylhexanoate and neopentyl glycol di-2-ethylhexanoate. A suitable example is given.

Therefore, the present invention also provides a cosmetic comprising an oil agent in which the pullulan fatty acid ester according to the present invention is dissolved. Such a cosmetic is obtained by blending an oil in which the pullulan fatty acid ester according to the present invention is dissolved into the cosmetic by mixing with other blending components. Here, the oil agent for dissolving the pullulan fatty acid ester is not particularly limited as long as it is generally used in cosmetics, and the above-described oil agent in which the pullulan fatty acid ester according to the present invention is easily soluble is preferably used. be able to. Such an oil agent may contain one or more oily components such as animal and vegetable oils, hydrocarbon oils, higher fatty acids, ester oils, higher alcohols, and silicones. In the present invention, the oil agent is preferably liquid oil. The oil according to the present invention preferably contains a hydrocarbon oil or an ester oil, and isododecane, glyceryl tri-2-ethylhexanoate, neopentyl glycol dicaprate, neopentyl glycol di-2-ethylhexanoate, and More preferably, it contains at least one selected from the group consisting of diisostearyl malate.

The blending amount of the pullulan fatty acid ester according to the present invention in the oil is not limited, but the pullulan fatty acid ester is usually 0.01% to 40%, preferably with respect to the total amount of the pullulan fatty acid ester and the oil. An amount of 0.1 to 20%, more preferably 1 to 15% is preferable.

The cosmetics containing the pullulan fatty acid ester according to the present invention may include optional ingredients such as additives generally used in cosmetics in addition to the oily components as described above constituting the oil. Can be added. For example, it is also a preferred embodiment to add pigments, surfactants, antioxidants, ultraviolet absorbers, film-forming agents, moisturizers, antiseptics, algal inhibitors, lame agents, fragrances, cosmetic ingredients, pigments and the like. . Moreover, you may mix | blend aqueous components, such as purified water.

The cosmetic containing the pullulan fatty acid ester according to the present invention can be prepared into various product forms according to the purpose. For example, it is prepared in the form of solid, paste, liquid, etc., specifically lipstick, lip balm, lip gloss, foundation, blusher, eye color, eyeliner, mascara, oil cleansing, nail treatment, hair styling etc. Used in hair cosmetics and sunscreens. The cosmetic according to the present invention may be manufactured according to a general cosmetic manufacturing method, and is not particularly limited.

The cosmetic containing the pullulan fatty acid ester according to the present invention is preferably an oily cosmetic. Moreover, the cosmetic containing the pullulan fatty acid ester according to the present invention is preferably a water-resistant cosmetic that exhibits good water resistance. A cosmetic containing the pullulan fatty acid ester according to the present invention has good usability (for example, smoothness), durability and uniformity.

Furthermore, the present invention also provides a method for producing a cosmetic, characterized in that the pullulan fatty acid ester according to the present invention is mixed and dissolved in an oil used in cosmetics as described above and blended in the cosmetic. In this method, suitable oil agents for use in cosmetics are as described above, and it is particularly preferable to include hydrocarbon oil and / or ester oil.

In this cosmetic production method, the mixing of these components for dissolving the pullulan fatty acid ester in the oil can be performed preferably in a wide range of 15 ° C. to 90 ° C., and can also be performed at room temperature. For example, the pullulan fatty acid ester and the oil agent may be mixed by heating (for example, at 60 ° C. or higher, preferably 70 to 90 ° C.). For example, a high-quality cosmetic composition can be obtained while simplifying the production process. In preparation, it is preferable to carry out at room temperature (15 ° C. to 30 ° C.).

In this method, when a pullulan fatty acid ester having a myristoyl group as a substituent (myristoylated pullulan) is mixed with an oil at room temperature, the hydrocarbon oil and / or ester oil contained in the oil is not limited. And at least one selected from the group consisting of isododecane, glyceryl tri-2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, diisostearyl malate, and neopentyl glycol dicaprate preferable.

In this method, when a pullulan fatty acid ester having a palmitoyl group as a substituent (palmitoylated pullulan) is mixed with the oil at room temperature, the hydrocarbon oil and / or ester oil contained in the oil is not limited. Although not particularly preferred, it is particularly preferably at least one selected from the group consisting of isododecane and neopentyl glycol di-2-ethylhexanoate.

The oil agent in which the pullulan fatty acid ester according to the present invention is dissolved by the above-described method may be blended into the cosmetic by adding other blending ingredients of the cosmetic and mixing (for example, mixing and stirring). The oil agent in which the pullulan fatty acid ester is dissolved can be mixed with other ingredients of the cosmetic at any temperature, for example, 15 ° C. to 90 ° C. Although not limited, after adding other compounding components to the oil agent in which the pullulan fatty acid ester is dissolved, the mixture may be heated to 50 ° C. to 90 ° C. and mixed.

The cosmetics obtained by this production method are as described above.

Hereinafter, the present invention will be described with reference to examples, but the technical scope of the present invention is not limited to the examples.

[Production Example 1] Production of pullulan fatty acid ester (myristoylated pullulan) (1)
Substituent: Myristoyl group substitution degree: 1.0
In a four-necked flask with a volume of 1 L, 100 parts of pullulan (Hayashibara Shoji Co., Ltd., trade name: food additive pullulan) (here “part” means parts by weight; the same applies hereinafter) and 800 parts of dimethylformamide (DMF) 51 parts of pyridine was charged and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 155 parts of myristoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the myristoylated pullulan thus obtained (here, means the number of hydroxyl groups substituted with an acyl group per glucose ring constituting the pullulan; the same shall apply hereinafter) according to the test method of JISＪK 0070. The hydroxyl value was measured, and calculated from the hydroxyl value based on the above formula, it was 1.0.

[Production Example 2] Production of pullulan fatty acid ester (myristoylated pullulan) (2)
Substituent: Myristoyl group Degree of substitution: 1.5
100 parts of pullulan, 800 parts of DMF, and 77 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 233 parts of myristoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the thus obtained myristoylated pullulan was 1.5 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 3] Production of pullulan fatty acid ester (myristoylated pullulan) (3)
Substituent: Myristoyl group Degree of substitution: 1.6
100 parts of pullulan, 800 parts of DMF and 82 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 248 parts of myristoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the myristoylated pullulan thus obtained was 1.6 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 4] Production of pullulan fatty acid ester (myristoylated pullulan) (4)
Substituent: Myristoyl group Degree of substitution: 2.0
100 parts of pullulan, 800 parts of DMF and 102 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 311 parts of myristoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the thus obtained myristoylated pullulan was 2.0 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 5] Production of pullulan fatty acid ester (myristoylated pullulan) (5)
Substituent: Myristoyl group Degree of substitution: 2.4
100 parts of pullulan, 800 parts of DMF and 123 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 373 parts of myristoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the myristoylated pullulan thus obtained was 2.4 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 6] Production of pullulan fatty acid ester (myristoylated pullulan) (6)
Substituent: Myristoyl group Degree of substitution: 2.5
100 parts of pullulan, 800 parts of DMF, and 128 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 388 parts of myristoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the myristoylated pullulan thus obtained was 2.5 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 7] Production of pullulan fatty acid ester (myristoylated pullulan) (7)
Substituent: Myristoyl group Degree of substitution: 2.8
100 parts of pullulan, 800 parts of DMF, and 143 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 435 parts of myristoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the myristoylated pullulan thus obtained was 2.8 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 8] Production of pullulan fatty acid ester (palmitoylated pullulan) (1)
Substituent: Palmitoyl group Degree of substitution: 1.0
100 parts of pullulan, 800 parts of DMF and 51 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 173 parts of palmitoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the palmitoylated pullulan thus obtained was 1.0 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 9] Production of pullulan fatty acid ester (palmitoylated pullulan) (2)
Substituent: Palmitoyl group Degree of substitution: 1.5
100 parts of pullulan, 800 parts of DMF, and 77 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 259 parts of palmitoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the palmitoylated pullulan thus obtained was 1.5 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 10] Production of pullulan fatty acid ester (palmitoylated pullulan) (3)
Substituent: Palmitoyl group Degree of substitution: 1.6
100 parts of pullulan, 800 parts of DMF and 82 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed liquid of 277 parts of palmitoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, and stirring was further performed for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the palmitoylated pullulan thus obtained was 1.6 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 11] Production of pullulan fatty acid ester (palmitoylated pullulan) (4)
Substituent: Palmitoyl group Substitution degree: 2.0
100 parts of pullulan, 800 parts of DMF and 102 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 346 parts of palmitoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the thus obtained palmitoylated pullulan was 2.0 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 12] Production of pullulan fatty acid ester (palmitoylated pullulan) (5)
Substituent: Palmitoyl group Substitution degree: 2.4
100 parts of pullulan, 800 parts of DMF and 123 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 415 parts of palmitoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the palmitoylated pullulan thus obtained was 2.4 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 13] Production of pullulan fatty acid ester (palmitoylated pullulan) (6)
Substituent: Palmitoyl group Degree of substitution: 2.5
100 parts of pullulan, 800 parts of DMF, and 128 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 432 parts of palmitoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the palmitoylated pullulan thus obtained was 2.5 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 14] Production of pullulan fatty acid ester (palmitoylated pullulan) (7)
Substituent: Palmitoyl group Substitution degree: 2.8
100 parts of pullulan, 800 parts of DMF, and 143 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 484 parts of palmitoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the palmitoylated pullulan thus obtained was 2.8 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 15] Production of pullulan fatty acid ester (stearoylated pullulan) Substituent: Stearoyl group substitution degree: 2.0
100 parts of pullulan, 800 parts of DMF and 102 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 381 parts of stearoyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the stearoylated pullulan thus obtained was 2.0 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Production Example 16] Production of pullulan fatty acid ester (lauroylated pullulan) Substituent: Lauroyl group substitution degree: 2.0
100 parts of pullulan, 800 parts of DMF and 102 parts of pyridine were charged into a 1 L four-necked flask and dissolved. While maintaining the temperature of this solution at 90 ° C., a mixed solution of 275 parts of lauroyl chloride and 1000 parts of toluene was added dropwise over 1 hour, followed by further stirring for 5 hours. Thereafter, reprecipitation and washing were performed by adding methanol. The washed precipitate was dried and pulverized with a mill mixer to obtain the desired product.

The degree of substitution in the lauroylated pullulan thus obtained was 2.0 when the hydroxyl value was measured according to the test method of JIS K-0070 and calculated from the hydroxyl value based on the above formula.

[Example 1]
Various oils (95 parts) were added to 5 parts of the pullulan fatty acid ester obtained in Production Examples 1 to 16, and the state of the solution after stirring at room temperature (25 ° C. in this case) was observed.

Table 1 shows the results observed using the pullulan fatty acid esters obtained in Production Examples 1 to 7, and Table 2 shows the results obtained using the pullulan fatty acid esters obtained in Production Examples 8 to 14, respectively.

As shown in Table 1, the pullulan fatty acid ester (substitution degree 1.6 to 2.4) obtained in Production Examples 3 to 5 having a myristoyl group as a substituent is extremely good even at room temperature against various oils. It showed solubility or good solubility. On the other hand, the myristoylated pullulan (substitution degree 1.5 or less or 2.5 or more) obtained in Production Examples 1, 2, 6, and 7 tended to have a high solubility in oils at room temperature.

Further, as shown in Table 2, the pullulan fatty acid ester (substitution degree 1.6 to 2.4) obtained in Production Examples 10 to 12 having a palmitoyl group as a substituent is isododecane and di-2-ethylhexanoic acid neo It showed very good solubility in pentyl glycol even at room temperature, and also showed good solubility in other oil agents listed in Table 2. On the other hand, compared with them, the palmitoylated pullulan (substitution degree 1.5 or less or 2.5 or more) obtained in Production Examples 8, 9, 13, and 14 tends to greatly reduce the solubility in oil at room temperature. It was in.

Table 3 compares the observation results of this example for myristoylated pullulan and palmitoylated pullulan obtained in Production Examples 4 and 11 with those of stearoylated pullulan and lauroylated pullulan obtained in Production Examples 15 and 16. Showed. All of these pullulan fatty acid esters have a degree of substitution of 2.0, but have different substituents.

As shown in Table 3, the myristoylated pullulan obtained in Production Example 4 and the palmitoylated pullulan obtained in Production Example 11 exhibited good solubility in oils even at room temperature. Compared with their solubility, the stearoylated pullulan obtained in Production Example 15 and the lauroylated pullulan obtained in Production Example 16 tended to greatly reduce the solubility in oils at room temperature.

[Example 2]
95 parts of various oil agents were added to 5 parts of the pullulan fatty acid ester obtained in Production Examples 1 to 16, and the state of the solution after heating and stirring at 80 ° C. was observed.

Table 4 shows the results observed using the pullulan fatty acid esters obtained in Production Examples 1 to 7, and Table 5 shows the results observed using the pullulan fatty acid esters obtained in Production Examples 8 to 14, respectively.

As shown in Table 4, when heated, the pullulan fatty acid ester (substitution degree 1.6 to 2.4) obtained in Production Examples 3 to 5 having a myristoyl group as a substituent was used for all the oils used. And showed very good solubility. On the other hand, the myristoylated pullulan (substitution degree of 1.5 or less or 2.5 or more) obtained in Production Examples 1, 2, 6, and 7 is higher than that of Production Examples 3 to 5 even when heated. Also clearly showed low solubility.

Further, as shown in Table 5, when heated, the pullulan fatty acid esters (substitution degree 1.6 to 2.4) obtained in Production Examples 10 to 12 having palmitoyl groups as substituents were used in all the oils used. On the other hand, it showed very good solubility. On the other hand, the palmitoylated pullulan (substitution degree 1.5 or less or 2.5 or more) obtained in Production Examples 8, 9, 13, and 14 is higher than that of Production Examples 10 to 12 with respect to the oil even when heated Also clearly showed low solubility.

Table 6 compares the observation results of this example for myristoylated pullulan and palmitoylated pullulan obtained in Production Examples 4 and 11 with those of stearoylated pullulan and lauroylated pullulan obtained in Production Examples 15 and 16. Showed. All of these pullulan fatty acid esters have a degree of substitution of 2.0, but have different substituents.

As shown in Table 6, the myristoylated pullulan obtained in Production Example 4 and the palmitoylated pullulan obtained in Production Example 11 exhibited extremely good solubility in all the oils used when heated. On the other hand, the stearoylated pullulan obtained in Production Example 15 and the lauroylated pullulan obtained in Production Example 16 showed only significantly lower solubility in oils than in Production Examples 4 and 11, even when heated. .

[Example 3]
Using the pullulan fatty acid ester (myristoylated pullulan, substitution degree 2.0) obtained in Production Example 4, a test sample of a sunscreen composition was prepared according to the formulation shown in Table 7. First, components (2) and (16) were mixed and stirred at 25 ° C., and components (1), (3) to (11) and (14) were sequentially added thereto, and then mixed and stirred at 80 ° C. Furthermore, what mixed separately stirring components (12), (13), (15) was added, and the test sample 1 was prepared by mixing and stirring at 80 degreeC.

For comparison, in place of the pullulan fatty acid ester obtained in Production Example 4 [component (16)], the pullulan fatty acid ester obtained in Production Example 2 (myristoylated pullulan, substitution degree 1.5) [component (17) ] And the pullulan fatty acid ester (myristoylated pullulan, substitution degree 2.8) [component (18)] obtained in Production Example 7 were used to prepare Comparative Samples 1 and 2 with the same formulation and procedure, respectively.

Furthermore, a sample containing no pullulan fatty acid ester was prepared as a negative control.

The pullulan fatty acid ester obtained in Production Example 4 was extremely excellent in solubility in glyceryl tri-2-ethylhexanoate [component (2)], which is an ester oil.

A water resistance test was performed using the sunscreen composition sample prepared as described above. First, a sunscreen composition sample was applied to a slide glass, and after drying, the weight was measured. After running water for a certain period of time, it was dried and weighed again. The water resistance of the sunscreen composition was evaluated by the ratio of the dry weight after running water treatment to the dry weight before running water treatment (sample remaining ratio after running water treatment). The results are shown in Table 8.

As is apparent from Table 8, nearly 90% of the sunscreen composition (test sample 1) to which the pullulan fatty acid ester obtained in Production Example 4 was added remained after running water treatment, and its water resistance was a comparative sample. It was significantly better than the sunscreen compositions of 1 and 2 and the control sample.

Furthermore, a sensory test on the feeling of use, its sustainability, and uniformity was performed on these sunscreen composition samples. As a result, the test sample 1 showed better results than the comparative samples 1 and 2 and the negative control sample for any of them.

[Example 4]
Using the pullulan fatty acid ester (palmitoylated pullulan, substitution degree 2.0) obtained in Production Example 11, a test sample of a mascara composition was prepared according to the formulation shown in Table 9. First, components (1) and (4) were mixed and stirred at 60 ° C., components (5) to (10) were sequentially added thereto, and mixed and stirred at 60 ° C. to prepare test sample 2.

For comparison, in place of the pullulan fatty acid ester obtained in Production Example 11 [component (1)], the pullulan fatty acid ester obtained in Production Example 9 (palmitoylated pullulan, substitution degree 1.5) [component (2) ] And Palmitoylated Dextrin [Component (3)], respectively, were used to prepare Comparative Samples 3 and 4 with similar formulations and procedures.

The pullulan fatty acid ester obtained in Production Example 11 was extremely excellent in solubility in light liquid paraffin, which is a hydrocarbon oil. On the other hand, the palmitoylated dextrin used for the comparative sample was excellent in solubility when mixed with light liquid paraffin, but the pullulan fatty acid ester obtained in Production Example 9 (palmitoylated pullulan) was mixed with light liquid paraffin. Slight turbidity was observed when

The water resistance test was carried out using the mascara composition sample prepared as described above. First, a mascara sample was applied to the hair bundle, and after drying, the weight was measured. This was stirred in demineralized water for a certain period of time, then dried and weighed again. The water resistance of the composition for mascara was evaluated by the ratio of the dry weight after the running water treatment to the dry weight before the running water treatment (the remaining ratio of the sample after the running water treatment). The results are shown in Table 10.

As is clear from Table 10, over 80% of the composition for mascara (test sample 2) to which the pullulan fatty acid ester obtained in Production Example 11 was added remained after running water treatment, and its water resistance was a comparative sample. It was superior to 3 and 4.

Furthermore, a sensory test on the feeling of use, its sustainability, and uniformity was performed on these mascara composition samples. As a result, the test sample 2 showed better results than the comparative samples 3 and 4 for any of them.

[Example 5]
Using the pullulan fatty acid ester (myristoylated pullulan, substitution degree 2.4) obtained in Production Example 5, a test sample of a composition for lipstick was prepared according to the formulation shown in Table 11. First, components (1) to (7), (10), (15) and (16) were mixed and stirred while heating at 60 ° C. to prepare Phase A. Separately, component (11) is kneaded into components (8), (9), and (17) mixed and stirred, and then components (12) to (14) are kneaded and heated at 60 ° C. B phase was prepared. Phase A was added to phase B, mixed and stirred while heating at 60 ° C., poured into a mold, cooled, and solidified to prepare test sample 3.

For comparison, in place of the pullulan fatty acid ester [component (17)] obtained in Production Example 5, the pullulan fatty acid ester obtained in Production Example 2 (myristoylated pullulan, substitution degree 1.5) [component (18) ] And the pullulan fatty acid ester (myristoylated pullulan, substitution degree 2.8) [component (19)] obtained in Production Example 7 were used to prepare comparative samples 5 and 6 with the same formulation and procedure, respectively.

In addition, the pullulan fatty acid ester obtained in Production Example 5 was very excellent in solubility in diisostearyl malate and neopentyl glycol dicaprate, which are ester oils. On the other hand, the pullulan fatty acid ester obtained in Production Example 2 used in the comparative sample and the pullulan fatty acid ester obtained in Production Example 7 are slightly turbid when mixed with diisostearyl malate and neopentyl glycol dicaprate. Admitted.

Using the lipstick composition sample prepared as described above, a sensory test was conducted by 50 female monitors. The evaluation was carried out in five grades for the following items.

Smooth ... 5 points Somewhat smooth ... 4 points Normal ... 3 points Somewhat not smooth ... 2 points Not smooth ... 1 point The average score is shown in Table 12.

As is clear from Table 12, the lipstick composition (test sample 3) to which the pullulan fatty acid ester obtained in Production Example 5 was added has a smoother feel than the lipstick compositions of Comparative Samples 5 and 6. It was a thing.

[Example 6]
Using the pullulan fatty acid ester (palmitoylated pullulan, substitution degree 1.6) obtained in Production Example 10, a test sample of the composition for foundation was prepared according to the formulation shown in Table 13. First, components (3), (4) and (17) are mixed and stirred at 25 ° C., and then components (1), (2) and (5) to (9) are sequentially added thereto, and then mixed and stirred at 60 ° C. did. To this, components (10) to (16) separately mixed and stirred at 60 ° C. were added, and mixed and stirred at 60 ° C. to prepare test sample 4. As the oil, component (3) neopentyl glycol di-2-ethylhexanoate and component (4) isododecane were used.

As a result of conducting a sensory test on the feeling of use, its sustainability, and uniformity, the test sample 4 thus obtained was all good.

[Example 7]
Using the pullulan fatty acid ester (palmitoylated pullulan, substitution degree 2.4) obtained in Production Example 12, a test sample of the eye cream composition was prepared according to the formulation shown in Table 14. First, components (5) and (12) were mixed and stirred at 25 ° C., and components (1) to (4) and (6) to (8) were sequentially added thereto, and then mixed and stirred at 80 ° C. Further, components (9) to (11) and (13), which were separately mixed and stirred at 80 ° C., were added, and mixed and stirred at 80 ° C. to prepare test sample 5. The component (5) neopentyl glycol di-2-ethylhexanoate was used as the oil.

As a result of conducting a sensory test on the feeling of use, its sustainability, and uniformity, the test sample 5 thus obtained was all good.

The pullulan fatty acid ester according to the present invention exhibits high solubility in oily components, and particularly shows good solubility even under non-heating conditions such as room temperature, so that it does not impair the feeling of use of cosmetics, etc. It can be advantageously used for blending a pullulan component in a cosmetic under a harsh environment. The pullulan fatty acid ester according to the present invention can also be advantageously used to impart water resistance to cosmetics.

All publications, patents and patent applications cited herein are hereby incorporated by reference in their entirety.

Claims

A pullulan fatty acid ester which is soluble in an oil agent at room temperature, wherein the substituent introduced into the hydroxyl group of pullulan is a myristoyl group and / or palmitoyl group, and the degree of substitution of the hydroxyl group by the substituent is 1.6 to 2.4.
A cosmetic comprising an oil agent in which the pullulan fatty acid ester according to claim 1 is dissolved.
The cosmetic according to claim 2, wherein the oil agent comprises hydrocarbon oil and / or ester oil.
The hydrocarbon oil and / or ester oil is selected from the group consisting of isododecane, glyceryl tri-2-ethylhexanoate, neopentyl glycol dicaprate, neopentyl glycol di-2-ethylhexanoate, and diisostearyl malate The cosmetic according to claim 2 or 3, wherein the cosmetic is at least one.
The cosmetic according to any one of claims 2 to 4, which is a water-resistant cosmetic.
A method for producing a cosmetic, characterized in that the pullulan fatty acid ester according to claim 1 or 2 is mixed with an oil and dissolved, and then blended into the cosmetic.
The method of Claim 6 that an oil agent contains hydrocarbon oil and / or ester oil.
The method according to claim 6 or 7, wherein the pullulan fatty acid ester is mixed with the oil at room temperature.
The pullulan fatty acid ester has a myristoyl group as the substituent, and the hydrocarbon oil and / or ester oil contained in the oil agent is isododecane, tri-2-ethylhexanoic acid glyceryl, di-2-ethylhexanoic acid neo The method according to claim 8, which is at least one selected from the group consisting of pentyl glycol, diisostearyl malate, and neopentyl glycol dicaprate.
The pullulan fatty acid ester has a palmitoyl group as the substituent, and the hydrocarbon oil and / or ester oil contained in the oil is selected from the group consisting of isododecane and di-2-ethylhexanoic acid neopentyl glycol. 9. The method of claim 8, wherein there is at least one.
The method according to any one of claims 6 to 10, wherein the cosmetic is a water-resistant cosmetic.