Polyethers, cosmetic bases, and cosmetics

Abstract

The present invention provides a polyether represented by formula (1) (the symbols of which are defined in the description). This polyether is suited to various applications, including a cosmetic base.

Description

Technical Field

[0001] The present invention relates to polyethers, cosmetic bases, and cosmetics.

Background Art

[0002] Polyethers produced by ring-opening addition polymerization with cyclic ethers such as ethylene oxide and propylene oxide, or by dehydration condensation of polyhydric alcohols, are used in various applications such as cosmetic bases because it is easy to control the balance between hydrophilicity and lipophilicity and the molecular weight.

[0003] In the field of skin care cosmetics, polyhydric alcohols such as glycerin and water-soluble polymers such as hyaluronic acid are often blended for the purpose of enhancing the moisturizing effect. However, cosmetics obtained by blending a large amount of polyhydric alcohols and water-soluble polymers may lead to a deterioration in the feeling of use, such as being prone to stickiness or having poor skin compatibility. Therefore, in Patent Documents 1 and 2, a cosmetic composition containing a specific polyether is disclosed as a cosmetic that can achieve both a high moisturizing effect and a good feeling of use without stickiness.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the cosmetics field, surfactants are sometimes used to stably add hydrophobic components such as fragrances, preservatives, active ingredients, and oils to cosmetics. However, there is a need to further reduce the amount of surfactants used to improve the feel of the product, such as reducing stickiness, and to reduce irritation. However, when the amount of surfactants used is reduced, the transparency of the cosmetic may decrease when multiple types of oils with different polarities, such as hydrocarbon oils and fats, are used. In addition, when the amount of surfactants is reduced, the low-temperature stability decreases. For example, if the cosmetic freezes at around -4°C, some components in the cosmetic may precipitate, and even after the cosmetic returns to room temperature, the precipitate may not dissolve and remain in the cosmetic.

[0006] In light of these circumstances, there is a need to develop cosmetic bases that can produce cosmetics with good transparency, good low-temperature stability, good moisturizing effect, and a non-greasy, pleasant feel, even with reduced use of surfactants.

[0007] The object of the present invention is to provide a polyether useful as a cosmetic base that can produce cosmetics with good transparency, good low-temperature stability, good moisturizing effect, and a non-greasy feel, even when the amount of surfactant used is reduced. [Means for solving the problem]

[0008] In view of the above situation, the inventors have conducted diligent studies and found that a polyether of a specific structure can solve the above problems. Specifically, when the amount of surfactant used is reduced, cosmetics containing hydrophobic components may become non-uniform, their transparency may decrease, and their low-temperature stability may decrease. However, it has been found that by using a polyether of a specific structure, even when the amount of surfactant used is reduced, the low-temperature stability of cosmetics containing hydrophobic components can be improved, and at the same time, the effect of reducing stickiness in cosmetics and a high moisturizing effect can be obtained. Based on this finding, the present invention is as follows. [1] Equation (1):

[0009] [ka]

[0010] [In the formula, R 1 , R 2 , and a number of R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, (The number of hydrogen atoms in (R 1 ~R 3 ) / (The number of hydrocarbon groups in (R 1 ~R 3 ) is 20 or less, GL is a glycerin residue, CH2CH2O is an ethylene glycol residue, CH2CH2CH2O is a 1,3-propanediol residue, C n H 2n O is an alkanediol residue having 4 to 8 carbon atoms, a, b, c, and d are the average degrees of polymerization of GL, CH2CH2O, CH2CH2CH2O, and C n H 2n O, respectively, a is a number from 0 to 30, b is a number from 0 to 80, a + b is a number from 1 to 80, c is a number from 0 to 60, d is a number from 0 to 60, c + d is a number from 1 to 70, (a + b) / (c + d) is a number from 0.2 to 8, and n is a number from 4 to 8.] A polyether represented by. [2] A cosmetic base comprising the polyether according to [1]. [3] A cosmetic comprising the cosmetic base according to [2] in an amount of 0.1 to 30% by mass based on the total amount of the cosmetic. [Advantages of the Invention]

[0011] According to the present invention, a polyether can be obtained that can be used as a cosmetic base that can impart moisturizing effects, non-stickiness, and low-temperature stability to cosmetics.

[0012] Furthermore, a cosmetic composition containing a predetermined amount of the polyether-based cosmetic base of the present invention provides a non-greasy, pleasant feel, high moisturizing effect, and maintains good transparency and low-temperature stability even when the amount of surfactant used in the cosmetic composition is reduced. [Modes for carrying out the invention]

[0013] In this specification, numerical ranges defined using "~" include the numbers at both ends (upper and lower limits) of "~". For example, "2~5" means 2 or greater and 5 or less.

[0014] <Polyether> The polyether of the present invention is of the following formula (1):

[0015] [ka]

[0016] It is represented as follows. The polyether of the present invention may be used alone or in combination of two or more types. The definitions of the symbols in formula (1) will be explained in order below.

[0017] In equation (1), R 1 , R 2 , and a number of R 3 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Polyethers having hydrocarbon groups with 21 or more carbon atoms may have reduced moisturizing effects, transparency, or low-temperature stability in cosmetics.

[0018] Examples of hydrocarbon groups include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. The hydrocarbon group is preferably an alkyl group or an alkenyl group. Both alkyl and alkenyl groups may be linear or branched.

[0019] The hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, and hexyl groups. The hydrocarbon group having 1 to 20 carbon atoms is most preferably a methyl group.

[0020] (R 1 ~R 3 (Number of hydrogen atoms inside) / (R) 1 ~R 3 The ratio of hydrogen atoms to hydrocarbon groups (hereinafter sometimes referred to as "hydrogen atom / hydrocarbon group") is 20 or less, preferably 15 or less, and more preferably 10 or less, from the viewpoint of suppressing stickiness, transparency, and low-temperature stability in cosmetics. Note that the hydrogen atom / hydrocarbon group ratio may be 0. Also, in this specification, R 1 ~R 3 When the number of hydrocarbon groups inside is 0, the hydrogen atom / hydrocarbon group ratio is interpreted as ∞ (infinity).

[0021] As described in the Examples section below, the hydrogen atom / hydrocarbon group of the polyether (i.e., (R 1 ~R 3 (Number of hydrogen atoms inside) / (R) 1 ~R 3 The number of hydrocarbon groups inside is the result of acetylating a polyether. 13 From the integrated signal of the carbonyl carbon derived from the acetyl group and the integrated signal of the terminal CH3 derived from the hydrocarbon group, obtained by 13C-NMR measurement, the following formula is derived: Hydrogen atom / hydrocarbon group = Integral value of the signal from the carbonyl carbon derived from the acetyl group / Integral value of the signal from the terminal CH3 derived from the hydrocarbon group It can be calculated by [method].

[0022] The acetylation method described above is not particularly limited, and known methods can be used, but the method using pyridine and acetic anhydride, as described in the Examples section below, is preferred. 13 1C-NMR measurement can be performed as described in the Examples section below.

[0023] as needed, 13 In addition to CNMR measurement 1 By combining measurements such as H-NMR, DEPT135, and 2D NMR (HHCOSY, HMQC, HMBC, NOESY), it is possible to calculate the number of hydrogen atoms / hydrocarbon groups.

[0024] In equation (1), GL is a glycerol residue. Here, "glycerol residue" refers to the residue in equation (2). 、 Expression(3 a ) , or formula (3b) :

[0025] [ka]

[0026] (In the formula, * represents R 3 This is the bonding position. It means the base represented by . Below Below, the "base represented by formula (2)", the "base represented by formula (3a)", and the "base represented by formula (3b)" may be abbreviated as "base (2)", "base (3a)", and "base (3b)", respectively.

[0027] If GL (glycerol residue) is present in the polyether of the present invention, group (2) 、 group(3 a ) , and base (3b) of all The following may be present. When GL (glycerol residue) is present in the polyether of the present invention, preferably group (2) 、 group(3 a ) , and base (3b) of allIt exists.

[0028] If GL (glycerol residue) is present in the polyether of the present invention, The molar ratio of group (2) / (group (3a) and group (3b)) (hereinafter, Molar ratio of base (2) / base (3) (It should be written as follows:) From the viewpoint of suppressing stickiness, transparency, and low-temperature stability in cosmetics, the molar ratio is preferably 40 / 60 to 99 / 1, more preferably 40 / 60 to 90 / 10, and even more preferably 50 / 50 to 80 / 20. The molar ratio of group (2) / group (3) is 13 It can be calculated by 13C-NMR measurement. Specifically, the integral value of the signal of the methine carbon of group (2) (around 71 ppm) and group (3) a ) and base (3b) By comparing this with the integral value of the signal at the methine carbon (around 79 ppm), the molar ratio of group (2) to group (3) can be calculated.

[0029] In formula (1), CH2CH2O is an ethylene glycol residue. Here, "ethylene glycol residue" means a group having a structure obtained by removing one hydroxyl group (HO-) and the hydrogen atom (H) from the other hydroxyl group (-OH) of ethylene glycol (HO-CH2CH2-OH). Note that the ethylene glycol residue may be a group formed from a compound other than ethylene glycol (e.g., ethylene oxide), as long as it has the above structure.

[0030] In formula (1), CH2CH2CH2O is a 1,3-propanediol residue. Here, a "1,3-propanediol residue" refers to a group having a structure obtained by removing one hydroxyl group (HO-) and the hydrogen atom (H) from the other hydroxyl group (-OH) of 1,3-propanediol (HO-CH2CH2CH2-OH). Note that the 1,3-propanediol residue may be a group formed from a compound other than 1,3-propanediol, as long as it has the above structure.

[0031] In equation (1), C n H 2nO is an alkanediol residue with 4 to 8 carbon atoms. Here, "alkanediol residue with 4 to 8 carbon atoms" refers to an alkanediol (HO-C) with 4 to 8 carbon atoms. n H 2n This refers to a group having a structure obtained by removing one hydroxyl group (HO-) from a -OH group (n=4~8) and removing a hydrogen atom (H) from the other hydroxyl group (-OH). The alkanediol may be linear or branched. Note that the alkanediol residue with 4 to 8 carbon atoms may be a group formed from a different compound than the alkanediol with 4 to 8 carbon atoms, as long as it has the above structure. The "1,2-butanediol residue" and the like described later have the same meaning as the "alkanediol residue with 4 to 8 carbon atoms".

[0032] Examples of alkanediol residues with 4 to 8 carbon atoms include 1,2-butanediol residues, 1,3-butanediol residues, 1,4-butanediol residues, 1,2-pentanediol residues, 1,3-pentanediol residues, 1,4-pentanediol residues, 1,5-pentanediol residues, neopentyl glycol residues, 1,2-hexanediol residues, 1,3-hexanediol residues, 1,4-hexanediol residues, 1,5-hexanediol residues, 1,6-hexanediol residues, 3-methyl-1,5-pentanediol residues, 1,2-heptanediol residues, 1,7-heptanediol residues, and 1,8-octanediol residues.

[0033] C n H 2n O is considered to have moisturizing effect, transparency, and low-temperature stability in cosmetics. Preferably, it is an alkanediol residue having 4 to 6 carbon atoms. More preferably, the residues are 1,2-butanediol residues, 1,3-butanediol residues, 1,4-butanediol residues, 1,5-pentanediol residues, or 1,6-hexanediol residues. More preferably, the residues are 1,3-butanediol residues, 1,4-butanediol residues, or 1,6-hexanediol residues. Particularly preferred are 1,3-butanediol residues or 1,6-hexanediol residues.

[0034] Polyethers containing alkanediol residues with 9 or more carbon atoms may have reduced transparency or low-temperature stability in cosmetics.

[0035] In equation (1), a, b, c, and d are GL, CH2CH2O, CH2CH2CH2O, and C, respectively. n H 2n This represents the average degree of polymerization of O. Therefore, these values ​​may all be decimals.

[0036] From the viewpoint of suppressing stickiness, transparency, and low-temperature stability in the cosmetic composition, a is a number from 0 to 30, preferably a number from 0 to 15, and more preferably a number from 0 to 10. Here, "a is 0" means that GL is not present. When b is 0, from the viewpoint of transparency and low-temperature stability in the cosmetic composition, a is preferably a number from 2 to 10, and more preferably a number from 3 to 10.

[0037] b is a number between 0 and 80, preferably between 0 and 50, and more preferably between 0 and 30, from the viewpoint of moisturizing effect, transparency, and low-temperature stability in the cosmetic composition. Here, "b is 0" means that CH2CH2O is not present. When a is 0, b is preferably a number between 4 and 50 from the viewpoint of transparency and low-temperature stability in the cosmetic composition.

[0038] a+b is a number from 1 to 80, preferably a number from 2 to 70, and more preferably a number from 3 to 60, from the viewpoint of suppressing stickiness, transparency, and low-temperature stability in cosmetics.

[0039] c is a number between 0 and 60, preferably between 0 and 40, and more preferably between 0 and 30, from the viewpoint of moisturizing effect, transparency, and low-temperature stability in the cosmetic composition. Here, "c is 0" means that CH2CH2CH2O is not present. When d is 0, c is preferably a number between 2 and 30, from the viewpoint of transparency and low-temperature stability in the cosmetic composition.

[0040] d is a number from 0 to 60, preferably from 0 to 40, and more preferably from 0 to 30, from the viewpoint of moisturizing effect in cosmetics. Here, "d is 0" means C n H 2n This means that O is not present. When c is 0, d is preferably a number between 2 and 30 from the viewpoint of transparency and low-temperature stability in cosmetics.

[0041] c+d is a number from 1 to 70, preferably from 2 to 50, and more preferably from 3 to 40, from the viewpoint of moisturizing effect in cosmetics.

[0042] (a+b) / (c+d) is a number between 0.2 and 8, preferably between 0.25 and 5, and more preferably between 0.33 and 4, from the viewpoint of moisturizing effect, stickiness suppression, transparency, and low-temperature stability in cosmetics. In this specification, when c+d is 0, (a+b) / (c+d) is interpreted as ∞ (infinity).

[0043] In equation (1), n ​​is C n H 2n This refers to the number of carbon atoms in oxygen, which is between 4 and 8. From the viewpoint of transparency and low-temperature stability in cosmetics, n is preferably between 4 and 6, more preferably 4 or 6.

[0044] In equation (1), the slash " / " represents GL, CH2CH2O, CH2CH2CH2O, and C n H 2n This indicates that there is no restriction on the order of O, that is, they can exist in any order. Therefore, (i)GL, CH2CH2O, CH2CH2CH2O, and C n H 2nO may be bonded to each other randomly, (ii) GL, CH2CH2O, CH2CH2CH2O, and C n H 2n One or more of the O molecules may form blocks with each other, (iii) GL, CH2CH2O, CH2CH2CH2O, and C n H 2n O may be bonded to include both embodiments of (i) and (ii) above. For example, multiple CH2CH2O may form a block, and this block, GL, CH2CH2CH2O, and C n H 2n O may be randomly bonded. If there are three or more CH2CH2O molecules in one molecule, it is preferable that a (CH2CH2O)3 block is formed.

[0045] The weight-average molecular weight (Mw) of the polyether of the present invention, calculated from the chromatogram obtained by gel permeation chromatography (GPC), is preferably 300 to 10,000, and more preferably 500 to 8,000, from the viewpoint of suppressing stickiness in cosmetics.

[0046] The polyether of the present invention can be produced by known methods. For example, (i) a reaction intermediate can be produced by a dehydration condensation reaction of a polyhydric alcohol at 80°C to 130°C and atmospheric pressure in the presence of an acid catalyst such as sulfuric acid, and (ii) thereafter, the polyether of the present invention can be produced by carrying out an etherification reaction between the obtained reaction intermediate and an alkyl halide or alkenyl halide at 80°C to 130°C in the presence of a catalyst such as potassium hydroxide.

[0047] The polyether of the present invention can be used as a base for cosmetics. Furthermore, the polyether of the present invention can be used as a plasticizer, a detergent, or a wetting agent.

[0048] <Cosmetic bases and cosmetics> The present invention provides a cosmetic base comprising the polyether of the present invention. The cosmetic base of the present invention may be used alone or in combination of two or more types. The present invention also provides a cosmetic containing the cosmetic base of the present invention in an amount of 0.1 to 30% by mass of the total cosmetic composition.

[0049] By using the cosmetic base of the present invention, it is possible to impart a high moisturizing effect and a non-greasy, pleasant feel to cosmetics, while relatively reducing the amount of surfactant contained in the cosmetics.

[0050] The cosmetic composition of the present invention is not particularly limited and may be any of the following: an aqueous cosmetic composition, a water-in-oil or oil-in-water emulsion cosmetic composition, or an oily cosmetic composition. Examples of cosmetic compositions include skincare cosmetics such as lotions, serums, emulsions, creams, masks, and sunscreen creams; body cosmetics; makeup removers such as cleansing oils and cleansing waters; skin cleansing products such as body soaps, hand soaps, and facial cleansing pastes; hair cosmetics such as shampoos, conditioners, hair liquids, hair oils, hair tonics, and hair growth products; and makeup cosmetics such as makeup bases, liquid foundations, and BB creams.

[0051] From the viewpoint of suppressing stickiness, the content of the cosmetic base of the present invention is 0.1 to 30% by mass, preferably 0.5 to 15% by mass, relative to the total cosmetic composition of the present invention.

[0052] The cosmetic composition of the present invention preferably contains water (more preferably purified water). Furthermore, the cosmetic composition of the present invention may optionally contain other components different from the cosmetic base and water of the present invention, to the extent that they do not impair the effects of the present invention. The other components are not particularly limited, as long as they are components commonly used in cosmetics. Examples of other components include humectants, hydrocarbons, higher alcohols, higher fatty acids and their triglycerides, ester oils, animal and vegetable oils and fats, silicones, vitamins, UV absorbers, water-soluble polymers, antioxidants, cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants, metal ion chelating agents, ethanol, thickeners, preservatives, dyes, pigments, and fragrances. The other components may be used individually or in combination of two or more.

[0053] If the cosmetic composition of the present invention is a lotion, serum, or emulsion and other ingredients are used, the total amount of the other ingredients is preferably 0.1 to 80% by mass, more preferably 0.5 to 40% by mass, relative to the entire lotion, serum, or emulsion of the present invention, from the viewpoint of moisturizing effect, freshness, and feel (e.g., refreshing feeling). Water is the remainder of the lotion, serum, or emulsion of the present invention (i.e., the remainder of the lotion, serum, or emulsion other than the cosmetic base and other ingredients of the present invention).

[0054] When the cosmetic composition of the present invention is a cream, liquid foundation, or sunscreen cream and other ingredients are used, the total amount of the other ingredients is preferably 5 to 99% by mass, more preferably 10 to 85% by mass, relative to the entire cream, liquid foundation, or sunscreen cream of the present invention, from the viewpoint of emollient effect and moisture evaporation suppression effect. Water is the remainder of the cream, liquid foundation, or sunscreen cream of the present invention (i.e., the remainder of the cream, liquid foundation, or sunscreen cream other than the cosmetic base and other ingredients of the present invention).

[0055] When the cosmetic composition of the present invention is a shampoo or body soap and other ingredients are used, the total amount of the other ingredients is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, relative to the total amount of the shampoo or body soap of the present invention, from the viewpoint of cleansing properties. The water is the remainder of the shampoo or body soap of the present invention (i.e., the remainder of the shampoo or body soap other than the cosmetic base and other ingredients of the present invention).

[0056] When the cosmetic composition of the present invention is a treatment and other components are used, the total amount of the other components is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, relative to the entire treatment of the present invention, from the viewpoint of emollient effect and moisture evaporation suppression effect. Water is the remainder of the treatment of the present invention (i.e., the remainder of the treatment other than the cosmetic base and other components of the present invention).

[0057] When the cosmetic composition of the present invention is a cleansing oil and other components are used, the total amount of the other components is preferably 40 to 99.5% by mass, more preferably 60 to 99% by mass, relative to the total cleansing oil of the present invention, from the viewpoint of cleansing properties. Water is the remainder of the cleansing oil of the present invention (i.e., the remainder of the cleansing oil other than the cosmetic base and other components of the present invention).

[0058] When the cosmetic composition of the present invention is cleansing water and other ingredients are used, the total amount of the other ingredients is preferably 2 to 80% by mass, more preferably 5 to 60% by mass, relative to the total cleansing water of the present invention, from the viewpoint of cleansing properties. The water is the remainder of the cleansing water of the present invention (i.e., the remainder of the cleansing water other than the cosmetic base and other ingredients of the present invention).

[0059] When the cosmetic composition of the present invention is a facial cleansing paste and other ingredients are used, the total amount of the other ingredients is preferably 15 to 95% by mass, more preferably 30 to 85% by mass, relative to the entire facial cleansing paste of the present invention, from the viewpoint of cleansing properties. The water is the remainder of the facial cleansing paste of the present invention (i.e., the remainder of the facial cleansing paste other than the cosmetic base and other ingredients of the present invention). [Examples]

[0060] The present invention will be described in detail below with reference to examples and comparative examples. Unless otherwise specified, "%" in the component amounts below refers to "mass%".

[0061] (Manufacturing Example 1: Synthesis of Example Polyether 1) A four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and condenser was charged with 540g of triethylene glycol (manufactured by Kanto Chemical Co., Ltd.), 500g of 1,3-propanediol (manufactured by Kanto Chemical Co., Ltd.) as polyhydric alcohols, and 13.8g of sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) as a catalyst. After purging with nitrogen, the temperature was raised to 130°C, and a dehydration condensation reaction was carried out under nitrogen bubbling conditions. Subsequently, an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was adsorbed at a temperature of 90°C and a pressure of -0.097 MPa (gauge pressure) or less under nitrogen bubbling for 1 hour. The reaction intermediate was then filtered to obtain a reaction intermediate (hydroxyl value: 105 (mg KOH / g)). The hydroxyl value of this reaction intermediate was calculated according to JIS K-1557-1. The hydroxyl values ​​of other polyethers were also calculated in the same manner.

[0062] Subsequently, the reaction intermediate and 120 g of potassium hydroxide were charged into an autoclave equipped with a thermometer, pressure gauge, safety valve, nitrogen gas injection pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket. After purging with nitrogen, 120 g of methyl chloride was injected under pressure at a temperature of 80°C to 130°C, and the etherification reaction was carried out for 5 hours. After that, the crude product was removed from the autoclave, treated with an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd.), and then filtered to obtain Example Polyether 1 (hydroxyl value: 50 (mg KOH / g)).

[0063] (Manufacturing Example 2: Synthesis of Polyether 2) A four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and condenser was charged with 370g of glycerin (manufactured by Kanto Chemical Co., Ltd.) and 570g of 1,3-propanediol (manufactured by Kanto Chemical Co., Ltd.) as polyhydric alcohols, and 12.6g of sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) as a catalyst. After purging with nitrogen, the temperature was raised to 130°C and a dehydration condensation reaction was carried out under nitrogen bubbling conditions. Subsequently, an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was adsorbed at a temperature of 90°C and a pressure of -0.097 MPa (gauge pressure) or less under nitrogen bubbling for 1 hour. The reaction intermediate was then filtered to obtain the reaction intermediate (hydroxyl value: 320 (mg KOH / g)).

[0064] Subsequently, the reaction intermediate and 67 g of potassium hydroxide were charged into an autoclave equipped with a thermometer, pressure gauge, safety valve, nitrogen gas injection pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket. After purging with nitrogen, 51 g of methyl chloride was injected under pressure at a temperature of 80°C to 130°C, and the etherification reaction was carried out for 3 hours. After that, the crude product was removed from the autoclave, treated with an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd.), and then filtered to obtain Example Polyether 2 (hydroxyl value: 265 (mg KOH / g)). The molar ratio of group (2) / group (3) of Example Polyether 2 was calculated to be 72 / 28 by the following method.

[0065] (Calculation of the molar ratio of base (2) / base (3)) Example Polyether 2 13 ¹¹C-NMR measurements were performed using reverse-gate decoupling, and the integral value of the signal at the methine carbon of group (2) (around 71 ppm) and group (3) were obtained. a ) and base (3b) The molar ratio of group (2) / group (3) was calculated by comparing it with the integral value of the signal at the methine carbon (around 79 ppm). 13 The conditions for 1C-NMR measurement are as follows: · 13 C-NMR device: JNM-ECA600 (JEOL-NMR) • Solvent: D2O • Sample concentration: 100 mg / 0.6 mL ·Temperature: 25℃ • Total number of times: 256

[0066] (Production Example 3: Synthesis of Example Polyethers 3-12 and Comparative Example Polyethers 1-9) Polyethers 3-12 of the Examples and polyethers 1-9 of the Comparative Examples were synthesized using the same method as in Production Example 1 or 2. The polyhydric alcohols used in the dehydration condensation reaction and the alkyl or alkenyl halides used in the subsequent etherification reaction are shown in Tables 1 and 2.

[0067] (Manufacturing Example 4: Synthesis of Comparative Example Polyether 10) In an autoclave equipped with a thermometer, pressure gauge, safety valve, nitrogen gas inlet, agitator, vacuum exhaust pipe, cooling coil, and steam jacket, 100 g of 1,2-propanediol and 6.0 g of potassium hydroxide as a catalyst were charged. After purging with nitrogen, the temperature was raised to 115°C, and a mixture of 1626 g of propylene oxide and 1258 g of ethylene oxide was added over 8 hours under conditions of 0.5 MPa or less. After the addition was complete, the mixture was reacted at 115°C for 1 hour, and then treated under reduced pressure at 75-85°C for 1 hour to obtain a reaction intermediate (hydroxyl value: 106 (mg KOH / g)).

[0068] Next, 110 g of potassium hydroxide was placed in the autoclave, and after nitrogen purging, 50 g of methyl chloride was injected under pressure at a temperature of 80°C to 130°C, and the etherification reaction was carried out for 5 hours. After that, the reaction composition was removed from the autoclave, treated with adsorption using two adsorbents (Kyoward #700 and #1000), and then filtered to obtain comparative example polyether 10 (hydroxyl value: 5.0 (mg KOH / g)). The weight-average molecular weight (hereinafter sometimes abbreviated as "Mw") of comparative example polyether 10, measured under the conditions described below, was 1050. Note that comparative example polyether 10 differs structurally from the polyether of the present invention in that it has repeating units derived from propylene oxide (i.e., branched propylene oxide groups different from linear 1,3-propanediol residues).

[0069] (Manufacturing Example 5: Synthesis of Comparative Example Polyether 11) In an autoclave equipped with a thermometer, pressure gauge, safety valve, nitrogen gas inlet, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket, 152 g of glycerin and 7.0 g of potassium hydroxide were charged. After purging with nitrogen, the temperature was raised to 120°C, and a mixture of 734.5 g of glycidol and 1439.4 g of propylene oxide was added over 20 hours under conditions of 0.5 MPa or less. After the addition was complete, the mixture was reacted at 120°C for 2 hours. The reaction mixture was then removed from the autoclave, subjected to adsorption treatment for 1 hour, and filtered to obtain comparative example polyether 11. The Mw of comparative example polyether 11, measured under the conditions described later, was 1430. Note that comparative example polyether 11 differs structurally from the polyether of the present invention in that it has repeating units derived from glycidol and repeating units derived from propylene oxide (i.e., branched propyleneoxy groups).

[0070] The R of the obtained example polyethers 1-12 and comparative example polyethers 1-9 1 ~R 3 , hydrogen atom / hydrocarbon group (i.e., (R 1 ~R 3 (Number of hydrogen atoms inside) / (R) 1 ~R 3 (Ratio of the number of hydrocarbon groups inside), a-d, a+b, c+d, n, C n H 2n The raw materials for O, (a+b) / (c+d), and Mw are shown in Tables 1 and 2. The hydrogen atom / hydrocarbon group and Mw were calculated as follows.

[0071] (Calculation of hydrogen atoms / hydrocarbon groups) Hydrogen atom / hydrocarbon group (i.e., (R 1 ~R 3 (Number of hydrogen atoms inside) / (R) 1 ~R 3 The number of hydrocarbon groups inside is the result of acetylating a polyether. 13 From the integrated signal of the carbonyl carbon derived from the acetyl group and the integrated signal of the terminal CH3 derived from the hydrocarbon group, obtained by 13C-NMR measurement, the following formula is derived: Hydrogen atom / hydrocarbon group = Integral value of the signal from the carbonyl carbon derived from the acetyl group / Integral value of the signal from the terminal CH3 derived from the hydrocarbon group It was calculated using the following method. The specific steps are as follows:

[0072] <Acetylation> 4.0 mL of pyridine and 1.0 mL of acetic anhydride were weighed into a flask and shaken well. Then 1 g of polyether was added and shaken well, and the mixture was heated for 1 hour. After that, 1 mL of water was added and the mixture was heated for 10 minutes, and the acetic anhydride was removed to obtain the acetylated polyether.

[0073] < 13 C-NMR measurement> Regarding the obtained acetylated product 13 ¹¹C-NMR measurements were performed to calculate the integrated signal of the carbonyl carbon derived from the acetyl group at around 170 ppm and the integrated signal of the terminal CH3 derived from the hydrocarbon group at around 10-15 ppm (around 60 ppm if the hydrocarbon group is a methyl group). Using these, the above formula was derived from hydrogen atom / hydrocarbon group (i.e., (R 1 ~R 3 (Number of hydrogen atoms inside) / (R) 1 ~R 3 The number of hydrocarbon groups inside was calculated. 13 The conditions for the 1C-NMR measurement were as follows: · 13 C-NMR device: JNM-ECA600 (JEOL-NMR) • Solvent: CDCl3 • Sample concentration: 40 mg / 0.6 mL ·Temperature: 25℃ • Total number of times: 4096

[0074] (Calculation of Mw) Mw was calculated from gel permeation chromatography (GPC) under the following conditions: The GPC system consisted of a SHODEX® GPC101 dedicated GPC system, a SHODEX RI-71s differential refractometer, a SHODEX KF-G guard column, and three SHODEX KF804L columns mounted in sequence. The column temperature was 40°C, and tetrahydrofuran was flowed at a flow rate of 1 ml / min as the developing solvent. 0.1 ml of a 0.1% tetrahydrofuran solution of the obtained example polyether or comparative example polyether was injected, and the Mw was calculated from the chromatogram, which represents the refractive index intensity and elution time, using the BORWIN GPC calculation program.

[0075] [Table 1]

[0076] [Table 2]

[0077] (Evaluation of the transparency of aqueous solutions or dispersions containing olive oil and squalane) A 2.0% example polyether or comparative example polyether, 3.0% PEG-40 hydrogenated castor oil and 3.0% polysorbate 80 as surfactants, 0.3% olive oil and 0.1% squalane as oils, and the remainder purified water were placed in a beaker and stirred until homogeneous to prepare an aqueous solution or dispersion of the example polyether or comparative example polyether.

[0078] A dispersion of Reference Example 1 was prepared by adding 3.0% PEG-40 hydrogenated castor oil and 3.0% polysorbate 80 as surfactants, 0.3% olive oil and 0.1% squalane as oils, and the remainder purified water to a beaker and stirring until homogeneous.

[0079] A dispersion of Reference Example 2 was prepared by adding 5.0% PEG-40 hydrogenated castor oil and 5.0% polysorbate 80 as surfactants, 0.3% olive oil and 0.1% squalane as oils, and the remainder purified water to a beaker and stirring until homogeneous.

[0080] 50 mL of the prepared aqueous solution or dispersion at 25°C was filled into a 110 mL glass container (Maruemu Co., Ltd. screw tube No. 8, 110 mL), and the legibility of letters (font: MS Gothic, font size: 28pt) placed 5 cm away from the glass container was determined. Transparency was evaluated according to the following criteria. The results are shown in Table 3. <Evaluation Criteria> ◎: The aqueous solution is transparent and the text is clearly legible. ○: The aqueous solution is semi-transparent, but the text is legible. ×: The dispersion is cloudy and the text is illegible, or the dispersion has separated.

[0081] [Table 3]

[0082] (Manufacturing Example 6: Manufacturing of Example Cosmetics 1-15, Comparative Example Cosmetics 1-11, and Reference Example Cosmetics 1 and 2) The polyethers of the examples or comparative examples, PEG-40 hydrogenated castor oil, common ingredients, and purified water were mixed and stirred in the amounts shown in Table 4 or Table 5 to produce cosmetic formulations 1 to 15 of the examples, cosmetic formulations 1 to 11 of the comparative examples, and cosmetic formulations 1 and 2 of the reference examples. The composition of the common ingredients is shown in Table 6. In Table 6, "BG" is a cosmetic labeling name used by the Japan Cosmetic Industry Association and refers to 1,3-butylene glycol.

[0083] (Evaluation of lack of stickiness) Ten men and women (ages 25-50) served as panelists. Each panelist applied 1.0g of each cosmetic obtained in Manufacturing Example 6 to the inside of their right forearm and scored the stickiness according to the following criteria. The total scores of the ten panelists were calculated, and the degree of stickiness was evaluated according to the following criteria. The results are shown in Tables 4 and 5. <Scoring Criteria> 3 points: Does not feel sticky. 2 points: Slightly sticky. 1 point: Feels sticky <Evaluation Criteria> ◎: Total score of 25 points or more ○: Total score between 20 and 24 points △: Total score is 19 points or less

[0084] (Evaluation of moisturizing effect) Ten men and women (ages 25-50) served as panelists. In a constant temperature and humidity chamber set at 20°C and 50% relative humidity, 1.0g of each cosmetic obtained in Production Example 6 was applied to the inner side of each panelist's right forearm. Stratum corneum moisture content was measured before application and one hour after application using a skin surface stratum corneum moisture content measuring device (SKICON-200EX, manufactured by IBS Co., Ltd.). The relative value of stratum corneum moisture content was calculated, with the pre-application value set to 1, and scored according to the following criteria. The total scores for the ten participants were calculated, and the moisturizing effect was evaluated according to the following criteria. The results are shown in Tables 4 and 5. <Scoring Criteria> 3 points: Relative value is 3 or higher 2 points: Relative value is 2 or greater, but less than 3. 1 point: Relative value is less than 2 <Evaluation Criteria> ◎: Total score of 25 points or more ○: Total score between 20 and 24 points △: Total score is 19 points or less

[0085] (Transparency assessment) 50 mL of each cosmetic obtained in Production Example 6 was filled into 110 mL glass containers (Maruemu Co., Ltd. screw-cap tube No. 8, 110 mL), and the legibility of text (font: MS Gothic, font size: 28pt) placed 5 cm away from the glass container was determined. Transparency was evaluated according to the following criteria. The results are shown in Tables 4 and 5. <Evaluation Criteria> ◎: The cosmetic product is transparent and the text is clearly legible. ○: The cosmetic product is semi-transparent, but the text is legible. ×: The cosmetic product is cloudy and the text is illegible, or the cosmetic product has separated.

[0086] (Evaluation of low-temperature stability) 30 mL of each cosmetic composition obtained in Production Example 6 was filled into 50 mL glass containers and stored in a light-blocked -4°C constant temperature bath for 3 months. After returning to room temperature, the low-temperature stability was evaluated according to the following criteria. The results are shown in Tables 4 and 5. <Evaluation Criteria> ○: The cosmetic remained transparent. ×: Precipitation or separation occurred in the cosmetic product.

[0087] [Table 4]

[0088] [Table 5]

[0089] [Table 6]

[0090] As is clear from the table above, the polyethers in Examples 1 to 12, which correspond to the polyether of the present invention, were excellent in all of the above evaluations. In contrast, as is clear from the table above, the comparative examples polyethers 1 to 11 were insufficient in one or more of the above evaluations.

[0091] R 1 ~R 3 In comparative example polyether 1, where the group is a hydrogen atom and the hydrogen atom / hydrocarbon group ratio is infinite, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, comparative example cosmetic composition 1, which contained comparative example polyether 1, lacked stickiness, transparency, and low-temperature stability.

[0092] In comparative example polyether 2, where a+b exceeded 80, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, comparative example cosmetic composition 2, which included comparative example polyether 2, exhibited insufficient non-stickiness, transparency, and low-temperature stability.

[0093] In comparative example polyether 3, where (a+b) / (c+d) was less than 0.2, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, comparative example cosmetic composition 3, which included comparative example polyether 3, exhibited insufficient non-stickiness, moisturizing effect, transparency, and low-temperature stability.

[0094] In comparative example polyether 4, where (a+b) / (c+d) exceeded 8, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, comparative example cosmetic composition 4, which included comparative example polyether 4, exhibited insufficient non-stickiness, moisturizing effect, transparency, and low-temperature stability.

[0095] In comparative example polyether 5, where a+b was less than 1, the transparency of the dispersion containing olive oil and squalane was insufficient. In comparative example cosmetic composition 5, which contained comparative example polyether 5, the lack of stickiness, moisturizing effect, transparency, and low-temperature stability were insufficient.

[0096] In comparative example polyether 6, where the hydrogen atom / hydrocarbon group ratio exceeded 20, d exceeded 60, and c+d exceeded 70, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, comparative example cosmetic composition 6, which contained comparative example polyether 6, exhibited insufficient non-stickiness, moisturizing effect, transparency, and low-temperature stability.

[0097] In comparative example polyether 7, where both c and d are 0 and (a+b) / (c+d) is ∞, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, comparative example cosmetic composition 7, which included comparative example polyether 7, exhibited insufficient non-stickiness, moisturizing effect, transparency, and low-temperature stability.

[0098] R 1 ~R 3 In comparative example polyether 8, in which the number of carbon atoms in the hydrocarbon group exceeds 20, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, comparative example cosmetic composition 8, which contained comparative example polyether 8, exhibited insufficient moisturizing effect, transparency, and low-temperature stability.

[0099] In comparative example polyether 9, where n was greater than 8, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, comparative example cosmetic composition 9, which included comparative example polyether 9, exhibited insufficient moisturizing effect, transparency, and low-temperature stability.

[0100] Comparative example polyether 10, which is a copolymer of ethylene oxide and propylene oxide and has a different structure from the polyether of the present invention, exhibited insufficient transparency in the dispersion containing olive oil and squalane. Furthermore, comparative example cosmetic composition 10, which included comparative example polyether 10, exhibited insufficient transparency and low-temperature stability.

[0101] Comparative example polyether 11, a copolymer of glycidol and propylene oxide, has a different structure from the polyether of the present invention, and the dispersion containing olive oil and squalane exhibited insufficient transparency. Furthermore, comparative example cosmetic composition 11, which included comparative example polyether 11, exhibited insufficient transparency and low-temperature stability.

[0102] (Example prescription) Tables 7 to 20 below show examples of formulations of cosmetics (lotions, serums, emulsions, oil-in-water creams, water-in-oil creams, shampoos, conditioners, cleansing oils, cleansing waters, pump foamers, body soaps, facial cleansing pastes, liquid foundations, and sunscreen creams) containing the polyether of the present invention. The ingredient amounts shown in Tables 7 to 20 are based on the total cosmetic composition. In addition, the cosmetic names used by the Japan Cosmetic Industry Association are used as appropriate for each ingredient listed in Tables 7 to 20 below. Note that the present invention is not limited to the formulation examples below.

[0103] [Table 7]

[0104] [Table 8-1]

[0105] [Table 8-2]

[0106] [Table 9-1]

[0107] [Table 9-2]

[0108] [Table 10-1]

[0109] [Table 10-2]

[0110] [Table 11]

[0111] Table 11-2

[0112] Table 12

[0113] Table 13

[0114] Table 14

[0115] Table 15

[0116] Table 16

[0117] Table 17

[0118] Table 18

[0119] Table 19

[0120] Table 20 [Industrial applicability]

[0121] The polyether of the present invention is suitable for various applications, such as a base for cosmetics.

[0122] This application is based on Japanese Patent Application No. 2024-057119, which is fully contained herein.

Claims

1. Formula (1): 【Chemistry 1】 [In the formula, R １ , R ２ , and a number of R ３ Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. (R １ ~R ３ (Number of hydrogen atoms inside) / (R) １ ~R ３ The ratio of the number of hydrocarbon groups inside is 20 or less. GL is a glycerol residue, and is a residue of formula (2), formula (3a), or formula (3b): 【Chemistry 2】 (In the formula, * represents R) ３ This is the bonding position. It is a base represented by, CH ２ CH 2 O is an ethylene glycol residue, CH ２ CH ２ CH ２ O is a 1,3-propanediol residue, C ｎ H ２ｎ O is an alkanediol residue with 4 to 8 carbon atoms. a, b, c, and d are GL and CH, respectively. ２ CH ２ O, CH ２ CH ２ CH ２ O, and C ｎ H ２ｎ This is the average degree of polymerization of O. a is a number between 0 and 30. b is a number between 0 and 80. a + b is a number between 1 and 80. c is a number between 0 and 60. d is a number between 0 and 60. c + d is a number between 1 and 70. (a+b) / (c+d) is a number between 0.2 and 8, and n is a number between 4 and 8. A polyether represented by, A cosmetic base comprising a polyether in which, when GL is present, all of the groups represented by formula (2), formula (3a), and formula (3b) are present, and the molar ratio of the group represented by formula (2) to (the group represented by formula (3a) and the group represented by formula (3b)) is 40 / 60 to 99 / 1.

2. A cosmetic composition comprising the cosmetic base described in claim 1 in an amount of 0.1 to 30% by mass relative to the total cosmetic composition.

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