Polyether, cosmetic base, and cosmetic

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

Polyethers, cosmetic bases and cosmetics

[0001] The present invention relates to a polyether, a cosmetic base, and a cosmetic.

[0002] Polyethers produced by ring-opening addition polymerization of cyclic ethers such as ethylene oxide and propylene oxide, or by dehydration condensation of polyhydric alcohols, are used in a variety of applications, such as cosmetic bases, because it is easy to control the balance of 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 to enhance moisturizing effects. However, cosmetics obtained by blending large amounts of polyhydric alcohols and water-soluble polymers may lead to poor usability, such as stickiness and poor skin compatibility. Therefore, Patent Documents 1 and 2 disclose cosmetic compositions containing specific polyethers as cosmetics that can achieve both high moisturizing effects and a good, non-sticky usability.

[0004] JP 2004-83541 A JP 2020-105123 A

[0005] In the field of cosmetics, surfactants are sometimes used to stably add hydrophobic ingredients such as fragrances, preservatives, active ingredients, and oils to cosmetics, but there is a demand for further reductions in the amount of surfactant used in order to improve the feel during use, such as stickiness, and to reduce irritation. However, reducing the amount of surfactant used can sometimes result in a decrease in the transparency of the cosmetic when multiple oils with different polarities, such as hydrocarbon oils and fats, are used. Furthermore, reducing the amount of surfactant used can reduce low-temperature stability. For example, when a cosmetic is frozen at around −4° C., some components in the cosmetic precipitate, and even after the cosmetic is returned to room temperature, the precipitates may not dissolve and remain in the cosmetic.

[0006] In view of these circumstances, there is a need for the development of a cosmetic base that can provide a cosmetic having good transparency, good low-temperature stability, good moisturizing effect, and a good non-sticky feel when used, even when the amount of surfactant used is reduced.

[0007] An object of the present invention is to provide a polyether useful as a cosmetic base, which can provide a cosmetic having good transparency, good low-temperature stability, good moisturizing effect, and a good non-sticky feel when used, even when the amount of surfactant used is reduced.

[0008] The present inventors conducted extensive research in light of the above situation and found that polyethers with specific structures can solve the above problems. Specifically, reducing the amount of surfactant used can lead to non-uniformity in cosmetics containing hydrophobic components, reduced transparency, and reduced low-temperature stability. However, it was found that by using polyethers with specific structures, even when the amount of surfactant used is reduced, the low-temperature stability of cosmetics containing hydrophobic components can be improved, while at the same time reducing stickiness and providing high moisturizing effects in the cosmetics. Based on this finding, the present invention is as follows. [1] Formula (1):

[0009]

[0010] [In the formula, R １ , R ２ , and a R ３ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and (R １ ~R ３ (number of hydrogen atoms in R １ ~R ３ the ratio of the number of hydrocarbon groups in the alkyl group to the alkyl group (number of hydrocarbon groups in the alkyl group) is 20 or less, GL is a glycerin residue, CH ２ CH2O 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 having 4 to 8 carbon atoms; a, b, c, and d are GL, CH, ２ CH２ O, CH ２ CH ２ CH ２ O, and C ｎ H ２ｎ a is an average degree of polymerization of 0, 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.] [2] A cosmetic base comprising the polyether described in [1] above. [3] A cosmetic base comprising the cosmetic base described in [2] above in an amount of 0.1 to 30% by mass relative to the total cosmetic.

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

[0012] Furthermore, a cosmetic containing a predetermined amount of the cosmetic base made of the polyether of the present invention can provide a non-sticky, pleasant feel in use and a high moisturizing effect, and can maintain good transparency and good low-temperature stability even when the amount of surfactant used in the cosmetic is reduced.

[0013] In this specification, any numerical range defined using "to" is intended to include both the upper and lower limits of the range. For example, "2 to 5" means 2 or more and 5 or less.

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

[0015]

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

[0017] In formula (1), R １ , R ２ , and a R ３are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Polyethers having a hydrocarbon group having 21 or more carbon atoms may result in a decrease in the moisturizing effect, transparency, or low-temperature stability of the cosmetic.

[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 the alkyl group and the alkenyl group 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 the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a tert-butyl group, and a hexyl group. The hydrocarbon group having 1 to 20 carbon atoms is most preferably a methyl group.

[0020] (R １ ~R ３ (number of hydrogen atoms in R １ ~R ３ The ratio of the number of hydrocarbon groups in the hydroxyl group (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 viewpoints of suppressing stickiness, transparency, and low-temperature stability in the cosmetic. Note that the ratio of hydrogen atom / hydrocarbon group may be 0. In addition, in the present specification, R １ ~R ３ When the number of hydrocarbon groups in is 0, the ratio of hydrogen atoms / hydrocarbon groups is interpreted as ∞ (infinity).

[0021] As will be described in the Examples section below, the hydrogen atom / hydrocarbon group of the polyether (i.e., (R １ ~R ３ (number of hydrogen atoms in R １ ~R ３ The number of hydrocarbon groups in the １３ The integral value of the signal of the carbonyl carbon derived from the acetyl group obtained by C-NMR measurement and the terminal CH ３From the integral value of the signal of the carbonyl carbon derived from the acetyl group, the following formula was calculated: hydrogen atom / hydrocarbon group = integral value of the signal of the carbonyl carbon derived from the acetyl group / terminal CH ３ The integral of the signal can be calculated as

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

[0023] as needed, １３ Not only C-NMR measurement １ The hydrogen atoms / hydrocarbon groups can be calculated by combining measurements such as H-NMR, DEPT135, and two-dimensional NMR (HHCOSY, HMQC, HMBC, NOESY).

[0024] In formula (1), GL is a glycerin residue. Here, the "glycerin residue" refers to a group represented by formula (2) or formula (3):

[0025]

[0026] (Wherein * represents R ３ (wherein the bond position is the bond position with the glycerin residue). The glycerin residue may be a group formed from a compound other than glycerin, as long as it is a group having a structure represented by formula (2) or formula (3). Hereinafter, "a group represented by formula (2)" and "a group represented by formula (3)" may be abbreviated as "group (2)" and "group (3)", respectively.

[0027] When GL (glycerin residue) is present in the polyether of the present invention, both group (2) and group (3) may be present. When GL (glycerin residue) is present in the polyether of the present invention, both group (2) and group (3) are preferably present.

[0028] When GL (glycerin residue) is present in the polyether of the present invention, the molar ratio of group (2) / group (3) is preferably 40 / 60 to 99 / 1, more preferably 40 / 60 to 90 / 10, and even more preferably 50 / 50 to 80 / 20, from the viewpoints of suppressing stickiness, transparency, and low-temperature stability in the cosmetic. １３ Specifically, the molar ratio of group (2) / group (3) can be calculated by comparing the integral value of the signal of the methine carbon of group (2) (near 71 ppm) with the integral value of the signal of the methine carbon of group (3) (near 79 ppm).

[0029] In formula (1), CH ２ CHO is an ethylene glycol residue. Here, "ethylene glycol residue" refers to ethylene glycol (HO-CH ２ The ethylene glycol residue refers to a group having a structure obtained by removing one hydroxy group (HO-) and removing a hydrogen atom (H) from the other hydroxy group (-OH) (CH-OH). The ethylene glycol residue may be a group formed from a compound other than ethylene glycol (for example, ethylene oxide) as long as it has the above structure.

[0030] In formula (1), CH ２ CH ２ CH ２ O is a 1,3-propanediol residue. Here, the term "1,3-propanediol residue" refers to 1,3-propanediol (HO-CH ２ CH ２ The 1,3-propanediol residue refers to a group having a structure obtained by removing one hydroxy group (HO-) and removing a hydrogen atom (H) from the other hydroxy group (-OH) from the 1,3-propanediol residue (CH-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 is a group having the above structure.

[0031] In formula (1), C ｎ H ２ｎO is an alkanediol residue having 4 to 8 carbon atoms. Here, the term "alkanediol residue having 4 to 8 carbon atoms" refers to an alkanediol having 4 to 8 carbon atoms (HO-C ｎ H ２ｎ It means a group having a structure obtained by removing one hydroxy group (HO-) and removing a hydrogen atom (H) from the other hydroxy group (-OH, n = 4 to 8). The alkanediol may be either linear or branched. The alkanediol residue having 4 to 8 carbon atoms may be a group formed from a compound different from the alkanediol having 4 to 8 carbon atoms, as long as it is a group having the above structure. The "1,2-butanediol residue" described below and the like have the same meaning as the "alkanediol residue having 4 to 8 carbon atoms."

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

[0033] C ｎ H ２ｎ From the viewpoints of the moisturizing effect, transparency, and low-temperature stability in the cosmetic, O is preferably an alkanediol residue having 4 to 6 carbon atoms, more preferably a 1,2-butanediol residue, a 1,3-butanediol residue, a 1,4-butanediol residue, a 1,5-pentanediol residue, or a 1,6-hexanediol residue, even more preferably a 1,3-butanediol residue, a 1,4-butanediol residue, or a 1,6-hexanediol residue, and particularly preferably a 1,3-butanediol residue or a 1,6-hexanediol residue.

[0034] Polyethers having an alkanediol residue having 9 or more carbon atoms may result in a decrease in transparency or low-temperature stability in cosmetics.

[0035] In formula (1), a, b, c, and d are GL, CH, ２ CH ２ O, CH ２ CH ２ CH ２ O, and C ｎ H ２ｎ The average degree of polymerization of O is 0. Therefore, these may all be decimal numbers.

[0036] From the viewpoints of suppressing stickiness, transparency, and low-temperature stability in the cosmetic, 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 absent. When b is 0, from the viewpoints of transparency and low-temperature stability in the cosmetic, a is preferably a number from 2 to 10, and more preferably a number from 3 to 10.

[0037] From the viewpoint of the moisturizing effect, transparency, and low-temperature stability in the cosmetic, b is a number from 0 to 80, preferably a number from 0 to 50, and more preferably a number from 0 to 30. Here, "b is 0" means that CH ２ CH ２ It means that there is no O. When a is 0, b is preferably a number from 4 to 50 from the viewpoint of transparency and low-temperature stability in the cosmetic.

[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 viewpoints of suppressing stickiness, transparency, and low-temperature stability in the cosmetic.

[0039] From the viewpoint of the moisturizing effect, transparency, and low-temperature stability in the cosmetic, c is a number from 0 to 60, preferably a number from 0 to 40, and more preferably a number from 0 to 30. Here, "c is 0" means that CH ２ CH ２ CH ２ It means that there is no O. When d is 0, c is preferably a number from 2 to 30 from the viewpoint of transparency and low-temperature stability in the cosmetic.

[0040] From the viewpoint of the moisturizing effect in the cosmetic, d is a number from 0 to 60, preferably a number from 0 to 40, and more preferably a number from 0 to 30. Here, "d is 0" means that C ｎ H ２ｎ It means that there is no O. When c is 0, d is preferably a number from 2 to 30 from the viewpoint of transparency and low-temperature stability in the cosmetic.

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

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

[0043] In formula (1), n ​​is C ｎ H ２ｎ O, and is a number of 4 to 8. From the viewpoint of transparency and low-temperature stability in the cosmetic, n is preferably a number of 4 to 6, and more preferably 4 or 6.

[0044] The slash " / " in formula (1) represents GL, CH ２ CHO, CH ２ CH ２ CH ２ O, and C ｎ H ２ｎ There is no restriction on the order of GL, CH, and O, that is, they can be present in any order. ２ CHO, CH ２ CH ２ CH ２ O, and C ｎ H ２ｎ O may be randomly bonded to each other, (ii) GL, CH ２ CHO, CH ２ CH ２ CH ２ O, and C ｎ H ２ｎ(iii) any one or more of GL, CH ２ CHO, CH ２ CH ２ CH ２ O, and C ｎ H ２ｎ O may be bonded in a manner including both of the above (i) and (ii). For example, multiple CH ２ CH ２ O forms a block, and this block, GL, and CH ２ CH ２ CH ２ O and C ｎ H ２ｎ O may be bonded randomly. Three or more CH ２ CH ２ When O is present, (CH ２ CH ２ O) ３ It is preferable that a block of the formula (I) is formed.

[0045] The weight-average molecular weight (Mw) of the polyether of the present invention, calculated from a chromatogram obtained by gel permeation chromatography (GPC), is preferably 300 to 10,000, 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 a known method, for example, by (i) producing a reaction intermediate by a dehydration condensation reaction of a polyhydric alcohol in the presence of an acid catalyst such as sulfuric acid at 80°C to 130°C under normal pressure, and (ii) subsequently carrying out an etherification reaction of the reaction intermediate with an alkyl halide or an alkenyl halide in the presence of a catalyst such as potassium hydroxide at 80°C to 130°C.

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

[0048] <Cosmetic base and cosmetic> 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 based on the total cosmetic.

[0049] By using the cosmetic base of the present invention, a high moisturizing effect and a good non-sticky feel can be imparted to the cosmetic, and the amount of surfactant contained in the cosmetic can be relatively reduced.

[0050] The cosmetic of the present invention is not particularly limited and may be any of aqueous cosmetics, water-in-oil or oil-in-water emulsion cosmetics, and oil-based cosmetics. Examples of cosmetics include skin care cosmetics such as lotions, beauty serums, emulsions, creams, packs, and sunscreen creams; body cosmetics; makeup removers such as cleansing oils and cleansing waters; skin cleansers such as body soaps, hand soaps, and facial cleansing pastes; hair cosmetics such as shampoos, treatments, hair liquids, hair oils, hair tonics, and hair growth agents; and makeup cosmetics such as makeup bases, liquid foundations, and BB creams.

[0051] The content of the cosmetic base of the present invention is 0.1 to 30% by mass, preferably 0.5 to 15% by mass, based on the total mass of the cosmetic of the present invention, from the viewpoint of suppressing stickiness.

[0052] The cosmetic of the present invention preferably contains water (more preferably purified water). Furthermore, the cosmetic of the present invention may contain other components different from the cosmetic base and water of the present invention, as needed, as long as the effects of the present invention are not impaired. There are no particular limitations on the other components, 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, sequestering agents, ethanol, thickeners, preservatives, colorants, pigments, and fragrances. Only one type of other component may be used, or two or more types may be used in combination.

[0053] When the cosmetic 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, based on the total amount of the lotion, serum, or emulsion of the present invention, from the viewpoints of moisturizing effect, freshness, and feel when used (e.g., a refreshing feeling). Water refers to 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 of the present invention and other ingredients).

[0054] When the cosmetic 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, based on the total amount of the cream, liquid foundation, or sunscreen cream of the present invention, from the viewpoints of emollient effect and moisture evaporation inhibitory 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 of the present invention and other ingredients).

[0055] When the cosmetic 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, based on the total amount of the shampoo or body soap of the present invention, from the viewpoint of cleansing performance. 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 of the present invention and other ingredients).

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

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

[0058] When the cosmetic of the present invention is a 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, based on the total amount of the cleansing water of the present invention, from the viewpoint of cleansing performance. Note that 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 of the present invention and other ingredients).

[0059] When the cosmetic 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, based on the entire facial cleansing paste of the present invention, from the viewpoint of cleansing performance. 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 of the present invention and other ingredients).

[0060] The present invention will be described in detail below with reference to examples and comparative examples. In the following, "%" in the amounts of components means "% by mass" unless otherwise specified.

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

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

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

[0064] Then, 67 g of the reaction intermediate and potassium hydroxide were charged into an autoclave equipped with a thermometer, pressure gauge, safety valve, nitrogen gas inlet tube, stirrer, vacuum exhaust tube, cooling coil, and steam jacket, and nitrogen substitution was performed. 51 g of methyl chloride was then pressure-charged at a temperature of 80 ° C to 130 ° C, and the etherification reaction was carried out for 3 hours. The crude product was then removed from the autoclave, adsorbed with an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd.), and 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 using the following method and was found to be 72 / 28.

[0065] (Calculation of the molar ratio of group (2) / group (3)) Example Polyether 2 １３ C-NMR measurement was performed with inverse gate decoupling, and the molar ratio of group (2) / group (3) was calculated by comparing the integral value of the signal of the methine carbon of group (2) (around 71 ppm) with the integral value of the signal of the methine carbon of group (3) (around 79 ppm). １３ The conditions for C-NMR measurement are as follows: １３ C-NMR device: JNM-ECA600 (JEOL-NMR) ・Solvent: D ２ O Sample concentration: 100 mg / 0.6 mL Temperature: 25°C Number of accumulations: 256

[0066] (Production Example 3: Synthesis of Example Polyethers 3 to 12 and Comparative Example Polyethers 1 to 9) Example polyethers 3 to 12 and comparative example polyethers 1 to 9 were synthesized in the same manner 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] (Production Example 4: Synthesis of Comparative Example Polyether 10) An autoclave equipped with a thermometer, a pressure gauge, a safety valve, a nitrogen gas inlet tube, a stirrer, a vacuum exhaust tube, a cooling coil, and a steam jacket was charged with 100 g of 1,2-propanediol and 6.0 g of potassium hydroxide as a catalyst, and after purging with nitrogen, the temperature was raised to 115°C, and a mixture of 1,626 g of propylene oxide and 1,258 g of ethylene oxide was added over 8 hours under conditions of 0.5 MPa or less. After completion of the addition, the mixture was reacted at 115°C for 1 hour and then treated under reduced pressure at 75 to 85°C for 1 hour to obtain a reaction intermediate (hydroxyl value: 106 (mg KOH / g)).

[0068] Next, 110 g of potassium hydroxide was charged into the autoclave, and after nitrogen substitution, 50 g of methyl chloride was pressure-charged at a temperature of 80 ° C to 130 ° C, and an etherification reaction was carried out for 5 hours. Thereafter, the reaction composition was removed from the autoclave, adsorbed with two adsorbents (Kyoward #700 and #1000), and then filtered to obtain Comparative Polyether 10 (hydroxyl value: 5.0 (mg KOH / g)). The weight average molecular weight (hereinafter sometimes abbreviated as "Mw") of Comparative Polyether 10 measured under the conditions described below was 1050. Note that Comparative Polyether 10 differs in structure from the polyethers of the present invention in that it has a repeating unit derived from propylene oxide (i.e., a branched propyleneoxy group different from the linear 1,3-propanediol residue).

[0069] (Production Example 5: Synthesis of Comparative Polyether 11) 152 g of glycerin and 7.0 g of potassium hydroxide were charged into an autoclave equipped with a thermometer, pressure gauge, safety valve, nitrogen gas inlet tube, stirrer, vacuum exhaust tube, cooling coil, and steam jacket. After nitrogen substitution, the temperature was raised to 120°C, and a mixture of 734.5 g of glycidol and 1,439.4 g of propylene oxide was added over 20 hours at 0.5 MPa or less. After completion of the addition, the reaction was carried out 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 Polyether 11. The Mw of Comparative Polyether 11 measured under the conditions described below was 1,430. Note that Comparative Polyether 11 has a structure different from the polyethers of the present invention in that it contains 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 to 12 and Comparative Example Polyethers 1 to 9 １ ~R ３ , hydrogen atom / hydrocarbon group (i.e., (R １ ~R ３ (number of hydrogen atoms in R １ ~R ３ Ratio of the number of hydrocarbon groups in the 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 ratio and Mw were calculated as follows.

[0071] (Calculation of hydrogen atoms / hydrocarbon groups) １ ~R ３ (number of hydrogen atoms in R １ ~R ３ The number of hydrocarbon groups in the １３ The integral value of the signal of the carbonyl carbon derived from the acetyl group obtained by C-NMR measurement and the terminal CH ３ From the integral value of the signal of the carbonyl carbon derived from the acetyl group, the following formula was calculated: hydrogen atom / hydrocarbon group = integral value of the signal of the carbonyl carbon derived from the acetyl group / terminal CH３ The signal integral was calculated as follows:

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

[0073] < １３ C-NMR measurement> About the obtained acetylated product １３ C-NMR measurement was performed, and the integral value of the signal of the carbonyl carbon derived from the acetyl group at around 170 ppm and the terminal CH derived from the hydrocarbon group at around 10 to 15 ppm were obtained. ３ The integral value of the signal of the hydrogen atom / hydrocarbon group (i.e., (R １ ~R ３ (number of hydrogen atoms in R １ ~R ３ The number of hydrocarbon groups in the １３ The conditions for C-NMR measurement were as follows: １３ C-NMR device: JNM-ECA600 (JEOL-NMR) ・Solvent: CDCl ３ Sample concentration: 40 mg / 0.6 mL Temperature: 25°C Number of accumulations: 4096

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

[0075]

[0076]

[0077] (Evaluation of Transparency of Aqueous Solution or Dispersion Containing Olive Oil and Squalane) A beaker was charged with 2.0% of the Example polyether or Comparative Example polyether, 3.0% of PEG-40 hydrogenated castor oil and 3.0% of Polysorbate 80 as surfactants, 0.3% of olive oil and 0.1% of squalane as oil agents, and the remainder, purified water, and the mixture was 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 oil agents, 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 oil agents, 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 (110 mL screw tube No. 8 manufactured by Maruemu Co., Ltd.), and the legibility of letters (font: MS Gothic, font size: 28 pt) placed 5 cm away from the glass container was judged, and transparency was evaluated according to the following criteria. The results are shown in Table 3. <Evaluation criteria> ◎: The aqueous solution is transparent and the letters are clearly legible ○: The aqueous solution is translucent but the letters are legible ×: The dispersion is milky and the letters are illegible or the dispersion has separated

[0081]

[0082] (Production Example 6: Production of Example Cosmetics 1 to 15, Comparative Example Cosmetics 1 to 11, and Reference Example Cosmetics 1 and 2) Example polyether or Comparative Example polyether, 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 Example Cosmetics 1 to 15, Comparative Example Cosmetics 1 to 11, and Reference Example Cosmetics 1 and 2. The compositions of the common ingredients are shown in Table 6. Note that "BG" in Table 6 is the cosmetic name indicated by the Japan Cosmetic Industry Association and stands for 1,3-butylene glycol.

[0083] (Evaluation of non-stickiness) Ten men and women (aged 25 to 50) served as panelists. 1.0 g of each cosmetic obtained in Production Example 6 was applied to the inside of the right forearm of each panelist, and the panelists were rated for stickiness according to the following criteria. The total score of the 10 panelists was calculated, and the non-stickiness was evaluated according to the following criteria. The results are shown in Tables 4 and 5. <Scoring criteria> 3 points: No stickiness 2 points: Slight stickiness 1 point: Stickiness <Evaluation criteria> ◎: Total score is 25 points or more ○: Total score is 20 points or more and 24 points or less △: Total score is 19 points or less

[0084] (Evaluation of Moisture-Retaining Effect) Ten men and women (aged 25 to 50 years) served as panelists. In a constant-temperature, constant-humidity room set at a temperature of 20°C and a relative humidity of 50%, 1.0 g of each cosmetic product obtained in Production Example 6 was applied to the inside of the right forearm of each panelist. Before application and one hour after application, the moisture content of the stratum corneum was measured using a skin surface stratum corneum moisture content measuring device (SKICON-200EX, manufactured by IBS Co., Ltd.). The relative value of the moisture content of the stratum corneum was calculated, assuming the value before application to be 1, and scored according to the following criteria. The total score of the 10 panelists was 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 of 3 or more 2 points: relative value of 2 or more but less than 3 1 point: relative value less than 2 <Evaluation Criteria> ⊚: total score of 25 points or more ○: total score of 20 points or more but less than 24 points △: total score of 19 points or less

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

[0086] (Evaluation of Low-Temperature Stability) 30 mL of each cosmetic obtained in Production Example 6 was filled into a 50 mL glass container and stored in a light-shielded thermostatic chamber at -4°C 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.

[0087]

[0088]

[0089]

[0090] As is clear from the table, Example Polyethers 1 to 12, which correspond to the polyethers of the present invention, were excellent in all of the above evaluations. In contrast, Comparative Example Polyethers 1 to 11 were insufficient in any of the above evaluations.

[0091] R １ ~R ３ In Comparative Example 1, where R is a hydrogen atom and the ratio of hydrogen atoms to hydrocarbon groups is ∞, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, Comparative Example 1, which contained Comparative Example 1, was insufficient in terms of non-stickiness, transparency, and low-temperature stability.

[0092] The transparency of the dispersion containing olive oil and squalane was insufficient for Comparative Polyether 2, in which a+b exceeded 80. Furthermore, Comparative Cosmetic 2, which contained Comparative Polyether 2, was insufficient in terms of non-stickiness, transparency, and low-temperature stability.

[0093] In Comparative Polyether 3, in which (a+b) / (c+d) was less than 0.2, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, Comparative Cosmetic 3, which contained Comparative Polyether 3, was insufficient in terms of non-stickiness, moisturizing effect, transparency, and low-temperature stability.

[0094] The transparency of the dispersion containing olive oil and squalane was insufficient for Comparative Polyether 4, in which (a+b) / (c+d) exceeded 8. Furthermore, Comparative Cosmetic 4, which contained Comparative Polyether 4, was insufficient in terms of non-stickiness, moisturizing effect, transparency, and low-temperature stability.

[0095] In Comparative Polyether 5, in which a+b was less than 1, the transparency of the dispersion containing olive oil and squalane was insufficient. Comparative Cosmetic 5, which contained Comparative Polyether 5, was insufficient in terms of non-stickiness, moisturizing effect, transparency, and low-temperature stability.

[0096] The transparency of a dispersion containing olive oil and squalane was insufficient for Comparative Polyether 6, in which the ratio of hydrogen atoms to hydrocarbon groups exceeded 20, d exceeded 60, and c+d exceeded 70. Furthermore, Comparative Cosmetic 6, which contained Comparative Polyether 6, was insufficient in terms of non-stickiness, moisturizing effect, transparency, and low-temperature stability.

[0097] In Comparative Example 7, in which both c and d were 0 and (a + b) / (c + d) was infinity, the transparency of the dispersion containing olive oil and squalane was insufficient. Furthermore, Comparative Example 7, which contained Comparative Example 7, was insufficient in terms of non-stickiness, moisturizing effect, transparency, and low-temperature stability.

[0098] R １ ~R ３In Comparative Example 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 8, which contained Comparative Example Polyether 8, was insufficient in moisturizing effect, transparency, and low-temperature stability.

[0099] The transparency of the dispersion containing olive oil and squalane was insufficient for Comparative Polyether 9, in which n was greater than 8. Furthermore, Comparative Cosmetic Preparation 9, which contained Comparative Polyether 9, was insufficient in moisturizing effect, transparency, and low-temperature stability.

[0100] Comparative Polyether 10, a copolymer of ethylene oxide and propylene oxide with a structure different from that of the polyether of the present invention, exhibited insufficient transparency in a dispersion containing olive oil and squalane. Furthermore, Comparative Cosmetic 10, which contained Comparative Polyether 10, exhibited insufficient transparency and low-temperature stability.

[0101] Comparative Polyether 11, a copolymer of glycidol and propylene oxide, differs in structure from the polyether of the present invention, and the transparency of a dispersion containing olive oil and squalane was insufficient. Furthermore, Comparative Cosmetic 11, which contains Comparative Polyether 11, was insufficient in transparency and low-temperature stability.

[0102] (Formulation Examples) Formulation examples of cosmetics containing the polyether of the present invention (lotion, serum, emulsion, oil-in-water cream, water-in-oil cream, shampoo, treatment, cleansing oil, cleansing water, pump foamer, body soap, facial cleansing paste, liquid foundation, sunscreen cream) are shown in Tables 7 to 20 below. The amounts of ingredients shown in Tables 7 to 20 are values ​​based on the entire cosmetic. In addition, the cosmetic name indicated by the Japan Cosmetic Industry Association has been used as the name of each ingredient listed in Tables 7 to 20 below, as appropriate. It should be noted that the present invention is not limited to the following formulation examples.

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

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

[0122] This application is based on Japanese Patent Application No. 2024-057119, the contents of which are incorporated in their entirety herein.

Claims

1. Formula (1): [In the formula, R １ , R ２ , and a R ３ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and (R １ ~R ３ (number of hydrogen atoms in R １ ~R ３ the ratio of the number of hydrocarbon groups in the alkyl group to the alkyl group (number of hydrocarbon groups in the alkyl group) is 20 or less, GL is a glycerin residue, CH ２ CH2O 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 having 4 to 8 carbon atoms; a, b, c, and d are GL, CH, ２ CH ２ O, CH ２ CH ２ CH ２ O, and C ｎ H ２ｎ a is an average degree of polymerization of 1 to 80, 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.

2. A cosmetic base comprising the polyether according to claim 1.

3. A cosmetic comprising the cosmetic base according to claim 2 in an amount of 0.1 to 30% by mass based on the total amount of the cosmetic.

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