JP2009096750A - Oil agent for cosmetic, and cosmetic formulated with the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil agent for a cosmetic which has good extension and close adhering feeling during applying, is free from the stickiness after the application and also is excellent in the transpiration inhibitory effect of moisture through the skin, and a cosmetic comprising the same. <P>SOLUTION: Provided is an oil agent for a cosmetic comprising a polyalkylene glycol expressed by the following formula (1): R<SP>1</SP>O-(CH<SB>2</SB>CH<SB>2</SB>CH<SB>2</SB>CH<SB>2</SB>O)n-R<SP>2</SP>[wherein, R<SP>1</SP>, R<SP>2</SP>are each the same or different H, or a 12-20C fatty acid residue, and the ratio occupied by the 12-20C fatty acid residues in the R<SP>1</SP>, R<SP>2</SP>is 0.55 to 0.95; n is a mean number of addition of an oxytetramethylene group; and 3≤n≤30], and a cosmetic prepared by blending the same. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a cosmetic oil and a cosmetic containing the same.

In cosmetics, oil agents are widely used to impart smoothness and moist feeling to the skin and hair. In addition, the oil agent forms an oil film that is in close contact with the skin, thereby suppressing transdermal moisture transpiration, and is effective in improving dry skin that causes skin roughness and fine lines. The film formed by the oil is also useful as a base film for makeup cosmetics. To prevent the base film from moving without being able to follow the movement of the skin, It is important to form a base film having high adhesion to the skin.
Oils that have high adhesion to the skin and suppress transdermal moisture transpiration are highly occlusive, such as petrolatum, beeswax, and shea fat, and are excellent in properties from paste to solid oils. When used, it has the disadvantage of giving an unpleasant feel such as oiliness and stickiness. In addition, the animal and plant-derived oils have poor storage stability, and the odor and hue may deteriorate over time.

In order to solve these problems, an amphiphilic oil agent having appropriate hydrophilicity has been proposed. It is known that polyalkylene glycol derivatives modified with ethylene oxide or propylene oxide have moderate hydrophilicity and thus can suppress oiliness and stickiness. For example, cosmetics characterized by containing oligomeric esters of divalent carboxylic acids and polyalkylene glycols (for example, Patent Document 1), ester oils obtained by reacting alkylene oxide and fatty acids with polyglycerin (for example, Patent Document 2) has been proposed.
However, Patent Documents 1 and 2 are superior in terms of non-stickiness, good skin familiarity, and moisturizing properties, but they do not provide a feeling of close contact with the skin and are insufficient in the effect of suppressing transdermal moisture transpiration. It was.

On the other hand, besides ethylene oxide and propylene oxide derivatives, tetrahydrofuran and alkylene oxide copolymers and derivatives thereof (Patent Document 3), monotetramethylene glycol or polytetramethylene glycol and alkylene oxide block copolymers derivatives (Patent Documents 4 and 5) Certain surfactants have been proposed.
In Patent Document 3, a random polymer of tetrahydrofuran and alkylene oxide is disclosed as a specific example. However, although the exemplified compounds are excellent in dispersibility of the inorganic powder and compatibility with the oil, the feeling of use and the percutaneous properties are disclosed. It was insufficient in terms of the suppression effect of moisture transpiration. In Patent Documents 4 and 5, although it is excellent in rinsing with water and maintaining the moisturizing property after washing, it is insufficient in terms of adhesion to the skin and the effect of suppressing transdermal moisture transpiration.

In this way, it has the excellent skin adhesion and transdermal moisture transpiration control effect of the highly occlusive oil agent, the ease of application of the alkylene oxide derivative when applied, and the non-stickiness after application. A compatible cosmetic oil and a cosmetic comprising the same have not been developed.
JP 2007-45776 A JP 2005-97139 A JP 2003-400345 A JP 2007-91697 A JP 2007-91698 A

  An object of the present invention is an oil for cosmetics comprising a polyalkylene glycol derivative having good spreading and feeling of adhesion to the skin at the time of application, no stickiness after application, and excellent transpiration moisture transpiration control effect. It is to provide cosmetics containing.

That is, the present invention is as follows.
(1) A cosmetic base comprising a polyalkylene glycol derivative represented by the following formula (1).
^{_{R 1 O- (CH 2 CH 2}} CH 2 CH 2 O) n-R 2 ··· (1)
(In the formula, R ¹ and R ² are the same or different hydrogen atoms and fatty acid residues having 12 to 20 carbon atoms, and the proportion of the fatty acid residues having 12 to 20 carbon atoms in R ¹ and R ² is 0.5 to 0.95, where n is the average number of moles added of the oxytetramethylene group, and 3 ≦ n ≦ 30.
(2) A cosmetic comprising the cosmetic oil described above.

  The cosmetic oil of the present invention is a polyalkylene glycol derivative that has good spreading and feeling of adhesion to the skin at the time of application, has no stickiness after application, and is excellent in the effect of suppressing transdermal moisture transpiration, and contains it Cosmetics are also very useful.

Hereinafter, the present invention will be described in detail.
In the polyalkylene glycol derivative represented by the formula (1), R ¹ and R ² are the same or different and which may hydrogen atom, a fatty acid residue having 12 to 20 carbon atoms. The ratio of the fatty acid residue having 12 to 20 carbon atoms in R ¹ and R ² is 0.55 to 0.95, preferably 0.65 to 0.85, and more preferably 0.70 to 0.00. 80. If it is less than 0.55, a sticky feeling after application is produced, and the feeling of adhesion to the skin and the effect of suppressing transdermal moisture transpiration are insufficient, and if it exceeds 0.95, the spread during application deteriorates.
The fatty acid residue having 12 to 20 carbon atoms that is R ¹ and R ² is preferably a fatty acid residue having 14 to 18 carbon atoms, and more preferably a fatty acid residue having 16 carbon atoms. When the number of carbon atoms is less than 12, the effect of suppressing adhesion to the skin and transdermal moisture transpiration is insufficient, and when the number of carbon atoms exceeds 20, the spread at the time of application becomes poor.

The fatty acid residue may be a saturated fatty acid, an unsaturated fatty acid, a branched fatty acid, or a hydroxyl group-substituted fatty acid residue, but a saturated fatty acid residue is more preferable in terms of obtaining a feeling of adhesion to the skin.
The types of fatty acids are lauric acid, tridecanoic acid, isotridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, isostearic acid, nonadecanoic acid, arachidic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, palmito Examples include oleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, arachidonic acid, and hydroxystearic acid, and one or more of these may be used. Preferred are myristic acid, palmitic acid and stearic acid, and particularly preferred is palmitic acid.

The oxytetramethylene group is an essential component for obtaining spread and adhesion to the skin at the time of application, and n is an average added mole number of the oxytetramethylene group, 3 ≦ n ≦ 30, preferably 4 ≦ n ≦ 20, more preferably 6 ≦ n ≦ 12. When n is less than 3, the spread at the time of application is poor, the feeling of adhesion to the skin is not obtained, and polytetramethylene glycol with n exceeding 30 is difficult to obtain industrially.
In addition, the content of monotetramethylene glycol as a monomer and ditetramethylene glycol as a dimer is less than 30% by weight with respect to a polyoxytetramethylene unit polymerized with an oxytetramethylene group. Is preferred, more preferably less than 3% by weight, still more preferably less than 1% by weight. When the total content of monotetramethylene glycol and ditetramethylene glycol contained in the polyoxytetramethylene unit is 30% by weight or more, there is a tendency that the spreading during application tends to be poor, and it is difficult to obtain a feeling of adhesion to the skin . The content of monotetramethylene glycol and ditetramethylene glycol in the oxytetramethylene unit can be reduced by subjecting to a reduced pressure treatment at 150 ° C. or higher and 30 mmHg or lower for 1 hour or more before the esterification.

The content of monotetramethylene glycol and ditetramethylene glycol contained in the polyoxytetramethylene unit can be quantified by the following method. When the hydrolyzate is extracted with hexane after alkaline hydrolysis of the polyalkylene glycol derivative of the present invention, it can be separated into a hexane phase containing a decomposed fatty acid, a polytetramethylene glycol phase, and an aqueous phase. Next, the polytetramethylene glycol phase and the aqueous phase are collected, dehydrated and filtered to obtain a polytetramethylene glycol phase. The content of monotetramethylene glycol and ditetramethylene glycol is calculated from the peak area obtained by gas chromatography measurement.
The oxytetramethylene unit indicates a raw material oxytetramethylene glycol.

  The polyalkylene glycol derivative represented by the formula (1) of the present invention can be produced by a known method. For example, it can be obtained by an esterification reaction between polytetramethylene glycol and a fatty acid or a transesterification reaction with a fatty acid ester.

  The blending amount of the cosmetic oil of the present invention in the cosmetic is usually 0.01 to 80% by weight, preferably 0.1 to 40% by weight, and particularly preferably 1 to 20% by weight.

Moreover, the oil agent of this invention can further improve the feeling of contact | adherence to skin by using water-soluble polymer together. Water-soluble polymers can be broadly classified into natural polymers and synthetic polymers. Natural polymers are classified into polysaccharides in which monosaccharides are linked by glycosidic bonds and polypeptides in which amino acids are linked by peptide bonds. Synthetic polymers generally refer to polymers obtained by polymerizing monomers such as vinyl compounds, but there are also those obtained by chemically modifying polysaccharides. Specific compounds include, for example, gum arabic, carrageenan, guar gum, roast bean gum, pectin, tragacanth, starch, xanthan gum, dextrin, fructan, pullulan, sodium hyaluronate, sodium alginate as polypeptides, gelatin, collagen, Polysaccharides such as sodium polyglutamate, sodium polyacrylate, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, polyacrylamide, acrylamide / acrylic acid copolymer, polyethylene glycol, polyglycerin, polymethacryloyloxyethyl phosphorylcholine, methacryloyloxyethyl phosphorylcholine / Butyl methacrylate copolymer, ethyl cellulose, carboxymethyl cellulose, hydroxye Le cellulose, hydroxypropyl cellulose, methyl cellulose, nitrocellulose, cationized cellulose, propylene glycol alginate, synthetic polymers such as cationic guar gum.
Among them, sodium hyaluronate, collagen, polymethacryloyloxyethyl phosphorylcholine and methacryloyloxyethyl phosphorylcholine / butyl methacrylate copolymer are preferable, and methacryloyloxyethyl phosphorylcholine / butyl methacrylate copolymer is particularly preferable in consideration of adhesion to the skin. It is a coalescence (weight average molecular weight: 100,000 to 800,000). The amount of the water-soluble polymer incorporated in the cosmetic is not particularly limited, but is usually 0.01 to 5% by weight, preferably 0.05 to 4% by weight, more preferably 0.1 to 3% by weight. % Blended.

In the cosmetic of the present invention, various components generally used in cosmetics, quasi-drugs, and pharmaceuticals can be blended as necessary without departing from the effects of the present invention. For example, hydrocarbons, higher alcohols, higher fatty acids and their triglycerides, ester oils, animal and vegetable oils, silicones, vitamins, UV absorbers, antioxidants, cationic surfactants, anionic surfactants, amphoteric interfaces Examples include activators, nonionic surfactants, sequestering agents, ethanol, thickeners, preservatives, dyes, pigments, and fragrances.
In addition, the form formed by blending the cosmetic oil of the present invention is not particularly limited, and any of water-in-oil or oil-in-water emulsified cosmetics and oily cosmetics may be used. Shampoo, hair conditioner, body soap , Facial cleansers, lotions, emulsions, skin creams, makeup removers, lipsticks, and the like. Particularly preferred are emulsions, skin creams, lipsticks and the like.

The present invention will be specifically described with reference to examples. The hydroxyl value (OHV) and ester value (EV) were measured in accordance with the method described in Japanese Industrial Standard (JIS) (hydroxyl value; JIS K-1557 6.4, ester value; JIS K-0070 3.1. And JIS K-0070 4.1). Further, the ratio of fatty acid residues having a carbon number of 12 to 20 occupying the R ¹ and R ² and esterification ratio was calculated by the following method.
Esterification rate = [EV of esterified product / (EV of esterified product + OHV of esterified product)]
<Synthesis Example of Compound 1> Palmitic acid ester of polytetramethylene glycol (8.6 mol) [esterification rate = 0.75]
Polytetramethylene glycol (n = 8.6, hydroxyl value = 180.3, raw material name: PTG650 manufactured by Hodogaya Chemical Co., Ltd.) 622 g and palmitic acid (NAA-160 manufactured by NOF Corporation) 385 g at 200 ° C. For 10 hours to obtain 958 g of polytetramethylene glycol palmitate. Since the ester value was 85.2 and the hydroxyl value was 28.4, the esterification rate was 0.75.

  According to the synthesis example, compounds 2 to 4 (polyalkylene glycol derivatives of the present invention) and compounds 5 to 9 (comparative substances) shown in Table 1 were synthesized.

<Synthesis Example of Compound 10> 6.5 mol of tetrahydrofuran (THF) of lauryl alcohol / 0.0 mol of propylene oxide (PO) random adduct 186 g of lauryl alcohol, 468 g of tetrahydrofuran (THF) and 7 BF · THF as a catalyst .9 g was charged, and the air in the autoclave was replaced with dry nitrogen. Next, 580 g of propylene oxide (PO) was added dropwise at 35 to 50 ° C. over 10 hours using a dropping device. Thereafter, it was aged at 50 ° C. for 5 hours and cooled. Further, 4.8 g of 48% NaOH aqueous solution was added, and then treated with an adsorption treatment agent (manufactured by Kyowa Chemical Industry Co., Ltd .: Kyoward 600 and Kyoward 1000), filtered, and reduced pressure (−0.095 MPa (gauge pressure)). )), And dehydration under reduced pressure at 130 ° C., to obtain 1,230 g of a random adduct of lauryl alcohol in THF 6.5 mol / PO 10.0 mol.
<Synthesis Example of Compound 11> Isostearic acid ester of trioxytetramethylene (3.2 mol) / polyoxyethylene (20.0 mol) block copolymer tritetramethylene glycol (n = 3.2; PTG250 Hodogaya Chemical Co., Ltd.) 250 g of potassium hydroxide as a catalyst and 2.4 g of catalyst were charged into the autoclave, the air in the autoclave was replaced with dry nitrogen, and the catalyst was completely dissolved at 150 ° C. with stirring. Next, 970 g of ethylene oxide was dropped with a dropping device and stirred for 1 hour. Thereafter, the reaction composition is taken out by an autoclave, neutralized with phosphoric acid to pH 6 to 7, and treated at 100 ° C. for 1 hour under reduced pressure (−0.095 MPa (gauge pressure)) to remove the contained water. did. Further, filtration was performed to remove the salt produced after the treatment, and a trioxytetramethylene (3.2 mol) / polyoxyethylene (20.0 mol) copolymer (1160 g) was obtained.
The obtained trioxytetramethylene (3.2 mol) / polyoxyethylene (20.0 mol) copolymer 500 g and isostearic acid (EMERSOL874 Cognis Japan Co., Ltd.) 250 g were reacted at 200 ° C. for 10 hours, 690 g of isostearic acid ester of trioxytetramethylene (3.2 mol) / polyoxyethylene (20.0 mol) block copolymer was obtained. Since the ester value was 95.0 and the hydroxyl value was 5.0, the esterification rate was 0.95.

<Quantification of monotetramethylene glycol and ditetramethylene glycol contained in polyoxytetramethylene unit>
100 g of a 2N aqueous sodium hydroxide solution was added to 100 g of the polyalkylene glycol derivative of Compound 1, and the mixture was reacted in a four-necked flask equipped with a Dimroth condenser at 80 ° C. for 6 hours to hydrolyze into fatty acid and polytetramethylene glycol. The obtained hydrolyzate was transferred to a separatory funnel, 100 mL of hexane was added thereto, and the mixture was sufficiently shaken at room temperature. When this was allowed to stand for 2 hours, it was separated into a hexane phase, a polytetramethylene glycol phase, and an aqueous phase, so that the polytetramethylene phase and the aqueous phase were recovered in an insulator flask. In order to remove the water from the recovered material, treatment was performed at 110 ° C. under normal pressure for 1 hour under a nitrogen stream, and further under reduced pressure (−0.095 MPa (gauge pressure)) at 110 ° C. for 1 hour, filtered to obtain poly 61 g of tetramethylene glycol was obtained. Since the obtained polytetramethylene glycol had a hydroxyl value of 180.2, it was confirmed that hydrolysis reaction and fatty acid separation were possible.

(Measurement conditions for gas chromatography)
Preparation of standard solution: Monotetramethylene glycol was diluted with methanol to prepare methanol solutions of 0.25 w / v%, 0.5 w / v, 1.0 w / v%, and 2.0 w / v% (calibration curve). For creation). A standard solution for preparing a calibration curve was similarly prepared for ditetramethylene glycol.
Preparation of sample solution: 1 g of a pretreated sample to be measured was diluted in 10 mL of methanol to prepare a 10 w / v% methanol solution.
Column: DB-1 (manufactured by J & W) (length 30 mm × inner diameter 0.25 mm, membrane pressure 0.25 μm)
Carrier gas: Helium gas inlet temperature: 300 ° C
Detector temperature: 300 ° C
Split ratio: “100: 1”
Column temperature: 100 ° C (5 minutes) → Increased temperature at 10 ° C / minute → 300 ° C (10 minutes)
Detector: Flame ionization detector Gas chromatographic analysis is performed under the above conditions, and from the calibration curve prepared in advance, the content of monotetramethylene glycol and ditetramethylene glycol contained in polytetramethylene glycol is determined. It was measured.

<Examples 1-5 and Comparative Examples 1-8>
As shown in Table 3, using the compounds 1 to 4 of the present invention as the component (a), the compounds 5 to 11 and petrolatum as the component (a ′), selecting the components shown in Table 2 as common addition components, A skin cream was prepared by the preparation method.

<Preparation method>
The oil phase and the aqueous phase were separately dissolved at 80 ° C. After confirming complete dissolution, the aqueous phase was gradually added to the oil phase. Then, emulsification was performed at 80 ° C. for 5 minutes using a homomixer (rotation speed: 6000 rpm). Then, it cooled with stirring to 40 degreeC, and obtained the skin cream.
<Evaluation method>
A “Nobing at the time of application” A 20-person expert panelist conducted a usability test, and each panelist evaluated the grade when applied to the skin cream and the back of the hand in 4 grades based on the following absolute evaluation. . And the score of all the panelists was totaled for every sample, and 30 or more points were set as the pass. However, if 3 or more panelists gave a score of 0, they were rejected.

<Absolute evaluation criteria>
(Score): (Evaluation)
3: Good spreading at the time of application 2: Elongation at the time of application is slightly good 1: Elongation at the time of application is slightly bad 0: Very little elongation at the time of application B “No stickiness after application” 20 experts A panel test is performed, and skin cream is applied to the back of the hand, and after 3 minutes have passed since the skin cream is thoroughly applied to the skin, each panelist evaluates it according to the following absolute rating in 4 grades and gives a score. It was. And the score of all the panelists was totaled for every sample, and 30 or more points were set as the pass. However, if 3 or more panelists gave a score of 0, they were rejected.
<Absolute evaluation criteria>
(Score): (Evaluation)
3: Little stickiness of the skin after application 2: Little stickiness of the skin after application 1: Feeling the skin sticky after application 0: The skin after application is very sticky

C “Skin Adhesion” Regarding “Skin Adhesion”, 20 expert panelists applied the skin creams of each Example and Comparative Example, and then applied makeup on the foundation for 5 hours. The state after was evaluated in four stages as follows. And the score of all the panelists was totaled for every sample, and 30 or more points were set as the pass. However, if 3 or more panelists gave a score of 0, they were rejected.
(Score): (Evaluation)
3: A feeling that the skin cream is uniformly adhered to the skin is obtained, and there is no break-up or twist.
2: A feeling that the skin cream adheres slightly uniformly to the skin is obtained, and the cosmetic break-up and twisting do not occur much.
1: The feeling that the skin cream is uniformly adhered to the skin is not obtained so much, and the makeup break-up and twisting occur.
0: A feeling that the skin cream is uniformly adhered to the skin is not obtained at all, and the makeup collapse or twisting occurs remarkably.

D “Transdermal moisture transpiration suppression effect” With regard to “Transdermal moisture transpiration suppression effect”, the amount of transdermal water transpiration before and after sample application on the inner part of the forearm was measured for Evaporeimeter EP1 (Co., Ltd.). ) Manufactured by Yayoi Co., Ltd.), and the rate of change in transdermal moisture transpiration was calculated from the following formula.
[Change rate of transdermal water transpiration (%)] = [(transdermal water transpiration after sample application-transdermal water transpiration before sample application) / transdermal water transpiration before sample application] × 100
The measurement was performed in a constant temperature and humidity chamber at room temperature of 25 ° C. and humidity of 40%, and in order to stabilize the body temperature, the test was performed after waiting for 30 minutes or more in the constant temperature and humidity chamber.
For each sample, the average value of the rate of change in the transdermal moisture transpiration rate of all subjects was calculated and judged according to the following four-step evaluation criteria. (The smaller the rate of change, the better the effect of suppressing transdermal moisture transpiration, and the higher the evaluation).
(4 step criteria)
(Average value of change rate of transdermal moisture transpiration): (Judgment)
<-15%: Very good (◎)
-15% or more and less than -5%: Good (◯)
-5% or more and less than 0%: Somewhat bad (△)
0% or more: Defect (x)

  From Examples 1 to 5, the cosmetics containing the oil agent of the present invention has good spread and good adhesion to the skin in any sample, no stickiness after application, and suppression of transdermal moisture transpiration. Excellent effect.

  On the other hand, in Comparative Examples 1-6, sufficient effect is not acquired. In Comparative Example 1, since the type of fatty acid is acetic acid having less than 12 carbon atoms, the adhesion to the skin and the effect of suppressing transdermal moisture transpiration were insufficient. In Comparative Example 2, since the type of fatty acid is behenic acid having more than 20 carbon atoms, the spreading at the time of application was poor. In Comparative Example 3, since the average added mole number n of the oxytetramethylene group was less than 3, the spread at the time of coating was poor, and the adhesion to the skin was insufficient. In Comparative Example 4, since the esterification rate was less than 0.55, the feeling of adhesion to the skin and the effect of suppressing transdermal moisture transpiration were insufficient, and the stickiness after application was strong. In Comparative Example 5, since the esterification rate exceeded 0.95, the spread at the time of application was poor. In Comparative Example 6, since THF and PO were randomly copolymerized, the spread at the time of application was poor, the feeling of adhesion to the skin, the effect of suppressing transdermal moisture transpiration was insufficient, and the sticky feeling after application was strong. . In Comparative Example 7, since ethylene oxide was added to tritetramethylene glycol and then esterified with fatty acid, the feeling of adhesion to the skin and the effect of suppressing transdermal moisture transpiration were insufficient. In Comparative Example 8, since an oil agent other than the present invention was used, the spread at the time of application was poor, and the stickiness after application was strong.

Claims (2)

A cosmetic oil comprising a polyalkylene glycol derivative represented by the following formula (1):
R ¹ O— (CH ₂ CH ₂ CH ₂ CH ₂ O) n—R ² (1)
(In the formula, R ¹ and R ² are the same or different hydrogen atoms and fatty acid residues having 12 to 20 carbon atoms, and the proportion of the fatty acid residues having 12 to 20 carbon atoms in R ¹ and R ² is 0.5 to 0.95, where n is the average number of moles added of the oxytetramethylene group, and 3 ≦ n ≦ 30.   A cosmetic comprising the cosmetic oil according to claim 1.